EP0611989B1

EP0611989B1 - Solid processing composition for silver halide color photographic light-sensitive materials and processing method for the same

Info

Publication number: EP0611989B1
Application number: EP19940300373
Authority: EP
Inventors: Hiroshi Yamashita
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 1993-01-19
Filing date: 1994-01-19
Publication date: 1997-11-19
Anticipated expiration: 2014-01-19
Also published as: DE69406817T2; DE69406817D1; EP0611989A1

Description

This invention relates to a solid processing composition for a silver halide color photographic light-sensitive material suitable for preserving the environment of the earth and excellent in aging preservability; and to a method of processing a silver halide color photographic light-sensitive material in which the solid processing composition is used.
In processes for color developing a silver halide color photographic light-sensitive material, silver halide exposed to light is reduced to silver and, at the same time, an oxidized aromatic primary amine developing agent reacts with a coupler so as to form a dye. Meanwhile the halogen ion produced by reducing the silver halide is eluted and then accumlates in the developer solution. During this reaction the color developing agent is consumed or removed from the solution with the photographic light-sensitive material, so that the concentration of the developing agent is lowered. Therefore, when processing silver halide photographic light-sensitive materials in series through an automatic processor, it is necessary to provide means for keeping the concentration of the developer within a specific range so as to avoid any possible finished development quality variation which may be produced by concentration variation of the developer component. Usually the concentration of the developer is maintained with a replenisher to compensate any shortage and to dilute any unnecessary increased concentration. When such a replenisher is used, a large quantity of a waste solution (so-called overflow solution) is produced and is discarded. This has raised serious economical and environmental problems.
To reduce the overflow, it has been proposed to add a regenerator to the overflow so that it may be used again as replenisher or to use only a small amount of replenisher as a concentrated solution. However the system for recycling the overflow has the disadvantage that extra space for a stock tank and so forth is required and, in addition, that the operations become complicated for a photofinisher. In recent years, particularly, it has been difficult to introduce this system of using regenerated overflow into a small-scaled photofinisher (so-called a mini-lab.) where an on-site processing service is carried out. On the other hand, the use of a concentrated replenisher may be suitable particularly for a small-scaled photofinisher, because this system is space-saving without requiring any extra equipment. However, this system still has the following disadvantages.
When preparing a concentrated replenisher, there is a limit on the concentration which may be obtained because color developing agents are low in solubility. Further, a conventional color developing composition is normally supplied in several separate parts to prevent components of the developing composition reacting chemically with each other, because the necessary components are supplied in the state of an aqueous solution. When preparing a replenisher, the parts of the replenisher are added together and then dissolved. Therefore, once a replenisher is prepared, it cannot be preserved for a long period, because a chemical reaction gradually occurs and the replenisher deteriorates. Thus when a concentrated replenisher is used, not only is the undesirable chemical reaction accelerated because the component concentration in the replenisher is made higher, but also there may be a danger that variations in the photographic processing characteristics may be produced by the deterioration of the replenisher.
There are further disadvantages in that transportation cost is increased and a large space is required for storage, because conventional processing compositions are generally in the form of aqueous solutions stored in plastic bottles. A related problem is how to discard empty plastic bottles. In Europe, for example, it is now the situation that a strong legislative movement has actively sought, for example, the recycling of plastics, the prohibition of their use, or the use of decomposable plastics.
To solve these problems, use of solid processing compositions has been considered. Japanese Patent Publication Open to Public Inspection (hereinafter abbreviated to JP OPI Publication) No. 2-109042/1990 discloses a granulated color developing composition and JP OPI Publication No. 51-61837/1976 discloses a tablet type processing composition. However, when trying to achieve replenishment of a small amount in a method such as that mentioned above, other new problems have been raised. These result from when the replenishment is made smaller in amount, it is necessary to add a color developing agent and an alkali capable of neutralizing the developer. This alkali has to maintain a higher pH value than what was used previously. Furthermore to meet the increasing demand for making processing time shorter, it has also been required to make color developing agents higher in concentration and pH value. Thus potassium carbonate which has so far been used as an alkali is not sufficient to maintain a suitable pH. Thus a strong alkali such as potassium hydroxide has been required. It was, however, found that potassium hydroxide is highly deliquescenct and requires peculiar drying conditions when a solid developing composition is prepared. Furthermore even when a solid type developing composition finished as a product is packed in moisture-resistant packaging, there is the disadvantage that the product must be used up at once.
There was also the problem, that when a granule or tablet solid processing composition whose main component is potassium carbonate is prepared, the strength of the resulting granule or tablet was not sufficient. For example, when the hardness of the tablet was insufficient, the tablet was sometimes cracked or broken off due to shock when dropped or vibrated during transportation.
USP-4756996 discloses the use of LiOH as an alkaline agent in aqueous colour developers.

Brief Description of the Drawings

Fig. 1 illustrates a schematic perspective view showing an example of processing composition supplying means with a peal-open system; and
Fig. 2 illustrates an example of processing composition supplying means in a system for cutting a series of packages into two parts.

It is accordingly an object of the invention to provide a solid processing composition for a silver halide color photographic light-sensitive material, that has the following features, and to provide a method of processing a silver halide color photographic light-sensitive material, in which the abovementioned solid processing composition is used.
These features are that the environment can be improved by reducing the amount of waste liquid and plastic bottle packaging material;

that the processing composition is excellent in aging preservability, and particularly excellent in fluidity or strength; and
that when processing a light-sensitive material in series, the processing can be performed rapidly and the photographic characteristics of the light-sensitive material can be maintained safely.

