JPH0792622A - Solid processing agent for color developing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a solid processing agent for color-developing a photosensitive material small in decrease of breaking strength and a p-phenylenediamine type color developing agent and not deteriorated in solubility even in the case of storing and handling it in a quite inadequate environment and improved in resistance to attaching and blocking even after long storage. CONSTITUTION:This solid processing agent for color-developing a photosensitive material is prepared by separately weighing the p-phenylenediamine type color developing agent and a polyalkylene glycol having an average molecular weight of 2,000-20,000 in advance and mixing them to give a proportion of 5-20 weight% color developing agent and 1-30 weight% polyalkylene glycol.

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 silver halide color photographic light-sensitive materials, and more specifically, a decrease in breaking strength with time is remarkably suppressed, and further deterioration of solubility and adhesion with time are improved. The present invention relates to a solid processing agent for color development of a silver halide color photographic light-sensitive material.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material (hereinafter, also referred to as a light-sensitive material) is processed by exposure, development, desilvering, washing, stabilization and the like. Processing is usually carried out by an automatic processor (hereinafter also referred to as an automatic processor). In that case, a replenisher replenishing method is generally widely used, and the activity of the processing solution in the processing tank is controlled to be constant. ing. In the case of the replenisher replenishing method, the purpose is to dilute the eluate from the photosensitive material, correct the evaporation amount, and replenish the consumption component, and a large amount of overflow liquid is usually discharged due to the supply of the liquid.

On the other hand, in recent years, regulations on the dumping of photographic waste liquid into the ocean and regulations on the disposal of plastic materials have been strengthened worldwide, and it is required to develop a new system that eliminates photographic waste liquid and does not use a plastic bottle for liquid agent. ing. In addition, safety regulations for packaging materials have been strengthened in order to ensure the safety of transportation of liquid hazardous materials, which has led to an increase in cost. Furthermore, in the minilab store, which has been increasing rapidly in recent years, there is a lot of work by immature workers due to cost reduction and lack of manpower, and due to the difficulty of preparatory solution dissolution or dilution preparation work, accidents due to erroneous dissolution occur one after another, There have been many complaints about the replenishment system.

Therefore, in the photographic industry, there is a strong demand for the development of a solid chemical replenishing system which produces almost no photographic waste liquid, uses no bottle, and does not require any dissolving work.

As a method for responding to this demand, Japanese Patent Laid-Open No. 5-11
Japanese Patent Publication No. 9454 discloses a method in which almost all processing components are solidified and directly charged into a processing tank.

By the way, the treating agent is stored in various atmospheres after manufacturing until it reaches the user's hand, and after reaching the user's hand and before use. For example, in some parts of Southeast Asia, an automatic processing machine may be installed in a place without dehumidifying and cooling functions. Because of ease of use, the treatment agent is often stored near the processing machine, and in the rainy season, the atmosphere near the treatment agent storage location becomes hot and humid with a temperature of 30 to 45 ° C and a relative humidity of 70 to 80%. There are cases. On the other hand, the treating agent may become extremely low temperature such as −10 to −30 ° C. in the process of transportation in winter in cold regions such as Siberia,
There is concern about deterioration of the treatment agent due to storage, and a stable treatment agent that is not affected by the storage environment is desired. Further, it is generally known that a photographic processing agent stays for several years at the longest until it is used in transportation and market, and improvement of storability over time is required.

[0007]

DISCLOSURE OF THE INVENTION As a result of various studies by the present inventors on solid processing agents containing a paraphenylenediamine type color developing agent, when stored for a long period of time in the air, the solid processing agent absorbs moisture or the like to give a solid. It was found that the shape of the processing agent collapsed, the compound serving as the color developing agent was decomposed and reduced, and the solid processing agents adhered to each other to cause blocking. In addition, there are problems such as cracking, cracking, etc. due to vibration during transportation after storage, the shape of the solid processing agent (granular or tablet-like) cannot be maintained, and it is said to be a poor input when used in an automatic processor. It has been found that the above causes. If a very hard solid processing agent is used as a countermeasure against these problems, it will take a long time to dissolve and cannot be put to practical use.Furthermore, when these are used in an automatic processor, sticking may occur, which may hinder the processing. found.

