EP0611986A1

EP0611986A1 - Solid photographic processing composition for silver halide color photographic light-sensitive material

Info

Publication number: EP0611986A1
Application number: EP94102254A
Authority: EP
Inventors: Ichiro C/O Konica Corporation Tsuchiya; Shigeharu C/O Konica Corporation Koboshi
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 1993-02-15
Filing date: 1994-02-14
Publication date: 1994-08-24

Abstract

Disclosed is a solid photographic processing composition for silver halide photographic light-sensitive material comprising a support and provided thereon, a silver halide emulsion layer, wherein the composition is in the form of tablets prepared by compressing a powder or granules comprising at least one photographic processing agent component, and each mechanical strength Z of said tablets is within the range:

0.3 < Z ≦ 3.5

wherein Z is the ratio of the crushing strength (Kg) of the tablet to the major axis length (mm) of the tablet.

Description

FIELD OF THE INVENTION

The present invention relates to a solid photographic processing composition for silver halide photographic light-sensitive material, more specifically a solid photographic processing composition for silver halide photographic light-sensitive material having excellent solubility, practically sufficient strength and remarkably improved chemical stability.

BACKGROUND OF THE INVENTION

Silver halide color photographic light-sensitive materials (hereinafter also referred to as light-sensitive materials or photographic materials) are processed in developing, desilvering, washing, stabilizing and other processes after exposure. Silver halide black-and-white photographic light-sensitive materials are developed and fixed after exposure. A black-and-white developer or a color developer, a bleacher or a bleach-fixer, a fixer, tap water or deionized water, a stabilizing solution and a dye stabilizer are used for development, desilvering, fixing, washing, waterless washing and dye stabilization, respectively.
The liquids capable of performing these processes are called processing solutions. Each processing solution is usually kept at a temperature of 30 to 40°C, in which the light-sensitive material is immersed and processed.
These processes are usually carried out by sequentially transporting the light-sensitive material through processing tanks containing the above processing solutions, using an automatic processing machine or another means.
The automatic processing machine mentioned herein is generally a processing machine having a developing portion, a fixing portion, a desilvering portion, a washing or stabilizing portion and a drying portion, and a means for automatically sequentially transporting the photographic light-sensitive material to the processing tanks.
In carrying out processing using such an automatic processing machine, the processing solution in each processing tank is supplemented with a processing agent to keep the activity of the processing solution in the processing tank constant.
For this purpose, it is a common practice to prepare a replenisher containing the processing agent dissolved therein.
Specifically, processing is carried out while supplying the previously prepared replenisher from the replenisher tank to the processing tank as appropriate.
In this case, the replenisher to be stored in the replenisher tank is usually prepared in a separate place, but in mini-labs etc., the replenisher is usually prepared in a given amount in a replenisher tank equipped near the processing tank in the processing machine at a time by manual dissolution or mixing dissolution using a mechanical mixer.
The silver halide photographic light-sensitive material processing agent (hereinafter also referred to as photographic processing agent) is supplied in the form of powder or liquid; it is prepared as a solution by manually dissolving the powder in a given amount of water. In the case of a liquid processing agent, it is prepared as a dilution by adding a given amount of water and stirring the mixture, since it is supplied in a concentrated state.
Replenisher tanks may be set by the automatic processing machine, requiring considerable space. Also, in recently-increasing mini-labs, replenisher tanks are housed in the automatic processing machine; in this case as well, sufficient space must be available for the replenisher tanks, each of which should contain at least 5 to 10 liters of replenisher.
Any processing agent for replenishment is divided in some parts to ensure constantly good performance in photographic processing. For example, the color developer replenisher is divided in three or four parts, and the bleach-fixer replenisher for color photography is supplied in two parts: a part of the oxidant ferric salt of organic acid and a part of the reducing agent thiosulfate. In preparing the replenisher, said dense part of ferric salt of organic acid and said dense part of thiosulfate are mixed together and diluted with a given amount of water before using.
Said dense parts are placed in containers such as plastic containers, which containers are packed in outer packages, such as corrugated cardboard boxes, for 1 unit of commercial distribution.
The processing agent for replenishment in a kit of part agents is dissolved, diluted, mixed and then diluted to a given volume before using. Said processing agent for replenishment has the following drawbacks:
First, almost all conventional kits comprise dense aqueous solutions concentrated for improved operability, most of which are very dangerous because of extreme pH values of not higher than 2.0 or not lower than 12.0 in that they are harmful to the human body by skin contact etc. Also, many of them are strong oxidants or reducing agents, possessing very dangerous corrosivity in transport by ships or aircraft. The aqueous solution is subject to limitation as to solubility, being heavier and bulkier than in the case of solid. Since the concentrated solution is a dangerous article as stated above, its containers must be sufficiently tough to prevent destruction and spillage even if it is fallen; plastic container disposal poses a problem.
Second, the part agents are separately contained in respective containers; some processing agents for replenishment comprise several bottles of part agents so that each unit of commercial distribution thereof involves a considerable number of containers, which requires much space for storage and transportation. For example, the color developer replenishing agent for CPK-2-20QA, a processing solution for color printing paper, is available in 10-liter units, wherein part A (a kit including a preservative), part B (a kit including a color developing agent) and part C (alkaline agent) are each contained in a 500-ml plastic container. Similarly, the bleach-fixer replenisher is available in 8-liter units, wherein three part agents are contained in respective bottles. The stabilizer replenisher is available in 10-liter units, wherein two part agents are contained in respective bottles. These replenishing agents are stored and transported in respective outer packages of various sizes. The outer package size ranges from about 17 x 14 x 16.5 cm for the stabilizer replenisher to about 18.5 x 30.5 x 22.5 cm for the bleach-fixer replenisher; it is not possible to pile packages of replenishers in storing or transporting them or in stocking them at dealer shops unless they are of the same kind, so that much space is required.
The third drawback concerns the problem of waste container disposal. In recent years, there has been strong demand for environmental conservation and saving resources mainly in Europe and the United States; in the photographic industry, plastic container disposal has been of major concern. Specifically, although plastic containers for photographic use are cheap, conveniently storable and transportable and excellent in chemical resistance, they pose problems of accumulation in the environment because they are hardly biodegradable, and emission of large amounts of carbon dioxide upon burning, which contribute to global warming and acid rain. As for the problems posed on the user side, they include decrease in the available working area due to occupation of the narrow working space by crowding plastic containers, which are too tough to compress.
The fourth drawback is poor chemical stability.
Usually, the life time of a replenisher is at most 2 weeks even in the presence of a floating lid. However, with the trend toward replenishing rate reduction, it has recently been common to use a 10-liter replenisher over a period of more than 1 month in a mini-lab receiving an order of 30 rolls of color films daily on average.
In this case, the replenisher in the replenishing tank is often much more frequently in contact with air than the processing solution in the processing tank; replenishing often fails to have the desired effect due to replenisher deterioration. Accordingly, attempts have been made to reduce the replenishing tank capacity to 5 liters or reduce the replenishing kit unit to 5 liters. However, this approach involves another drawback of the necessity of additional packing material.
For example, in preparing a color developer replenisher for color printing paper, a given volume of water is placed in the replenisher tank, after which dense kit A, which contains a preservative, is added, followed by stirring, and dense kit B, which contains a color developing agent, is then added, followed by stirring, and dense kit C, which contains an alkaline agent, is then added, followed by stirring, and finally water is added to make a given volume. This series of procedures is liable to be accompanied by some problems. For example, in case of insufficient stirring or a failure to add the starting water, the color developing agent tends to crystalize, and the resulting crystal can stay in the bellows pump and fail to be supplied so that the photographic performance becomes labile or the bellows pump breaks. Also, the dense kits are not always used immediately after production; they may be used even 1 year after production; in some cases, performance becomes labile due to oxidation of the color developing agent or preservative.
The color developer replenisher prepared from dense kits or powder is also known to pose some problems in the replenisher tank. For example, if the replenisher remains unused for a long time, crystals can deposit on the inside wall of the replenisher tank, the replenisher becomes susceptible to oxidation, and tar forms. Under some storage conditions, other problems arise, including separation of easily-crystallizing components of the replenisher, such as the color developing agent, at low temperatures; some makers specify replenisher storage conditions and instruct the users to keep their replenishers under those conditions.
As stated above, when a replenisher, e.g., a color developer replenisher for color printing paper, is prepared using a commonly used dense kit or powder, the above-mentioned problems arise; similar problems arise in the case of bleach-fixer, bleacher and fixer. For example, the bleach-fixer is characterized by considerably poor storage stability. This is because the bleach-fixer is usually of high acidity and considerably low pH for neutralizing the alkalinity of the dye fixer carried over by the printing paper being processed because the bleach-fixing process immediately follows the process with a color developer of high pH. It is said that at low pH values, any bleach-fixer comprising a thiosulfate and an oxidant is considerably poor in storage stability and cannot be replenished at low replenishing rates. The same applies to the fixer and stabilizer.
Another problem is that the replenisher becomes increasingly dense in answer to the recent trend toward replenishing rate reduction and rapid processing; it has recently been a common practice to concentrate the replenisher to the limit of solubility.
This deteriorates replenisher storage stability, thus posing many practical problems such as crystal separation.
On the other hand, in addition to the above method of preparing a replenisher using a dense kit or powder, another method is known wherein a dense kit is added as such.
In this method, supplying means such as a bellows pump are used to supply the dense kit as such directly to the processing tank and a given volume of replenishing water is added independently, to improve the low efficiency in dissolving operation. This method really obviates solution preparing operation and is free of the problem of poor storage stability because no replenisher solution is prepared, in comparison with the above method, wherein the replenisher is prepared from a dense kit or powder.
However, this method also involves many problems. The major problem is the increased size of the automatic processing machine because of the necessity for a dense kit tank for supplying the dense kit and a pump for supplying the dense kit. For example, in the case of CPK-2-20, a processing solution for color printing paper, the dense kit of color developer replenisher is divided in three parts; the dense kit of bleach-fixer replenisher, three parts; and the dense kit of stabilizer replenisher, two parts. To supply all these dense kits, eight tanks and eight pumps are required. In the conventional replenishing method, three tanks and three pumps are sufficient, since each replenisher requires one tank and one pump. In short, more tanks and more pumps than in the conventional method are required for supplying the dense kits, and a pump for water used to prepare the replenisher is also required. Also, since bellows pump precision is not so high, it is difficult to accurately discharge a plurality of solutions simultaneously, which can result in an imbalanced composition.
Moreover, dense kits are difficult to maintain due to proneness to crystallization near the outlet of the replenisher nozzle because they are dense solutions. Another problem is that the bellows pump is insufficient in supplying accuracy so that replenishing accuracy fluctuates widely during supply of a dense replenisher, resulting in very labile photographic performance. Still another problem is that the amount of waste plastic containers remains unchanged, in comparison with the conventional replenishing method, even when dense kits are supplied.
In addition to the above methods, some proposals have been made to obviate the use of plastic containers and improve replenisher chemical stability.
For example, Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) Nos. 133332/1979 and 155038/1979 disclose powdered photographic processing agents, and Japanese Patent O.P.I. Publication Nos. 109042/1990, 109043/1990, 39735/1991 and 39739/1991 disclose methods using granular photographic processing agents having a particular average grain size. Although the methods described in these publications serve to improve replenisher stability without using plastic containers because they use no liquid photographic processing agent, they have drawbacks such as blocking during storage cause dissolution failure or dust formation at the time of processing solution preparation deteriorates the working environment when the processing agent is a powder.
In the case of granular processing agents as well, dust scattering cannot be perfectly prevented, though blocking and other undesirable phenomena are mitigated to some extent.
To solve these problems, tableted photographic processing composition are proposed in WO 92/200B and other publications.
Such tableted photographic processing composition are faulty in that their solubility is much lower than that of powdery or granular photographic processing composition, though they offer a solution to the above-described problem of dust scattering. Accordingly, Japanese Patent O.P.I. Publication No. 61837/1976 discloses photographic tablets containing a disintegrating agent. However, the disintegrating agent described in this publication, based on a water-swellable colloid, was found to have an important drawback that when a processing solution is prepared from tablets containing it, the colloid adheres to the racks and transport rollers etc. of the automatic processing machine, which can stain the processed light-sensitive material. As a means of promoting tablet dissolution, foaming tablets are known in the field of pharmaceuticals, for instance. This is a method of promoting dissolution by internal disintegration of tablets based on foaming action at dissolution. However, this method requires a foaming agent to cause foaming action, resulting in a drawback that processing agent components in a more amount than the essentially desired is required due to reduction in processing performance per tablet when non-essential components are added to the photographic processing agent, while the desired foaming effect can be maintained by containment of a large amount of a foaming agent in cases of agents of low active ingredient content per tablet like pharmaceuticals.
Against this background the present inventors investigated the solubility of photographic processing tablets, and found that the solubility can be controlled without addition of special additives such as a disintegrating agent and foaming agent by adjusting tablet strength.
This possibility is not described in any of the above-mentioned patent publications, never expected from the present invention.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide an automatic processing machine obviating the use of liquid chemicals dangerous in transport and handling to allow the use of solid chemicals without troublesome operation by the user.
It is another object of the present invention to provide a solid photographic processing composition having excellent solubility and practically sufficient strength.
The present inventors found that the above problems can be solved by a solid photographic processing composition for silver halide photographic light-sensitive material in the form of tablets prepared by compressing a powder or granules comprising at least one processing agent component, wherein mechanical strength Z falls within the range:

$0.3 < Z ≦ 3.5$

where Z is the ratio of the crushing strength (kg) of the tablet to the major axis length (mm) of the tablet. The present invention is hereinafter described in more detail.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 is a cross-sectional view of a processing agent receiving portion and processing agent supplying means in an automatic processing machine equipped with a means of replenishing water supplier.
Figure 2 is a plane view and oblique view of a tablet supplying apparatus and a plane view of a package.
Figure 3 shows the correlation between the compressing surface of hardness meter and the direction of the major axis of a tablet.
Figure 4 shows the correlation between compressing direction for crushing in measurement and compressing direction in compression molding of a tablet.
In these figures, the symbols represent the following:

1: Processing tank
2: Processing portion
3: Filter
4: Circulatory pipe
5: Circulatory pump
6: Waste liquid discharge pipe
7: Heater
8: Processing amount information detector and processing agent supply controller
11: Solid processing agent receiving portion
12: Separating wall
13: Solid photographic processing composition (tablet)
14: Filtering means (section)
41: Pipe (for replenishing water supply)
42: Water replenishing means
43: Replenishing water tank
150: Processing agent cartridge
151: Solid photographic processing composition
152: Package
153: Peel open cylinder
154: Tablet inlet
155: Receiving portion
156: Package winding shaft
157: Handle
158: Clamper
M: Winding shaft driving motor

DETAILED DESCRIPTION OF THE INVENTION

Although a known method can be used to form tablets by compression tabletting, it is preferable to produce tablets by granulating and then tabletting a powdery solid processing agent. This method is advantageous in that photographic performance is stable as a result of improvement in solubility and storage stability, in comparison with solid processing agents prepared solely by mixing and tabletting solid processing agent components.
For forming tablets, known granulating methods can be used, including tumbling granulation, extrusion granulation, compressive granulation, disintegration granulation, stirring granulation, fluidized bed granulation and spray drying granulation. In forming tablets, it is preferable to use a granulation product having an average grain size of 100 to 800 µm, more preferably 200 to 750 µm, since unevenness in the composition, or so-called segregation, is not likely upon granulation product mixing and compression. In addition, the grain size distribution is preferably such that not less than 60% of the grains fall within the range of ± 100 to 150 µm apart from the average grain size. In compressing the granulation product obtained, a known compressing machine, such as a hydraulic press, a single tabletting machine, a rotary tabletting machine or a briquetting machine, can be used.
Although the solid processing agent obtained by compression can take any shape, cylindrical agents, i.e., so-called tablets, are preferred from the viewpoint of productivity and handling quality.
More preferably, components such as an alkali agent, a reducing agent, a bleaching agent and a preservative, are separately granulated, whereby the above effect is enhanced.
The mechanical strength Z of the solid photographic processing composition of the present invention is more than 0.3 and not more than 3.5, preferably between 0.5 and 3.0. Mechanical strength values of under 0.3 result in a very brittle solid photographic processing composition not suitable for practical use. Mechanical strength values exceeding 3.0 result in loss of solid photographic processing composition elasticity, which in turn lead to cracking tendency and significant deterioration of its solubility. Here, the mechanical strength Z is defined by the following equation:

$Z = Crushing strength of a tablet (kg)/Longitudinal length of a tablet (mm)$

A tablet is defined to be a solid agent pressed into a fixed shape through compression molding. The crushing strength of a tablet is represented by a value of pressure applied to the tablet to destroy it in the direction perpendicular to that of compression molding for the tablet (namely, in parallel with a compressed plane of the tablet in compression molding). The measurement conditions were a room temperature of 25 °C and a humidity of 50 % RH, and a measurement was taken by the use of a SPEED CHECKER TS-50N (produced by Okada Seiko Co., Ltd.), the value was measured under the compressing speed of 5 to 78 mm/min. With regard to the compressing speed, the optimum one is selected depending upon the size and the form of a tablet agent.
When a tablet is in a shape of a disk, the longitudinal length of the tablet agent is defined to be a diameter of the disk, while when it is polygonal, the longitudinal length is defined to be a distance between a plane of the tablet which is in parallel to the compressing surface of a hardness tester (which is different from a compressing surface of a tablet in compression molding) and a point or a surface of the tablet which is farthest from the plane in the crushing direction of the hardness tester. When a tablet is in an irregular shape representing a combination of an ellipse, a circle and a polygon, the longitudinal length is defined to be the maximum length of the tablet whose both ends are respectively in contact with compressing surfaces of the hardness tester. Mechanical strength Z is concretely measured as Figures 3A through 3F and Figure 4.
Although the tablets of the present invention may take any form, disk-like tablets are preferred from the viewpoint of productivity and handling. In the case of a disk-like tablet, the major axis length of the tablet is the diameter of the tablet, which may be set at any level according to purpose of use, preferably 5 to 50 mm, more preferably 7 to 30 mm from the viewpoint of productivity. On the other hand, the ratio x/h of the major axis length x and thickness h of the tablet is preferably within the range 1.0-6.0, more preferably 2.5-5.0. If the ratio decreases below 1.0, tablet thickness increases, resulting in deteriorated solubility and productivity. If the ratio exceeds 6.0, the desired strength cannot be obtained.
Although the solid photographic processing composition relating to the present invention may be used in any mode of use according to purpose, it is preferable, from the viewpoint of automatic processing agent size reduction, waste liquid volume reduction, etc., to add it as a replenisher directly to a processing chamber of the automatic processing agent.
From the viewpoint of productivity, the tablets of the present invention preferably have a weight of 0.1 to 30 g per tablet. A p-phenylenediamine compound having a water-solubilizing group is preferably used as a color developing agent in the color developer for the present invention, since it enhances the desired effect of the invention and causes little fogging.
The p-phenylenediamine compounds having a water-solubilizing group are advantageous over the p-phenylenediamine compounds having no water-solubilizing group, such as N,N-diethyl-p-phenylenediamine, that they do not contaminate the light-sensitive material and are not irritative to skin upon skin contact. In addition, their use in combination with the color developer for the present invention allows more efficient accomplishment of the desired object of the invention.
The p-phenylenediamine compound for the present invention has at least one water-solubilizing group as described above on the amino group or benzene nucleus thereof. Preferred water-solubilizing groups include:
-(CH₂)_n-CH₂OH,
-(CH₂)_m-NHSO₂-(CH₂)_n-CH₃,
-(CH₂)_m-O-(CH₂)_n-CH₃,
-(CH₂CH₂O)_nC_mH_2m+1 (m and n independently represent an integer of not less than 0), a -COOH group and a -SO₃H group.
Examples of color developing agents preferably used for the present invention are C-1 through C-16 described on pages 26 through 31 of Japanese Patent Application No. 203169/1990.

The color developing agent described above is used normally in the form of a salt such as hydrochloride, sulfate or p-toluenesulfonate.
The above-mentioned color developing agents may be used singly or in combination, and may be used in combination with black-and-white developing agents such as phenidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone and Metol as desired.
It is a preferred mode of embodiment of the present invention to add a compound represented by the following formula A or B to the color developer relating to the present invention, whereby the desired effect of the invention is enhanced.
Specifically, it is effective in that not only the storage stability of tablets and other forms of solid processing agent improve in comparison with other compounds, but also sufficient strength is maintained. Another advantage is that photographic performance becomes stable and fogging in the unexposed portion is suppressed.

wherein R₁ and R₂ independently represent an alkyl group, an aryl group,

or a hydrogen atom, provided that they do not represent a hydrogen atom concurrently. The alkyl groups represented by R₁ and R₂ may be identical or not, each of which preferably has 1 to 3 carbon atoms. These alkyl groups may have a carboxylate group, a phosphate group, a sulfonate group or a hydroxyl group.
R' represents an alkoxy group, an alkyl group or an aryl group. The alkyl groups and aryl groups for R₁, R₂ and R' include those having a substituent. R₁ and R₂ may bind together to form a ring, such as a heterocyclic ring like piperidine, pyridine, triazine or morpholine.

wherein R₁₁, R₁₂ and R₁₃ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group or heterocyclic group; R₁₄ represents a hydroxyl group, a hydroxyamino group, a substituted or unsubstituted alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, carbamoyl group or amino group. The heterocyclic group is a 5- or 6-membered ring comprising C, H, O, N, S and halogen atoms, whether saturated or unsaturated. R₁₅ represents a divalent group selected from the group consisting of -CO-, -SO₂- and