According to the invention, there is provided a solid processing composition for a silver halide color photographic light-sensitive material which is a color developing composition comprising a p-phenylenediamine color developing agents and lithium hydroxide.
The solid type processing composition is preferably in tablet or granule form;
The tablet is preferably obtained by compressing and molding particles.
The solid processing composition according to the invention preferably contains at least one of the compounds represented by the following Formula [A].
wherein L represents an alkylene group; A represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid residual group, a hydroxy group, an amino group, an ammonio group, a carbamoyl group or a sulfamoyl group; and R represents a hydrogen atom or an alkyl group;
The solid processing composition according to the invention preferably comprises a mixture of granules containing lithium hydroxide and granules containing a p-phenylenediamine type color developing agent. It preferably further comprises granules of formula (A) as defined above.
The invention further provides a process for the preparation of a solid processing composition in tablet form which comprises tabulating a mixture of granules containing lithium hydroxide and granules containing a p-phenylenediamine type color developing agent.
The mixture preferably contains granules of compounds of formula [A]. Each type of granule is preferably separately granulated before mixing.
Lithium hydroxide used in the invention may optionally be either in anhydride or hydrate form.
A granulated composition in the context of the invention means a granule that is prepared by applying a granulation process to a powder and has a granule size within the range of 50 to 5000µm.
A tablet composition in the context of the invention means a tablet prepared by compression-molding a powder to take a specific configuration, or prepared by granulating a powder and then compression-molding the granule to take a specific configuration.
Among the above-mentioned solid processing compositions, a tablet composition is preferably used because it more remarkably displays the effects of the invention.
Methods of preparing the preferable tablet composition include, for example, granulating a powder solid processing composition and then subjecting it to a tableting process. When making use of this method, the resulting tablet composition has improved solubility and preservability compared to a solid processing composition prepared simply by mixing the components of a solid processing composition and then tableting it in a tableting process. As a result, the resulting composition can have the advantage that its photographic characteristics are stabilized.
Suitable granulating methods include for example, any well-known method such as a convoluting granulation method, an extruding granulation method, a compression granulation method, a pulverizing granulation method, a stirring granulation method, a fluidized-bed granulation method, and a spray-drying granulation method. The average granule size of the resulting granules is within the range of, preferably, 100 to 800µm and, more preferably, 200 to 750µm. If the average granule size is smaller than 100µm or larger than 800µm, the components of the granule lack uniformity and may cause undesirable segregation when the granules are mixed up and then compressed.
Also, it is preferable that not less than 60% of all the resulting granules have a granule-size distribution within the deviation range of ±100 of 150µm.
To compress the resulting granules, any well-known compressor may be used, such as a hydraulic press, a single tableting machine, a rotary tableting machine and a briquetting machine. A solid type processing composition prepared in a compression process can take any configuration. However, a processing composition of a cylindrical type i.e. a so-called tablet type is preferably used, because of improved productivity and handling efficiency.
It is more preferable that components such as alkali, a reducer, an oxidizer or a preservative are separately granulated in the course of carrying out a granulation, because the foregoing effect can be better displayed. Particularly, the color developing composition is preferably granulated separately from the alkali.
In order to improve the solubility of the solid processing composition and the effect of the invention, the bulk density of a solid processing composition is preferably within the range of 1.0 g/cm³ to 2.5 g/cm³ when the processing composition is of a tablet type. If the bulk density thereof is less than 1.0 g/cm³, the strength of the resulting solid is reduced and, if the bulk density is more than 2.5 g/cm³, the solubility of the resulting solid is decreased. When the solid processing composition is of a granule or powder type, the bulk density thereof is preferably within the range of 0.40 to 0.95 g/cm³.
When processing a silver halide color photographic light-sensitive material in series by making use of a solid processing composition of the invention, the amount replenished is preferably not more than 150 ml per m² of the light-sensitive material and particularly preferably not more than 100 ml. The term, "an amount replenished", herein stated also includes the amount of water supplied (i.e., the amount of water replenished) when the solid type color developing composition and the water for dissolving it are replenished separately. Further, when the time required for carrying out color development is not longer than 30 seconds, the effect of the invention can be better displayed.
Now, the compounds represented by Formula [A] will be detailed, more precisely.
In the formula, L preferably represents a straight-chain or branched-chain alkylene group having 1 to 10 carbon atoms which may have a substituent and, among them, one having 1 to 5 carbon atoms is preferred. A more preferred example of L includes a methylene group, an ethylene group, a trimethylene group and a propylene group. The substituent thereof includes, for example, a carboxy group, a sulfo group, a phosphono group, a phcsphinic acid residual group, a hydroxy group, and an alkyl-substitutable ammonio group. Among them, the preferable examples include a carboxy group, a sulfo group, a phosphono group and a hydroxy group. A represents a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residual group, a hydroxy group, an alkyl-substitutable amino group, an alkyl-substitutable ammonio group (preferably having 1 to 5 carbon atoms), an alkyl-substitutable carbamoyl group (preferably having 1 to 5 carbon atoms) or an alkyl-substitutable sulfamoyl group (preferably having 1 to 5 carbon atoms). Among them, the preferable examples include a carboxy group, a sulfo group, a hydroxy group, a phosphono group and an alkyl-substitutable carbamoyl group. Examples of -L-A include, preferably, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group and a hydroxyethyl group and, among them, the particularly preferable examples include a carboxymethyl group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group and a phosphonoethyl group. R represents a hydrogen atom, a straight-chain or the branched-chain alkyl group having 1 to 10 carbon atoms, which may have a substituent and, among them, an alkyl group having 1 to 5 carbon atoms is preferred. Suitable substituents include, for example, a carboxy group, a sulfo group, a phosphono group, a sulfinic acid residual group, a hydroxy group, an alkyl-substitutable amino group, an alkyl-substitutable ammonio group, an alkyl-substitutable carbamoyl group, an alkyl-substitutable sulfamoyl group, a substitutable alkylsulfonyl group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonyl group, an alkyl-substitutable amino group, an arylsulfonyl group, a nitro group, a cyano group and a halogen atom. There may optionally be two or more substituents. The preferable examples of R include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group and a hydroxyethyl group. Among them, the particularly preferable examples thereof include a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group and a phosphonoethyl group, provided that L and R may complete, together with the nitrogen atom to which they are attached, a ring.
Next, among the compounds represented by Formula [A], some typical examples thereof will be given below. However, the invention shall not be limited to the compounds given below.