The decrease in breaking strength is due to the fact that the solid processing agent in which the para-phenylenediamine color developing agent is present contains an alkali agent having hygroscopicity and deliquescent, so that its deliquescent property causes a high water content over time. This is because the binding force of the treating agent kept when the water content is low decreases. Further, the para-phenylenediamine type color developing agent has a poor binding force, and when the replenishment and the speeding up are performed, when the component ratio of the color developing agent in the whole solid processing agent is increased, it is further deteriorated.

The decomposition of the compound is also due to this increase in water content.

In order to complement the binding force, sufficient effects cannot be obtained only by using polyhydroxyaldehydes, polyhydroxyketones, celluloses, starches and glycogens which are generally used in medicine. It was

Therefore, a first object of the present invention is to reduce the breaking strength of the solid processing agent and the decrease of the paraphenylenediamine type color developing agent and to improve the solubility even when stored and handled in a bad environment. It is an object of the present invention to provide a color developing solid processing agent for silver halide color photographic light-sensitive materials which does not impair the above.

A second object is to provide a solid developing agent for color developing for silver halide color photographic light-sensitive materials, which has improved adhesion and blocking of the solid processing agent when stored for a long period of time.

[0013]

The above object of the present invention is to preliminarily divide and weigh 5 to 20% by weight of a paraphenylenediamine color developing agent and 1 to 30% by weight of a polyalkylene glycol having an average molecular weight of 2000 to 20000. % Silver halide color photographic light-sensitive material solid developing agent for color development, the solid processing agent being in a form selected from granules and tablets, polyalkylene glycol being polyethylene glycol, para-phenylenediamine color developing agent Is a compound represented by the general formula [I] (Chemical Formula 1), [II] (Chemical Formula 2) or [III] (Chemical Formula 3), and the paraphenylenediamine color developing agent is 4-amino-3. -Methyl-N-ethyl-N
-[Β- (methanesulfonamido) ethyl] aniline sulfate or 4-amino-3-methyl-N-ethyl-β- (hydroxyethyl) aniline sulfate, containing at least a para-phenylenediamine color developing agent The granules to be formed and the granules containing an alkali agent are separately formed in advance, and the granules are formed by mixing each of them, or the tablets are formed by mixing each of them and punching. It

That is, the present inventors set the component ratio of the para-phenylenediamine type color developing agent to a specific range and further contained a polyalkylene glycol having a specific average molecular weight in a specific range of the component ratio, whereby the above problem was solved. The present invention has been made by finding that the above can be solved.

JP-A-51-61837 and JP-A-4-254853 are known to describe solid processing agents containing polyethylene glycol, which suggest the constitution of the present invention. There is nothing.

The present invention will be described in detail below.

The solid processing agent of the present invention is in the form of powder, granules,
Although it may be in the form of tablets, granules or tablets are preferable, and tablets are more preferable, from the viewpoint of the accuracy of addition when the solid processing agent is added to the dissolution tank or directly to the processing layer. The granules referred to here are particles having a particle size of 50 to 5000 μm obtained by granulating powder, and tablets are
It refers to powder or granules compression-molded into a certain shape.

A preferable tablet manufacturing method is a method in which a powder processing agent is granulated and then a tableting step is performed to perform compression molding. There is an advantage that the solubility and the storability are improved and the photographic processing performance becomes stable as compared with a tablet formed by a tableting process by simply mixing a powder processing agent.

