JPH0792624A - Solid processing agent for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To stably prepare a solid processing agent without impairing its strength and to enhance solubility and to improve its storage stability by incorporating a specified compound. CONSTITUTION:This solid processing agent contains a compound represented by the formula in which R1 is an alkyl or alkenyl; R2 is H or an alkyl or hydroxyalkyl; each of R3 and R4 is H, hydroxy, an alkyl, or COOM2; each of M1 and M2 is H or an alkali metal atom; X is -CO- or -SO2-; Y is -O-, -S-, or -CONR5-; R5 is the same as R2; l is 0 or 1; m is 0, 1, or 2; and n is 1, 2, or 3.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid processing agent for silver halide photographic light-sensitive materials, and more specifically, a solid processing agent capable of producing a solid processing agent stably without deteriorating the strength and having excellent solubility. And a solid processing agent for a silver halide photographic light-sensitive material (hereinafter, also referred to as a solid processing agent) having improved storage stability.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials are
It is processed by processes such as development, desilvering, washing and stabilization.
Processing is usually carried out by an automatic processor, in which case a replenisher replenishing system is generally widely used and is controlled so as to keep the activity of the processing solution in the processing tank constant. In the case of the replenishment solution replenishment method, the purpose is to dilute the eluate from the sensitive material, correct the evaporation amount, and replenish the consumption component.
A large amount of overflow liquid is usually discharged.

On the other hand, in recent years, there has been a worldwide increase in regulations regarding the dumping of photographic waste liquid into the ocean and regulations on the disposal of plastic materials, and a new system that eliminates photographic waste liquid and does not use a bottle for liquid processing agents has been developed. Development is required. In addition, safety regulations for packaging materials have been strengthened to ensure the safety of transportation of liquid hazardous materials, which has led to an increase in cost. Furthermore, due to the lack of manpower in minilab stores, which has been rapidly increasing in recent years, accidents due to erroneous dissolution have occurred one after another in the work of dissolving or diluting the replenishing liquid, and many complaints have been made to the conventional replenishing system.

Therefore, in the photographic industry, there has been a strong demand for the development of a new replenishing system which produces almost no photographic waste liquid, uses no processing agent bottle, and does not require any dissolving operation.

As a method for responding to this demand, Japanese Patent Laid-Open No. 5-1194
Japanese Patent Laid-Open No. 54-54 discloses a method in which almost all processing agent components are tableted and directly replenished in a processing tank. Also, Japanese Patent Laid-Open No. 4-2134
Japanese Patent Laid-Open No. Hei 2-190942 discloses a method in which a powdery processing agent is set in an automatic developing machine for each part and directly replenished in a processing tank while weighing each necessary amount. The method using a granular treatment agent is disclosed, and both of them have the common point of using a solid treatment agent instead of the conventionally used liquid treatment agent, but the former two directly treat the solid treatment agent with a treatment tank. The latter is different in that it dissolves as a replenisher.

Generally, in order to produce a solid processing agent,
For example, in the case of a granular treatment agent, the treatment agent is pulverized, granulated while adding water and the like, and the obtained granulated product can be dried to obtain a desired granular treatment agent. It can be produced by compression molding a powdery treatment agent or a powdery treatment agent, and the above-mentioned publication describes that it is produced by a similar method.

In general, when a powder or granule is compression-molded into a tablet, it is known to use a lubricant in order to prevent defective molding due to friction between the powder particles and between the powder and the formulation machine. ing.

As such lubricants, for example, magnesium stearate and talc are known in pharmaceutical tablets, but these are insoluble in photographic processing liquids and are photographed by compression molding using the above lubricants. When a silver halide photographic light-sensitive material is processed using a processing solution obtained by dissolving processing tablets, a precipitate is generated in the processing tank, which causes clogging in the circulation system of the automatic processor and causes troubles. Alternatively, there is a problem in that floating substances or the like are generated and adhere to the surface of the light-sensitive material, and the film or paper is stained.

Further, although the above-mentioned lubricants have very excellent lubricity, they have another drawback that the strength of the obtained photographic processing tablet is lowered. This problem occurs, for example, when handling the solid processing agent, resulting in fine powder due to abrasion and the like,
It has been found that this causes equipment trouble due to clogging of fine powder during the production process or user handling, or causes an unfavorable situation in the work environment due to generation of dust.

Another problem with the solid processing agent is that the chemical reaction, particularly the oxidation reaction, proceeds inside the solid processing agent due to absorption of moisture in the air during storage, resulting in a decrease in the concentration of the main component essential for photographic processing. However, as a result, it was found that there is a drawback that the required photographic processing performance cannot be obtained.

[0011]

Therefore, an object of the present invention is to stably produce a solid processing agent without impairing the strength,
Another object of the present invention is to provide a solid processing agent for silver halide photographic light-sensitive materials, which is excellent in solubility and has improved storage stability of the solid processing agent. Still another object of the present invention is to provide a solid processing agent with less generation of powder (dust generation).

Other objects of the present invention will become apparent in the following specification.

[0013]

[Means for Solving the Problems] In order to achieve the above-mentioned object, the inventors of the present invention have made extensive studies on various compounds and conducted many experiments, and as a result, by using a compound having a specific structure, excellent lubricity was obtained. Not only that, but surprisingly, the inventors have found that the effects of the present invention are exhibited, and have completed the present invention.