n represents 0 or 1. Provided that n is 0, R₁₄ represents a group selected from an alkyl group, an aryl group and a heterocyclic group; R₁₃ and R₁₄ may cooperate to form a heterocyclic group.
Examples of the hydroxylamine compound represented by formula A are given in US Patent Nos. 3287125, 33293034 and 3287124 and other publications. Particularly preferable compounds are compound Nos. A-1 through A-39 described on pages 36 through 38 of Japanese Patent Application No. 203169/1990, compound Nos. 1 through 53 described on pages 3 through 6 of Japanese Patent O.P.I. Publication No. 33845/1991 and compound Nos. 1 through 52 described on pages 5 through 7 of Japanese Patent O.P.I. Publication No. 63646/1991.
Examples of the compound represented by formula B are compound Nos. B-1 through B-33 described on pages 40 through 43 of Japanese Patent Application No. 203169/1990 and compound Nos. 1 through 56 described on pages 4 through 6 of Japanese Patent O.P.I. Publication No. 33846/1991.
These compounds represented by formula A or B are used normally in the forms of free amine, hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate, acetate and others.
The color developer and black-and-white developer used for the present invention may incorporate a trace amount of sulfite as a preservative. Examples of such sulfites include sodium sulfite, potassium sulfite, sodium bisulfite and potassium bisulfite.
The color developer and black-and-white developer used for the present invention must contain a buffer. Examples of buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (boric acid), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).
Examples of developing accelerators which can be added as necessary include the thioether compounds disclosed in Japanese Patent Examined Publication Nos. 16088/1962, 5987/1962, 7826/1963, 12380/1969 and 9019/1970 and US Patent No. 3813247, the p-phenylenediamine compounds disclosed in Japanese Patent O.P.I. Publication Nos. 49829/1977 and 15554/1975, the quaternary ammonium salts disclosed in Japanese Patent O.P.I. Publication Nos. 137726/1975, 156826/1981 and 43429/1977 and Japanese Patent Examined Publication No. 30074/1969, the p-aminophenols disclosed in US Patent Nos. 2610122 and 4119462, the amine compounds disclosed in US Patent Nos. 2494903, 3128182, 4230796, 3253919, 2482546, 2596926 and 3582346 and Japanese Patent Examined Publication No. 11431/1966, the polyalkylene oxides disclosed in Japanese Patent Examined Publication Nos. 16088/1962, 25201/1967, 11431/1966 and 23883/1967 and US Patent Nos. 3128183 and 3532501, and 1-phenyl-3-pyrazolidones, hydrozines, meso-ionic compounds, ionic compounds and imidazoles.
Preferably, the color developer contains substantially no benzyl alcohol, specifically not more than 2.0 ml per liter of color developer, more preferably absolutely no benzyl alcohol. When the color developer contains substantially no benzyl alcohol, better results are obtained with less fluctuation in photographic properties in continuous processing, particularly less increase in the degree of staining.
For the prevention of fogging and other purposes, chlorine and bromine ions must be present in the color developer. In the present invention, it is preferable, from the viewpoint of developing speed, staining and minimum density fluctuation, that chlorine ions be contained at 1.0 x 10⁻² to 1.5 x 10⁻¹ mol/l, more preferably 4 x 10⁻² to 1 x 10⁻¹ mol/l. It is therefore preferable to prepare the solid processing agent to make the color developer in the processing tank have a concentration in the above range.
In the present invention, it is preferable, from the viewpoint of developing speed, maximum density, sensitivity and minimum density, that the color developer in the processing tank contain bromine ions at a concentration of 3.0 x 10⁻³ to 1.0 x 10⁻³ mol/l, more preferably 5.0 x 10⁻³ to 5 x 10⁻⁴ mol/l, and still more preferably 1 x 10⁻⁴ to 3 x 10⁻⁴ mol/l. In this case as well, it is preferable to prepare the solid processing agent to make the color developer in the processing tank have a bromine concentration within the above range.
Provided that chlorine ions are added directly to the color developer, examples of chlorine ion sources include sodium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride and cadmium chloride, with preference given to sodium chloride and potassium chloride.
Chlorine ions may also be supplied in the form of a counterpart salt of the color developer or the brightening agent added thereto. Examples of bromine ion sources include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide and thallium bromide, with preference given to potassium bromide and sodium bromide.
In addition to chlorine ions and bromine ions, the color developer and black-and-white developer used for the present invention may incorporate antifogging agents which are optionally selected as necessary. Antifogging agents which can be used include alkali metal halides such as potassium iodide and organic antifogging agents. Typical examples of organic antifogging agents include nitrogen-containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolidine and adenine.
From the viewpoint of the desired effect of the present invention, it is preferable to add a triazinylstilbene brightening agent to the color developer and black-and-white developer used for the present invention. Said brightening agent is preferably represented by the following formula E:

wherein X₂, X₃, Y₁ and Y₂ independently represent a hydroxyl group, a chlorine atom, a bromine atom or another halogen atom, an alkyl group, an aryl group,

or -OR₂₅. In the above formulas, R₂₁ and R₂₂ independently represent a hydrogen atom, an alkyl group (may be substituted) or an aryl group (may be substituted); R₂₃ and R₂₄ each represent an alkylene group (may be substituted); R₂₅ represents a hydrogen atom, an alkyl group (may be substituted) or an aryl group (may be substituted); M represents a cation.
Details of the groups in formula E and substituents therefor are the same as those described in line 8 from bottom, page 63, through line 3 from bottom, page 64, of Japanese Patent Application No. 240400/1990.
Examples of the compound represented by formula E are given below.
These compounds can be synthesized by known methods. Of the example compounds given above, E-4, E-24, E-34, E-35, E-36, E-37 and E-41 are preferably used. It is preferable to prepare the solid processing agent so that the amount of these compounds added falls within the range from 0.2 to 10 g, preferably from 0.4 to 5 g per liter of color developer.
The color developer and black-and-white developer used for the present invention may also incorporate organic solvents such as methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin and the compounds described in Japanese Patent Examined Publication Nos. 33378/1972 and 9509/1969 for increasing the solubility of the developing agent as necessary.
Auxiliary developing agents may be used in combination with the principal developing agent. Examples of such auxiliary developing agents include Metol, phenidone, N,N-diethyl-p-aminophenol hydrochloride and N,N,N',N'-tetramethyl-p-phenylenediamine hydrochloride.
It is also possible to use various additives such as antistaining agents, anti-sludge agents and developing accelerators.
It is preferable, from the viewpoint of efficient accomplishment of the desired effect of the present invention, that the color developer and the black-and-white developer incorporate one of the chelating agent represented by the following formula K and example compound Nos. K-1 through K-22, described in line 8 from bottom, page 63, through line 3 from bottom, page 64, of Japanese Patent Application No. 240400/1990.

wherein A₁ through A₄ independently represent a hydrogen atom, a hydroxyl group, -COOM or -PO₃(M)₂; M represents a hydrogen atom or an atom of alkali metal. E represents a substituted or unsubstituted alkylene group; a cycloalkylene group, a phenylene group, -R₅OR₅-, -R₅OR₅OR₅- or -R₅ZR₅-, Z represents >N-R₅-A₅ or >N-A₅. R₁ through R₅ independently represent a substituted or unsubstituted alkylene group.

Of these chelating agents, K-2, K-9, K-12, K-13, K-17 and K-19 are preferably used, with more preference given to K-2 and K-9, since their addition to the color developer enhances the effect of the invention.
It is preferable to add these chelating agents to the solid processing agent so that their amount falls within the range from 0.1 to 20 g, preferably from 0.2 to 8 g per liter of color developer or black-and-white developer.
The color developer and black-and-white developer may also contain anionic, cationic, amphoteric and nonionic surfactants.
Various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids and aromatic carboxylic acids may be added as necessary.
The bleaching agents which are preferably used in the bleacher or bleach-fixer relating to the present invention are ferric complex salts of the organic acid represented by the following formula C:

wherein A₁ through A₄, whether identical or not, independently represent -CH₂OH, -COOM or -PO₃M₁M₂ (M, M₁ and M₂ independently represent a hydrogen atom, an atom of alkali metal or ammonium); X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms.
The compound represented by formula C is described in detail below.
A₁ through A₄ in the formula are not described in detail here, since they are identical with A₁ through A₄ described in line 15, page 12, through line 3, page 15, of Japanese Patent Application No. 260628/1989.
A ferric complex salt of the organic acid represented by formula C is preferably used for the present invention, since a small amount is sufficient to solidify itself because of the high bleaching capability so that weight and size reduction is possible, and since it offers an additional effect of improving the storage stability of solid processing agent.
Examples of preferred compounds represented by the above formula C are given below.

The ferric complex salts of these compounds C-1 through C-12 may be sodium salts, potassium salts or ammonium salts thereof, which can be selected optionally. From the viewpoint of the desired effect of the present invention and solubility, ammonium salts of these ferric complex salts are preferably used.
Of the compounds exemplified above, C-1, C-3, C-4, C-5 and C-9 are preferred, with more preference given to C-1.
In the present invention, ferric complex salts of the following compounds and others can be used as bleaching agents for the bleacher or bleach-fixer in addition to the iron complex salts of the compound represented by the above formula C.