(19) HO-NH-CH₂CO₂H

(20) HO-NH-CH₂CH₂CO₂H

(26) HO-NH-CH₂CH₂SO₃H

(28) HO-NH-(CH₂)₃SO₃H

(29) HO-NH-(CH₂)₄SO₃H

(30) HO-NH-CH₂PO₃H₂

(32) HO-NH-CH₂CH₂PO₃H₂

(33) HO-NH-CH₂CH₂OH

(34) HO-NH- (CH₃)₃OH

(35) HO-NH-CH₂-PO₃H₂

(46) HONHCH₂CH(PO₃H₂)₂
Among the compounds, particularly preferable compounds include, for example, those of (2), (7), (14), (38), (39), (40) and (55). The compound may be used in the form of an alkali-metal salt or an ammonium salt.
The compounds represented by Formula [A] can be synthesized by alkylating (using, for example, nucleophilic substituting reaction, an adduct reaction and a Mannich reaction) hydroxylamines which are readily available on the market. The synthesis can be performed with reference to the procedures described in, for example, West German Patent Publication "Inorganica Chimica Acta", 93, (1984), pp. 101-108, and so forth.
The solid processing composition of the invention may consist of a single unit comprising in admixture the total components for processing a silver halide color photographic light-sensitive material or separate units comprising one or more components which are readily reactive with each other. Between the two cases, however, the single unit is preferable because of handling convenience and working efficiency. In this case, compounds readily chemically reactive with each other may optionally be present in a layer-shaped configuration in which one of the compounds is partitioned off from the other by a different compound inert to the above-mentioned two compounds or by a film or the like.
For example, a conventional developer replenisher may consist of three units, i.e., a color developing agent unit, a preserver unit and an alkali agent unit in view of storage stability. The present invention provides a solid processing composition consisting of a single unit in solid form which contains all the components, and which has good storage stability. Further, the single unit has the advantage that it requires only one supplying means.
When the solid color developing composition of the invention consists of a single unit, it is preferable to use anhydrous lithium hydroxide. Thus when the solid type color developing composition contains a deliquescent substance such as potassium carbonate or an acidic substance such as an aminopolycarboxylic acid or a salt of a paraphenylenediamine type color developing agent, moisture absorption and internal reaction can be inhibited. Thereby the effect of the invention can be better displayed by making use of anhydrous lithium hydroxide as an alkali.
The solid color developing composition of the invention preferably contains an aromatic sulfonic acid or salt thereof which inhibits an internal chemical reaction.
The nomenclature, "an aromatic sulfonic acid or a salt thereof' used herein means a compound in which a sulfonate is directly bonded to an unsaturated conjugate ring showing aromaticity, provided that the sulfonic acid group or the sulfonate may comprise either one or more rings and the ring showing aromaticity may contain a hetero atom or any substituent. A single compound may have plural rings showing aromaticity or may be a polymer. The sulfonates include, for example, an alkali metal salt such as a salt of lithium, sodium or potassium, or an ammonium salt.
The aromatic sulfonic acid or salt thereof preferably used in the invention include, for example, the compound represented by the following Formula [1] or [2].
wherein at least one of A through F represents a sulfonic acid group or a sulfonate and the others represent each independently a hydrogen atom, a halogen atom, an alkyl group or an alkenyl group.
wherein at least one of G through N represents a sulfonic acid group or a sulfonate and the others represent each independently a hydrogen atom, a halogen atom, an alkyl group or an alkenyl group.
In the above-given Formula [1] or [2], the alkyl or alkenyl group represented by A through F or G through N preferably has 1 to 10 carbon atoms, and the carbon chain may be either straight or branched.
Now, some typical examples of the compounds represented by Formula [1] or [2] will be given below. However, the invention shall not be limited thereto. Each exemplified compound is given in the form of a sodium salt. However, part or all of them may also be either a sulfonic acid salt or another salt.
Among the compounds given above, exemplified compounds (1-2), (1-14), (2-6) or (2-8) are preferably used. It is also preferable to use the compounds in the form of an alkali metal salt and particularly in the form of a sodium salt.
It is similarly preferable to include polyethylene glycol in the solid color developing composition as a compound capable of effectively inhibiting an internal chemical reaction. The average molecular weight of the above-mentioned polyethylene glycol suitable for use in the invention is preferably 300 to 50,000 and more preferably, 2,000 to 20,000. When polyethylene glycol is in the form of a liquid, it is preferably added in the course of granulating the solid composition. The effect of this compound is better when it is used together with the foregoing aromatic sulfonic acid or salt thereof.
The solid color developing composition of the invention contains a paraphenylenediamine type color developing agent. The typical exemplified compounds of the color developing agent used in the invention include, for example, compounds (C-1) through (C-16) given in JP OPI Publication No. 4-86741/1992, pp. 26-31, compounds (1) through (8) given in JP OPI Publication No. 61-289350/1986, and compounds (1) through (26) given in JP OPI Publication No. 3-246543/1991, pp.6-9. Among these compounds, the particularly preferable include compounds (C-1) and (C-3) given in JP Application No. 2-203169/1990, Exemplified Compounds (2) given in JP OPI Publication No. 61-289350/1986 and Exemplified Compound (1) given in JP OPI Publication No. 3-246543/1991.
In order for the effect of the invention to be improved, it is preferable that the solid color developing composition of the invention contains a triazinyl stilbene type fluorescent whitening agent. Such fluorescent whitening agents include, preferably, a compound represented by the following Formula [E].
wherein X₁, X₂, Y₁ and Y₂ represent each a hydroxyl group a halogen atom such as those of chlorine or bromine, an alkyl group, an aryl group,
or OR₂₅, in which R₂₁ and R₂₂ represent each independently a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group (including a substituent thereof), R₂₃ and R₂₄ independently represent each an optionally substituted alkylene group, R₂₅ represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, and M represents a cation.
The groups in Formula [E] and the substituents thereof are each synonymous with those described in JP OPI Publication No. 4-118649/1992, the 8th line from the bottom of p. 62 to the 3rd line from the bottom of p. 64. The typical compounds thereof include, for example, E-1 to E-45 given in ibid., pp. 65-67. Among them, E-4, E-24, E-34, E-35, E-36, E-37 and E-41 may preferably be used. These compounds are each added in an amount within the range of, preferably, 0.2 to 10 g per liter of a color developing solution and, particularly, 0.4 to 5 g.
Further, an auxiliary developing composition can also be used together with a developing agent. The well-known auxiliary developing compositions include, for example, N-methyl-p-aminophenol hexasulfate (that is so-called Metol), phenidone, N,N-diethyl-p-aminophenol hydrochloride and N,N,N',N'-tetramethyl-p-phenylenediamine hydrochloride. Usually, they are each added preferably in an amount within the range of 0.01 to 1.0 g per liter.
Besides the above, a variety of additives such as an antistaining agent, an antisludging agent and an interlayer-effect accelerating agent may also be used therein.
It is preferable that the color developing composition contains a chelating agent represented by the following Formula [K] and the exemplified compounds thereof K-1 through K-22, which are given in JP OPI Publication No. 4-118649/1992, the 9th line from the bottom of p. 69 to p. 75.
wherein E represents an alkylene group, a cycloalkylene group, a phenylene group (each of which are optionally substituted), -R₅OR₅-, -R₅OR₅OR₅- or -R₅ZR₅-; R₁ through R₅ independently represent each an optionally substituted alkylene group; Z represents =N-R₅-A₅ or =N-A₅; A₁ through A₅ independently represent each a hydrogen atom, a hydroxyl group, -CO₂M group or -PO₃(M)₂ group; and M represents a hydrogen atom or an alkali metal atom.
Among the above-given chelating agents, K-2, K-9, K-12, K-13, K-17 and K-19 may preferably be used. In particular, when K-2 and K-9 are added to a color developing solution, the effect of the invention is better displayed.
The chelating agent may be added in an amount of 0.1 to 20 g per liter of a color developing solution and more preferably 0.2 to 8 g.
Also, a color developing composition is also allowed to contain such a surfactant as a anionic, cationic, amphoteric or nonionic surfactant.
The solid processing composition applicable to the invention can be embodied by solidifying an alkali, a color developing agent and a reducing agent. Preferably the composition consists of not more than four units and most preferably a single unit in the case of preparing a tablet type processing composition. In the case where a solid type processing composition is prepared by separating it into not less than two units, the resulting plural tablets or granules are preferably put in one package.

EXAMPLES

Now, the invention will be detailed concretely with reference to the examples given hereafter. However, the invention shall not be limited thereto.

Example 1 (This example does not fall within the scope of the claims)

Under the following procedure, alkali particle samples and tablet samples were prepared.
In a bandamu mill (available on the market), 120.0 g of Tinopar SFP (produced by Ciba-Geigy), 16.0 g of sodium sulfite, 1400 g of potassium carbonate, 1.4 g of potassium bromide, 100 g of pentasodium diethylenetriamine pentaacetic acid and alkaline agents described in Table 1 were crushed so that the average grain size thereof was 10 µm. In a stirring granulator (available on the market), 10 ml of water was added to the above-mentioned fine powder to obtain a granule. Next, the resulting granule was dried in a fluid-bed type drier for 1 hour at 60 °C so that moisture was substantially removed therefrom. Thus, granule samples Nos. 1-1 through 1-10 were prepared. When the average grain size of the samples was measured by means of a screening method using a screen stipulated by JIS, it was in the range of 150 to 1500 µm.
Incidentally, in Procedure (C), when the alkaline agent was crushed at the relative humidity of 55 %, the deliquescence of potassium hydroxide and sodium was noticeable. After that, therefore, the crushing was conducted under a relative humidity of 40 % RH. With regard to the alkali used in the present invention, there was substantially no problem.
One half of the granules prepared by the above-described procedure was compression-tabulated so as to have a filled amount of 5.0 g per tablet by the use of Touch Press Correct Model 1527 HU manufactured by Kikusui Works, which was modified into a tabulating machine. Thus, 100 each of tablet sample Nos. 1-11 to 1-20 having a diameter of 17 mm were prepared as replenishing color developing compositions for color paper.
The resulting samples were evaluated as follows.

(Evaluation of Deliquescent Property)

A sample of 5.0 g (one piece in the case of a tablet) was put in a sample bottle remaining uncapped and was preserved in a thermostat having a temperature of 30°C and a relative humidity of 40%RH. Three samples were prepared in each procedure and deliquescence of the samples was observed in terms of deformation or moisture adherence.
The evaluation standards will be shown as follows.

×× :: Deliquescence occurred on the same day (within 6 hours);
× :: Deliquescence occurred on the next day;
Δ :: Deliquescence occurred within 3 days;
○ :: Deliquescence was produced within one week; and
ⓞ :: A configuration was maintained for not shorter than one week after starting a preservation.

(Measurement of fluidity of granules)

In an envelope made of polyethylene (10 cm x 10 cm) 5.0 g of the sample was placed. The envelope was sealed tightly by means of a heat seal and stored in a temperature-constant room at 60 °C and 40 %RH for 4 weeks. Angle of repose of the sample after being stored was measured.

(Measurement of strength of a tablet)

The hardness of 10 pieces of tablets was measured by means of a speed checker (produced by Okada Seiko Co., Ltd.), and the average value was defined to be degree of strength.

The results are shown in Table 1. LiOH shall represent lithium hydroxide anhydride, unless otherwise mentioned.

Table 1

No.	Alkali (Amount added)		Deliquescence	Angle of repose (degree)	Hardness (Kg)
1-1	―		Δ	46		Comparison
1-2	KOH	35g	××	48		Comparison
1-3	KOH	70g	××	50		Comparison
1-4	KOH	140g	××	unmeasurable		Comparison
1-5	NaOH	25g	××	unmeasurable		Comparison
1-6	NaOH	100g	××	unmeasurable		Comparison
1-7	LiOH	15g	Δ	43		Invention
1-8	LiOH	30g	Δ	40		Invention
1-9	LiOH	60g	○	39		Invention
1-10	LiOH	120g	○	39		Invention
1-11	―		Δ		20	Comparison
1-12	KOH	35g	×		20	Comparison
1-13	KOH	70g	××		19	Comparison
1-14	KOH	140g	××		17	Comparison
1-15	NaOH	25g	××		18	Comparison
1-16	NaOH	100g	××		16	Comparison
1-17	LiOH	15g	○		25	Invention
1-18	LiOH	30g	○		30	Invention
1-19	LiOH	60g	○		32	Invention
1-20	LiOH	120g	○		33	Invention

From the above-mentioned table, it can be understood that the alkaline agent of the present invention is not only excellent in deliquescence but also excellent in terms of fluidity after stored for a long time and also excellent in the strength of the tablets.