A method of solidifying a photographic processing agent is disclosed in JP-A-4-
29136, 4-85535, 4-85536, 4-8
5533, 4-85534, 4-172341, 2-19042
No. 2-109043, 3-39735, 3-39739, JP Sho
No. 51-61837, No. 54-155038, No. 52-88025, methods described in each publication such as British Patent No. 1,213,808, that is, as a granulation method for producing granules, for example, rolling granulation , Extrusion granulation, compression granulation, stirring granulation, fluidized bed granulation,
For compression molding to produce tablets, such as rolling fluidized bed granulation, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine,
A briquetting machine can be used.

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

The granulation can be carried out by any method such as dry granulation or wet granulation, but wet granulation is preferable from the viewpoint of granule strength of the granulated product. In the wet granulation, a solvent is added to the raw material powder for granulation. The solvent preferably used at this time is a polar solvent such as alcohol, acetone, acetonitrile or water, or a mixed solvent thereof may be used. More preferably, water is used from the viewpoint of explosion proof.

When the solid processing agent of the present invention is a granule, it is preferable that 60% by weight or more of the particles of the granule fall within the deviation of the average particle diameter ± 100 to 150 μm from the viewpoint of charging accuracy.

When the solid processing agent of the present invention is a tablet, the average particle size of the granulated product used for compression molding is such that when the granulated product is mixed and compression molded, the components become non-uniform, so-called segregation occurs. From the viewpoint of making it difficult, it is preferable to use one having a thickness of 100 to 800 μm, and more preferably 200 to 700 μm. Furthermore, the particle size distribution of the granulated product is such that the average particle size ± 60% by weight or more
Those having a deviation of 100 to 150 μm are preferable from the viewpoint of feeding accuracy.

When granulating the para-phenylenediamine color developing agent in the present invention, the granules containing the para-phenylenediamine color developing agent and the granules containing the alkaline agent are mixed without mixing with the alkali agent. In terms of the effect of the present invention, it is preferable to granulate by so-called granulation.
Furthermore, the effect of significantly improving the preservability and the reactivity can be obtained by the separate granulation. With this method, the same effect can be obtained when forming into tablets. Further, when the granulation is carried out by fractionation, the above-mentioned effect is further exhibited by fractionating with an alkali agent and a preservative.

The polyalkylene glycol used in the present invention may be added in the form of powder, granules, aqueous solution, or flakes. When the polyalkylene glycol is solid, it is preferably added during granulation, Even if added during granulation when compressed into tablets,
It may be added to a granulated product containing no polyalkylene glycol and mixed, or both may be used in combination, but it is preferable to add it at the time of 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 at the time of granulation, a granule containing a color developing agent, a granule containing an alkali agent, and a preservative are contained. It may be contained in any part of the granulated product, or may be added by dividing it into a plurality of parts, but it is particularly preferable to add it to a part containing an alkali agent from the viewpoint of the drying property of the granulated product after granulation. preferable.

As the strength parameter of the solid processing agent,
In the case of tablets, for example, it can be evaluated as the compressive breaking strength of tablets (breaking strength when pressure is applied in the long direction of the tablet), and Monsanto hardness meter, Stokes hardness meter, speed checker (Okada Seiko Co., Ltd.) Manufactured) and the like. Granules (Okada Seiko Co., Ltd.)
It can be evaluated by the value measured using a commercially available device or the like.

The term “preliminary divided weighing” as used in the present invention means per package when the solid processing agent is supplied in the case of granules, and per tablet in the case of tablets.

As the para-phenylenediamine color developing agent used in the present invention, those having at least one hydrophilic group on the amino group or benzene ring are advantageous in that they do not stain the light-sensitive material and cause less irritation to the skin. And is preferably used.

Specific hydrophilic groups include-(CH ₂ ) n-CH ₂ OH-(CH ₂ ) -NHSO _2- (CH ₂ ) n-CH _3- (CH ₂ ) m-O- (CH _{2) n-CH 3 - (} CH 2 CH 2 O) nCmH 2m + 1 -. (CH 2) m-CON (CmH 2m + 1) 2 (m and n each represent an integer of 0 or more) -COOH - SO ₃ H and the like are preferred.

