JPH0792623A - Solid processing agent for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:Not to cause storage deterioration with the lapse of time and to enhance processing stability by incorporating one selected from among specified compounds and another one selected from among the other specified compounds and/or one selected from among sugars in a solid processing agent. CONSTITUTION:This solid processing agent contains at least one of the compounds represented by formula I and at least one of the compounds represented by formula II and/or one of the sugars, and in formulae I and II, L is an alkylene; A is carboxy, sulfo, phosphono, phosphinic acid, hydroxy, amino, ammonio, carbamoyl, or sulfamoyl; R is H or an alkyl; R1 is an alkyl; R2 is an alkyl or H; R3 is an alkylene; and M is H, Na, K, or Li atom, or triethanol-ammonium.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color developing treatment agent for silver halide photographic light-sensitive materials, and more specifically, it dramatically improves the storability over time and does not cause precipitation during dissolution.
The present invention also relates to a solid processing agent for silver halide photographic light-sensitive materials, which is capable of uniformly maintaining the components constant and providing stable processing performance.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material (hereinafter referred to as a light-sensitive material) is processed by exposure, exposure, desilvering, washing, stabilization and other steps. Processing is usually carried out by an automatic processor (hereinafter referred to as an automatic processor), in which case the replenisher replenishment method is generally widely used, and the activity of the processing solution in the processing tank is controlled to be constant. There is. 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 disposal of photographic waste liquids and plastic materials have been increasing worldwide, and there is a demand for the development of a new system that eliminates photographic waste liquids and does not use plastic bottles for liquid agents. 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. Also, at minilab stores, which have been increasing rapidly in recent years, part-timers and feminization are advancing due to cost reduction and labor shortage, it is difficult to dissolve or prepare dilution solution of replenisher, and accidents due to erroneous dissolution occur one after another, complaints about replenishment system. Is coming out a lot.

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

[0005]

As a method for responding to this demand, WO92-20013 discloses a method in which almost all processing components are made into a solid processing agent and directly charged into a processing tank. However, in this method, the color developing agent has a substantially higher degree of concentration than the conventionally used liquid agent treating agents, so that it is clear that the storage stability of the treating agent deteriorates with time. It was In particular, in the case of tablet molding, it has been found that this storage stability becomes a problem because the internal reaction proceeds due to the compression heat and the like. In addition, since local concentration occurs during dissolution, precipitation easily occurs, which causes problems such as filter clogging and adhesion to the photosensitive material.

Further, it is essential that the color developing agent containing various components in various amounts contains the constituent components accurately in a determined amount, and if incorrect distribution is made, it is stable in processing. And causes serious problems for photographic performance.

In particular, the color developing agent is the most important one among the photographic processing agents for determining the photographic characteristics, and controlling the components thereof is a proposition in the art. The variation tolerance of the components is required to be ± 10% or less for main components such as color developing agents and alkalis, and ± 15% or less for auxiliary components such as optical brighteners. .
If a treating agent having a variation exceeding the above range is used, it causes development abnormalities such that it is excessively active or inactive.

In the case of liquid chemicals, since the components are uniformly dispersed by dissolution, it is easy to dispense a fixed amount. However, in the case of producing a solid processing agent, there is a problem in mixing properties, and it is very difficult to form a uniform component. In order to avoid this, there is a method in which the individual components are weighed one by one and mixed at the end, but this is complicated in the production process and is not preferable in terms of equipment, cost, management, and speed. This is a major problem in producing a color developing solid processing agent. Therefore, there is an urgent need to develop technology to solve these problems.

Therefore, the object of the present invention is to eliminate the above-mentioned drawbacks of the prior art, to prevent storage deterioration over time, and to prevent precipitation and precipitation, and to contain individual components in precisely determined amounts. The present invention provides a solid developing agent for color development having excellent processing stability.

[0010]

The above object of the present invention can be achieved by the following constitutions.

At least one selected from the compounds represented by the following general formula [I], at least one selected from the compounds represented by the following general formula [II], and / or at least one selected from the saccharides A solid processing agent for a silver halide photographic light-sensitive material, comprising:

[0012]

[Chemical 3]

In the formula, L represents an alkylene group, A represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group,
It represents a hydroxyl group, an amino group, an ammonio group, a carbamoyl group or a sulfamoyl group, and R represents a hydrogen atom or an alkyl group.