Example 2

A solid color developing composition for color paper use was prepared by the following procedure.

1) A tablet for replenishing a color developing composition for color paper use

Procedure (A)

In an air-jet pulverizer was pulverized 1200 g of a developing agent CD-3, 4-amino-3-methyl-N-ethyl-β-(hydroxy)ethylaniline sulfate, to have an average particle size of 10 µm. The resulting fine particles thereof were granulated by spraying 30 ml of water thereto at room temperature for about 5 minutes in a fluid-bed spray type granulator available on the market and the resulting granules were then dried at 60°C for 8 minutes. Thereafter, the granules were further dried in a vacuum at 40°C for 2 hours, so that the moisture of the granules was almost completely removed.

Procedure (B)

In the same manner as in Procedure (A) was pulverized and granulated, 1200 g of a preservative shown in Table 2, except that only 1.0 ml of water was sprayed. After the granulation was completed the granules were dried at 50°C for 10 minutes. Thereafter, the granules were dried in a vacuum at 40°C for 2 hours, so that the moisture of the granules was almost completely removed.

Procedure (C)

Tinopar SFP (manufactured by Ciba-Geigy AG.) of 300 g, 400 g of sodium sulfite, 3500 g of potassium carbonate, 3.0 g of potassium bromide, 250 g of diethylene triamine penta acetic acid penta sodium salt and an alkali shown in Table 2 were pulverized in the same manner as in Procedure (A). Thereafter, the resulting pulverized matter was mixed by a mixer available on the market. Then, the resulting mixtures were granulated in the same manner as in Procedure (A), except that 150 ml of water was used. After completing the granulation, the granules were dried in a vacuum at 40°C for 2 hours, so that the moisture of the granules was almost completely removed.

Procedure (D)

The resulting granules prepared in the above-described Procedures (A) through (C) were uniformly mixed at 25°C for 10 minutes by making use of a mixer in a room maintained at not higher than 40%RH.

Procedure (E)

One half of the resulting mixture prepared in the above-described Procedure (D) was compression-tableted so as to give a filled amount of 10.0 g per tablet by Touch Press Correct Model 1527HU manufactured by Kikusui Mfg. Works, which was remodeled into a tableting machine, so that 80 tablets having a diameter of 30 mm for replenishing a color developing composition for color paper use were prepared.
The resulting samples were evaluated as follows.

(Evaluation of Deliquescent Property)

A sample of 10.0 g (one piece in the case of a tablet) was put in a sample bottle remaining uncapped and was preserved in a thermostat having a temperature of 30°C and a relative humidity of 40%RH. Three samples were prepared in each procedure and deliquescence of the samples was observed in terms of deformation or moisture adherence.
The evaluation standards will be shown as follows.

×× :: Deliquescence occurred on the same day (within 6 hours)
× :: Deliquescence occurred on the next day;
Δ :: Deliquescence occurred within 3 days;
○ :: A deliquescence was produced within one week; and
ⓞ :: A configuration was maintained for not shorter than one week.

(Measurement of Residual Concentration of Developing Agent)

A sample of 10.0 g (or, one piece in the case of a tablet) was put in a polyethylene bag (having a size of 10cm x 10cm) and then tightly sealed by applying heat. The sealed bag was preserved for 3 weeks in a thermostat having a temperature of 50°C. The resulting sample was dissolved in a specific amount of water, and the concentration of the color developing agent remaining in the solution was measured.
Fluidity of granules and strength of tablets were measured in the same manner as in Example 1.
The results thereof will be shown in Table 2, wherein LiOH represents anhydrous lithium hydroxide, unless otherwise expressly stated.
Table 2 shows that when lithium hydroxide is used as an alkali, deliquescence is low and the residual concentration of a color developing agent is also high. The granule shows improved fluidity and the tablet shows improved strength. Further, when making use of a compound represented by Formula (A) as a preservative, better results are obtained. Table 2 also shows that better results can further be obtained when sodium p-toluene sulfonate is used as an aromatic sulfonate or when polyethylene glycol is used.
By comparing the results for tablets to to those for granule mixtures it can be seen that the effects of the invention are better in the case of a tablet. Also, from the viewpoint of the case of preparing compositions and the prevention of scattering fine powder, the preferable shape of the composition is of the tablet type.

Example 3

Granules were prepared in the same manner as in Procedure (A), (B) or (C) of Example 2 and were tableted in the same manner as in Procedure (E), so that three kinds of tablets were prepared separately. Disodium salt of Exemplified Compound (7) was used as a preservative and the compound shown in Table 2 (in an amount of 0.94 mols/kg) was used as an alkali. The weight of each tablet was 0.45 g for (A), 0.45 g for (B) and 1.60 g for (C).
A one-part tablet comprising a mixture of (A), (B) and (C) similar to those prepared in Example 2 was also prepared.

On the resulting samples, deliquescence evaluation and measurement of residual concentration of a developing agent were carried out in the same manner as in Example 2. The three kinds of tablets were put in one sample bottle and in one polyethylene bag, so that they were preserved and then evaluated. The results are shown in Table 3.

Table 3

No.	Tablet by part	Alkali	Deliquescence	Residual concentration of developing agent	Remarks
2-1	ABC in 3-parts	LiOH	ⓞ	93%	Invention
2-2	ABC in 1-part	LiOH	○	89%	Invention
2-3	ABC in 3-parts	LiOH·H₂O	○	91%	Invention
2-4	ABC in 1-part	LiOH·H₂O	Δ	82%	Invention
2-5	ABC in 3-parts	KOH	×	75%	Comparison
2-6	ABC in 1-part	KOH	××	66%	Comparison

As shown in Table 3, a solid color developing composition is more preferable when the color developing agent and an alkali are separated into plural units than when put into one unit, from the viewpoints of deliquescence and prevention of developing agent oxidation. However, when they are put into one part from the viewpoint of easier handling, deterioration can be inhibited by making use of anhydrous lithium hydroxide.

Example 4

A tablet for processing a color paper was prepared by the following procedure.

1) Tablet for replenishing a color developing composition for color paper use

Procedure (A)

In a bandamu-mill was pulverized 1200 g of developing agent CD-3, 4-amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]ethyl sulfonate to have an average particle size of 10 µm. The resulting fine particles thereof were granulated by adding 50 ml of water thereto at room temperature for about 7 minutes in a stirring granulator available on the market. Thereafter, the granules were dried at 40°C for 2 hours in a fluid-bed type drier, so that the moisture of the granules was almost completely removed therefrom. The resulting granules thereby prepared and 150 g of polyethylene glycol 6000 were uniformly mixed for 10 minutes by a mixer in a thermo-hydrostatic room at 25°C and not higher than 40%RH. Then, 4 g of sodium N-lauroylalanine was added and mixed together, taking 3 minutes. Thereafter, the resulting mixture was compression-tableted varying the filled amount per tablet as shown in Table 3, by a tableting machine, a remodeled Tough Press Correct Model 1527HU manufactured by Kikusui Mfg. Works, so that Tablet (A) for replenishing a color developing composition for color paper use was prepared.

Procedure (B)

1200g of Disodium disulfoethyl hydroxylamine was pulverized and granulated in the same manner as in Procedure (A), except that 60ml of water was added. After completing the granulation, the resulting granules were dried at 50°C for 30 minutes, so that the moisture of the granules was almost completely removed therefrom. Then, 4 g of sodium N-lauroylalanine was added to the resulting granules and mixed together by a mixer for 3 minutes in a thermo-hydrostatic room at 25°C and not higher than 40%RH. The resulting mixture was compression-tableted to have a filled amount of 1.0 g per tablet by a tableting machine, a remodeled Tough-Pressed-Collect Model 1527HU manufactured by Kikusui Mfg. Works, so that 1,000 tablets B for replenishing a color developing composition for color paper use were prepared.

