JP2002341496A - Solid processing agent for color-developing silver halide color photographic sensitive material and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid processing agent for color-developing a silver halide color photographic sensitive material which ensures slight diminution of a p-phenylenediamine color developing agent, does not impair its solubility and has high destruction resistance even when stored and handled in a unsuitable environment and suppresses sticking and blocking in long-term storage and to provide a method for producing the solid processing agent. SOLUTION: The solid processing agent contains 5-20 mass% p- phenylenediamine color developing agent, 1-30 mass% polyalkylene glycol having an average molecular weight of 2,000-20,000 and saccharides.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color developing agent for a silver halide color photographic light-sensitive material and a method for producing the same. More specifically, the present invention relates to a method for producing the same. The present invention relates to a solid processing agent for color development of a silver halide color photographic light-sensitive material having improved adhesion and a method for producing the same.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material (hereinafter, also referred to as a light-sensitive material) is subjected to processes such as development, desilvering, washing, and stabilization after exposure. The processing is usually performed in an automatic developing machine (hereinafter also referred to as an automatic developing machine). In this case, a replenisher replenishing method is generally widely used, and the replenisher is controlled so as to keep the activity of the processing solution in the processing tank constant. ing. In the case of the replenisher replenishment method, the purpose is to dilute the eluate from the light-sensitive material, correct the evaporation amount, and replenish the consumed components, and a large amount of the overflow liquid is usually discharged due to the supply of the liquid.

On the other hand, in recent years, regulations on marine waste disposal of photographic waste liquid and regulations on the disposal of plastic materials have been strengthened worldwide, and the development of a new system that eliminates photographic waste liquid and does not use a plastic bottle for liquids has been required. ing. In addition, safety regulations on packaging materials have been strengthened in order to ensure the safety of transporting liquid hazardous materials, resulting in an increase in cost. Furthermore, in the minilab stores, which have been increasing rapidly recently, work by inexperienced workers has increased due to cost reduction and labor shortage. Many complaints about the replenishment system have begun.

Accordingly, there is a strong demand in the photographic industry for the development of a solid chemical replenishment system that has little photographic waste, uses no bottles, and does not require any dissolution operation.

As a method for responding to this demand, Japanese Patent Laid-Open Publication No.
Japanese Patent Application Publication No. 119454 discloses a method of solidifying almost all the processing components and directly charging them into a processing tank.

[0006] By the way, the treatment agent is stored under various atmospheres until it reaches a user's hand after production and before it is used. For example, in some parts of Southeast Asia, autonomous machines may be installed in locations without dehumidification and cooling functions. For convenience, the treatment agent is often stored in the vicinity of the automatic processing machine, and in the rainy season or the like, the atmosphere near the treatment agent storage location has a temperature of 30 to 45 degrees.
In some cases, the temperature and the humidity may be as high as 70 to 80% at ℃. On the other hand, in the winter in cold regions such as Siberia, the treatment agent may be extremely low, such as -10 to -30 ° C, in the course of transportation and the like. There is a need for a stable treatment agent that does not suffer from this.
In addition, it is generally known that photographic processing agents can remain for several years if used long in transportation and markets,
There is a demand for an improvement in storage stability over time.

[0007]

The present inventors have conducted various studies on a solid processing agent containing a paraphenylenediamine-based color developing agent. It was found that the shape of the processing agent was lost, the compound serving as the color developing agent was decomposed and reduced, and solid processing agents were attached to each other to cause blocking. In addition, cracks and cracks may occur due to vibrations during transportation after storage, and the shape (granules and tablets) of the solid processing agent cannot be maintained. And so on. If a very hard solid processing agent is used as a measure against these problems, it takes a long time to dissolve and cannot be put to practical use.In addition, when these are used in an automatic developing machine, they may be fixed and may hinder the processing. found.

[0008] The decrease in breaking strength is attributed to the fact that the solid processing agent containing a paraphenylenediamine-based color developing agent contains a hygroscopic or deliquescent alkali agent and the like. This is because the bonding strength of the treating agent kept when the water content is low decreases. Further, the paraphenylenediamine-based color developing agent has a poor binding force, and is further deteriorated when the component ratio of the color developing agent to the entire solid processing agent is increased when performing low replenishment and speeding up.

The decomposition of the compound is also due to this increase in water content.
A sufficient effect could not be obtained only by using polyhydroxyaldehydes, polyhydroxyketones, celluloses, starches, and glycogens generally used for medicines to supplement the bonding strength.