Specific examples of the color developing agent preferably used in the present invention include the following compounds.

[0032]

[Chemical 4]

[0033]

[Chemical 5]

[0034]

[Chemical 6]

[0035]

[Chemical 7]

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

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

From the viewpoint of storage stability with time, it is preferable that the solid tablet for color development contains a saccharide. The saccharide in the present invention refers to a monosaccharide and a polysaccharide in which a plurality of these are glycosidic-bonded to each other.

The monosaccharide means a single polyhydroxyaldehyde, polyhydroxyketone 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. Although many sugars are represented by the general formula CnH ₂ nOn, they are defined as monosaccharides in the present invention, including compounds derived from the sugar skeleton represented by this general formula. Among these monosaccharides, preferred are sugar alcohols obtained by reducing aldehyde groups and ketone groups of sugars to form primary and secondary alcohol groups, and particularly preferred is hexite having 6 carbon atoms.

Polysaccharides include celluloses, starches,
Glycogen and the like are included, and celluloses include derivatives such as cellulose ethers in which some or all of the hydroxyl groups are etherified, and starches are various decomposition products until they are hydrolyzed to maltose. Includes 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.

[Exemplified Compounds] B- (1) Glycerin B- (2) D-trait B- (3) L-trait B- (4) meso-erythrette B- (5) D-arabit B- (6) L-Arabite 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-idit B- (14) L-idit B- (15) D-talit B- (16) L-talit B- (17) Dulcit B- (18) Alodulcit Specific example of the polysaccharide of the present invention Typical examples of compounds are 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- Limit Dextrin C- (7) β-Limit Dextrin C- (8) Phosphorylase Limit Dextrin C- (9) Soluble Starch C- (10) Thin Nori Starch C- (11) White Dextrin C- (12) Yellow Dextrin C- (13) British Gum C- (14) Pine Flow (trade name, manufactured by Matsutani Chemical Co., Ltd.) C- (15) Pa Index 100 (product name, manufactured by Matsutani Chemical Co., Ltd.) C- (16) Pa Index 1 (Product name, manufactured by Matsutani Chemical Co., Ltd.) C- (17) Pa index 2 (Product name, manufactured by Matsutani Chemical Co., Ltd.) C- (18) Pa index 3 (Product name, Matsutani Chemical Co., Ltd. stock Company-made C- (19) Pa index 4 (Product name, Matsutani Chemical Co., Ltd.) C- (20) Pa index 6 (Product name, Matsutani Chemical Co., Ltd.) C- (21) Foodtex (Product) Name, manufactured by Matsutani Chemical Co., Ltd.) C- (22) Max 1000 (trade name, manufactured by Matsutani Chemical Co., Ltd.) C- (23) Glister P (product name, manufactured by Matsutani Chemical Co., Ltd.) C- (24) TK-16 (product name, manufactured by Matsutani Chemical Co., Ltd.) C- (25) MPD (product name, manufactured by Matsutani Chemical Co., Ltd.) C- (26) H-PDX (product name, manufactured by Matsutani Chemical Co., Ltd.) C- (27) Stacodex (trade name, manufactured by Matsutani Chemical Co., Ltd.) C- (28) Mabit (trade name, manufactured by Hayashibara Shoji Co., Ltd.) C- (29) Pullulan (trade name, manufactured by Hayashibara Shoji Co., Ltd.) C- (30) Methylcellulose C- (31) Dimethy Cellulose C- (32) Trimethyl cellulose C- (33) Ethyl cellulose C- (34) Diethyl cellulose C- (35) Triethyl cellulose C- (36) Carboxymethyl cellulose C- (37) Carboxyethyl cellulose C- (38) Aminoethyl cellulose C -(39) Hydroxymethylcellulose C- (40) Hydroxyethylmethylcellulose C- (41) Hydroxypropylcellulose C- (42) Hydroxypropylmethylcellulose C- (43) Hydroxypropylmethylcellulose acetate succinate C- (44) Carboxymethylhydroxyethylcellulose The addition amount of these saccharides is preferably 5 to 15% by weight per unit weight of the solid color developing agent.