Procedure (C)

300g of Tinopar SFP (manufactured by Ciba-Geigy AG.), 37 g of sodium sulfite, 3 g of potassium bromide, 250 g of diethylene triamine pentaacetic acid, 2800 g of sodium p-toluene sulfonate, an alkali shown in Table 3, and 106 g of mannitol were pulverized in the same manner as in Procedure (A). Thereafter, the resulting pulverized matter was uniformly mixed by a mixer available on the market. Then, granulation was carried out in the same manner as in Procedure (A), except that 150 ml of water was added. After completing the granulation, the granules were dried at 60°C for 30 minutes, so that the moisture of the granules was almost completely removed therefrom. Then, 4 g of sodium N-lauroylalanine was added to the resulting granules and mixed together by a mixer for 3 minutes in a thermo-hydrostatic room at 25°C and not higher than 40%RH. The resulting mixture was compression-tableted to give a filled amount of 3.2 g per tablet by a tableting machine obtained by modifying Tough Press Correct Model 1527HU manufactured by Kikusui Mfg. Works, so that 1,000 tablets C for replenishing a color developing composition for color paper use were prepared.

Procedure (D)

Potassium carbonate of 3,500 g was pulverized and then granulated in the same manner as in Procedure (A). 150ml of water was added in the granulation. Thereafter, the resulting granules were dried at 700°C for 30 minutes, so that the moisture of the granules was almost completely removed therefrom.
The resulting granules thereby prepared and 150 g of polyethylene glycol 6000 were uniformly mixed for 10 minutes by a mixer in a thermo-hydrostatic room at 25°C and not higher than 40%RH. Then, 4 g of sodium N-lauroylalanine was added and mixed together taking 3 minutes. Thereafter, the resulting mixture was compression-tableted to give a filled amount of 3.0 g per tablet as shown in Table 3, by a tableting machine obtained by modifying Tough Press Correct Model 1527HU manufactured by Kikusui Mfg. Works, so that 1,000 Tablets D for replenishing a color developing composition for color paper use were prepared.

2) Tablet for replenishing a bleach-fixing composition for color paper use

Procedure (E)

1250g of ferric ammonium ethylenediamine tetraacetate 25g ethylenediamine tetraacetic acid, 250g of maleic acid and 46g of Pineflow (manufactured by Matsutani Chemical Co.) were pulverized and granulated in the same manner as in Procedure (C), except that 80 ml of water was added. After completing the granulation, the granules were dried at 60°C for 2 hours so that the moisture was almost completely removed therefrom. 20g of Sodium N-lauroylsarcosine was added to the resulting granules and they were then mixed in a thermo-hydrostatic room at 25°C and not higher than 40%RH by a mixer for 3 minutes. The resulting mixture was then compression-tableted so as to have a filled amount of 4.3 g per tablet by a tableting machine obtained by modifying Tough Press Correct Model 1527HU manufactured by Kikusui Mfg. Works, so that 340 Tablets A for replenishing a bleach-fixing composition for color paper use were prepared.

Procedure (F)

1640g of Ammonium thiosulfate, 750g of sodium sulfite, 40g of potassium bromide, 50g of p-toluene sulfinic acid and 55g of Pineflow were pulverized and granulated in the same manner as in Procedure (C), except that 100 ml of water was added. After completing the granulation, the resulting granules were dried at 60°C for 120 minutes, so that the moisture of the granules was almost completely removed therefrom. 20g of Sodium N-lauroyl sarcosine was added to the resulting granules and they were mixed in a thermo-hydrostat room at 25°C and not higher than 40%RH by a mixer for 3 minutes. The resulting mixture was then compression-tableted so as to give a filled amount of 3.35 g per tablet by a tableting machine obtained by modifying Tough Press Correct Model 1527HU manufactured by Kikusui Mfg. Works, so that 720 Tablets B for replenishing a bleach-fixing composition for color paper use were prepared.

3) Tablet for replenishing a stabilizing composition for color paper use

Procedure (G)

10g of Sodium carbonate monohydrate, 200g of disodium 1-hydroxyethane-1,1-disulfonate, 150g of Tinopar SFP, 300g of sodium sulfite, 200g of zinc sulfate heptahydrate, 150g of disodium ethylenediamine tetraacetate, 200g of ammonium sulfate, 10g of o-phenylphenol and 25g of Pineflow were pulverized and granulated in the same manner as in Procedure (C), except that 60 ml of water was added. After completing the granulation, the granules were dried at 70°C for 60 minutes, so that the moisture of the granules was almost completely removed therefrom. 10g of Sodium N-lauroyl sarcosine was added to the resulting granules and they were mixed in a thermo-hydrostat room at 25°C and not higher than 40%RH by a mixer for 3 minutes. The resulting mixture was then compression-tableted so as to have a filled amount of 3.14 g per tablet by a tableting machine obtained by modifying Tough Press Correct Model 1527HU manufactured by Kikusui Mfg. Works, so that 360 Tablets for replenishing a stabilizing composition for color paper use were prepared.

[Color Paper Processing Steps]

The method of the invention of processing a light-sensitive material using an automatic processor will be explained below.

A tablet supplying function, a liquid level detecting function, and a water supplying function were provided to a Konica Color Paper Type QA Processor Model CL-PP-718, and the following processing experiments were carried out. As for the tablet supplying function, liquid level detecting function, water supplying function and so forth, the devices shown in Figs. 3 and 5 illustrated in JP OPI Publication No. 5-119454/1993 were used. The devices thereof shown in the figures are detailed in the same application, pp. 44-53. The standard processing conditions of the processor were as follows.

Processing step	Temperature	Time
Color developing	39±0.3°C	22sec.
Bleach-fixing	35±1.0°C	22sec.
Stabilizing-1	33±3.0°C	20sec.
Stabilizing-2	33±3.0°C	20sec.
Stabilizing-3	33±3.0°C	20sec.
Drying	72±5.0°C	40sec.

A stabilizer was replenished to the 3rd tank (for stabilizing step-3) and the overflow flowed into the 2nd tank (for stabilizing step-2) and then into the 1st tank (for stabilizing step-1) in this order, which is a so-called cascade system.
The processing solutions for an automatic processor were prepared by the following procedures.

(1) Color developing tank solution (in 23.0 liters)

To an automatic color developing tank, 18 liters of warm water kept at 35°C were added. Thereto, 177 of each of tablets A through D for replenishing a color developing solution for color paper use were added and then dissolved. Thereafter, 23 starter tablets having the following chemical formula, which had separately been tableted as a starter component, were added and then dissolved. After completing the dissolution, warm water was added up to the marked line of the tank, and so a tank solution was prepared.

Color developing starter for color paper use (per liter)

Potassium chloride See Table 3

Potassium hydrogen carbonate 4.8 g

Potassium carbonate 2.1 g

(2) Bleach-fixing solution (in 23.0 liters)

To a bleach-fixing tank of an automatic processor, 15 liters of water was added and then 852 tablets A for replenishing a bleach-fixing solution for color paper use and 1704 tablets B with the same purpose were added and then dissolved. After completing the dissolution, warm water was added up to the marked line of the tank, so that a tank solution was completed.

(3) Stabilizing solution (15 liters each to the 1st to the 3rd tanks)

In each of the 1st, 2nd and 3rd stabilizing tanks of the automatic processor, 60 tablets for replenishing a stabilizing solution for color paper use were dissolved in 12 liters of warm water being kept at 35°C. Thereafter, warm water was added up to the marked line of the tank, so that a tank solution was prepared.
While the automatic processor was being made thermostatic, 20 pieces of each tablet for replenishing already prepared as above, were set in a replenishing tablet supplying device provided to the automatic processor. When one m² of color paper was processed, one of each of tablets A through D for replenishing a color developing solution, one tablet A and 2 tablets B each for replenishing a bleach-fixing solution, and one tablet for replenishing a stabilizing solution, were supplied. At the same time, replenishing warm water was so set as to be supplied in an amount shown in Table 3 to the color developing tank, in an amount of 42 ml to the bleach-fixing tank and in an amount of 247 ml to the stabilizing tank, by the warm water supplying device.
Konica Color QA Paper, Type A5, manufactured by Konica Corp. was used as the light-sensitive material subject to the tests. After imagewise exposing the light-sensitive material to light in an ordinary method, the exposed light-sensitive material was running processed in the foregoing processing steps. The running process was continuously carried out until the replenishment amount was twice the capacity of the color developing tank, which is referred to as 2R. The quantity of the light-sensitive materials processed per day was 0.05R.
A wedgewise exposed light-sensitive material was processed when at the start of the running process and when completing the running process, and the density of the processed light-sensitive materials was measured. Each maximum density (Dmax) in blue, green and red was also measured. For 20 of each of the tablets present in the replenishing tablet supplying device of the automatic processor, an observation was made on how the tablet shape varied until all the tablets C for replenishing a color developing solution were used up. The results are shown in Table 4.
The results in Table 3 show that the effects of the invention are a prevention of the variation of the tablet shape and of the processing stability when water was replenished to a color developing tank in an amount of not more than 150 ml per m² of a light-sensitive material, with a greater effect being obtained when water was replenished in an amount of not more than 100 ml per m² of the light-sensitive material.