A'-1: Ethylenediaminetetraacetic acid
A'-2: Trans-1,2-cyclohexanediaminetetraacetic acid
A'-3: Dihydroxyethylglycinic acid
A'-4: Ethylenediaminetetrakismethylenephosphonic acid
A'-5: Nitrilotrismethylenephosphonic acid
A'-6: Diethylenetriaminepentakismethylenephosphonic acid
A'-7: Diethylenetriaminepentaacetic acid
A'-8: Ethylenediaminediorthohydroxyphenylacetic acid
A'-9: Hydroxyethylethylenediaminetriacetic acid
A'-10: Ethylenediaminedipropionic acid
A'-11: Ethylenediaminediacetic acid
A'-12: Hydroxyethyliminodiacetic acid
A'-13: Nitrilotriacetic acid
A'-14: Nitrilotripropionic acid
A'-15: Triethylenetetraminehexaacetic acid
A'-16: Ethylenediaminetetrapropionic acid
A'-17: β-alaninediacetic acid

The bleacher may incorporate at least one of the imidazole described in Japanese Patent O.P.I. Publication No. 295258/1989, derivatives thereof and the compounds represented by formulas I through IX given in the same publication, whereby rapid processing is facilitated.
In addition to the above-mentioned developing accelerators, the example compounds given on pages 51 through 115 of Japanese Patent O.P.I. Publication No. 123459/1987, the example compounds given on pages 22 through 25 of Japanese Patent O.P.I. Publication No. 17445/1988 and the compounds described in Japanese Patent O.P.I. Publication Nos. 95630/1978 and 28426/1978 can also be used.
In addition to the above-mentioned additives, the bleacher or bleach-fixer may incorporate halides such as ammonium bromide, potassium bromide and sodium bromide, various brightening agents, defoaming agents and surfactants.
The fixing agents which are preferably used in the fixer or bleach-fixer for the present invention are thiocyanates and thiosulfates. The amount of thiocyanate added is preferably not less than 0.1 mol/l, more preferably not less than 0.5 mol/l, and still more preferably not less than 1.0 mol/l for processing a color negative film. The amount of thiosulfate added is preferably not less than 0.2 mol/l, more preferably not less than 0.5 mol/l for processing a color negative film. Also, the object of the present invention can be more efficiently accomplished by using a thiocyanate and a thiosulfate in combination.
In addition to these fixing agents, the fixer or bleach-fixer for the present invention may contain two or more pH regulators comprising various salts. It is also desirable to add a large amount of a re-halogenating agent such as an alkali halide or an ammonium halide, e.g., potassium bromide, sodium bromide, sodium chloride or ammonium bromide. Compounds which are known to be added to fixer or bleach-fixer, such as alkylamines and polyethylene oxides, may be added as appropriate.
It is preferable to add a compound represented by the following formula FA, described on page 56 of Japanese Patent O.P.I. Publication No. 295258/1989, to the fixer or bleach-fixer, whereby not only the effect of the invention is enhanced but also an additional effect is obtained in that sludge formation in the processing solution capable of fixing is significantly suppressed during prolonged processing of a small amount of light-sensitive material.

Compounds represented by formula FA can be synthesized by ordinary methods such as those described in US Patent Nos. 3335161 and 3260718. These compounds represented by formula FA may be used singly or in combination.
Good results are obtained when these compounds represented by formula FA are used in amounts of 0.1 to 200 g per liter of processing solution.
In the present invention, it is preferable to add a chelating agent having a ferric ion chelate stability constant of over 8 to the stabilizer. Here, the chelate stability constant is the constant which is well known in L.G. Sillen and A.E. Martell, "Stability Constants of Metal-Ion Complexes", The Chemical Society, London (1964), S. Chaberek and A.E. Martell, "Organic Sequestering Agents", Wiley (1959), and other publications.
Examples of chelating agents having a ferric ion chelate stability constant of over 8 include those described in Japanese Patent Application Nos. 234776/1990 and 324507/1989.
The amount of the above chelating agent used is preferably 0.01 to 50 g, more preferably 0.05 to 20 g per liter of stabilizer, within which content range good results are obtained.
Ammonium compounds are preferably added to the stabilizer, which are supplied as ammonium salts of various inorganic compounds. The amount of ammonium compound added preferably falls within the range from 0.001 to 1.0 mol, more preferably from 0.002 to 2.0 mol per liter of stabilizer.
The stabilizer preferably contains a sulfite.
The stabilizer preferably contains a metal salt in combination with the chelating agent described above. Examples of such metal salts include salts of Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb, Sn, Zn, Ti, Zr, Mg, Al and Sr, and it can be supplied as an inorganic salt such as halide, hydroxide, sulfate, carbonate, phosphate or acetate, or a water-soluble chelating agent. The amount of metal salt added preferably falls within the range from 1 x 10⁻⁴ to 1 x 10⁻¹ mol, more preferably from 4 x 10⁻⁴ to 2 x 10⁻² mol per liter of stabilizer.

EXAMPLES

Example 1

Color developer tablets for color printing paper were prepared as follows:

Procedure (1)

1200 g of the developing agent CD-3 [4-amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]aniline sulfate] was milled in a commercially available Hammer mill to a final average grain size of 30 µm. The fine powder thus obtained was granulated in a commercially available mixer granulator at room temperature for about 7 minutes while adding 50 ml of water. The granulation product was then dried in a fluidized bed dryer at 40°C for 2 hours to remove almost all the water therefrom. To the granulation product, 150 g of polyethylene glycol 6000 was added, followed by uniform mixing in a mixer for 10 minutes in a room kept at 25°C and under 40% RH. Next, 4 g of N-lauloylalanine sodium salt was added, followed by mixing for 3 minutes. The resulting mixture was subjected to compressive tabletting using a tabletting machine, a modification of Tough Press Correct 1527HU, produced by Kikusui Seisakusho, at the packing rates and strengths per tablet shown in Table 1, to yield 400 tablets of each of color developer tablet agent samples 1-1 through 1-14 for color printing paper.

Experiment

From the tablet agent samples obtained through the above-mentioned procedure, 10 tablets were picked up at random. They were measured in terms of hardness by the use of a SPEED CHECKER TS-50N (produced by Okada Seiko Co., Ltd.) at the crushing speed of 50 mm/min. From their average value, the hardness was obtained. The room temperature in measurement was 25 °C and the humidity was 50 % RH. In addition, the other 1 tablet was taken out separately and dropped from a height of 1 m.

Table 1

Sample No.	Tablet diameter d (mm)	Tablet weight w (g)	Strength Z = M/d	Fall test result	Dissolution time	Remark
1-1	15	1.00	0.17	D	3′50˝	Comparative
1-2	15	1.00	0.37	C	4′00˝	Inventive
1-3	15	1.00	0.81	B	4′01˝	Inventive
1-4	15	1.00	1.40	A	4′10˝	Inventive
1-5	15	1.00	2.27	A	4′24˝	Inventive
1-6	15	1.00	3.00	A	4′30˝	Inventive
1-7	15	1.00	3.60	B	8′27˝	Inventive
1-8	15	2.00	0.20	D	5′40˝	Comparative
1-9	15	2.00	0.40	C	5′45˝	Comparative
1-10	15	2.00	0.89	B	5′47˝	Inventive
1-11	15	2.00	1.47	A	5′53˝	Inventive
1-12	15	2.00	2.47	A	5′58˝	Inventive
1-13	15	2.00	2.80	A	6′00˝	Inventive
1-14	15	2.00	3.67	B	11′38˝	Comparative
Evaluation criteria for fall test D: Total breakage in single fall C: Partial cracking in single fall B: Cracking in 3 to 5 falls A: No defect seen in 5 falls

From Table 1, it is seen that tablet strength values of under 0.3 result in a lack of fall strength so that the tablets are not usable due to difficult handling and transportation, and that tablet strength values exceeding 3.5 result in extremely delayed dissolution, though desired hardness is obtained. On the other hand, the tablets of the present invention have practically sufficient strength and excellent solubility.

Example 2

Samples were prepared and tested in the same manner as in Example 1, except that CD-3 was replaced with CD-4 [4-amino-3-methyl-N-ethyl-β-hydroxyethylaniline sulfate]. Almost the same results as in Example 1 were obtained.

Example 3

Samples of bleaching tablet for color negative films were prepared as follows:

Bleacher replenisher tablets for color negative films

Procedure (2)

175 g of ammonium ferric 1,3-propanediaminetetraacetate monohydrate, 2 g of 1,3-propanediaminetetraacetic acid and 17 g of Pineflow (Matsutani Chemical Industry Co., Ltd.) were milled, mixed and granulated in the same manner as procedure (1) of Example 1. The amount of water added was 8 ml. The granulation product was then dried at 60°C for 30 minutes to remove almost all the water therefrom.

Procedure (3)

133 g of succinic acid, 200 g of ammonium bromide and 102 g of Pineflow were milled, mixed and granulated in the same manner as procedure (1). The amount of water added was 17 ml. The granulation product was then dried at 70°C for 60 minutes to remove almost all the water therefrom.

Procedure (4)

66.7 g of potassium sulfate, 60 g of potassium hydrogen carbonate and 8 g of mannitol were milled, mixed and granulated in the same manner as procedure (1). The amount of water added was 13 ml. The granulation product was then dried at 60°C for 60 minutes to remove almost all the water therefrom.