[0014]

[Chemical 4]

In the formula, R ₁ represents an alkyl group, R ₂ represents an alkyl group or a hydrogen atom, R ₃ represents an alkylene group, M represents a hydrogen atom, a sodium atom, a potassium atom, a lithium atom or triethanolammonium. Represents

The solid processing agent for a silver halide photographic light-sensitive material as described above, wherein the saccharide is a dextrin or a sugar alcohol.

The solid processing agent for a silver halide photographic light-sensitive material as described above, wherein the solid processing agent contains a carbonate and a p-phenylenediamine compound having a water-soluble group.

The solid processing agent for a silver halide photographic light-sensitive material as described in the above item, wherein the solid processing agent is in the form of tablets.

That is, the present inventors have conducted enormous experiments on solidifying a color developing agent and found a color developing agent exhibiting stable processing performance and stably existing as a solid. A solid treating agent containing a hydroxylamine salt, which has been conventionally used, has a hygroscopic property and a deliquescent property, so that the water content increases with time. As a result, inside the solid processing agent, the internal reaction proceeds due to the alkali + color developing agent + water, the generation of tar and the concentration of the effective main ingredient decrease due to unnecessary oxidation reaction, which results in unsatisfactory results in photographic processing performance. Occurs. In the case of compression molding, it is several 100K when compressed.
Since a pressure of g / cm ² or higher is applied, the internal reaction easily proceeds due to the heat of compression.

Further, as a problem peculiar to the color developing agent, it is necessary that the concentration of the active ingredient is kept constant. The color developing agent is usually a mixture obtained by mixing 5 to 6 or more kinds of components, and it is very difficult to mix these components in a solid state and uniformly disperse them. However, considering the simplification of the process and the productivity, it is possible to prepare a certain amount of color developing agent by mixing the individual components in a prescribed amount in advance, rather than separating and mixing the components one by one. It is much more advantageous and rational to separate a predetermined amount from the mixture.

However, the treating agent obtained when the components are not uniform during premixing is meaningless. These problems are caused by changing the hydroxylamine salt to a specific hydroxylamine derivative represented by the general formula [I] and containing at least one kind of the compound represented by the general formula [II]. The present invention has been accomplished by finding that it becomes possible to effectively and uniformly disperse the main component and solve the above problems.

The present invention will be specifically described below.

The color-developing solid processing agent of the present invention is a powder processing agent, a granular processing agent or a tablet, preferably a granular processing agent or a tablet from the viewpoint of charging accuracy. Most preferably, it is a tablet. Powder refers to an aggregate of fine grain crystals,
Granule refers to a granular material having a particle size of 50 to 5000 μm obtained by adding a granulation process to powder. A tablet refers to a powder or granules compressed into a certain shape, and the compression force is 400 to 300.
It is preferably 0 kg / cm ² .

A method for solidifying a photographic processing agent is described in Japanese Patent Application No. 2-
No. 135887, No. 2-203165, No. 2-203166, No. 2-203167
No. 2-203168, No. 2-300409, etc. can be used.

As a granulation method for forming granules or tablets, known methods such as rolling granulation, extrusion granulation, compression granulation and fluidized bed granulation can be used, and the obtained granules are granulated. It is preferable from the viewpoint of input accuracy that 60% or more of the object particles fall within a deviation of ± 100 to 150 μm.

A method for producing a tablet treating agent is described in JP-A-51-61837.
No. 54-155038, No. 52-88025, British Patent 1,213,808
It can be produced by the specification such as No. and the like and a known method, and the granule treating agent is described in the specifications such as JP-A Nos. 2-109042, 2-109043, 3-39735 and 3-39739. Further, the powder processing agent, JP-A-54-133332, British Patent 725,892,
It can be produced by a known method as described in the specifications such as 729,862 and German Patent 3,733,861.

First, the compound represented by the general formula [I] used in the present invention will be explained.

In the formula, L represents a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted, and has 1 to 5 carbon atoms.
Is preferred. Specifically, groups such as methylene, ethylene, trimethylene, and propylene are mentioned as preferable examples. As the substituent, a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group or an ammonio group which may be alkyl-substituted, represents a carboxyl group,
Preferred examples include a sulfo group, a phosphono group and a hydroxyl group. A is a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, an amino group which may be alkyl-substituted, an ammonio group which may be alkyl-substituted, a carbamoyl group which may be alkyl-substituted, or an alkyl-substituted one. A preferable sulfamoyl group is represented, and a carboxyl group, a sulfo group, a hydroxyl group, a phosphono group or a carbamoyl group which may be alkyl-substituted may be mentioned as a preferable example. Examples of -LA include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group,
Sulfoethyl group, sulfopropyl group, sulfobutyl group,
A phosphonomethyl group, a phosphonoethyl group, a hydroxyethyl group and the like can be mentioned as preferable examples, and a carboxymethyl group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group and a phosphonoethyl group can be mentioned as particularly preferable examples. R represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, and preferably has 1 to 5 carbon atoms. As the substituent, a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, an amino group which may be alkyl-substituted, an ammonio group which may be alkyl-substituted, a carbamoyl group which may be alkyl-substituted, or an alkyl-substituted group. Represents a sulfamoyl group which may be present. There may be two or more substituents. Preferred examples of R include a hydrogen atom, 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. ,
A carboxymethyl group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group can be mentioned as particularly preferable examples.
L and R may combine to form a ring.