Example 5

This example was performed in the same manner as in Example 4, in that each tablet was prepared and was then running processed; except that the time required for carrying out the color developing step was varied as shown in Table 5, and, the filled amount of tablet A for replenishing a color developing composition and the alkali contained in tablet C were each varied as shown in Table 5.
Also, the color developing agent contained in tablet A and the preservative contained in tablet B were each varied as shown in Table 5. Further, the amount of water replenished to the color developing tank was 81 ml per m² of the light-sensitive material and 7.0 g of potassium chloride was added as a starter when starting the running process.

The evaluations were made in the same manner as in Example 4 by observing both the maximum color density obtained when starting a running process and when completing the same process, and the variation of the tablet shape. The results are shown in Tables 5 and 6.

Table 5

No.	Color developing time	Color developing agent	Amt. of tablet A filled (g)	Alkali content of tablet C: ( )= Amt.contained (g)		Preservative contained in tablet B
4-1	45"	CD-3	0.81	KOH	(25)	Exemplified compound (7)
4-2	35"	CD-3	0.86	KOH	(32)	Exemplified compound (7)
4-3	27"	CD-3	0.94	KOH	(44)	Exemplified compound (7)
4-4	22"	CD-3	1.00	KOH	(48)	Exemplified compound (7)
4-5	45"	CD-3	0.81	LiOH	(11)	Exemplified compound (7)
4-6	35"	CD-3	0.86	LiOH	(14)	Exemplified compound (7)
4-7	27"	CD-3	0.94	LiOH	(19)	Exemplified compound (7)
4-8	22"	CD-3	1.00	LiOH	(20)	Exemplified compound (7)
4-9	22"	CD-3	1.00	LiOH	(20)	Exemplified compound (1)
4-10	22"	CD-3	1.00	LiOH	(20)	Exemplified compound (2)
4-11	22"	CD-3	1.00	LiOH	(20)	^*1 DEHA oxalate

^*1 Diethylhydroxyamine oxalate

Table 6

No.	When starting			When completing			Variation of tablet shape	Remarks
	Blue	Green	Red	Blue	Green	Red
4-1	3.10	2.46	1.98	2.99	2.34	1.87	×	Comparison
4-2	3.11	2.47	1.99	2.96	2.33	1.85	×	Comparison
4-3	3.10	2.47	1.98	2.74	2.03	1.57	××	Comparison
4-4	3.09	2.45	1.98	2.73	2.01	1.55	××	Comparison
4-5	3.10	2.46	1.97	3.09	2.45	1.95	○	Invention
4-6	3.10	2.46	1.97	3.08	2.45	1.94	○	Invention
4-7	3.11	2.47	1.97	3.08	2.45	1.95	○	Invention
4-8	3.11	2.47	1.98	3.08	2.44	1.95	○	Invention
4-9	3.10	2.46	1.98	3.06	2.42	1.94	○	Invention
4-10	3.09	2.46	1.97	3.07	2.43	1.94	○	Invention
4-11	3.09	2.46	1.97	3.02	2.39	1.90	○	Invention
^*1 Diethylhydroxyamine oxalate

From the results shown in Tables 5 and 6, it is clear that when the processing time for the color developing step was not longer than 30 seconds, the effect of the invention on the processing stability and the prevention of the variation of tablet configuration was better and that, when a compound represented by Formula [A] was used, the processing stability was improved.

Example 6

A tablet for processing a color negative film was prepared by the following procedure.

1) Tablet for replenishing a color developing composition for color negative film use

Procedure (1)

In a bandamu mill available on the market, 3750.0 g of potassium carbonate, 580.0 g of sodium sulfite, 1.4 g of potassium bromide, 240.0 g of pentasodium diethylene-triamine pentaacetic acid, 500.0 g of sodium p-toluene sulfonate and an alkaline agent described in Table 7 were crushed so that the average grain size thereof was 10 µm. In a stirring granulator available on the market, 500.0 g of PEG 6000, 800.0 g of mannitol and 160 ml of water were added to the above-mentioned fine powder and granulated for 7 minutes to obtain a granule. Next, the resulting granule was dried in a fluid-bed type drier available on the market for 120 minutes at 70 °C so that all moisture was substantially removed therefrom.

Procedure (2)

360.0g of Hydroxylamine sulfate 40.0 g of potassium bromide and 20.0 g of pyrocatechol-3,5-disodiumsulfonate were crushed in the same manner as in above Procedure (1). Then, 20.0 g of Pineflow (manufactured by Matsutani Chemical Co. ) and 3.5 ml of water were added to the above-mentioned fine powder, mixed and granulated for 7 minutes to obtain a granule. The resulting granule was dried for 60 minutes at 60 °C so that moisture was substantially removed therefrom.

Procedure (3)

650.0g of Color developing agent, CD-3 (4-amino-3-methyl-N-ethyl-β-(hydroxy)ethylaniline sulfate) was crushed in the same manner as in above Procedure (1). Then, 10 ml of water were added to the above-mentioned fine powder, mixed and granulated for 7 minutes to obtain a granule. The resulting granule was dried for 2 hours at 40 °C so that all moisture was substantially removed.

Procedure (4)

In a cross-rotary mixing machine available on the market were mixed the granules prepared in the above procedures (1) to (3) and 40.0 g of sodium lauryl sulfonate for about 7 minutes at a room temperature. The resulting mixture was tabulated by using a rotary tabulating machine (Clean Press Correct H18 manufactured by Kikusui Mfg. Works). Thus, 600 tablets each having a diameter of 25 mm and a weight of 10.0 g were obtained as replenishing color developing compositions for color negative film use.
The above-obtained tablet sample Nos. 6-1 to 6-10 were evaluated in the same manner as in Example 2.

The results are shown in Table 7.

Table 7

No.	Alkali (Amount added)		Deliquescence	Hardness (Kg)	Residual Concentration of CD-4
6-1	―		Δ	38	82	Comparison
6-2	KOH	(60g)	××	37	80	Comparison
6-3	KOH	120g	××	35	78	Comparison
6-4	KOH	170g	××	30	77	Comparison
6-5	NaOH	120g	××	34	89	Comparison
6-6	LiOH	60g	○	45	93	Invention
6-7	LiOH	120g	ⓞ	52	95	Invention
6-8	LiOH	170g	ⓞ	53	95	Invention

As is apparent from table 7, the tablets of the invention show improved deliquescence and hardness.

Example 7

Procedure (1)

In a bandamu mill available on the market, 150 g of a developing agent CD-4, [that is 4-amino-3-methyl-N-ethyl-β-(hydroxy)ethylaniline sulfate], was pulverized to have an average particle size of 10 µm. In a stirring type granulator available on the market, the resulting fine powder was granulated by adding 10 ml of water at room temperature for about 7 minutes and was then dried by a fluid-bed type drier at 40°C for 2 hours, so that the moisture of the granules was almost completely removed therefrom. To the resulting granules, 0.3 g of sodium N-lauroylalanine and 1.9 g of polyethylene glycol 6000 were added. The mixture thereof was then uniformly mixed for 10 minutes by a mixer in a thermo-hydrostatic room at 25°C and not higher than 40%RH. Next, the resulting mixture was compression-tableted to give an amount of 1.1 g per tablet by a tableting machine obtained by modifying Tough Press Correct 1527HU manufactured by Kikusui Mfg. Works, so that 126 tablets A for replenishing a color developing composition for color negative film use were prepared.