That is, the above object of the present invention is to provide a solid processing agent for a silver halide photographic light-sensitive material containing a compound represented by the general formula [I] (Chemical Formula 1), wherein the solid processing agent is for bleaching or bleach-fixing. A solid processing agent for bleaching, the solid processing agent for bleaching or bleach-fixing contains a ferric aminopolycarboxylic acid complex salt, the solid processing agent is a solid processing agent for color development, and the color development The solid processing agent for use contains a p-phenylenediamine color developing agent, and these solid processing agents are tablets.

JP-A-53-62524 and JP-A-62-56961 disclose treatment solutions containing the N-acyl amino acid compound represented by the general formula [I]. The effect is related to the performance of the processing solution (prevention of water droplet unevenness during drying of the light-sensitive material, prevention of tar in the color developing solution, etc.). It is not a suggestion or disclosure.
Further, JP-A-2-140300 and the like describe washing tablets containing an anionic surfactant containing an N-acyl amino acid compound. However, the above-mentioned publication relates to toilet wash tablets, which are used for the purpose of adhering to the inner surface of a toilet bowl to dissolve oil in water, and because the application is completely different from a photographic processing agent, the tablet components are also those of the present invention. Is very different from. Further, N- used in the above publication
Although an acylamino acid compound is used as a detergent, it does not disclose or suggest the effect or action of the present invention, and does not easily recall the present invention.

Under such circumstances, the present inventors have made extensive investigations to make the solid treating agent contain the compound represented by the general formula [I], thereby providing excellent production suitability and sufficient strength and dissolution. The inventors have invented a solid processing agent for silver halide photographic light-sensitive materials, which has excellent properties and is excellent in storage stability.

The present invention will be described in detail below.

The solid processing agent of the present invention is a powder, a granular processing agent and a tablet, preferably a granular processing agent and a tablet, and the tablet most significantly showing the effect of the present invention.
That is, the powder and granular processing agents have an effect of preventing non-uniformity of the filling amount in the packaging material or equipment due to poor flow, and the tablets have an effect of further preventing tableting trouble. .

The powder referred to in the present invention is an aggregate of fine crystal grains, and the granule is a powder obtained by adding a granulation step to a particle size of 50 to 50
5000μm refers to a granular material, the tablet refers to a powder or granules compression molded into a certain shape, as a tablet molding method is a method of forming a tablet after granulating the powder of the present invention It is more preferable from the viewpoint of the effect.

As a granulation method for forming granules, known methods such as rolling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation and fluidized bed granulation can be used. For tablet formation, the average particle size of the obtained granules is 100 to 2000 μm in terms of non-uniformity of components when mixing and granulating the granules, so-called segregation is unlikely to occur. It is preferable to use one, and more preferably 200 to 1500 μm. Further, the particle size distribution is preferably such that 50% or more of the granulated product particles have a deviation of ± 200 to 250 μm. The obtained granulated product is used as it is as granules.

When compressing the obtained granulated product under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a briquetting machine can be used. .

In the present invention, the processing tablet has a weight of 0.1.
~ 50g, more preferably 0.5-4
It is 0 g. If the weight exceeds 50 g, the dissolution time is
On the other hand, if the weight is less than 0.1 g, the number of charging operations for supplying a certain amount of tablets to the automatic developing machine increases, which poses a problem in terms of charging accuracy and durability of the supplying means.

[0023] As the bulk density of the tablet, the purpose viewpoint of the effect of the present invention is preferably ^{1.0g / cm 3 ~2.5g / cm 3} , further is 1.1g / cm ³ ~1.9g / cm ³ preferable. this is,
This is because when the bulk density is high, the dissolution time of the obtained tablet becomes small, and when it is small, the strength becomes problematic.

Next, the compound represented by the general formula [I] will be described in detail.

In the formula, R ₁ represents an alkyl group or an alkenyl group, R ₂ represents a hydrogen atom, an alkyl group or a hydroxyalkyl group, and R ₃ and R ₄ independently represent a hydrogen atom, a hydroxyl group, an alkyl group or --COOM. ₂ (M ₂ represents a hydrogen atom or an alkali metal atom), and X represents —CO— or —SO ₂ —.
Represents Y, —O—, —S— or —CONR ₅ — (R ₅ represents a hydrogen atom, an alkyl group or a hydroxyalkyl group), M ₁ represents a hydrogen atom or an alkali metal atom, and 1 represents 0 or 1, m is an integer of 0 to 2, and n is an integer of 1 to 3.

R ₁ is preferably a linear or branched alkyl group or alkenyl group having 5 to 20 carbon atoms, and R ₂ is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms or hydroxyalkyl. It is a base.

Next, specific examples of the compound represented by the general formula [I] will be shown below.

[0028]

[Chemical 2]

[0029]

[Chemical 3]

[0030]

[Chemical 4]

[0031]

[Chemical 5]

In addition to the above compounds, JP-A-62-56961, Nos. 4 to 4
The exemplified compounds [II] -1 to 55 described on page 6 can also be used.

The above exemplified compounds are known compounds or are commercially available and can be obtained by usual routes.