Typical examples of the compounds represented by the general formula [I] are shown below, but the present invention is not limited to these compounds.

[0030]

[Chemical 5]

[0031]

[Chemical 6]

[0032]

[Chemical 7]

[0033]

[Chemical 8]

Preferred compounds among the above are I-
2, I-3, I-7, I-8, I-10, I-11, I-13,
I-14, I-19, I-24, I-26, I-30, I-33, I
-36, I-38, I-42, I-47, I-52, I-55 and the like are mentioned, and particularly preferred are I-2 and I-.
7, I-13 and I-14.

The content of these compounds in the color developing solution is 0.3 to 25% (w / w), preferably 0.6 to 18% (w) per unit weight of the solid developing agent for color development (as a weight%).
/ W).

The compound represented by the general formula [I] can be synthesized by subjecting commercially available hydroxylamines to an alkylation reaction (nucleophilic substitution reaction, addition reaction, Mannich reaction). West German Patent 1159634 and "Inorganica Chemika Actor" (Inorganica
Chimica Acta), 93 (1984) 101-107, and the like.

The saccharides referred to in the present invention are monosaccharides, polysaccharides in which a plurality of these are glycoside-bonded to each other, and decomposition products thereof.

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 the aldehyde group and the ketone group of sugar to form primary and secondary alcohol groups, respectively.

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 compounds of the monosaccharide of the present invention are shown below.

[Exemplified Compound] B- (1) Glyceraldehyde B- (2) Dihydroxyacetone (including dimer) B- (3) D-erythrose B- (4) L-erythrose B- (5) D-threose B- (6) L-threose B- (7) D-ribose B- (8) L-ribose B- (9) D-arabinose B- (10) L-arabinose B- (11) D- Xylose B- (12) L-xylose B- (13) D-lyxose B- (14) L-lyxose B- (15) D-xylulose B- (16) L-xylulose B- (17) D-ribulose B -(18) L-ribulose B- (19) 2-deoxy-D-ribose B- (20) D-allose B- (21) L-allose B- (22) D-altrose B- (23) L -Altrose B- (24) D-gluco B- (25) L-glucose B- (26) D-mannose B- (27) L-mannose B- (28) D-growth B- (29) L-gulose B- (30) D-idose B -(31) L-idose B- (32) D-galactose B- (33) L-galactose B- (34) D-talose B- (35) L-talose B- (36) D-quinovose B- ( 37) Digitalose B- (38) Digitoxose B- (39) Cimarose B- (40) D-sorbose B- (41) L-sorbose B- (42) D-tagatose B- (43) D-fucose B- ( 44) L-fucose B- (45) 2-deoxy-D-glucose B- (46) D-psicose B- (47) D-fructose B- (48) L-fructose B- (49) L-rhamnose B -(50) D-Glucosamine B- (51) D-Gala Tosamine B- (52) D-mannosamine B- (53) D-glycero-D-galactoheptose B- (54) D-glycero-D-mannoheptose B- (55) D-glycero-L-mannoheptose B- ( 56) D-glycero-D-gloheptose B- (57) D-glycero-D-idoheptose B- (58) D-glycero-L-glucoheptose B- (59) D-glycero-L-taloheptose B- (60) D-Altroheptulose B- (61) D-Mannoheptulose B- (62) D-Altro-3-heptulose B- (63) D-Glucuronate B- (64) L-Glucuronate B- ( 65) N-acetyl-D-glucosamine B- (66) Glycerin B- (67) D-trait B- (68) L-trait B- (69) Eritrit (trade name, Mitsubishi Kasei Foods Eris) Litol) B- (70) D-arabit B- (71) L-arabit B- (72) Adnit B- (73) Xylit B- (74) D-sorbit B- (75) L-sorbit B- (76) ) D-Mannit B- (77) L-Mannit B- (78) D-Igit B- (79) L-Igit B- (80) D-Talit B- (81) L-Talit B- (82 ) Dulcit B- (83) Allodulcit The sugar alcohols preferably used among these exemplified compounds are B- (66) to (83), more preferably B- (69) and (74) to (83). ).