Procedure (5)

The granulation products obtained in the above procedures (2) through (4) were uniformly mixed in a mixer for about 10 minutes in a room conditioned at 25°C temperature and under 40% RH. To this mixture, 6 g of N-lauloylsalcosine sodium salt was added, followed by mixing for 3 minutes. The resulting mixture was subjected to compressive tabletting at the packing rates per tablet and diameters shown in Table 2, using a tabletting machine, a modification of Tough Press Correct 1527HU, produced by Kikusui Seisakusho, to yield 80 tablets of each of bleacher replenisher tablet samples 2-1 through 2-10 for color negative films.

Experiments

Strength determination, a fall test and a dissolution test were conducted in the same manner as in Example 1.

The results are given in Table 2.

Table 2

Sample No.	Tablet diameter d (mm)	Tablet weight w (g)	Strength Z = M/d	Fall test result	Dissolution time	Remark
2-1	30	10.0	0.27	D	4′22˝	Comparative
2-2	30	10.0	0.48	C - B	4′32˝	Inventive
2-3	30	10.0	1.71	B	5′10˝	Inventive
2-4	30	10.0	2.51	A	5′35˝	Inventive
2-5	30	10.0	3.58	B	9′11˝	Comparative
2-6	50	25.0	0.17	D	7′12˝	Comparative
2-7	50	25.0	0.34	C	7′22˝	Inventive
2-8	50	25.0	1.39	C - B	7′37˝	Inventive
2-9	50	25.0	2.45	A	7′46˝	Inventive
2-10	50	25.0	3.53	B	15′23˝	Comparative

From Table 2 above, it is seen that the tablets of the present invention have practically sufficient strength and excellent solubility even when their diameter is varied.

Example 4

Fixing tablets for color negative films were prepared as follows:

Fixer replenisher tablets for color negative films

Procedure (6)

2500 g of ammonium thiosulfate, 150 g of sodium sulfite, 150 g of potassium carbonate, 20 g of disodium ethylenediaminetetraacetate and 65 g of Pineflow (Matsutani Chemical Industry Co., Ltd.) were milled, mixed and granulated in the same manner as procedure (1). The amount of water added was 50 ml. Granulation was followed by drying at 60°C for 120 minutes to remove almost all the water from the granulation product.

Procedure (7)

The granulation product prepared in the above procedure (6) and 13 g of N-lauloylsalcosine sodium salt were mixed in a mixer for about 3 minutes in a room conditioned at 25°C temperature and under 40% RH. The mixture was subjected to compressive tabletting at the packing rates per tablet and diameters shown in Table 3, using a tabletting machine, a modification of Tough Press Correct 1527HU, produced by Kikusui Seisakusho, to yield 100 tablets of each of fixer replenisher tablet samples 3-1 through 3-12 for color negative films.

Stabilizer replenisher tablets for color negative films

Procedure (8)

1500 g of m-hydroxybenzaldehyde, 200 g of sodium laulyl sulfate, 600 g of disodium ethylenediaminetetraacetate, 650 g of lithium hydroxide monohydrate and 100 g of Pineflow were milled, mixed and granulated in the same manner as procedure (1). The amount of water added was 10 ml. Granulation was followed by drying at 50°C for 2 hours to remove almost all the water from the granulation product.

Procedure (9)

The granulation product prepared in the above procedure (8) was subjected to compressive tabletting at the packing rates per tablet and diameters shown in Table 4, using a tabletting machine, a modification of Tough Press Correct 1527HU, produced by Kikusui Seisakusho, in a room conditioned at 25°C temperature and under 40% RH. to yield 200 tablets of each of stabilizer replenisher tablet samples 4-1 thorough 4-12 for color negative films.

Experiments

The results are given in Tables 3 and 4.

Table 3

Sample No.	Tablet diameter d (mm)	Tablet weight w (g)	Strength Z = M/d	Fall test result	Dissolution time	Remark
3-1	15	1.25	0.28	D	2′32˝	Comparative
3-2	15	1.25	0.56	B	2′37˝	Inventive
3-3	15	1.25	2.11	A	4′10˝	Inventive
3-4	15	1.25	3.89	B	9′32˝	Comparative
3-5	20	3.33	0.29	D	4′32˝	Comparative
3-6	20	3.33	0.42	B	4′54˝	Inventive
3-7	20	3.33	1.97	A	6′13˝	Inventive
3-8	20	3.33	3.60	B	18′34˝	Comparative
3-9	30	10.00	0.28	D	5′30˝	Comparative
3-10	30	10.00	0.69	C	5′42˝	Inventive
3-11	30	10.00	1.80	A	7′42˝	Inventive
3-12	30	10.00	3.67	B	21′42˝	Comparative

Table 4

Sample No.	Tablet diameter d (mm)	Tablet weight w (g)	Strength Z = M/d	Fall test result	Dissolution time	Remark
4-1	5	0.50	0.28	D	14 min	Comparative
4-2	5	0.50	0.40	B	15 min	Inventive
4-3	5	0.50	2.30	A	20 min	Inventive
4-4	5	0.50	3.67	A	55 min	Comparative
4-5	10	0.75	0.25	D	35 min	Comparative
4-6	10	0.75	0.77	B	40 min	Inventive
4-7	10	0.75	2.49	A	55 min	Inventive
4-8	10	0.75	3.71	A	265 min	Comparative
4-9	15	1.25	0.21	D	50 min	Comparative
4-10	15	1.25	0.75	B	75 min	Inventive
4-11	15	1.25	2.62	A	120 min	Inventive
4-12	15	1.25	3.66	A	350 min	Comparative

Example 5

After imagewise exposure, the Konica QA paper type 5 (produced by konica Corporation) was processed according to the following processing steps, using the NPS-808 (produced by Konica Corporation), modified to have the configuration illustrated in Figure 1. The replenishing water in the replenishing tank was deionized water.

Processing step	Processing time	Processing temperature	Tank capacity
Color development	22 seconds	38.0°C	12 l
Bleach-fixation	22 seconds	37.5°C	12 l
Stabilization 1	22 seconds	35°C	12 l
Stabilization
2	22 seconds	35°C	12 l
Stabilization
3	22 seconds	35°C	12 l
Drying	50 seconds	55°C

Stabilization was achieved by the counterflow method from 3 to 1. The entire overflow from stabilization 1 was allowed to enter the bleach-fixing bath. Carry-over per m² of light-sensitive material was 45 ml from the color developing tank to the bleach-fixing tank, 50 ml from the bleach-fixing tank to the stabilizing tank and 40 ml from stabilization 1 to 2, from stabilization 2 to 3 and from stabilization 3 to drying.
The opening area of each of the color developing, bleach-fixing and stabilizing tanks was 4.5 cm² per liter of processing solution.
The ambient conditions for the automatic processing machine were 27°C temperature and 60% RH, and replenishing water was supplied upon the water loss due to evaporation reached 100 ml.
The amount of replenishing water was calculated using the equation (1) shown in Japanese Patent O.P.I. Publication No. 280042/1991. The light-sensitive material was continuously processed at 2.0 m² per day for 2 months.

The compositions of the processing solutions used are as follows:

Color developer
Potassium bromide	0.02 g
Potassium chloride	3.2 g
Potassium carbonate	30 g
Potassium sulfite	0.2 g
Sodium diethylenetriaminepentaacetate	2 g
Sodium nitrilotrimethylenephosphonate Tinopal SFP 2 g	2 g
Disodium N,N-bis(sulfonatoethyl)hydroxylamine 4-amino-3-methyl-N-ethyl-N-(β-	5 g
methanesulfonamidoethyl)aniline sulfate CD-3	7 g
Water was added to make a total quantity of 1 l, and pH was adjusted to 10.10.

Bleach-fixer
Ammonium ferric diethylenetriaminepentaacetate	100 g
Diethylenetriaminepentaacetic acid	2 g
Ammonium thiosulfate	120 g
Ammonium sulfite	40 g
Sulfinic acid	5 g
Ammonium bromide	10 g
Water was added to make a total quantity of 1 l, and pH was adjusted to 7.0.