The above compound may be added either by directly adding it to a powder or granular processing agent and mixing it, or by adding it together with other components during granulation and using it as a constituent component of the granule. It is possible to obtain the effects of the present invention.
Further, the effect of the present invention can be obtained by directly applying it to a compressor for pressure compression, but from the viewpoint of the effect of the present invention and workability, powder or granular It is preferable to use it by directly adding it to the treating agent.

The above compound is preferably used with an average particle size of 150 μm or less, more preferably 100 μm or less, most preferably 50 μm or less.

Further, the content of the above compound is preferably in the range of 0.01 to 10% by weight based on the solid processing agent,
It is more preferably in the range of 0.1 to 6% by weight, and the effects of the present invention will be most remarkable in this range.

Examples of the photographic processing agent used in combination with the compound represented by the general formula [I] include color developing agents, fixing agents, bleaching agents,
Stabilizers and the like can be mentioned.

The color developing agent used in the solid developing agent for color development according to the present invention is preferably a p-phenylenediamine compound having a water-soluble group.

Examples of the water-soluble group include those having at least one amino group of the p-phenylenediamine compound or on the benzene nucleus, and specific water-soluble groups include-(C
_{H 2) n'-CH 2 OH} , - (CH 2) m'-NHSO 2 - (CH 2) n'-CH 3,
_{- (CH 2) m'-O-} (CH 2) n'-CH 3, - (CH 2 CH 2 O) n'Cm'H 2
m ′ ₊₁ (m ′ and n ′ each represent an integer of 0 or more.) —COOH, —SO ₃ H group and the like are preferable.

Specific examples of the color developing agent preferably used in the present invention are shown below.

[0041]

[Chemical 6]

[0042]

[Chemical 7]

[0043]

[Chemical 8]

Among the above-illustrated color developing agents, particularly preferred in the present invention are exemplified compounds (1), (3),
(18) and (20).

The content of the color developing agent according to the present invention in the solid processing agent is from 5.0 to 99.99 from the viewpoint of the effect of the present invention.
The range of wt% is preferable, and more preferably 8.0 to 99.5 wt%.

Specific examples of the black and white developing agent include phenidone, hydroquinone, methole, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-3-pyrazolidone. , Hydroquinone monosulfonic acid and the like.

The alkaline agent used in the color developing agent according to the present invention is a compound exhibiting an alkalinity of pH 8 or more when it is made into an aqueous solution, and preferable specific examples thereof include sodium carbonate, potassium carbonate, sodium bicarbonate and sodium bicarbonate. Potassium carbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, potassium hydroxide, sodium hydroxide, lithium hydroxide, etc. Can be mentioned.

The color developer according to the present invention includes a chelating agent, a development accelerator, a development inhibitor (halide, etc.), a fluorescent whitening agent and a preserving agent which are usually used in a developing agent for silver halide photographic light-sensitive material. Agents and the like can be added as appropriate.

It is preferable that a solid preservative is allowed to coexist in the color developer according to 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. Is preferred.

These 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.

The solid treating agent according to the present invention contains the compound represented by the following general formula [H] to more effectively exhibit the effects of the present invention.

[0052]

[Chemical 9]

In the formula, R ₂₁ and R ₂₂ are each independently a hydrogen atom,
It represents a substituted or unsubstituted alkyl group.

The compound represented by the above general formula [H] according to the present invention is preferably a compound represented by the following general formula [H '] from the viewpoint of the present invention.

[0055]

[Chemical 10]

In the general formula [H '], L is a carbon number of 1 to 1.
It represents a linear or branched alkylene group of 10, preferably 1 to 5, and may be substituted. For example, methylene, ethylene, trimethylene, propylene and the like can be mentioned, and as the substituent, a carboxyl group, a sulfone group, a phosphone group, a phosphinic acid residue, a hydroxyl group, an ammonium group having about 1 to 5 carbon atoms which may be substituted. Etc.

A is a carboxyl group, a sulfone group, a phosphonic group, a phosphinic acid residue, a hydroxyl group, and a carbon number of 1 to 1.
About 5 amino groups which may be substituted with alkyl, having 1 to 1 carbon atoms
About 5 ammonio groups which may be alkyl-substituted, carbamoyl groups having about 1 to 5 carbon atoms which may be alkyl-substituted,
It represents an alkyl-substituted sulfamoyl group having about 1 to 5 carbon atoms and an optionally substituted alkylsulfonyl group.

Examples of A-L- include 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.

R ₂₃ represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and may be substituted. As a substituent, a carboxyl group, a sulfone group, a phosphone group,
Examples thereof include a phosphinic acid residue, a hydroxyl group and an ammonio group having about 1 to 5 carbon atoms which may be substituted with alkyl. Further, L and R may be connected to each other to form a ring.

Next, specific compounds will be exemplified, but the present invention is not limited to these compounds.

[0061]

[Chemical 11]

These compounds are used not only as free amines but also as salts such as hydrochlorides, sulfates, oxalates, p-toluenesulfonates, alkali metal salts and ammonium salts.

For the purpose of the present invention, the compound represented by the general formula [H] or [H '] is preferably solid.

Among these, particularly preferred compounds are H-
1, H-6, H-17, H-18 and H-25, and specific examples including salts thereof are shown below.