Specific examples of compounds of the polysaccharides and sugar decomposition products of the present invention are shown below.

C- (1) Maltose C- (2) Cellobiose C- (3) Trehalose C- (4) Gentiobiose C- (5) Isomaltose C- (6) Lactose C- (7) Raffinose C- (8) ) Genthianose C- (9) Stachyose C- (10) Xylan C- (11) Alavan C- (12) Glycogen C- (13) Dextran C- (14) Inulin C- (15) Levan C- (16) Galactan C- (17) Agarose C- (18) Amylose C- (19) Sucrose C- (20) Agarobiose C- (21) Methylcellulose C- (22) Dimethylcellulose C- (23) Trimethylcellulose C- (24) Ethylcellulose C- (25) Diethyl cellulose C- (26) Triethyl cellulose C- (27) Carboxymethyl cellulose C- (28) Carbo Ciethylcellulose C- (29) Aminoethylcellulose C- (30) Hydroxymethylcellulose C- (31) Hydroxyethylmethylcellulose C- (32) Hydroxypropylcellulose C- (33) Hydroxypropylmethylcellulose C- (34) Hydroxypropylmethylcellulose acetate Succi Nate C- (35) Carboxymethyl hydroxyethyl cellulose C- (36) α-dextrin C- (37) β-dextrin C- (38) γ-dextrin C- (39) σ-dextrin C- (40) ε-dextrin C- (41) α-limit dextrin C- (42) β-limit dextrin C- (43) Phosphorylase limit dextrin C- (44) Soluble starch C- (45) Thin starch starch C- (46) White dextrin C- (47) Yellow dextrin C- ( 48) British Gum C- (49) α-Cyclodextrin C- (50) β-Cyclodextrin C- (51) γ-Cyclodextrin C- (52) Hydroxypropyl-α-Cyclodextrin C- (53) Hydroxypropyl -β-Cyclodextrin C- (54) Hydroxypropyl-γ-cyclodextrin C- (55) Maltodextrin Dextrins preferably used among these exemplified compounds are C- (36) to (55), Particularly preferred are C- (49) to (50), (52), (53) and (55). The weight average molecular weight of the dextrin used in the present invention may be any, but it is preferably 10 to 1000.

Sugars are widely present in nature, and commercial products are easily available. Also, various derivatives can be easily synthesized by performing reduction, oxidation or dehydration reaction.

As a commercially available product, as a decomposed product of starch, Pine Flow, Paindex series, Foodtex, Max 100, Glister P, TK-16, MPD, H-PDX, Stakodex manufactured by Matsutani Chemical Industry Co., Ltd. , Oil Q series manufactured by Nippon Oil & Fats Co., Ltd.

The compound represented by the general formula [II] will be described.

In the formula, R ₁ represents a linear or branched, optionally substituted, saturated or unsaturated alkyl group having 1 to 40 carbon atoms, preferably 3 to 30 carbon atoms. R ₂ represents a hydrogen atom or a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a butyl group. Group and amyl group are mentioned, and a methyl group is particularly preferable. R ₃ represents a linear or branched saturated or unsaturated alkylene group having 1 to 10 carbon atoms, which may be substituted, and examples of the substituent include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, and a carboxybutyl group. And a carboxyamyl group. Preferred examples of R ₃ include methylene group, ethylene group, butylene group, propylene group, carboxymethylmethylene group, carboxyethylmethylene group, carboxymethylethylene group, carboxyethylethylene group, and particularly preferred is ethylene group. .

M represents a hydrogen atom, a sodium atom, a potassium atom, a lithium atom, or triethanolammonium.

Among the general formula [II], a more preferable example is the general formula [III].

[0050]

[Chemical 9]

In the formula, R ₄ represents an alkyl group, M ₁ represents a hydrogen atom, a sodium atom, a potassium atom, a lithium atom or triethanolammonium.

More specifically, R ₄ represents a linear or branched, optionally substituted, saturated or unsaturated alkyl group having 1 to 40 carbon atoms, preferably 3 to 30 carbon atoms. M ₁ is a hydrogen atom,
It represents a sodium atom, a potassium atom, a lithium atom, or triethanolammonium.