Accordingly, an object of the present invention is to provide a solid processing agent, such as a paraphenylenediamine-based color developing agent, which has a small reduction in performance and does not impair the solubility even when it is stored and handled in a poor environment. The object of the present invention is to provide a solid processing agent for color development of a silver halide color photographic light-sensitive material having the formula (I) and a method for producing the same.

[0011]

SUMMARY OF THE INVENTION The object of the present invention is to provide a method for preparing a paraphenylenediamine color developing agent in an amount of 5 to 20% by mass.
And a solid processing agent for color development of a silver halide color photographic light-sensitive material containing 1 to 30% by mass of a polyalkylene glycol having an average molecular weight of 2,000 to 20,000 and a saccharide, and the solid processing agent is in a form selected from granules and tablets. That the polyalkylene glycol is polyethylene glycol, that the paraphenylenediamine-based color developing agent is a compound represented by the above general formula [I], [II] or [III]; The main drug is 4-amino-3-methyl-N-ethyl-N-
[Β- (methanesulfonamido) ethyl] aniline sulfate or 4-amino-3-methyl-N-ethyl-β- (hydroxyethyl) aniline sulfate and contains at least a paraphenylenediamine-based color developing agent Granules and granules containing an alkaline agent are separately formed in advance, and granules formed by mixing the granules, or tablets formed by mixing and tableting are mixed. As a method for producing a solid processing agent for color development of a silver color photographic light-sensitive material, a part containing at least a paraphenylenediamine-based color developing agent and a part containing at least an alkali agent are granulated, and the part containing the alkali agent is granulated. When the average molecular weight 2000-20,000
A polyalkylene glycol is added, and then mixed with a granulated product obtained by granulating a part containing the paraphenylenediamine color developing agent, a solid processing agent for a silver halide color photographic light-sensitive material, This is achieved by a manufacturing method.

That is, the present inventors set the component ratio of the paraphenylenediamine-based color developing agent in a specific range, and further contained a polyalkylene glycol having a specific average molecular weight in a specific range, whereby the above problem was solved. It has been found that the present invention can be solved, and the present invention has been achieved.

JP-A-51-6183 describes a solid processing agent containing polyethylene glycol.
No. 7, Japanese Patent Application Laid-Open No. Hei 4-254853 is known, but there is nothing suggesting the constitution of the present invention.

Hereinafter, the present invention will be described in detail. The solid processing agent of the present invention may be in the form of powder, granules, or tablets, but is in the form of granules or tablets in terms of dosing accuracy when the solid processing agent is added to the dissolution tank or directly to the processing layer. It is more preferably, and more preferably in the form of a tablet. The term “granules” used herein refers to particles having a particle size of 50 to 5000 obtained by granulating powder.
The term “μm” refers to a granular material, and the term “tablet” refers to a product obtained by compressing powder or granules into a predetermined shape.

[0015] A preferred tablet production method is a method of granulating a powder treating agent, followed by a tableting step and compression molding. Compared with a tablet formed by a tableting process by simply mixing a powder processing agent, there is an advantage that solubility and storage stability are improved, and as a result, photographic processing performance is stabilized.

A method for solidifying a photographic processing agent is disclosed in
-29136, 4-85535, 4-8553
No. 6, No. 4-85533, No. 4-85534, No. 4
No. 172341, No. 2-109042, No. 2-10
Nos. 9043, 3-39735, 3-39939
No. JP-A-51-61837 and JP-A-54-155038.
No. 52-88025, British Patent No. 1,213,8
No. 08, etc., ie, granulation methods for producing granules include, for example, tumbling granulation, extrusion granulation, compression granulation, stirring granulation, fluidized bed granulation, and tumbling. For compression molding for producing tablets such as fluidized bed granulation, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, and a briquetting machine can be used.

The compression-molded solid processing agent can take any shape, but is preferably a cylindrical type, so-called tablet, from the viewpoint of productivity and handling, or from the problem of dust when used on the user side. .

Granulation can be carried out by any method such as dry granulation or wet granulation, but wet granulation is preferred in view of the granule strength of the granulated product. In wet granulation, granulation is performed by adding a solvent to the raw material powder. A solvent preferably used at this time is a polar solvent such as alcohol, acetone, acetonitrile, and water, or a mixed solvent thereof. It is more preferable to use water from the viewpoint of explosion-proof properties.

When the solid processing agent of the present invention is a granule, 60% by mass or more of the granule particle has an average particle size of ± 100 to 150 μm.
Is preferable from the viewpoint of the injection accuracy.