[0065]

[Chemical 12]

Examples of ferric aminopolycarboxylic acid complex salts used in the solid processing composition of the present invention include those disclosed in JP-A-6-13.
The ferric iron complex salt of the compound described in 50571 and pages 6 to 31 and the ferric iron complex salt of the compound described in JP-A-5-333507 and pages 5 to 8 can be used.

The following compounds can be given as preferable specific examples of the ferric aminopolycarboxylic acid complex salt.

A-1 ferric salt of ethylenediaminetetraacetic acid A-2 ferric salt of diethylenetriaminepentaacetic acid A-3 ferric salt of 1,3-propanediaminetetraacetic acid A-4 ferric salt of ethylenediaminedisuccinic acid A-4 -5 β-alanine diacetate ferric salt These salts of A-1 to A-5 can be used as salts of ammonium, potassium, sodium, lithium and the like, but ammonium salts, sodium salts and potassium salts are particularly preferable. .

From the viewpoint of the effect of the present invention, the content of the aminopolycarboxylic acid ferric iron complex salt in the solid processing agent according to the present invention is
10.0-99.99% by weight is preferred, more preferably 20.0-9
It is 0% by weight.

The fixing main agent in the solid processing agent for fixing or bleach-fixing according to the present invention is, from the viewpoint of processing speed,
Thiosulfates are preferably used, and specific examples thereof include ammonium thiosulfate, potassium thiosulfate, and sodium thiosulfate. In addition to the above thiosulfate, JP-A-4-14
No. 3755, Exemplified Compounds 1-65 and 4-
No. 143756, Exemplified Compounds 1 to 62, pp. 6 to 9,
The exemplified compounds 1 to 54 described in 4-143757, pages 4 to 7 can be used.

From the viewpoint of the effect of the present invention, the content of the fixing agent of the present invention in the solid processing agent is preferably 20 to 99.9% by weight, more preferably 30 to 90% by weight.

At least one selected from the compounds represented by the following general formulas [II] to [IV] is preferably used as the stabilizer main agent when the solid processing agent of the present invention is used for stabilization.

[0073]

[Chemical 13]

[Wherein, R _{6 to} R ₁₂ are each independently a hydrogen atom, —OH, —COOM, —PO ₃ M ₂ , —SO ₃ M, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. In the formula, M represents a hydrogen atom or an alkali metal atom, and n and m represent 0 or 1, but are not 0 at the same time. ]

[0075]

[Chemical 14]

[0076]

[Chemical 15]

The carbocycle and heterocycle formed by Z in the general formula [IV] may be a monocycle or a condensed ring, and Z is preferably a substituted aromatic carbocycle or heterocycle. .
As the substituent of Z, an aldehyde group, a hydroxyl group, an alkyl group (eg, methyl, ethyl, methoxyethyl, benzyl, carboxymethyl, sulfopropyl, etc.), an aralkyl group, an alkoxy group (eg, methoxy, ethoxy, methoxyethoxy, etc.), Halogen atom, nitro group, sulfo group, carboxy group, amino group (eg N, N-dimethylamino, N-ethylamino, N-phenylamino etc.), hydroxyalkyl group, aryl group (eg phenyl, p-methoxyphenyl etc.) ), Cyano group, aryloxy group (eg, phenoxy, p-carboxyphenyl, etc.), acyloxy group, acylamino group, sulfonamide group, sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dimethylsulfamoyl, etc.) , Carbamoyl groups (eg carbamoyl, N-methylcarbamoyl N, N-tetramethylene-carbamoyl, etc.) or a sulfonyl group (e.g. methanesulfonyl, ethanesulfonyl, benzenesulfonyl, is preferably a p- toluenesulfonyl and the like).

The carbon ring is preferably a benzene ring, and the heterocycle is preferably a 5- or 6-membered heterocycle. For example, the 5-membered ring is thiophene, pyrrole,
Furan, thiazole, imidazole, pyrazole, succinimide, triazole, tetrazole and the like, and the 6-membered ring includes pyridine, pyrimidine, triazine,
Thiadiazine and the like can be mentioned respectively.

Examples of the condensed ring include naphthalene, benzofuran, indole, thionaphthalene, benzimidazole, benzotriazole and quinoline.

Typical examples of the compounds represented by the general formulas [II] to [IV] are shown below, but the invention is not limited thereto.

[0081]

[Chemical 16]

[0082]

[Chemical 17]

[0083]

[Chemical 18]

[0084]

[Chemical 19]

[0085]

[Chemical 20]

[0086]

[Chemical 21]

[0087]

[Chemical formula 22]

In addition to the free form, the above-mentioned compounds are preferably sodium salts and potassium salts.

In addition to the above compounds, Exemplified Compounds I-1 to I-30 described on pages 7 to 11 of JP-A-4-313753 and Exemplified Compound II described on pages 11 to 16 of the publication. -1 to II-50,
And Exemplified compounds III-1 described on pages 16 to 19 of the publication.
~ III-28 can also be used.

The content of these compounds in the solid processing composition is 5% by weight or more, preferably 10 to 80% by weight.