Typical examples of the compounds represented by the general formula [II] are shown below, but the present invention is not limited to these compounds.

[0054]

[Chemical 10]

[0055]

[Chemical 11]

[0056]

[Chemical 12]

[0057]

[Chemical 13]

[0058]

[Chemical 14]

[0059]

[Chemical 15]

[0060]

[Chemical 16]

[0061]

[Chemical 17]

[0062]

[Chemical 18]

[0063]

[Chemical 19]

Of these exemplified compounds, those preferably used are 2-4, 2-7, 2-10, 2-13, 2-16,
2-37, 2-40, 2-43, 2-46, 2-49, 2-70, 2
-73, 2-76, 2-79, 2-82, particularly preferably 2-4, 2-7, 2-10, 2-13, 2-16.

In the present invention, the addition amount of the compound represented by the general formula [II] is preferably 0.05% (W / W) to 10 per unit weight (as weight%) of the solid developing agent for color development.
% (W / W), more preferably 0.1% (W / W) to 5% (W / W)
Is.

In the present invention, a p-phenylenediamine compound having a water-soluble group is preferably used.

Examples of the water-soluble group include those having at least one amino group on the p-phenylenediamine compound or on the benzene nucleus. Specific examples of the water-soluble group 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 group, —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.

[0069]

[Chemical 20]

[0070]

[Chemical 21]

[0071]

[Chemical formula 22]

Among the p-phenylenediamine compounds exemplified above, the exemplified compounds X- (1), X- (3) and X- (18) are particularly preferable in the present invention.

The carbonate preferably used in the present invention is supplied by potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate alone or in combination.

Among the color developing solid processing agents of the present invention, granules or tablets are preferably used because of high replenishment accuracy and easy handling.

To solidify the photographic processing agent, a concentrated liquid or fine powder or particles photographic processing agent and a water-soluble binder are kneaded and molded, or a water-soluble binding agent is formed on the surface of the temporarily molded photographic processing agent. Arbitrary means such as forming a coating layer by spraying can be adopted (Japanese Patent Application No. 2-135887, No. 2-203165, No.
2-203166, 2-203167, 2-203168, 2-300409
No.).

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

As the granulation method for tablet formation, known methods such as rolling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation and spray drying granulation are used. Can be done.
For tablet formation, the average particle size of the obtained granules is 100-800 μm in that when the granules are mixed and compressed under pressure, the components become nonuniform, so-called segregation does not easily occur. It is preferable to use one, more preferably 200 to 700 μm
Is. Furthermore, the particle size distribution is ± 100 for 60% or more of granulated particles.
Those within a deviation of ˜150 μm are preferred. 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. The solid processing agent obtained by compression under pressure can have any shape, but from the viewpoint of productivity and handleability, or from the problem of dust when used on the user side, a cylindrical type, a so-called tablet is used. preferable.

More preferably, at the time of granulation, the above-mentioned effect becomes more remarkable by separately granulating each component such as an alkali agent, a reducing agent, a bleaching agent and a preservative.

A method for producing a tablet processing agent is described in, for example, Japanese Patent Laid-Open No.
51-61837, 54-155038, 52-88025, British patent
It can be produced by a general method described in the specification such as 1,213,808, and further, the granule treating agent is disclosed in JP-A-2-09042, 2-10
It can be produced by a general method described in the specifications such as 9043, 3-39735 and 3-39739. Furthermore, the powder processing agent is, for example, JP-A-54-133332, British Patent 725,892,
It can be produced by a general method as described in the specifications such as German Patent No. 729,862 and German Patent No. 3,733,861.

[0080]

【Example】

 Example 1 A tablet was prepared according to the following procedure.

Operation (A) Additive (I) in the amounts shown in Table 1, sodium p-toluenesulfonate 200 g, Tinopearl SFP 30 g, diethylenetriaminepentaacetic acid pentasodium 30 g, and additive (II) in the amounts shown in Table 1, all of them. Granulate 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 for 6 hours in the dryer, and made water content rate 1% or less. Finally it was sifted through a 16 mesh screen.

Operation (B) p-phenylenediamine compound CD-3 (X- (1))
150 g and polyethylene glycol (average molecular weight 4000) 100
g is added in small amounts with a commercial mixing granulator and granulated.
The amount of water added was 20 ml. Then, it dried at 40 degreeC for 12 hours in the dryer, and made water content rate 1% or less. Finally this
Sifted through a 16 mesh screen.