Sugars are widely present in nature, and commercial products are easily available. Oxidation of various derivatives,
It can be easily synthesized by reduction or dehydration reaction.

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

[0046]

[Chemical 8]

The content of ethylene oxide in the polyalkylene glycol of the present invention is preferably 60% by weight or more, more preferably 70% by weight or more, from the viewpoint of preventing the solubility and the strength from decreasing. In addition, the average molecular weight in the present invention means that calculated by the hydroxyl value.

Specific examples of polyalkylene glycol compounds are shown below.

[0049]

[Chemical 9]

A solid preservative is preferably present in the solid processing composition of the present invention, and the granulated product containing the developing agent is obtained by mixing the developing agent and the preservative and granulating the mixture. Preferably. As preservatives, sulfites (sodium sulfite, potassium sulfite, etc.), bisulfites (sodium bisulfite, potassium bisulfite, etc.), metabisulfites (sodium metabisulfite, potassium metabisulfite, etc.), hydroxylamine Examples include derivatives.

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

[0052]

[Chemical 10]

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

The optionally substituted alkyl group represented by R ₁₃ and R ₁₄ preferably has 1 to 3 carbon atoms and may 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 compounds H-12 to H-20 and H-27 can be used in the form of alkali metal salts (sodium salt, potassium salt, lithium salt, etc.).

[0057]

[Chemical 11]

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

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

[0060]

[Chemical 12]

The solid color developing agent according to the present invention preferably contains an alkaline agent, and examples of the alkaline 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
-Sodium hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like can be mentioned.

The solid processing agent for color development of the present invention contains, as a development accelerator, Japanese Patent Publication Nos. 37-16088, 37-5987 and 38-
7826, 44-12380, 45-9019 and U.S. Pat.
Thioether compounds represented by No. 13,247, etc.
No. 44-30074, JP-A Nos. 50-137726, 56-156826 and
Quaternary ammonium salts typified by 52-43429, p-aminophenols described in U.S. Patents 2,610,122 and 4,119,462, U.S. Patents 2,494,903, 3,128,182, 4,
No. 230,796, No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Pat. , Ionic compounds, imidazoles and the like can be contained as necessary.

In the present invention, a compound releasing chlorine ion, bromine ion and iodine ion can be added to the solid developing agent for color development for the purpose of preventing fog.

Further, it is preferable to add a chelating agent represented by the general formula [K] described on pages 19 to 20 of JP-A No. 4-118649 to the solid developing agent for color development of the present invention. Furthermore, the solid developing agent for color development may contain anionic, cationic, amphoteric and nonionic surfactants.

To solidify the photographic processing agent, a concentrated liquid or fine powder or particulate photographic processing agent and a water-soluble binder are kneaded and molded, or the surface of the temporarily molded photographic processing agent is water-soluble. Any means such as forming a coating layer by spraying an agent can be adopted (JP-A-4-29136, 4-85535,
4-85536, 4-85533, 4-85534, 4-172341).

[0066]

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

Example 1 Preparation of Color Development Solid Treatment Tablet for Color Paper Operation (A) Bis (2-sulfoethyl) hydroxylamine disodium salt 40 g, sodium p-toluenesulfonate 170 g, Chinopearl SFP (Ciba Geigy) 30 g, 25 g of sodium diethylenetriamine pentaacetate and polyalkylene glycol (described in Tables 1 and 2) in the amounts described in Tables 1 and 2, all of which are granulated by adding water little by little with a commercially available mixing granulator. The amount of water added was 25 ml. Then, it dried at 60 degreeC in the dryer for 6 hours, and made the water content rate 1% or less. Finally this 16
Sifted through a mesh. The granulated material A was obtained by the above.