In particular, the solid developing agents containing the above-illustrated color developing agents or the ferric iron complex salts of aminopolycarboxylic acids are apt to cause tableting troubles and deterioration of the main ingredient during storage. The application of the present invention is preferable because the effect of the present invention is remarkably exhibited.

[0092]

EXAMPLES Examples of the present invention will be described in detail below.
Embodiments of the present invention are not limited to this.

Example 1 A color negative film color developing tablet was prepared according to the following procedure.

Operation (1) Potassium carbonate; 3750.0 g, sodium sulfite; 580.0
g, diethylenetriamine pentaacetic acid 5 sodium; 240.0
g in a commercially available hammer mill until the average particle size is 10 μm. Polyethylene glycol # 6000 on this fine powder
(Manufactured by Nippon Oil & Fats Co., Ltd.); 500.0 g and mannitol; 800.0
After granulating g in a commercial stirred granulator at room temperature for about 7 minutes by adding 100 ml of water, the granulate was dried at 70 ° C. for 120 minutes using a commercial fluidized bed dryer. To almost completely remove the water content of the granulated product.

Operation (2) Hydroxylamine sulfate; 360.0 g, potassium bromide; 40.
After crushing 0g, 1,2-dihydroxy-3,5-disulfobenzene disodium; 20.0g in the same manner as in step (1), add Pineflow (Matsuya Chemical Industry Co., Ltd.); 20.0g, and mix and granulate. . The amount of water added is 3.5 ml, and after granulation, it is dried at 60 ° C. for 60 minutes to almost completely remove the water content of the granulated product.

Operation (3) The developing agent CD-4 [4-amino-3-methyl-N-ethyl-β- (hydroxy) ethylaniline sulfate]; 650.0 g was added.
After pulverizing in the same manner as in (1), granulating by adding 10 ml of water at room temperature for about 7 minutes, and then granulating the product with a fluidized bed drier.
The granulated product is dried at 2 ° C for 2 hours to almost completely remove water.

Operation (4) The granule samples prepared in the above operations (1) to (3) were mixed at room temperature with a commercially available cross rotary mixer for 10 minutes, and the compounds shown in Tables 1 and 2 were added. The amounts described in Nos. 1 and 2 were added and mixed for 3 minutes to obtain a mixed granulated product sample. Next, the obtained mixed granules were mixed with a rotary tableting machine (Kikusui Seisakusho).
Continuous pressing was performed with Clean Press Collect H18) to obtain a color negative film color development replenishing tablet sample having a diameter of 30 mm, a thickness of 10.0 mm and a weight of 12.0 g.

(Experiment-1) The granulation mixture and 5 tablet samples obtained in the above operation (4) were dissolved in 1 liter of water,
The solubility (solubility) of the solution was observed.

(Experiment-2) The mixture obtained in the above operation (4) was molded into a tablet having a diameter of 30 mm, a thickness of 10.0 mm and a weight of 12.0 g using a commercially available hydraulic press and a cylindrical mold having an inner diameter of 30 mm. . Next, when this tablet sample was extracted from the mold, the pressure required for extraction was measured using a load cell. This operation was repeated 10 times, and the average value was used as the discharge pressure. The smaller this value is, the easier it is for the tablet after molding to come off the mold, and the more excellent the lubricity is.

(Experiment-3) Ten tablets obtained in the above operation (4) were measured for hardness in the diameter direction with a tablet hardness meter (Okada Seiko Co., Ltd .; Speed Checker), and the average value was calculated. It was

(Experiment-4) In the above operation (4), the appearance of the 50th to 100th tablets and the 100th to 200th tablets in the continuous tableting was observed and evaluated as the tableting property.

(Experiment-5) Twenty tablet samples obtained in the above operation (4) were put into an NTN parts feeder (NTN Corporation: K-N40RH4).
/ CD58 / Z15) was used and vibration was applied for 3 hours, and the friability was calculated as the following formula from the change in tablet weight before and after the experiment. It is indicated that the smaller this value is, the more the dust generation during handling can be prevented.

[0103]

[Equation 1]

(Experiment 6) The tablet sample obtained in the above operation (4) was put in a polyethylene bag, sealed with a heat sealer, and stored for 1 month in a room conditioned at 50% RH at 30 ° C. After that, it was dissolved in the same manner as in (Experiment-1), and the solubility (solubility) of the solution was observed. Further, the amount of the color developing agent in the solution was measured, and the residual rate was calculated by the following formula. The closer this value is to 100%, the better the storage stability of the solid processing agent over time.

[0105]

[Equation 2]

(Experiment 7) The mixed granules obtained in the above operation (4) were allowed to flow out from a funnel having a diameter of 12 mm to evaluate the fluidity.

The results of the above experiments are shown in Tables 1 and 2.

In the table, the numbers of the additives are the numbers of the exemplified compounds, and the addition amount is shown as% by weight with respect to the mixed granules.