Stabilizer
Water	800 g
1,2-benzisothiazolin-3-one	0.1 g
1-hydroxyethylidene-1,1-diphosphonic acid	5.0 g
Ethylenediaminetetraacetic acid	1.0 g
Tinopal SFP (produced by Ciba-Geigy)	2.0 g
Ammonium sulfate	2.5 g
Zinc chloride	1.0 g
Magnesium chloride	0.5 g
o-phenylphenol	1.0 g
Sodium sulfite	2.0 g
Water was added to make a total quantity of 1 l, and 50% sulfuric acid or 25% aqueous ammonia was added to obtain a pH of 8.0.

Processing tablets for color printing paper were prepared in accordance with the following procedures:

1) Color developer replenisher tablets for color printing paper

Procedure (A)

1200 g of the developing agent CD-3 [4-amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]aniline sulfate] was milled in a commercially available hammer mill to a final average grain size of 10 µm. The fine powder thus obtained was granulated in a commercially available mixer granulator at room temperature for about 7 minutes while adding 50 ml of water. The granulation product was then dried in a fluidized bed dryer at 40°C for 2 hours to remove almost all the water therefrom. To the granulation product, 150 g of polyethylene glycol 6000 was added, followed by uniform mixing in a mixer for 10 minutes in a room kept at 25°C and under 40% RH. Next, 4 g of N-lauloylalanine sodium salt was added, followed by mixing for 3 minutes. The resulting mixture was subjected to compressive tabletting using a tabletting machine, a modification of Tough Press Correct 1527HU, produced by Kikusui Seisakusho, at a packing rate of 3.2 g per tablet, to yield 400 tablets of color developer replenisher tablet agent A for color printing paper.

Procedure (B)

120 g of disodium disulfoethylhydroxylamine was milled, mixed and granulated in the same manner as procedure (A). The amount of water added was 6.0 ml. The granulation product was then dried at 50°C for 30 minutes to remove almost all the water therefrom. To the granulation product, 4 g of N-lauloylalanine sodium salt was added, followed by uniform mixing in a mixer for 3 minutes in a room kept at 25°C and under 40% RH. The resulting mixture was subjected to compressive tabletting using a tabletting machine at a packing rate of 1.0 g per tablet, to yield 100 tablets of color developer replenisher tablet agent B for color printing paper.

Procedure (C)

30.0 g of Tinopal SFP (produced by Ciba-Geigy), 3.7 g of sodium sulfite, 0.3 g of potassium bromide, 25 g of diethylenetriaminepentaacetic acid, 280 g of sodium p-toluenesulfonate, 20 g of potassium hydroxide and 10.6 g of mannitol were milled in the same manner as procedure (A) and then uniformly mixed in a commercially available mixer, after which the mixture was granulated in the same manner as procedure (A). The amount of water added was 20 ml. Granulation was followed by drying at 60°C for 30 minutes to remove almost all the water from the granulation product. To the granulation product, 4 g of N-lauloylalanine sodium salt was added, followed by uniform mixing in a mixer for 3 minutes in a room kept at 25°C and under 40% RH. The resulting mixture was subjected to compressive tabletting using a tabletting machine, a modification of Tough Press Correct 1527HU, produced by Kikusui Seisakusho, at a packing rate of 3.2 g per tablet, to yield 100 tablets of color developer replenisher tablet agent C for color printing paper.

Procedure (D)

350 g of potassium carbonate was milled and granulated in the same manner as procedure (A). After granulation while adding 20 ml of water, the granulation product was dried at 700°C for 30 minutes to remove almost all the water therefrom. To the granulation product, 15 g of polyethylene glycol 6000 was added and mixed uniformly in a mixer for 10 minutes in a room kept at 25°C and under 40% RH. Next, 4 g of N-lauloylalanine sodium salt was added, followed by mixing for 3 minutes. The resulting mixture was subjected to compressive tabletting using a tabletting machine, a modification of Tough Press Correct 1527HU, produced by Kikusui Seisakusho, at the packing rates per tablet shown in Table 1, to yield 110 tablets of color developer replenisher tablet agent D for color printing paper.

2) Bleach-fixer replenisher tablets for color printing paper

Procedure (E)

1250 g of ammonium ferric diethylenediaminepentaacetate monohydrate, 25 g of ethylenediaminetetraacetic acid, 250 g of maleic acid and 46 g of Pineflow (Matsutani Chemical Industry Co., Ltd.) were milled, mixed and granulated in the same manner as procedure (C). After granulation while adding 80 ml of water, the granulation product was dried at 60°C for 2 hours to remove almost all the water therefrom. To the granulation product, 15 g of N-lauloylsalcosine sodium salt was added, followed by uniform mixing in a mixer for 3 minutes in a room kept at 25°C and under 40% RH. The resulting mixture was subjected to compressive tabletting using a tabletting machine, a modification of Tough Press Correct 1527HU, produced by Kikusui Seisakusho, at a packing rate of 5.8 g per tablet, to yield 170 tablets of bleach-fixer replenisher tablet agent A for color printing paper.

Procedure (F)

1640 g of ammonium thiosulfate, 750 g of sodium sulfite, 40 g of potassium bromide and 50 g of p-toluenesulfinic acid were milled, mixed and granulated in the same manner as procedure (C). After granulation while spraying 100 ml of water, the granulation product was dried at 60°C for 120 minutes to remove almost all the water therefrom. To the granulation product, 20 g of N-lauloylsalcosine sodium salt was added, followed by uniform mixing in a mixer for 3 minutes in a room kept at 25°C and under 40% RH. The resulting mixture was subjected to compressive tabletting using a tabletting machine, a modification of Tough Press Correct 1527HU, produced by Kikusui Seisakusho, at a packing rate of 9.2 g per tablet, to yield 180 tablets of bleach-fixer replenisher tablet agent B for color printing paper.

3) Stabilizer replenisher tablets for color printing paper

Procedure (G)

10 g of sodium carbonate monohydrate, 200 g of disodium 1-hydroxyethane-1,1-diphosphonate, 150 g of Tinopal SFP, 300 g of sodium sulfite, 20 g of zinc sulfate heptahydrate, 150 g of disodium ethylenediaminetetraacetate, 200 g of ammonium sulfate, 10 g of o-phenylphenol and 25 g of Pineflow were milled, mixed and granulated in the same manner as procedure (C). After granulation while adding 60 ml of water, the granulation product was dried at 70°C for 60 minutes to remove almost all the water therefrom. To the granulation product, 10 g of N-lauloylsalcosine sodium salt was added, followed by uniform mixing in a mixer for 3 minutes in a room kept at 25°C and under 40% RH. The resulting mixture was subjected to compressive tabletting using a tabletting machine, a modification of Tough Press Correct 1527HU, produced by Kikusui Seisakusho, at a packing rate of 3.1 g per tablet, to yield 360 tablets of stabilizer replenisher tablet agent for color printing paper.
These tablets were adjusted to appropriate strength as shown in Table 5.
Next, each tablet agent was sealed in a laminated polymer resin film of PET/polyvinyl alcohol-ethylene copolymer/polyethylene at 1 tablet for each of color developer replenisher tablet agents A through D, 1 tablet for each of bleach-fixer replenisher tablet agents A and B and 1 tablet for the stabilizer replenisher tablet agent, and consecutive 20 packages were prepared as a cartridge. Next, after each of the above-described replenisher tablet cartridge was shaken for 6 hours using a commercially available vibrator, tablets were added using the supplying apparatus illustrated in Figure 1. The setting was such that one tablet was added upon processing of 1 m² of color printing paper, and 76 ml of replenishing water for the color developing bath, 42 ml of replenishing water for the bleach-fixing bath and 247 ml of replenishing water for the stabilizing bath would be supplied from the replenishing water tank simultaneously.
Continuous processing was continued until 20 m² of color printing paper was processed, and the tablet supplying apparatus and tablet dissolution condition were observed at each process.

The results are given in Table 6.