Operation (B) 145 g of Exemplified Compound D-1, D-17 or D-18 and the amount of polyalkylene glycol shown in Tables 1 and 2 were added to a commercial mixing granulator by adding water little by little. Grain. The amount of water added was 20 ml. Then, it dried at 40 degreeC in the dryer for 12 hours, and made the water content rate 1% or less. Finally it was sifted through a 16 mesh screen. Thereby, a granulated product B was obtained.

Operation (C) 135 g of sodium p-toluenesulfonate, 3.5 g of sodium sulfite, 65 g of potassium hydroxide, polyalkylene glycol (described in Tables 1 and 2) in the amounts described in Tables 1 and 2, potassium carbonate 330 g, and Granulate by adding water little by little with a commercially available mixing granulator. The amount of water added was 33 ml. Then, it dried at 40 degreeC in the dryer for 12 hours, and made the water content rate 1% or less. Finally it was sifted through a 16 mesh screen. Thereby, a granulated product C was obtained.

Operation (D) The granulated products A, B and C granulated in the above operations (A) to (C) are mixed for 10 minutes in a mixer so that the weight% shown in Tables 1 and 2 will be achieved. . Next, the mixture is tableted by a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho. The filling amount per tablet was 10.0 g, and the tablets were molded at a compression pressure of 990 kg / cm ² .

The obtained solid processing agent had a diameter of approximately 30 mm and a thickness of
It was a 10 mm cylindrical type.

The composition ratio of each tablet is shown in Tables 1 and 2 below.

[0073]

[Table 1]

[0074]

[Table 2]

Operation (E) Operation D in an environment room where the temperature and humidity are controlled to 45 ° C. and 55% relative humidity.
Two tablets prepared in Step 1 were stacked, the glass bottle was tightly stoppered, and stored in the environment room for 1 week.

The adhesion (sticking state) of the stored tablets was examined.

Further, the tablets after this storage were agitated with a magnetic stirrer in a thermostatic chamber whose temperature was controlled at 40 ° C. (150 r.p.
While being dissolved in 500 ml of water, the solubility was evaluated.

Further, the compression fracture strength of the stored tablets was measured by a speed checker (manufactured by Okada Seiko Co., Ltd.), and the reduction rate was calculated by setting the compression fracture strength before storage to 100%.

Evaluation Criteria Adhesive No sticking: ○ Two tablets are stuck: × Solubility Complete dissolution within 30 minutes: ○ Complete dissolution within 30 to 60 minutes: △ Complete dissolution within 60 minutes or more: × The evaluation results are shown in Table 3.

[0080]

[Table 3]

Example 2 Preparation of Color Developing Solid Treated Tablet for Color Negative Operation (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 commercial mixing granulator while adding water little by little. The final amount of water added was 20 ml. After that, it was dried in a dryer at 40 ° C. for 12 hours, and the water content was adjusted to 1% or less. Finally this 16
Sifted through a mesh. Thereby, a granulated product F was obtained.

Operation (G) 400 g of hydroxylamine sulfate, 50 g of potassium bromide,
Granulate 20 g of diethylenetriamine pentaacetic acid and polyalkylene glycol (described in Tables 4 and 5) in amounts shown in Tables 4 and 5 while adding water little by little with a commercially available mixing granulator. The final amount of water added was 30 ml. After that, it was dried in a dryer at 40 ° C. for 10 hours so that the water content was 1% or less. Finally it was sifted through a 16 mesh screen. Thereby, a granulated product G was obtained.

Operation (H) 150 g of Exemplified Compound D-3 and polyalkylene glycol (described in Tables 4 and 5) in the amounts described in Tables 4 and 5 were added to a composition by a commercial mixing granulator while adding water little by little. Granulate.
The final amount of water added was 20 ml. Then in the dryer 40
It was dried at ℃ for 12 hours to make the water content below 1%. Finally it was sifted through a 16 mesh screen. Thereby, a granulated product H was obtained.