(Evaluation Criteria) Solubility and Solubility after Storage x: Precipitate or floating substance is observed. Δ: No clear precipitate or floating substance is observed, but turbidity is observed in the solution. ○: Turbidity. No tableting property, no precipitation, etc. ×: Product defects (cracks or chips) occur in 90% or more of the whole △: Product defects (cracks or chips) occur in approximately 5 to 10% of the whole ○: No product defects occur Liquidity x: Average outflow rate was 16 g / sec, the way of outflow was uneven, and changed from 2 to 30 g / sec ○: Average outflow rate was 24 to 30 g / sec, outflow Was very uniform

[0110]

[Table 1]

[0111]

[Table 2]

As is clear from Tables 1 and 2, the solid processing agent containing the compound of the present invention is excellent in solubility and can be stably manufactured, and further, a large strength can be obtained. It can be seen that not only can this be done, but also the wear and tear in the manufacturing process can be greatly reduced and the generation of dust can be suppressed. It can be seen that this not only provides shape stability during transportation and handling of the tablet itself, but also improves the working environment by preventing dust. Furthermore, it can be seen that deterioration of the main agent over time can also be prevented.

Example 2 Instead of CD-4 used in Example 1, exemplified compound (6),
Sample 1-10 of Example 1 except that (18) and (20) were used.
When the same operation and experiment were carried out, the same results as in Example 1 were obtained.

Example 3 A color negative film bleaching tablet was prepared according to the following procedure.

Operation (5) 1,3-Propanediamine tetraacetic acid ferric ammonium monohydrate; 1900 g, 1.3-Propanediamine tetraacetic acid; 95.0 g, potassium bromide; 860.0 g, succinic acid; 960.0 g, succinic acid 420.0 g of disodium hexahydrate was crushed in the same manner as in step (1), and 30.0 g of Demol MS (manufactured by Kao Corporation); mannite; 150.0 g were added and mixed to make the amount of water added to 90 ml. And granulate. After the granulation, the granulated product is dried at 60 ° C. for 120 minutes to almost completely remove the water content of the granulated product.

Operation (6) 50.0 g of β-cyclodextrin was added to the granulated product prepared in the above operation (5) and mixed for 10 minutes as in the operation (3), and then the compounds shown in Table 3 were described in Table 3. And mix for 3 minutes. Next, the mixture was continuously tableted in the same manner as in the operation (4) to prepare a color negative film bleaching tablet sample having a diameter of 30 mm, a thickness of 10.0 mm and a weight of 10.7 g.

<Experiment> Using the granulation mixture and the tablet sample obtained in the operation (6), the same experiments as in (Experiment-1) to (Experiment-5) of Example 1 were performed. However, the amount of dissolved water used for the solubility evaluation in (Experiment-1) was 250 ml per five tablet samples, and the addition weight of the sample used in the lubricity evaluation for (Experiment-2) was 10.7 g. did.

The results are shown in Table 3. The evaluation criteria are the same as in Example 1.

[0119]

[Table 3]

As is clear from Table 3, the solid processing composition containing the compound of the present invention is excellent in production stability, storage stability, solubility, strength and dust generation as in Example 1. I understand.

Example 4 Exemplified compound A-1, in place of 1,3-propanediaminetetraacetic acid ferric ammonium monohydrate used in Example 3,
Sample 2 of Example 3 except that A-2, A-4 and A-5 were used
When an operation and an experiment were performed in the same manner as in −10, almost the same result as in Example 3 was obtained.

Example 5 Color negative film fixing treated tablets were prepared according to the following procedure.

Operation (7) Ammonium thiosulfate; 2500.0 g, sodium sulfite;
160.0g, potassium carbonate; 20.0g, ethylenediamine 4
Disodium acetate: 20.0 g was pulverized in the same manner as in the operation (1), and 65 g of Pine Flow (Matsuya Chemical Industry Co., Ltd.) was added thereto and mixed and granulated. The amount of water added is 50 ml, and after granulation, 60 ℃
Dry for 120 minutes to almost completely remove water from the granulated product.

Operation (8) The granules prepared in the above operation (7) and the compounds shown in Table 4 were mixed with the mixer shown in Table 4 in a room whose humidity was adjusted to 25% or less and 40% RH or less. Mix for 3 minutes. Then manipulate the mixture (4)
Tableting for fixing a color negative film having a diameter of 30 mm, a thickness of 10.0 mm and a weight of 10.6 g was prepared by carrying out continuous tableting in the same manner as in.

<Experiment> Using the granulation mixture and the tablet sample obtained in the operation (8), the same experiments as (Experiment-1) to (Experiment-5) of Example 1 were conducted. However, the amount of dissolved water used in the solubility evaluation in (Experiment-1) was 200 ml per five tablet samples, and the addition weight of the sample used in the lubricity evaluation in (Experiment-2) was 10.6 g. did.

The results are shown in Table 4. The evaluation criteria are the same as in Example 1.

[0127]

[Table 4]

As is clear from Table 4, the solid processing composition containing the compound of the present invention is excellent in production stability, storage stability, solubility, strength and dust generation as in Example 1. I understand.

Example 6 Color negative film stabilizing treated tablets were prepared according to the following procedure.

Operation (9) m-Hydroxybenzaldehyde; 1500.0 g, Megafac F116 (manufactured by Dainippon Ink and Chemicals); 40.0 g, ethylenediaminetetraacetic acid disodium; 250.0 g, lithium hydroxide monohydrate; 160.0 g ( As in 1), pulverize and add pine flow; 100.0 g, mix and granulate. The amount of water added is 8
After granulating to 0 ml, the granulated product is dried at 50 ° C. for 2 hours to almost completely remove the water content of the granulated product.