When the solid processing agent of the present invention is a tablet, the average particle size of the granules used for compression molding is such that when the granules are mixed and compression-molded, the components become non-uniform, so-called segregation. It is preferable to use one having a thickness of 100 to 800 μm from the viewpoint of making it harder, more preferably 200 to 700 μm.
It is. Further, the particle size distribution of the granulated particles is preferably such that 60% by mass or more is within a deviation of an average particle size of ± 100 to 150 μm from the viewpoint of the injection accuracy.

When granulating the paraphenylenediamine-based color developing agent of the present invention, the granulated material containing the paraphenylenediamine-based color developing agent and the granulated material containing the alkaline agent are separated without mixing with an alkali agent. It is preferable from the viewpoint of the effect of the present invention to perform granulation by so-called separation granulation.
Furthermore, the effect that the preservability and the reactivity are remarkably improved by the separate granulation can be obtained. This method has the same effect when it is formed into a tablet. In the case of fractional granulation, the above effect is further exerted by fractionating from an alkali agent and a preservative.

The form in which the polyalkylene glycol used in the present invention is added may be any of powder, granule, aqueous solution and flake. When the polyalkylene glycol is solid, it is preferably added during granulation. When compression-shaping into tablets, even when added during granulation,
The mixture may be added to the granulated material not containing polyalkylene glycol and mixed, or both may be used in combination. However, it is preferable to add the mixture during granulation. When the polyalkylene glycol is a liquid, it is preferably added as a liquid during granulation.

When the granules used for compression molding are separately granulated when added during granulation, granules containing a color developing agent, granules containing an alkali agent, and a preservative are contained. Even if it is contained in any part of the granulated product, it may be added in a plurality of parts, but it is particularly preferable to add to the part containing the alkaline agent from the viewpoint of drying property of the granulated product after granulation. preferable.

As parameters of the strength of the solid processing agent,
In the case of tablets, it can be evaluated, for example, as a tablet compressive breaking strength (breaking strength when pressure is applied to the tablet in the longitudinal direction), and can be evaluated using a Monsanto hardness meter, a Stoke hardness meter, a speed checker (Okada Seiko Co., Ltd.) ) Can be measured. For granules, use grano (Okada Seiko Co., Ltd.)
) Can be evaluated by values measured using commercially available equipment.

As the paraphenylenediamine-based color developing agent used in the present invention, those having at least one hydrophilic group on an amino group or a benzene ring are advantageous in that they do not contaminate the photosensitive material and cause little irritation to the skin. And is preferably used.

[0026] Specific hydrophilic _{groups, - (CH 2) n -CH2OH} - (CH 2) -NHSO 2 - (CH 2) n -CH 3 - (CH 2) m -O- (CH 2) _{n -CH 3 - (CH 2 CH} 2 O) n C m H 2m + 1 - (CH 2) m -CON (C m H 2m + 1) 2 (m and n each represent an integer of 0 or more.) —COOH—SO ₃ H are preferred.

The following are specific examples of the color developing agent preferably used in the present invention.

[0028]

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[0029]

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[0030]

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[0031]

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Of these, preferred are (D-1), (D
-3), (D-17) and (D-18), and more preferably (D-1) and (D-3). These compounds may be hydrated salts or anhydrous salts.

The content of these compounds in the color developing tablet is 5 to 20% by mass. Preferably, it is 5 to 15% by mass from the viewpoint of the effect of the present invention.

The solid tablet for color development of the present invention contains a saccharide from the viewpoint of storage stability over time. The saccharide referred to in the present invention refers to a monosaccharide and a polysaccharide in which a plurality of these are glycoside-linked to each other.

Monosaccharides include single polyhydroxy aldehydes, polyhydroxy ketones and their reduced derivatives,
It is a general term for a wide range of derivatives such as oxidized derivatives, deoxy derivatives, amino derivatives and thio derivatives. Many sugar, is represented by the general formula C _n H _2n O _n, a compound derived from a sugar skeleton represented by the general formula be included, in the present invention is defined as monosaccharides. Preferred among these monosaccharides are
These are sugar alcohols in which the aldehyde group and ketone group of the sugar have been reduced to primary and secondary alcohol groups, respectively, and particularly preferably a hexite having 6 carbon atoms.