Operation (I) The granules F, G and H are adjusted to the weight% shown in Tables 4 and 5 (however, if the total of the weight% of F, G and H is not 100%, , Polyalkylene glycol (as listed in Tables 4 and 5) to 100%) and mixed in a mixer. Each mixture was tableted with a tableting machine modified from Kikusui Seisakusho's Tough Press Collect 1527HU to a filling amount of 10.0 g and compressed at a compression pressure of 990 kg / cm ² to give solid processing agents (tablets) 40 to 78. It was made. The solid processing agent obtained was a cylinder with a diameter of approximately 30 mm and a thickness of 10 mm.

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

[0086]

[Table 4]

[0087]

[Table 5]

Procedure (J) The tablets prepared in procedure (I) were stored and evaluated in the same manner as procedure (E). The results are shown in Table 6.

[0089]

[Table 6]

Example 3 Operation (K) Exemplified compound B-is shown in Granules F of tablet 53 in Table 4 of Example 2.
(11) or C- (14) is 1 as shown in Table 7.
Granules F'were prepared in the same manner as in the operation (F) by adding 5 to 10% to the tablets.

Operation (L) Color developing agent in 1 tablet of the granulated product prepared in operation (K),
Granules F ', G and I were mixed in a mixer so that the content of each polyalkylene glycol was 10%.

Operation (M) The mixture of operation (L) was tabletted as in operation (I).

The prepared tablets were placed in a petri dish and stored in an environment room where the temperature and humidity were adjusted to 25 ° C. and 40% relative humidity for 1 week.
The content of the color developing agent in one tablet after storage was measured,
The residual rate was calculated by setting the content rate before storage to 100%.

The evaluation results are shown in Table 7.

[0095]

[Table 7]

Example 4 Operation (N) A composition comprising 150 g of Exemplified Compound D-1, D-3, D-17 or D-18 and polyalkylene glycol (described in Tables 8 and 9) was granulated with a pulverizer. Grind until the diameter is 100 μm or less,
Granulation was performed by adding water little by little with a commercially available stirring granulator. The amount of water added was 8% by weight based on the composition. Then, it dried at 40 degreeC in the dryer for 12 hours, and made the water content rate 1% or less. Finally, this was passed through a 16-mesh screen and a 150-mesh screen, and what remained on the 150-mesh screen was designated as Granule J.

Operation (O) Bis (2-sulfoethyl) hydroxylamine disodium salt 80 g, sodium p-toluenesulfonate 190 g, Chinopearl SFP (manufactured by Ciba Geigy) 30 g, all of which were pulverized to a particle size of 100 μm or less Granulation was performed while adding water little by little with a stirring granulator. The amount of water added was 12 ml. Then, it dried at 60 degreeC in the dryer for 6 hours, and made the water content rate 1% or less. Finally this is 16 mesh and 150
The mixture was passed through a mesh screen, and what remained on the 150 mesh screen was designated as Granule K.

Procedure (P) 80 g of hydroxylamine sulfate, 10 g of potassium bromide, 1,
10 g of 2-dihydroxybenzene-3,5-diphosphonic acid disodium salt monohydrate, all of which were ground to a particle size of 100 μm or less, and then granulated with a stirring granulator while adding 5 ml of water. After that, it was dried in a dryer at 60 ° C. for 5 hours so that the water content was 1% or less. Finally this is 16 mesh and 15
The mixture was passed through a 0-mesh screen, and what remained on the 150-mesh screen was designated as Granule L.

Operation (Q) 330 g of potassium carbonate, sodium p-toluenesulfonate 1
50g, sodium sulfite 5g, lithium hydroxide monohydrate
10 g and diethylenetriamine pentaacetic acid 5 sodium 5 g
A granulated product M was prepared in the same manner as in the operation (P) except that the amount of water added was 20 ml using the mixture of

Procedure (R) The procedure of Procedure (P) was repeated except that a mixture of 750 g of potassium carbonate, 100 g of sodium sulfite, 50 g of diethylenetriamine pentaacetic acid 5 sodium salt and 100 g of p-toluenesulfonic acid was used, and the amount of water added was 40 ml. To produce a granulated product N.