Table 6

Process No.	Appearance of tablet supplying apparatus	Tablet residence condition	Remark
1	Tablet fragments adhering to packaging material hampered winding, resulting in tablet supplying apparatus shutdown upon processing of 2 m² of color printing paper.	1 tablet always remained undissolved.	Comparative
2	Normally functioned until 20 m² of color printing paper was processed.	2 tablets always remained undissolved.	Inventive
3	Normally functioned until 20 m² of color printing paper was processed.	2 tablets always remained undissolved.	Inventive
4	Normally functioned until 20 m² of color printing paper was processed.	10 or more tablets remained undissolved, resulting in processing solution circulation pump shutdown upon completion of processing of 10 m² of color printing paper.	Comparative

From Table 6, it is seen that when tablets whose strength Z is under 0.3 are used in an automatic processing machine equipped with a tablet feeder, a lack of strength to vibration results in tablet breakage. Using such tablets interferes with the tablet supplier by their fragments, resulting in tablet supplier shutdown. Also, strength Z values exceeding 3.5 result in considerably deteriorated solubility, leading to accumulation of undissolved tablets in the dissolution chamber, though the desired strength is obtained.
As a result, the undissolved tablets clog the processing solution circulatory pump, also resulting in an important trouble of automatic processing machine shutdown. However, the tablets of the present invention, are sufficiently strong to endure vibration, allowing continuous processing without any trouble with only 1 or 2 tablets remaining undissolved in the dissolution chamber. Also, the photographic performance obtained in processing with the tablets of the present invention was satisfactory in every aspect.
The present invention makes it possible to provide an automatic processing machine allowing the use of solid chemicals without no troublesome operation by the user as a result of obviation of liquid chemicals involving the risk in transportation or handling.

Example 6

Processing tablet for a color negative film were prepared under the following procedure.

1) Tablet for color development replenishing use for a color negative film

In a hammer mill available on the market, 3750.0 g of potassium carbonate, 580.0 g of sodium sulfite, 240.0 g of pentasodium diethylenetriamine pentaacetic acid and 500.0 g of sodium p-toluenesulfonate were crushed until the average grain size becomes 10 µm. To this fine powder, 500.0 g of PEG 6000 and 800.0 g of Mannit were added, and the mixture was stirred for about 7 minutes and at room temperature in a stirring granulator available on the market. Thus a granule is produced. After that, the granulated product was dried at 70 °C for 120 minutes by the use of a fluid-layer drier available on the market so that moisture content of the granulated product was removed almost completely.

Procedure (2)

After 360.0 g of hydroxylamine sulfate, 40.0 g of potassium bromide and 20.0 g of disodium pyrocatecol-3,5-disulfonate were crushed in the same manner as Procedure (1), 20.0 g of Pineflow (produced by Matsutani Chemical) was added and tabletted. The added amount of water was arranged to be 3.5 ml. After tabletting, the granule was dried at 60 ° for 60 minutes, and the moisture therein was removed almost completely.

Procedure (3)

In the same manner as in Procedure (1), 650.0 g of CD-4 [4-amino-3-methyl-N-ethyl-β-(hydroxy)ethylaniline sulfate, which is a color developing agent, was crushed. After that, 10 ml of water was added thereto for 7 minutes at room temperature for granulating. After that, the granulated product was dried at 40 °C for 2 hours by the use of a fluid-layer drier available so that moisture content of the granulated product was removed almost completely.

Procedure (4)

granules prepared in the above-mentioned procedures (1) to (3) were mixed at room temperature for 10 minutes by the use of a cross-rotary type mixer available on the market. In addition, 40.0 g of N-sodium myristoyl alanine was added thereto and mixed for 3 minutes. The mixed granulation prepared in the above-mentioned manner was subjected to consecutive tabletting by the use of a rotary tabletting machine (Clean Press Collect H18 produced by Kikusui Seisakusho Co., Ltd.) so that 600 pcs of tablets for color developer replenishing use for a color negative film having a diameter of 30 mm and a weight of 12.0 g.

The tablet samples prepared in the above-mentioned procedure was subjected to evaluation in the same manner as in Example 1. Table shows the results thereof.
Additional Example wherein the Diameter and the Thickness were changed

Table 7

Sample No.	Tablet diameter d(mm)	Tablet thickness h(mm)	d/h	Tablet weight (g)	Strength Z	Fall test result
1	10	12	0.83	0.96	3.2	B
2	10	10	1.0	0.8	2.6	A
3	10	5	2.0	0.4	2.1	A
4	10	4	2.5	0.32	1.7	A
5	10	2	5.0	0.16	0.7	B
6	10	1.6	6.2	0.13	0.3	B
7	30	36	0.83	39.6	3.4	B
8	30	25	1.2	27.5	3.2	B
9	30	10	3.0	17.0	2.3	A
10	30	6	5.0	6.6	1.2	A
11	30	4.8	6.2	5.3	0.9	B

From Table 7, the tablets of the present invention have practically sufficient strength.

Claims

A solid photographic processing composition for silver halide color photographic light-sensitive material comprising a support and provided thereon, a silver halide emulsion layer, wherein the composition is in the form of tablets prepared by compressing a powder or a granule comprising at least one photographic processing agent component, and each mechanical strength Z of said tablets is within the range:

$0.3 < Z ≦ 3.5$

wherein Z is the ratio of the crushing strength (Kg) of the tablet to the major axis length (mm) of the tablet.
The solid photographic processing composition of claim 1, wherein said mechanical strength Z is within the range of 0.5 to 3.0.
The solid photographic processing composition of claim 1, wherein said photographic processing agent is p-phenylenediamine compound.
The solid photographic processing composition of claim 3, wherein said p-phenylenediamine compounds has a water-solubilizing group.
The solid photographic processing composition of claim 4, further comprising a compound represented by Formula A or Formula B:
wherein R₁ and R₂ independently represent an alkyl group, an aryl group,
or a hydrogen atom, provided that they do not represent a hydrogen atom concurrently. The alkyl groups represented by R₁ and R₂ may be identical or not, each of which preferably has 1 to 3 carbon atoms. These alkyl groups may have a carboxylate group, a phosphate group, a sulfonate group or a hydroxyl group. R' represents an alkoxy group, an alkyl group or an aryl group. The alkyl groups and aryl groups for R₁, R₂ and R' include those having a substituent. R₁ and R₂ may bind together to form a ring, such as a heterocyclic ring like piperidine, pyridine, triazine or morpholine;
wherein R₁₁, R₁₂ and R₁₃ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group or heterocyclic group; R₁₄ represents a hydroxyl group, a hydroxyamino group, a substituted or unsubstituted alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, carbamoyl group or amino group. The heterocyclic group is a 5- or 6-membered ring comprising C, H, O, N, S and halogen atoms, whether saturated or unsaturated. R₁₅ represents a divalent group selected from the group consisting of -CO-, -SO₂- and
n represents 0 or 1. Provided that n is 0, R₁₄ represents a group selected from an alkyl group, an aryl group and a heterocyclic group; R₁₃ and R₁₄ may cooperate to form a heterocyclic group.
The solid photographic processing composition of claim 3, further comprising a compound represented by Formula K:
wherein A₁ through A₄ independently represent a hydrogen atom, a hydroxyl group, -COOM or -PO(M)₂; M represents a hydrogen atom or an atom of an alkali metal; E represents a substituted or unsubstituted alkylene group, a cycloalkylene group, a phenylene group, -R₅OR₅-, -R₅OR₅OR₅- or -R₅ZR₅-, Z represents 〉N―R₅-A₅ or 〉N―A₅ ; R₁ through R₅ independently represent a substituted or unsubstituted alkylene group.
The solid photographic processing composition of claim 1, wherein said photographic processing agent is a ferric complex salt of a compound represented by Formula C:
wherein A₁ through A₄, whether identical or not, independently represent -CH₂OH, -COOM or -PO₃M₁M₂ (M, M₁ and M₂ independently represent a hydrogen atom, an atom of alkali metal or ammonium); X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms.
The solid photographic processing composition of claim 1, wherein the tablet is disk-like tablet, and the major axis length of the tablet is the diameter of the tablet, and the diameter of the tablet is within the range of 5 mm to 50 mm, and the ratio x/h of the major axis length x and thickness h of the tablet is within the range of 1.0 to 6.0.