Polysaccharides include celluloses, starches,
Glycogens and the like are included, celluloses include derivatives such as cellulose ethers in which some or all of the hydroxyl groups are etherified, and starches are various degradation products from hydrolysis to maltose. Including certain dextrins. Cellulose may be in the form of an alkali metal salt from the viewpoint of solubility. Those preferably used in these polysaccharides are celluloses and dextrins,
More preferred are dextrins.

Specific examples of the monosaccharide of the present invention are shown below. [Exemplary compound] B- (1) glycerin B- (2) D-trait B- (3) L-trait B- (4) meso-erythret B- (5) D-arabit B- (6) L-arabit B- (7) Adnit B- (8) Xylit B- (9) D-Sorbit B- (10) L-Sorbit B- (11) D-Mannit B- (12) L-Mannit B- (13) ) D-id B- (14) L-id B- (15) D-talit B- (16) L-talit B- (17) Zulcit B- (18) Allozulcit Specific exemplary compound of the polysaccharide of the present invention. Is shown below.

C- (1) α-dextrin C- (2) β-dextrin C- (3) γ-dextrin C- (4) δ-dextrin C- (5) ε-dextrin C- (6) α- Limiting dextrin C- (7) β-Limiting dextrin C- (8) Phosphorylase Limiting dextrin C- (9) Soluble starch C- (10) Thinner starch C- (11) White dextrin C- (12) Yellow dextrin C- (13) British gum C- (14) Pine flow (trade name, manufactured by Matsutani Chemical Industry Co., Ltd.) C- (15) Paindex 100 (trade name, manufactured by Matsutani Chemical Industry Co., Ltd.) C- (16) Paindex 1 (Trade name, manufactured by Matsutani Chemical Industry Co., Ltd.) C- (17) Paindex 2 (trade name, manufactured by Matsutani Chemical Industry Co., Ltd.) C- (18) Pie Dex 3 (trade name, manufactured by Matsutani Chemical Industry Co., Ltd.) C- (19) Paindex 4 (trade name, manufactured by Matsutani Chemical Industry Co., Ltd.) C- (20) Paindex 6 (trade name, manufactured by Matsutani Chemical Industry Co., Ltd.) C- (21) Foodtex (trade name, manufactured by Matsutani Chemical Industry Co., Ltd.) C- (22) Max 1000 (trade name, manufactured by Matsutani Chemical Industry Co., Ltd.) C- (23) Glister P (trade name, Matsutani Chemical Co., Ltd.) C- (24) TK-16 (trade name, manufactured by Matsutani Chemical Industry Co., Ltd.) C- (25) MPD (trade name, manufactured by Matsutani Chemical Industry Co., Ltd.) C- (26) H-PDX (trade name) C- (27) Stakodex (trade name, manufactured by Matsutani Chemical Industry Co., Ltd.) C- (28) Mavit (trade name, manufactured by Hayashibara Shoji Co., Ltd.) C- (29) Pullulan (Trade name, manufactured by Hayashibara Shoji Co., Ltd.) C- (30) Methylcellulose C- (31) Dimethylcellulose C- (32) Trimethylcellulose C- (33) Ethylcellulose C- (34) Diethylcellulose C- (35) Triethylcellulose C- (36) Carboxymethylcellulose C- (37) Carboxyethylcellulose C- (38) Aminoethylcellulose C- (39) Hydroxymethylcellulose C- (40) Hydroxyethylmethylcellulose C- (41) Hydroxypropylcellulose C- (42) Hydroxy Propylmethylcellulose C- (43) Hydroxypropylmethylcellulose acetate succinate C- (44) Carboxymethylhydroxyethylcellulose The content of these saccharides is determined by solid color development. 5-15% by weight per unit weight of the agent.

Saccharides exist widely and naturally, and commercially available products are easily available. Oxidation of various derivatives,
It can be easily synthesized by performing a reduction or dehydration reaction.

As the polyalkylene glycol in the present invention, those represented by the following general formula [A] are preferably used.

[0041]

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Wherein A, B and C are each —CH ₂
CH ₂ O-,

[0043]

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--CH ₂ CH ₂ CH ₂ O-- or

[0045]

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Represents R ₁₂ represents a substituted or unsubstituted lower alkyl group (eg, methyl group, ethyl group, propyl group) or a hydroxyl group. n1, n2 and n3 each represent 0 or an integer of 1 to 500. However, this compound has an average molecular weight in the range of 2000 to 20,000 and is water-soluble.

The content of ethylene oxide in the polyalkylene glycol of the present invention is preferably at least 60% by mass, more preferably at least 70% by mass, in order to prevent a decrease in solubility and strength. In addition, the average molecular weight in the present invention refers to a value calculated from a hydroxyl value.