Operation (S) The granulated products J, K and M produced by the above operation were mixed in a mixer for 10 minutes so as to have the weight% shown in Table 8.
This was designated as mixer O.

Operation (T) The granulated products J, L and N produced by the above operation were mixed in a mixer for 10 minutes so that the weight% thereof shown in Table 9 would be obtained.
This was designated as a mixer P.

Experiment (A) 30 g of each of the mixtures O and P was sampled, placed in a glass bottle, tightly capped, and stored for 1 week in an environment room where the temperature and humidity were adjusted to 45 ° C. and 55% RH. The mixture after storage is passed through a 16-mesh sieve, and the granules remaining on the sieve make it sticky (blocking).
Was evaluated.

Furthermore, the mixture after storage was stirred with a magnetic stirrer in a thermostatic bath whose temperature was controlled at 40 ° C. (150 r.
pm) and dissolved in 1500 ml of water to evaluate the solubility.

Evaluation Criteria Adhesion No granules remained on the screen: ○ Granules remained on the screen: × Solubility Complete dissolution within 30 minutes: ○ Complete dissolution within 30 to 60 minutes: △ 60 minutes Completely dissolved by the above: × Experiment (B) 30 g of each of the mixtures O and P was sampled, placed in an open petri dish, and stored in an environment room at 25 ° C and 45% RH for 1 week. After storage, the strength was evaluated by sieving with a 150-mesh sieve and testing the generation of fine powder.

Evaluation Criteria No occurrence: ◎ Almost no occurrence: ◯ Granules break and fine powder is generated: × The results are shown in Tables 8 and 9.

[0107]

[Table 8]

[0108]

[Table 9]

From the above results, it is understood that the average molecular weight of the polyalkylene glycol is preferably 2000 to 20000, more preferably 2000 to 15000, and the polyalkylene glycol is more preferably A- (4) to (8).

Further, it is understood that the weight% of the polyalkylene glycol with respect to the whole solid processing agent is preferably 1 to 30% by weight, more preferably 3 to 20% by weight, further preferably 5 to 20% by weight.

The weight percentage of the para-phenylenediamine color developing agent to the total solid processing agent is preferably 5 to 20% by weight, more preferably 5 to 15% by weight.

[0112]

According to the present invention, even when the solid developing agent for color development is stored for a long time in a bad environment, the breaking strength and the decrease in the color developing agent are small, and the solubility is not impaired. Adhesion and blocking are improved.

Claims (6)

[Claims] 1. A para-phenylenediamine color developing agent, which has been preliminarily divided and weighed, is 5 to 20% by weight and an average molecular weight is 2000 to.
1 to 30% by weight of polyalkylene glycol which is 20000
A solid processing agent for color development of a silver halide color photographic light-sensitive material characterized by containing. 2. The solid processing agent for color development of a silver halide color photographic light-sensitive material according to claim 1, wherein the 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 silver halide according to claim 1, wherein the para-phenylenediamine color developing agent is a compound represented by the following general formula [I], [II] or [III]. Solid processing agent for color development of color photographic light-sensitive materials. [Chemical 1] [In the formula, 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,
It represents a methoxyethyl group, a sulfoalkyl group or a β-methanesulfonamidoethyl group. ] [Chemical 2] [In the formula, 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. ] [Chemical 3] [In the formula, 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 para-phenylenediamine color developing agent is 4-amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] aniline sulfate or 4-amino-
The solid processing agent for color development of a silver halide color photographic light-sensitive material according to claim 1, which is 3-methyl-N-ethyl-β- (hydroxyethyl) aniline sulfate. 6. A granule containing at least a para-phenylenediamine color developing agent and a granule containing an alkali agent are separately formed in advance, and the granules are formed by mixing them, or each is mixed. The solid processing agent for color development of a silver halide color photographic light-sensitive material according to claim 2, which is a tablet formed by post-tabletting.