Operation (10) The granules prepared in the above operation (9) and the compounds shown in Table 5 were mixed in a room where the amount shown in Table 5 was adjusted to 25% or less and 40% RH or less in a room. Mix for 3 minutes. Next, the mixture is continuously tableted in the same manner as in step (4), and the diameter is 25 mm and the thickness is 10.0 m.
A color negative film stabilizing tablet sample having m and a weight of 6.4 g was prepared.

<Experiment> Using the granulation mixture and the tablet sample obtained in the operation (10), the same experiments as (Experiment-1) to (Experiment-5) of Example 1 were performed. However, the amount of dissolution water used for the solubility evaluation in (Experiment-1) was 4.5 liters per tablet sample. The added weight of the sample used in the lubricity evaluation of (Experiment-2) was 9.0 g.

The results are shown in Table 5. The evaluation criteria are the same as in Example 1.

[0134]

[Table 5]

As is clear from Table 5, the solid processing composition containing the compound of the present invention is excellent in production stability, storage stability, solubility, strength and dust generation as in Example 1. I understand.

Example 7 Colored paper color-developed processed tablets were prepared according to the following procedure.

Operation (11) The developing agent CD-3 [4-amino-3-methyl-N-ethyl-N- [β-
(Methanesulfonamide) ethyl] aniline sulfate]; 15
Grind 00.0 g in a commercially available hammer mill to an average particle size of 10 μm. Polyethylene glycol # on this fine powder
6000; 1000.0 g was added and granulated by adding 50 ml of water for about 7 minutes at room temperature in a commercial stirring granulator, and then the granulated product was dried at 40 ° C for 2 hours in a fluidized bed dryer. Then, the water content of the granulated product is almost completely removed.

Operation (12) Disulfoethylhydroxylamine disodium salt; 40
0.0 g, sodium p-toluenesulfonate; 1700.0 g,
Chino Pearl SFP (manufactured by Ciba Geigy); operate 300.0g (1
As in 1), pulverize and add 240.0 g of Pine Flow (Matsuya Chemical Industry) to granulate. The amount of water added was 60.0 ml, and after granulation, the granules were dried for 120 minutes to almost completely remove water.

Operation (13) Potassium carbonate; 3300.0 g, sodium sulfite 37.0 g, diethylenetriamine pentaacetic acid 5 sodium salt; 330.0 g, p-
After crushing sodium toluenesulfonate (130.0 g) and lithium hydroxide monohydrate (340.0 g) in the same manner as in step (11),
Mannitol; 600.0g, polyethylene glycol # 600
0; Add 1000.0 g and mix evenly with a commercially available mixer.
Then, in the same manner as in step (11), the amount of water added is 100 ml, and granulation is performed. After the granulation, the granulated product is dried at 60 ° C for 30 minutes to almost completely remove the water content of the granulated product.

Operation (14) The granule samples prepared in the above operations (11) to (13) were mixed at room temperature for 10 minutes using a commercially available cross rotary mixer, and then the compounds shown in Table 6 were described in Table 6. And add for 3 minutes. The mixed granules obtained in this way were rotary pressed (Kikusui Seisakusho Co., Ltd., Clean Press Collect).
H18), continuous tableting was performed to obtain a color paper color developing tablet sample having a diameter of 30 mm, a thickness of 10.0 mm and a weight of 10.2 g.

Experiments similar to (Experiment-1) to (Experiment-6) of Example 1 were conducted using the tablet sample obtained in the operation (14). However, the amount of dissolved water used for the solubility evaluation in (Experiment-1) was 500 ml per five tablets, and (Experiment-
The addition weight of the sample used in the lubricity evaluation of 2) is 1
It was 0.2 g.

The results are shown in Table 6. The evaluation criteria are the same as in Example 1.

[0143]

[Table 6]

As is clear from Table 6, the solid processing composition containing the compound of the present invention is excellent in production stability, storage stability, solubility, strength and dust generation, as in Example 1. I understand.

Example 8 Color paper bleach-fixing tablets were prepared according to the following procedure.

Operation (15) Diethylenetriamine pentaacetic acid ferric ammonium monohydrate; 6000.0 g, diethylenetriamine pentaacetic acid; 300.0
g, sodium carbonate monohydrate; 500.0 g was crushed in the same manner as in step (13), and polyethylene glycol # 4000 (NOF Corporation)
(Manufactured by K.K.); 2000.0 g is added and mixed and granulated. The amount of water added was 200 ml, and after granulation, the granulated product was dried for 3 hours at 60 ° C. to almost completely remove water.

Operation (16) Ammonium thiosulfate; 8000.0 g, sodium sulfite;
2000.0 g is pulverized in the same manner as in the operation (13), pine flow 500.0 g is added to this, and mixed and granulated. The amount of water sprayed is 150
After granulation, the granules are dried at 60 ° C for 120 minutes to almost completely remove water from the granules.

Operation (17) After mixing the granule samples prepared in the above operations (15) to (16) at room temperature for 10 minutes using a commercially available cross rotary mixer, the compounds shown in Table 7 are shown in Table 7. And add for 3 minutes. Next, the mixture was continuously tableted in the same manner as in the operation (14) to obtain a color paper bleach-fixing tablet sample having a diameter of 30 mm, a thickness of 10.0 mm and a weight of 10.7 g.