Specific examples of the polyalkylene glycol are shown below.

[0049]

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It is preferable that a solid preservative is present in the solid processing agent of the present invention. Further, a granulated product containing a developing agent is obtained by mixing the developing agent and the preservative and granulating the mixture. Preferably it is. Preservatives include sulfites (sodium sulfite, potassium sulfite, etc.), bisulfites (sodium bisulfite, potassium bisulfite, etc.), metabisulfites (sodium metabisulfite, potassium metabisulfite, etc.), hydroxylamine Derivatives and the like.

Examples of the hydroxylamine derivative include compounds represented by the following general formula [H].

[0052]

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In the formula, R ₁₃ and R ₁₄ each represent an optionally substituted alkyl group, aryl group, heterocyclic group, R ₁₅
It represents a CO group or a hydrogen atom, and R ₁₃ and R ₁₄ may combine with each other to form a nitrogen-containing heterocyclic group. R ₁₅ represents an alkyl group, an alkoxy group, an aryl group or an amino group.

[0054] R _13, an alkyl group which may be substituted represented by R ₁₄ may be preferably one having 1 to 3 carbon atoms, be the same or different. As the substituent, a hydroxyl group,
Examples thereof include a sulfo group, a phosphone group, an alkoxy group, a carbamoyl group, and a cyano group.

Next, preferred examples of the hydroxylamine derivative represented by the general formula [H] are shown. The compound H-1
2-H-20 and H-27 can be used in the form of an alkali metal salt (sodium salt, potassium salt, lithium salt, etc.).

[0056]

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These compounds are usually free amines,
Hydrochloride, sulfate, p-toluenesulfonate, oxalate,
It is used in the form of a phosphate, acetate or the like, and is preferably a solid.

Particularly preferred compounds are H-1, H
-6, H-17, H-18 and H-25, and specific examples of the salts are shown below.

[0059]

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The solid color developing agent according to the present invention preferably contains an alkali agent. Examples of the alkali agent include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, disodium phosphate and tripotassium phosphate. , Disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate, potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-2-hydroxybenzoic acid Examples thereof include sodium (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

The solid processing agent for color development of the present invention may be used as a development accelerator in JP-B-37-16088 and JP-B-37-5608.
987, 38-7826, 44-12380
No. 45-9019 and U.S. Pat. No. 3,813,2.
Thioether compounds represented by No. 47, etc.
JP-A-4-30074, JP-A-50-137726, and JP-A-5-137726
Quaternary ammonium salts represented by U.S. Pat. Nos. 6,156,826 and 52-43429, U.S. Pat.
P-aminophenols described in Nos. 22 and 4,119,462; U.S. Pat. Nos. 2,494,903 and 3,1.
28,182, 4,230,796, 3,25
No. 3,919, JP-B-41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926 and 3,582,346, and other 1-phenyl-3 compounds. -Pyrazolidones, hydrazines,
Mesoionic compounds, ionic compounds, imidazoles and the like can be contained as necessary.

In the present invention, a compound capable of releasing chlorine ions, bromine ions and iodide ions for the purpose of preventing fog and the like can be added to a solid processing agent for color development.

It is preferable to add a chelating agent represented by the general formula [K] described in JP-A-4-118649, pp. 19 to 20, to the solid processing agent for color development of the present invention. Further, the solid processing agent for color development may contain anionic, cationic, amphoteric or nonionic surfactants.

To solidify the photographic processing agent, a concentrated solution or fine powder or particulate photographic processing agent and a water-soluble binder are kneaded and molded, or a water-soluble binder is added to the surface of the temporarily formed photographic processing agent. Any means can be adopted such as forming a coating layer by spraying an agent (Japanese Patent Application Laid-Open Nos. 4-29136 and 4-8).
No. 5535, No. 4-85536, No. 4-85533
Nos. 4-85534 and 4-172341).

[0065]

EXAMPLES The present invention will be described below with reference to specific examples, but embodiments of the present invention are not limited thereto.