Operation (C) 100 g of sodium p-toluenesulfonate, 4.0 g of sodium sulfite, 30 g of potassium hydroxide, 100 g of polyethylene glycol (average molecular weight 4000) and 330 g of potassium carbonate were added little by little with a commercially available mixing granulator. Then granulate. The amount of water added was 33 ml. Then, it dried at 40 degreeC for 12 hours in the dryer, and made water content rate 1% or less. Finally it was sifted through a 16 mesh screen.

Operation (D) All the granulated materials granulated in the above operations (A) to (C) and the additive (III) are mixed for 10 minutes in the mixer shown in Table 1. Next, the mixture is tableted by a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho. The filling amount was 11.0 g, and molding was performed at a compression pressure of 990 kg / cm ² .

The obtained solid processing agent was made into a cylindrical shape having a diameter of 30 mm.

The following experiments were conducted on the solid processing agent thus obtained.

Experiment (1) Each tablet was allowed to stand in an environment chamber under the following conditions, and after standing, each tablet was dissolved in 150 ml of water to evaluate its solubility.

[0088] Solubility evaluation ○ ・ ・ ・ Complete dissolution △ ・ ・ ・ Slightly insoluble residue remains × ・ ・ ・ A large number of insoluble residues occur and oil out on the liquid surface Experiment (2) Put each tablet in aluminum packaging The aluminum packaging material was opened after being sealed and stored under the following conditions, and the expansion coefficient of the tablet diameter before and after storage was calculated.

[0089] Experiment (3) Each of 100 tablets was tabletted, and 10 tablets were randomly sampled from each and dissolved in 150 ml of water. The content of the p-phenylenediamine compound, K ₂ CO ₃ , and the optical brightener Tinopearl SFP (abbreviated as FWD) in the solution was measured, and the degree of variation was represented by standard deviation.

The results are shown in Tables 1 and 2.

[0091]

[Table 1]

[0092]

[Table 2]

In the table, DEHA: Diethylhydroxyamine PVA: Polyvinyl alcohol Pine flow: Product name of dextrin degradation product manufactured by Matsutani Chemical Industry Co., Ltd. As apparent from the results of Tables 1 and 2, the combination of the present invention was used. For the first time, it was found that it exhibits excellent effects such as solubility, storability (expansion), and no component variation. Further, more preferable results can be obtained by using the compound of the general formula [II] and the saccharide together.

Further, the addition amount of the compound of the general formula [I] is
It is preferably 0.3 to 25% (w / w) per unit weight of the solid developing agent for color development (as a weight%), more preferably 0.6.
The range is up to 18% (W / W). The addition amount of the compound of the general formula [II] is 0.05% (W / W) to 10% (W / W), more preferably 0.1 to 5% (W / W).

Example 2 Procedure (E) Additive (I) 1500 g, sodium p-toluenesulfonate 6
000g, Tinopearl SFP 1200g, Additive (II-1) 120
0 g is ground using a commercially available hammer mill until the average particle size becomes 10 μm. This fine powder was mixed with a commercially available stirring granulator to obtain 300 m of water.
The mixture was granulated and kneaded for 6 minutes while adding l.

The granulated product was dried using a commercially available fluidized bed dryer.
The drying was performed while controlling the drying temperature to 60 ° C. After drying, the granules were sized using a 1.0 mm screen to obtain granule sample (E).

Operation (F) 8000 g of the p-phenylenediamine compound (1) and 2000 g of the additive (II-2) are ground using a commercially available hammer mill until the average particle size becomes 10 μm. This fine powder was granulated and kneaded for 6 minutes while adding 300 ml of water with a commercially available stirring granulator.

The granulated product was dried using a commercially available fluidized bed dryer.
The drying was performed while controlling the drying temperature to 45 ° C. After drying, the granules were sized using a 1.0 mm screen to give granule sample (F).

Procedure (G) Sodium p-toluenesulfonate 2800 g, sodium sulfite 80 g, lithium hydroxide monohydrate 800 g, potassium carbonate 7
000 g, diethylenetriaminepentaacetic acid pentasodium 700
g, polyethylene glycol (average molecular weight 4000) 2500
g and 1000 g of the additive (II-2) are pulverized using a commercially available hammer mill until the average particle size becomes 10 μm. This fine powder was granulated and kneaded for 6 minutes by adding 600 ml of water with a commercially available stirring granulator.

The granulated product was dried using a commercially available fluidized bed dryer.
The drying was performed while controlling the drying temperature to 50 ° C. After drying, the granules were sized with a 1.0 mm screen to give granule sample (G).