Procedure (2)

After pulverizing 69.4 g of hydroxylamine sulfate and 4 g of Pineflow (manufactured by Matsutani Chemical Co.) in the same manner as in Procedure (1), they were mixed and granulated. 3.5 ml of water was added and, after completing the granulation, the granules were dried at 60°C for 30 minutes, so that the moisture of the granules was almost completely removed therefrom. To the resulting granules, 0.3 g of sodium N-lauroylalanine was added. The mixture thereof was further mixed for 3 minutes by a mixer in a thermo-hydrostatic room at 25°C and not higher than 40%RH. Next, the resulting mixture was compression-tableted to give an amount of 0.56 g per tablet by a tableting machine in the same manner as in Procedure (1), so that 120 tablets B for replenishing a color developing composition for color negative film use were prepared.

Procedure (3)

20g of diethylenetriamine pentaacetic acid, 15g of disodium 1-hydroxyethane-1,1-diphosphonate, 72.8g of potassium sulfite 375g of potassium carbonate, 3g of anhydrous lithium hydroxide 3.7g of sodium bromide of 3.7 g and 22g of mannitol were pulverized in the same manner as in Procedure (1) and mixed up together. Thereto 40 ml of water was added, and the resulting mixture was granulated. After completing the granulation, the granules were dried at 70°C for 60 minutes, so that the moisture of the granules was almost completely removed. To the resulting granules, 2 g of sodium N-lauroylalanine was added. The mixture thereof was mixed for 3 minutes by a mixer in a thermo-hydrostatic room at 25°C and not higher than 40%RH. Next, the resulting mixture was compression-tableted to give an amount of 3.9 g per tablet by a tableting machine in the same manner as in Procedure (1), so that 120 tablets C for replenishing a color developing composition for color negative film use were prepared.

2) Tablet for replenishing a bleaching solution for color negative film use

Procedure (4)

175g of Ferric ammonium 1,3-propanediamine tetraacetate monohydrate, 2g of 1,3-propanediamine tetraacetic acid and 17g of Pineflow (manufactured by Matsutani Chemical Co.) were pulverized in the same manner as in Procedure (1) and then mixed up together. Thereto, 8ml of water was added, so that the resulting mixture was granulated. After completing the granulation, the granules were dried at 60°C for 30 minutes, so that the moisture of the granules was almost completely removed therefrom.

Procedure (5)

133g of Succinic acid, 200g of ammonium bromide and 10.2g of Pineflow were pulverized, mixed and then granulated. Thereto, 17ml of water was added, and the mixture was granulated. After completing the granulation, the granules were dried at 70°C for 60 minutes, so that the moisture of the granules was almost completely removed therefrom.

Procedure (6)

66.7g of Potassium nitrate, 60g of potassium hydrogen carbonate and 8g of mannitol of 8 g were pulverized, mixed and then granulated in the same manner as in Procedure (1). Thereto, 13ml of water was added in an amount of 13 ml, and the mixture was granulated. After completing the granulation, the granules were dried at 60°C for 60 minutes, and the moisture of the granules was almost completely removed moisture of the granules was almost completely removed therefrom.

Procedure (7)

The granules prepared in the above-mentioned Procedures (4) through (6) were uniformly mixed together for 10 minutes by a mixer in a thermo-hydrostatic room at 25°C and not higher than 40%RH. To the resulting mixed granules, 6 g of sodium N-lauroylsarcosine was added and then mixed for 3 minutes. The resulting mixture was compression-tableted to give an amount of 6.78 g per tablet by a tableting machine obtained by modifying Tough Press Correct 1527HU manufactured by Kikusui Mfg. Works, so that 80 tablets for replenishing a bleaching solution for color negative film use were prepared.

3) Tablet for replenishing a fixing solution for color negative film use

Procedure (8)

2500g of Ammonium thiosulfate, 150g of sodium sulfite, 20g of disodium ethylenediamine tetraacetate and 65g of Pineflow (manufactured by Matsutani Chemical Co.) were pulverized, mixed and then granulated in the same manner as in Procedure (1). Thereto, 50ml of water was added and the mixture was granulated. After completing the granulation, the granules were dried at 60°C for 120 minutes, so that the moisture of the granules was almost completely removed therefrom.

Procedure (9)

The granules prepared in the above-mentioned Procedure (8) and 13 g of sodium N-lauroylsarcosine were mixed by a mixer in a thermo-hydrostatic room at 25°C and not higher than 40%RH. The resulting mixture was then compression-tableted to give an amount of 9.3 g per tablet by a tableting machine obtained by modifying Tough Press Correct 1527HU manufactured by Kikusui Mfg. Works, so that 280 tablets for replenishing a fixing solution for color negative film use were prepared.

4) Tablet for replenishing a stabilizing solution for color negative film use

Procedure (10)

150g of m-Hydroxybenzaldehyde, 20g of sodium laurylsulfate, 60g of disodium ethylenediaminetetraacetate, the alkali indicated in Table 6, and 10g of Pineflow were pulverized, mixed and then granulated in the same manner as in Procedure (1). Thereto, 10ml of water was added and the mixture was granulated. After completing the granulation, the granules were dried at 50°C for 2 hours, so that the moisture of the granules was almost completely removed therefrom.

Procedure (11)

The granules prepared in the above-mentioned Procedure (10) were compression-tableted to give an amount of 0.48 g per tablet by a tableting machine obtained by modifying Tough Press Correct 1527HU manufactured by Kikusui Mfg. Works in a thermo-hydrostatic room at 25°C and not higher than 40%RH, so that 280 tablets for replenishing a stabilizing solution for color negative film use were prepared.
The above-mentioned procedures were repeated, so that the tablets in number necessary for carrying out the following experiments were prepared.

[Color negative film processing step]

A Konica Color Negative Film Processor Model CL-KP-50QA was modified so as to be provided with a tablet supplying function, a liquid level detecting function, a warm water supplying function and so forth. The following processing experiments were carried out by making use of the above-mentioned automatic processor.

The standard processing conditions for the automatic processor were as follows.

Processing step	Temperature	Time
Color developing	38±0.3°C	3min.15sec.
Bleaching	38±1.0°C	45sec.
Fixing-1	38±1.0°C	45sec.
Fixing-2	38±1.0°C	45sec.
Stabilizing-1	38±3.0°C	20sec.
Stabilizing-2	38±3.0°C	20sec.
Stabilizing-3	38±3.0°C	20sec.
Drying	60°C	60sec.

The stabilizing solution was replenished to the 3rd tank (for stabilizing step-3) and the overflow therefrom flowed into the 2nd tank (for stabilizing step-2) and then to the 1st tank (for stabilizing step-1); and the fixing solution was replenished to the 2nd tank (for fixing step-2) and the overflow therefrom flowed into the 1st tank (for fixing step-1) and then to the 1st tank (for stabilizing step-1); that is a so-called cascade system.
Processing solutions applicable to the automatic processor were prepared by the following procedures.

(1) Color developing tank solution (in 21.0 liters)

To an automatic color developing tank, 15 liters of warm water being kept at 35°C was added. Thereto, 118 of each of tablets A and B and 236 tablets C each for replenishing a color developing solution for color negative film use were added and then dissolved. Thereafter, 21 starter tablets having the following composition, which had separately been tableted as a starter component, were added and then dissolved. After completing the dissolution, warm water was added up to the marked line of the tank, so that a tank solution was completed.

Color developing starter for color negative film use (per liter)

Sodium bromide 0.8 g

Sodium iodide 2.0 mg

Sodium hydrogen carbonate 3.0 g

Potassium carbonate 0.5 g

(2) Bleaching solution (in 5.0 liters)

To the bleaching tank of the automatic processor, 3.0 liters of warm water being kept at 35°C was added and 350 tablets for replenishing a bleaching solution for color negative film use, which were prepared in the same manner as in the example, were added and dissolved. Thereafter, 5 starter tablets having the following composition, which had separately been tableted as a starter component, were added and dissolved. After completing the dissolution, warm water was added up to the marked line of the tank, so that a tank solution was prepared.