Example 1 Preparation of Color-Developed Solid-Processed Tablet for Color Paper Procedure (A) Bis (2-sulfoethyl) hydroxylamine disodium salt 40 g, sodium p-toluenesulfonate 17
0 g, Tinopearl SFP (manufactured by Ciba Geigy) 30 g,
25 g of sodium diethylenetriaminepentaacetate and polyalkylene glycol (described in Tables 1 and 2) are listed in Tables 1 and 2, and all of them are granulated by adding water little by little using a commercially available mixing granulator. The amount of water added was 25 ml. Then, it was dried in a dryer at 60 ° C. for 6 hours to reduce the water content to 1% or less. Finally, this was sifted through a 16 mesh screen.
Thus, granulated product A was obtained. Operation (B) 145 g of the exemplified compound D-1, D-17 or D-18 and the polyalkylene glycol are listed in Tables 1 and 2, and these are granulated by adding water little by little using a commercially available mixing granulator. The amount of water added was 20 ml. Then, in the dryer at 40 ℃
For 12 hours to reduce the water content to 1% or less. Finally, this was sifted through a 16 mesh screen. Thus, granulated product B was obtained. Operation (C) 135 g of sodium p-toluenesulfonate, 3.5 g of sodium sulfite, 65 g of potassium hydroxide, and the amount of polyalkylene glycol (described in Tables 1 and 2) described in Tables 1 and 2,
330 g of potassium carbonate and these are granulated by adding water little by little using a commercially available mixing granulator. The amount of water added was 33 ml. Then, it was dried in a dryer at 40 ° C. for 12 hours to reduce the water content to 1% or less. Finally, this was sifted through a 16 mesh screen. Thus, granulated product C was obtained. Operation (D) The granules A, B, and C obtained by the operations (A) to (C) are mixed in a mixer for 10 minutes so as to have the mass% shown in Tables 1 and 2. Next, the mixture is tableted by a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho. Filling amount per tablet is 990 kg / cm as 10.0 g
Molded at a compression pressure of ² .

The obtained solid processing agent had a diameter of about 30 mm,
It was a cylindrical type having a thickness of 10 mm. The component ratio of each tablet is shown in Tables 1 and 2 below.

[0068]

[Table 1]

[0069]

[Table 2]

Operation (E) Two tablets prepared in Operation D were stacked in an environment room conditioned and adjusted to a temperature of 45 ° C. and a relative humidity of 55%, sealed in a glass bottle, and stored in the environment room for one week. .

The adhesiveness (sticking state) of the stored tablets was examined. Further, the tablet after storage was stirred with a magnetic stirrer in a thermostat controlled at 40 ° C. (15).
0r. p. m. )) While dissolving in 500 ml of water to evaluate the solubility.

Further, the compression breaking strength of the stored tablets was measured with a speed checker (manufactured by Okada Seiko Co., Ltd.), and the reduction rate was determined with the compression breaking strength before storage being 100%. Table 3 shows the evaluation results.

[0073]

[Table 3]

Example 2 Preparation of Color-Developed Solid-Processed Tablet for Color Negative Procedure (F) 400 g of potassium carbonate, 55 g of sodium sulfite, 15 g of sodium hydroxide, and polyalkylene glycol (described in Tables 4 and 5) in the amounts described in Tables 4 and 5 All of these are granulated with a commercially available mixing granulator while adding water little by little. The amount of water added was finally 20 ml. Thereafter, drying was performed in a dryer at 40 ° C. for 12 hours to reduce the water content to 1% or less. Finally, this was sifted through a 16 mesh screen. Thus, a granulated product F was obtained. Operation (G) Hydroxylamine sulfate 400 g, potassium bromide 50
g, 20 g of diethylenetriaminepentaacetic acid, and polyalkylene glycol (described in Tables 4 and 5) are granulated in the amounts shown in Tables 4 and 5 while adding water little by little using a commercially available mixing granulator. The amount of water added was finally 30 ml. Then in the dryer 4
After drying at 0 ° C. for 10 hours, the water content was reduced to 1% or less. Finally, this was sifted through a 16 mesh screen. Thus, a granulated material G was obtained. Operation (H) 150 g of Exemplified Compound D-3 and a polyalkylene glycol (described in Tables 4 and 5) are granulated with a commercially available mixing granulator while adding water little by little using a commercially available mixing granulator. . The amount of water added was finally 20 ml. Thereafter, the resultant was dried in a dryer at 40 ° C. for 12 hours to reduce the water content to 1% or less. Finally, this was sifted through a 16 mesh screen. Thus, a granulated material H was obtained. Operation (I) The granules F, G, and H were adjusted to have the mass% shown in Tables 4 and 5 (provided that the total mass% of F, G, and H was 100%
For those that did not, polyalkylene glycol (as described in Tables 4 and 5) was added and mixed in a mixer (100%). A tableting machine in which each mixture was modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho, the filling amount per tablet was 990 kg / tablet as 10.0 g.
tableting with a compression pressure of cm ² and solid processing agents (tablets) 39-7
5 was produced. The obtained solid processing agent has a diameter of approximately 30 m.
m, a cylindrical shape having a thickness of 10 mm.