Experiments similar to (Experiment-1) to (Experiment-5) of Example 1 and the following (Experiment-8) were carried out using the granulated mixture tablet sample obtained in the operation (17).

However, the amount of dissolved water used for the solubility evaluation in (Experiment-1) was 300 ml per 5 tablets,
The added weight of the sample used in the lubricity evaluation of (Experiment-2) was 10.7 g.

(Experiment-8) The tablet sample obtained in the above operation (17) was placed in a polyethylene bag, sealed with a heat sealer, and stored for 1 month in a room conditioned at 30 ° C. and 50% RH. After that, it was dissolved in the same manner as in (Experiment-1), and the solubility (solubility) of the solution was observed. Further, the amount of sulfurous acid in the solution was measured, and the residual rate was calculated by the following formula. The closer this value is to 100%, the better the storage stability of the solid processing agent over time.

[0152]

[Equation 3]

The results are shown in Table 7. The evaluation criteria are the same as in Example 1.

[0154]

[Table 7]

As is clear from Table 7, the solid processing composition containing the compound of the present invention is excellent in production stability, storage stability, solubility, strength and dust generation as in Example 1. I understand.

Example 9 Exemplified compounds A-1 and A- were used in place of the diethylenetriaminepentaacetic acid ferric ammonium monohydrate used in Example 8.
Sample 6 of Example 8 except that 3, A-4 and A-5 were used.
When the same operation and experiment as in Example 7 were performed, almost the same results as in Example 8 were obtained.

Example 10 A tablet for stabilizing color paper was prepared according to the following procedure.

Operation (18) Sodium carbonate monohydrate; 500.0 g, 1-hydroxyethane-1,1-diphosphonic acid trisodium; 3000.0 g, ethylenediaminetetraacetic acid disodium; 150.0 g, o-phenylphenol; 70.0 g Is pulverized in the same manner as in the operation (13), polyethylene glycol # 6000; 500.0 g is added thereto, and they are mixed and granulated. Add 60 ml of water, and after granulation,
Dry for 0 minutes to remove almost completely the water content of the granulated product. The compounds listed in Table 8 were added to the granules thus prepared.
Add the indicated amount and mix for 3 minutes at 25 ° C. in a room conditioned to 40% RH or less using a mixer.

Next, the mixture was continuously tableted in the same manner as in the operation (14) to obtain a tablet sample for stabilizing color paper having a diameter of 30 mm, a thickness of 10.0 mm and a weight of 11.0 g.

<Experiment> The same experiment as (Experiment-1) to (Experiment-5) of Example 1 was performed using the granulation mixture and the tablet sample obtained in the operation (18). However, the amount of dissolved water used in the solubility evaluation in (Experiment-1) was 2.2 liters per tablet sample, and the addition weight of the sample used in the lubricity evaluation in (Experiment-2) was 11.0 g. And

The results are shown in Table 8. The evaluation criteria are the same as in Example 1.

[0162]

[Table 8]

As is clear from Table 8, the solid processing composition containing the compound of the present invention is excellent in production stability, storage stability, solubility, strength and dust generation as in Example 1. I understand.

[0164]

INDUSTRIAL APPLICABILITY According to the present invention, a silver halide photographic light-sensitive material capable of stably producing a solid processing agent without deteriorating the strength, having excellent solubility, and having improved storage stability of the solid processing agent A solid processing agent for use can be provided. Further, it is possible to provide a solid processing agent for silver halide photographic light-sensitive materials, which produces less powder (dust).

Claims (6)

[Claims] 1. A solid processing agent for a silver halide photographic light-sensitive material, comprising at least one compound represented by the following general formula [I]. [Chemical 1] [In the formula, R ₁ represents an alkyl group or an alkenyl group, and R ₂
Represents a hydrogen atom, an alkyl group or a hydroxyalkyl group, R ₃ and R ₄ independently represent a hydrogen atom, a hydroxyl group, an alkyl group or —COOM ₂ (M ₂ represents a hydrogen atom or an alkali metal atom), and X represents -CO- or -SO ₂ -, Y represents the -O
-, - S-, or -CONR ₅ - (R ₅ represents a hydrogen atom, an alkyl group or hydroxyalkyl group) represents, M ₁ is a hydrogen atom or an alkali metal atom, l is 0 or 1, m is 0 Is an integer of 2 and n is an integer of 1 to 3. ] 2. The solid processing agent for a silver halide photographic light-sensitive material according to claim 1, wherein the solid processing agent is a bleaching or bleach-fixing solid processing agent. 3. The solid processing agent for a silver halide photographic light-sensitive material according to claim 2, wherein the solid processing agent contains at least one ferric aminopolycarboxylic acid complex salt. 4. The solid processing agent for silver halide photographic light-sensitive materials according to claim 1, wherein said solid processing agent is a solid processing agent for color development. 5. The solid processing agent for a silver halide photographic light-sensitive material according to claim 4, wherein the solid processing agent contains at least one p-phenylenediamine type color developing agent. 6. The solid processing agent for silver halide photographic light-sensitive materials according to claim 1, wherein the solid processing agent is a tablet.