Operation (H) The granule sample (E) (4600 g), the granule sample (F) (3400 g) and the granule sample (G) (12000 g) were separately taken and mixed for 10 minutes using a commercially available cross rotary mixer. The sample (H) was used.

Operation (I) 100 g of the additive (III) (crushed to a particle size of 100 μm or less) was added to the granules (H), and the mixture was mixed for 5 minutes using a commercially available cross rotary mixer to obtain granules. Sample (I)
And

Operation (J) Granule sample (I) was tableted under a compression pressure of 1400 kg / cm ² by modifying a commercially available rotary tableting machine. The produced tablet sample was a cylindrical type having a weight of about 10.6 g, a diameter of 30 mm and a thickness of about 10 mm.

Experiment (4) The tablet sample prepared in the operation (J) was evaluated in the same manner as in the experiment (1).

Experiment (5) The tablet sample prepared in the operation (J) was evaluated in the same manner as in the experiment (2).

Experiment (6) The hardness of the tablet sample stored in Experiment 5 after storage was measured with a modified compression fracture strength tester TS-50N (manufactured by Okada Seiko Co., Ltd.).

The results are shown in Table 3.

[0108]

[Table 3]

As is clear from Table 3, the combination of the present invention exhibits excellent effects on solubility and storability (expansion, hardness deterioration) at high temperature and high humidity.

Example 3 For the granule sample (E), the additive (III) (particle size 100 μm
0.5% by weight was added thereto, and the mixture was mixed by a cross rotary type mixer for 10 minutes. Then, a commercially available rotary type tableting machine was modified and tableted at a compression pressure of 1400 kg / cm ² . The produced tablet sample was a cylindrical type having a weight of 10.0 g, a diameter of 30 mm and a thickness of about 10 mm.

The tablet samples were evaluated in the same manner as in Experiments (4) to (6) of Example 2. The results are shown in Table 4.

[0112]

[Table 4]

As is clear from Table 4, the combination of the present invention can effectively improve the solubility and the storage stability.

Example 4 The following experiment was conducted on the granular sample (H).

Experiment (7) About 50 g of the granule sample placed in an aluminum packaging material and hermetically sealed, it was stored in a small environment tester (0 ° C. → 60 ° C. → 0 ° C .: temperature change program 5 ° C./1 Hr) for 30 days. After storage, remove the granule sample from the aluminum packaging material and use the micro-type electromagnetic sifter (M
Vibration classification was performed for 30 seconds with a −100 type). At that time, the weight% of the granules remaining on the 1.5 mm mesh was calculated to evaluate the degree of blocking of the granules.

Further, as an evaluation of the fluidity of the granules, the granule samples after storage were put on a hard glass funnel (diameter 75 mm, foot diameter 7 mm, foot length 80 mm), and the falling state was observed.

Degree of fall 5 Completely clogged and does not fall even if vibration is applied 4 Clogged several times, requiring violent shaking of the funnel every time 3 Clogged several times, but slight vibration The test was conducted in the same manner as in Experiment 1 (8). Evaluation was performed in the same manner as in Experiment 1 (8). However, the solubility was evaluated by dissolving 10.6 g of each granule sample in 150 ml of water.

The results are shown in Table 5.

[0119]

[Table 5]

As is clear from Table 5, when the combination of the present invention is used, deterioration of storage stability (blocking or fluidity) in the granular state is prevented and excellent solubility is exhibited.

Example 5 The granule sample (E) was evaluated in the same manner as in the experiment (7).

The results are shown in Table 6.

[0123]

[Table 6]

As is clear from Table 6, in the present invention, deterioration of storage stability (blocking or fluidity) in a granular state can be effectively prevented.

Example 6 Operation (K) 9000 g of potassium carbonate, 1400 g of sodium sulfite, 600 g of diethylenetriaminepentaacetic acid pentasodium, 1200 g of polyethylene glycol (average molecular weight 6000), 1900 g of sodium p-toluenesulfonate, 500 g of additive (I), addition 1000 g of agent (II-1) is used with a commercially available hammer mill to obtain an average particle size of 10
Grind to μm. This fine powder was granulated and kneaded for 6 minutes while adding 500 ml of water with a commercially available stirring granulator.

The granulated product was dried using a commercially available fluidized bed drier.
The drying was performed while controlling the drying temperature to 55 ° C. A granule sample (K) was prepared by drying and sizing with a 1.0 mm screen.