The component ratios of each tablet are shown in Tables 4 and 5 below.

[0076]

[Table 4]

[0077]

[Table 5]

Operation (J) The tablets prepared in operation (I) were stored and evaluated in the same manner as in operation (E). Table 6 shows the results.

[0079]

[Table 6]

Example 3 Operation (K) Exemplified compound B was added to the granulated product F of the tablet 43 in Table 4 of Example 2.
As shown in Table 7,-(11) or C- (14) was added to each tablet at 5, 10, and 15%, respectively, and a granulated product F 'was prepared in the same manner as in the operation (F). Operation (L) The color developing agent in one tablet of the granules prepared in the operation (K),
Granules F ', G and I were mixed in a mixer such that the content of each of the polyalkylene glycols was 10%. Procedure (M) The mixture of procedure (L) was tableted as in procedure (I).

The prepared tablets were placed in a petri dish, and were heated at 25 ° C.
It is stored for 1 week in an environment room adjusted to a relative humidity of 40% and the content of the color developing agent in one tablet after storage is measured. I asked.

Table 7 shows the evaluation results.

[0083]

[Table 7]

Example 4 Procedure (N) Exemplified Compound D-1, D-3, D-17 or D-18 1
A composition comprising 50 g and a polyalkylene glycol (described in Tables 8 and 9) was pulverized with a pulverizer until the particle size became 100 μm or less, and water was added little by little using a commercially available stirring granulator to perform granulation. The amount of water added was 8% by mass based on the composition.
Then, it was dried in a dryer at 40 ° C. for 12 hours to reduce the water content to 1% or less. Finally, add this to 16 mesh and 1
The mixture was passed through a 50-mesh sieve, and what remained on the 150-mesh sieve was designated as granulated product J. Procedure (O) Bis (2-sulfoethyl) hydroxylamine disodium salt 80 g, sodium p-toluenesulfonate 19
0 g, Tinopearl SFP (manufactured by Ciba Geigy) 30 g,
After all of these were pulverized to a particle size of 100 μm or less, the mixture was granulated with a stirring granulator while adding water little by little.
The amount of water added was 12 ml. Then, in the dryer 60
Drying at 6 ° C. for 6 hours reduced the water content to 1% or less. Finally, this is sieved through 16 mesh and 150 mesh sieves,
What remained on the 150-mesh sieve was designated as granulated material K. Procedure (P) Hydroxylamine sulfate 80 g, potassium bromide 10
g, 1,2-dihydroxybenzene-3,5-diphosphonic acid disodium salt monohydrate (10 g), all of which were pulverized to a particle size of 100 μm or less, and then formed while adding 5 ml of water with a stirring granulator. Granulated. Then in the dryer 60
After drying at 5 ° C. for 5 hours, the water content was reduced to 1% or less. Finally, this is sieved through 16 mesh and 150 mesh sieves,
What remained on the 150-mesh sieve was designated as granulated product L. Procedure (Q) A mixture of 330 g of potassium carbonate, 150 g of sodium p-toluenesulfonate, 5 g of sodium sulfite, 10 g of lithium hydroxide monohydrate and 5 g of pentasodium diethylenetriaminepentaacetate was used except that the amount of water added was 20 ml. Granules M were prepared in the same manner as in the operation (P). Procedure (R): 750 g of potassium carbonate, 100 g of sodium sulfite, 50 g of sodium diethylenetriaminepentaacetate 50 g and p-
A granulated product N was prepared in the same manner as in the operation (P), except that a mixture of 100 g of toluenesulfonic acid was used and the amount of water added was changed to 40 ml. Operation (S) The granules J, K and M produced by the above operation were mixed in a mixer for 10 minutes so as to have the mass% shown in Table 8. This was designated as mixture O. Operation (T) The granules J, L and N produced by the above operation were mixed for 10 minutes in a mixer so as to have the mass% shown in Table 9. This was designated as mixture P. Experiment (A) 30 g of each of the mixtures O and P was taken, placed in a glass bottle, sealed, and stored for one week in an environment room controlled at 45 ° C. and 55% RH. The mixture after storage was passed through a 16-mesh sieve, and the adhesion (blocking property) was evaluated based on the granules remaining on the sieve.