Bleaching starter for color negative film use (per liter)

Potassium bromide 10.0 g

Sodium hydrogen carbonate 1.5 g

Potassium carbonate 3.5 g

(3) Fixing solution (in 4.5 liters each for the 1st and 2nd tanks)

In each of the 1st and 2nd fixing tanks of the automatic processor 136 tablets for replenishing a fixing solution for color negative film use were dissolved in 3.0 liters of warm water being kept at 35°C, respectively. Thereafter, warm water was added up to the marked line of the tank, so that a tank solution was completed.

(4) Stabilizing solution (in 3.2 liters each for the 1st to the 3rd tanks)

In each of the 1st, 2nd and 3rd stabilizing tanks of the automatic processor 20 tablets for replenishing a stabilizing solution for the color negative film were dissolved in 3.0 liters of warm water being kept at 35°C, respectively. Thereafter, warm water was added up to the marked line of the tank, so that the tank solution was completed.
While the automatic processor was being kept thermostatic, 20 of each of the tablets already prepared for replenishing the respective solutions were set in a tablet replenisher supplying device provided to the automatic processor. When 8 rolls of 135-size/24-exposure film were processed, one tablet A, one tablet B and two tablets C for replenishing a color developing solution, 4 tablets for replenishing a bleaching solution, 8 tablets for replenishing a fixing solution and one tablet for replenishing a stabilizing solution, were supplied to the tablet supplying device. At the same time, replenishing warm water was set to be supplied in an amount of 154.4 ml to the color developing tank, 27.2 ml to the bleaching tank, 204.8 ml to the fixing tank and 320 ml to the stabilizing tank, from a warm water supplying device, respectively.
A color negative film, Konica Color Super DD 100 manufactured by Konica Corp., was exposed imagewise to light and processed in the foregoing processing steps. After completing the process, the stains produced on the rear surface of the processed film were evaluated. The deliquescence of the tablet for replenishing a stabilizing solution was also evaluated in the same manner as in Example 1. The results thereof will be shown in Table 7. Table 7

No. Alkali (Amt. added) Stain on rear surface Deliquescence Remarks

1 K₂CO₃ (200g) × ×× Comparison

2 LiOH·H₂O (65g) ○ ⓞ Invention
Evaluation standard of stains produced on a rear surface:

× :: White unevenness produced;
Δ :: Slight unevenness produced; and
○ :: Almost no stain produced.

Evaluation standard of deliquescence:

The same as in Example 2.
From Table 7, it can be seen that, when LiOH is used as an alkali, the stains produced on the rear surface of the processed film are reduced and deliquescence is improved.

Example 8

Each of the tablets was prepared in the same manner as in Example 4. One of each of tablets A, B, C and D for replenishing a color developing composition, total 4 tablets, were packed as one package. A series of 20 fractionized packages were packaged in a 4-side sealing system by making use of a peel-open type packaging material. Further, one tablet A and 2 tablets B for replenishing a bleach-fixing composition, total 3 tablets, were packed as one package and a series of 20 packages were packaged in the same manner as in the case of the tablets for replenishing a color developing composition.
One tablet for replenishing a stabilizing composition was packed as one package and then 20 packages were prepared as above.
The peel-open packaging material was prepared by making use of Tocello CMPSO11C as a sealant film and then laminating the sealant film on a non-stretched polypropylene film surface of a non-stretched polypropylene film/a stretched polypropylene film.
The prepared peel-open film and a non-stretched polypropylene film/a stretched polypropylene film were heat-sealed together in a manner such that the above-mentioned tablets were packed between them.
A running experiment was carried out under the same conditions as in No.3-12 shown in the foregoing Table 4, except that the tablet supplying means was changed so that the package was opened immediately before replenishing the tablet.
Water-supplying device and so forth were arranged in the same as in Example 4, that is, based upon those described in JP Application No. 4-111502/1992.
Fig. 1 illustrates a perspective view showing an example of solid processing composition supplying devices 140 suitable for use with the invention, wherein the solid processing composition was supplied to a processing tank by peeling off a package containing the solid type processing composition.
The leading edge of a 4-side sealed package containing a solid type processing composition was attached to take-up spool 142 serving as a fixing means through roller 141. When a subject light-sensitive material was processed, it was detected by a processed quantity information detecting means. When a specific processed quantity is reached, a signal is sent from a processing composition supply controlling means, to the motor of take-up spool 142, that was also serving as a processing composition supplying means, so that it rotates. Thereby a package containing a solid type processing composition is moved forward by a specified length, so that the necessary amount of the solid type processing composition is put in the processing tank. Any means for moving a package may be used, for example, a means for detecting a notch provided in advance to a package, means for detecting a printed pattern, or means for detecting a processing composition contained in a package. In short, such means for moving a package as mentioned above is to be capable of precisely detecting the number of necessary solid type processing compositions and moving them through roller 141 or take-up spool 142. Roller 141 was provided for the purpose of fixing or positioning a package and, thereby, a package is peeled off by two take-up spools and the required amount of the solid type processing composition is put into the processing tank.
Figs. 2(a) and 2(b) illustrate each a system for dividing and cutting a series of packages into two parts.
Wherein, when a subject light-sensitive material is processed, it is detected by a processed quantity information detecting means. When a specific processed quantity is reached, a signal is sent from the processing composition supplying means to transport rollers 502. At the same time as transport rollers 502 are rotated, the ceramic or stainless steel-made circular edge 301 is rotated to cut the lower part of the series of packages 603 into 2 parts, so that solid type processing composition 10 is put into the processing tank. When cutting a series of packages into 2 parts, the packages are spread out towards both sides of suction guide 202 by suction so that solid type processing composition can readily drop. Empty package 603 containing no solid type processing composition 10 was moved out of position by transport rollers 401 when the next solid processing composition 10 is ready to be dropped and is then scrapped in package container 101.
When using any one of the processing composition supplying means, it has been found that the same excellent photographic characteristics as obtained in No. 3-12 shown in Table 4 of Example 4 can be obtained, and that these means were advantageous from the viewpoints of the preservability and handling convenience of the solid tablet processing composition.
The above-mentioned processing composition supplying means can be applied to compositions not only of a solid tablet type but also of a powder or granule type.

Claims

A solid processing composition for a silver halide color photographic light-sensitive material, wherein the composition is a color developing composition comprising a p-phenylenediamine type color developing agent and lithium hydroxide.
The solid processing composition of claim 1, comprising anhydrous lithium hydroxide.
The solid processing composition of claim 1 or 2, wherein said composition is in a form of a tablet or granule.
The solid processing composition of claim 1, 2 or 3, wherein said composition further comprises a compound represented by the following Formula (A):
wherein L represents an alkylene group; A represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxy group, an amino group, an ammonio group, a carbamoyl group or a sulfamoyl group; and R represents a hydrogen atom or an alkyl group.
The solid processing composition of any one of the preceding claims, wherein said composition further comprises an aromatic sulfonic acid or salt thereof.
The solid processing composition of any one of the preceding claims, wherein said color developing composition comprises a mixture of granules containing lithium hydroxide and granules containing a p-phenylenediamine type color developing agent.
The solid processing composition of claim 6, wherein the mixture further comprises granules containing a compound represented by the Formula (A) as defined in claim 4.
The solid processing composition of any one of the preceding claims, wherein said composition is in the form of a tablet.
A process for the preparation of the solid processing composition of claim 8, which comprises tabletting a mixture of granules containing lithium hydroxide and granules containing a p-phenylenediamine type color developing agent.
A process according to claim 9, wherein the mixture further comprises granules defined in claim 7.
A process according to claim 9 or 10 wherein, before mixing, each type of granule in the mixture of granules is separately granulated.
A method of processing an exposed silver halide color photographic light-sensitive material comprising:
(a) developing the exposed material with a developer, and

(b) replenishing the developer with a solid processing composition as defined in any one of claims 1 to 8 or as prepared by the process defined in claim 9, 10 or 11.