Procedure (L): Hydroxylamine 1/2 sulfate 3200 g, potassium bromide 4
00 g, disodium pyrocatechol-3,5-disulfonate 1
80 g and 240 g of the additive (II-2) were pulverized in the same manner as in the operation (K), granulated, dried and sized. The amount of water added during granulation is 12
0 ml, the drying temperature was 55 ° C. The granule thus prepared was used as a granule sample (L).

Operation (M) 3500 g of p-phenylenediamine compound X-3 and 500 g of additive (II-3) were pulverized, granulated, dried and sized in the same manner as in operation (K). The amount of water added during granulation was 150 ml, and the drying temperature was 45 ° C. The granules thus prepared were used as a granule sample (M).

Operation (N) 12000 g of the granule sample (K), 900 g of the granule sample (L) and 1900 g of the granule sample (M) were separately taken and mixed for 10 minutes using a commercially available cross rotary mixer. The granule sample (N) was used.

Operation (O) 75 g of the additive (III) (pulverized to a particle size of 100 μm or less) was added to the granules (N), and the mixture was mixed for 5 minutes using a commercially available cross rotary mixer to prepare granules. The sample (O) was used.

Operation (P) The above-mentioned granule sample (O) was tableted under a compression pressure of 1400 kg / cm ² by modifying a commercially available rotary tableting machine. The produced tablet sample was a cylindrical type having a weight of about 11.0 g, a diameter of 30 mm and a thickness of about 10 mm.

The following experiments were conducted on the tablet samples thus obtained.

Experiment (9) Evaluation was carried out in the same manner as in Experiments (1) to (3) and (6). However, in Experiment (3), the content of the p-phenylenediamine compound, hydroxylamine · 1/2 sulfate (HAS), and KBr in the solution was measured to change the degree of variation.

The results are shown in Table 7.

[0135]

[Table 7]

As is clear from Table 7, it was found that the combination of the present invention exhibited excellent effects in solubility, storability (diameter expansion, hardness) and component variation.

Example 7 Additive (III) (particle size 100) was added to the granule sample (K).
0.5 wt%) was added and mixed by a cross rotary type mixer for 10 minutes, and then a commercially available rotary type tableting machine was modified to form tablets at a compression pressure of 1400 kg / cm ² . The produced tablet sample was a cylindrical type having a weight of 11.5 g, a diameter of 30 mm and a thickness of about 10 mm.

The tablet samples were evaluated in the same manner as in Experiments 1, 2, and 6.

The results are shown in Table 8.

[0140]

[Table 8]

As is clear from Table 8, the effect of the present invention is exhibited by the combination of the present invention.

Example 8 The granules (N) were tested and evaluated in the same manner as in Example 4. However, the solubility was determined by dissolving 11 g in 150 ml of water. The results are shown in Table 9.

[0143]

[Table 9]

As shown in Table 9, the effect of the present invention is exhibited only by the combination of the present invention.

Example 9 The granules (K) were evaluated in the same manner as in Experiment 7. The results are shown in Table 10.

[0146]

[Table 10]

As is clear from Table 10, the effect of the present invention is exhibited by the combination of the present invention.

[0148]

According to the present invention, a solid developing agent for color development, which does not cause storage deterioration with time and does not cause precipitation or precipitation, contains individual components in precisely determined amounts and has excellent processing stability. Can be provided.

Claims (4)

[Claims] 1. At least one selected from compounds represented by the following general formula [I], at least one selected from compounds represented by the following general formula [II], and / or at least selected from saccharides. A solid processing agent for a silver halide photographic light-sensitive material, which contains one kind. [Chemical 1] [In the formula, L represents an alkylene group, A represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, an amino group, an ammonio group, a carbamoyl group or a sulfamoyl group, and R represents a hydrogen atom or an alkyl group. Represents ] [Chemical 2] [In the formula, R ₁ represents an alkyl group, R ₂ represents an alkyl group or a hydrogen atom, R ₃ represents an alkylene group, and M represents a hydrogen atom, a sodium atom, a potassium atom, a lithium atom or triethanolammonium. . ] 2. The solid processing agent for silver halide photographic light-sensitive materials according to claim 1, wherein the saccharide is a dextrin or a sugar alcohol. 3. The solid processing agent for a silver halide photographic light-sensitive material according to claim 1, wherein the solid processing agent contains a carbonate and a p-phenylenediamine compound having a water-soluble group. 4. The solid processing agent for silver halide photographic light-sensitive materials according to claim 1, 2 or 3, wherein said solid processing agent is in the form of tablets.