Further, the mixture after storage was stirred with a magnetic stirrer in a thermostat controlled at 40 ° C. (15 minutes).
0r. p. m. ) While dissolving in 1500 ml of water to evaluate the solubility. Experiment (B) 30 g of each of the mixtures O and P was taken, placed in an open petri dish, and stored for one week in an environment room controlled at 25 ° C. and 45% RH. After storage, it was sieved through a 150-mesh sieve, and the reduction in strength was evaluated by testing the generation of fine powder. Evaluation criteria No occurrence: ◎ Almost no occurrence: ○ Granules are broken and fine powder is generated: × The results are shown in Tables 8 and 9.

[0086]

[Table 8]

[0087]

[Table 9]

From the above results, it is found that the average molecular weight of the polyalkylene glycol is preferably 2,000 to 20,000, more preferably 2,000 to 15,000, and the polyalkylene glycol is more preferably A- (4) to (8).

Further, the mass% of the polyalkylene glycol with respect to the whole solid treating agent is preferably 1 to 30 mass%, more preferably 3 to 20 mass%, and still more preferably 5 to 2 mass%.
It turns out that it is 0 mass%.

The mass% of the paraphenylenediamine color developing agent based on the total solid processing agent is preferably 5 to 20 mass%, more preferably 5 to 15 mass%.

[0091]

According to the present invention, even when the color developing solid processing agent is stored for a long period of time in a poor environment, the decrease in the color developing agent is small, the solubility is not impaired, and the breaking strength is strong.
Furthermore, adhesion and blocking between the solid processing agents are improved.

Claims (7)

[Claims] 1. A silver halide color photograph comprising: 5 to 20% by mass of a paraphenylenediamine-based color developing agent, 1 to 30% by mass of a polyalkylene glycol having an average molecular weight of 2,000 to 20,000 and saccharides. A solid processing agent for color development of photosensitive materials. 2. The solid processing agent for color development of a silver halide color photographic light-sensitive material according to claim 1, wherein said solid processing agent is in a form selected from granules and tablets. 3. The solid processing agent for color development of a silver halide color photographic light-sensitive material according to claim 1, wherein the polyalkylene glycol is polyethylene glycol. 4. The method according to claim 1, wherein the paraphenylenediamine color developing agent is a compound represented by the following general formula [I], [II] or [III]. The solid processing agent for color development of a silver halide color photographic light-sensitive material described in the above item. Embedded image [Wherein, R ₁ and R ₃ may be the same or different and each represents a methyl group, an ethyl group, a propyl group or a hydroxyethyl group. R ₂ is a hydroxyethyl group,
Represents a methoxyethyl group, a sulfoalkyl group or a β-methanesulfonamidoethyl group. ] [Wherein, R ₄ and R ₅ each represent an alkyl group having 1 to 4 carbon atoms, and R ₆ represents a linear or branched alkylene group having 3 to 4 carbon atoms. ] [Wherein, R ₇ represents an alkyl group, and R ₈ represents an alkylene group having 2 or more carbon atoms in the main chain. R ₉ and R ₁₀ may be the same or different and each represents a hydrogen atom or an alkyl group having 4 or less carbon atoms. R ₁₁ represents a substituent. n represents an integer of 0 to 4, and when n is 2 or more, R ₁₁ may be the same or different. ] 5. The method according to claim 1, wherein the paraphenylenediamine-based color developing agent is 4-amino-3-methyl-N-ethyl-N-
5. [β- (methanesulfonamido) ethyl] aniline sulfate or 4-amino-3-methyl-N-ethyl-β- (hydroxyethyl) aniline sulfate. 2. The solid processing agent for color development of a silver halide color photographic light-sensitive material according to item 1. 6. A granule containing at least a paraphenylenediamine-based color developing agent and a granule containing an alkaline agent are separately formed in advance, and the granules formed by mixing the granules or the granules are mixed. The tablet according to any one of claims 2 to 5, wherein the tablet is formed by post-tabletting.
The solid processing agent for color development of a silver halide color photographic light-sensitive material described in the above item. 7. A polystyrene having an average molecular weight of 2,000 to 20,000 when granulating a part containing at least a paraphenylenediamine-based color developing agent and a part containing at least an alkaline agent. A method for producing a solid processing agent for a silver halide color photographic light-sensitive material, comprising adding an alkylene glycol, and thereafter mixing the resultant with a granulated product obtained by granulating a part containing the paraphenylenediamine-based color developing agent.