JPH07248584A - Solid processing agent for development for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a tablet type silver halide photographic sensitive material having stable preservability with the lapse of time. CONSTITUTION:In the solid processing agent for development of the silver halide photographic sensitive material containing at least one kind of an alkaline agent selected from among carbonate, phosphate and borate and a developing principal chemical, each of the alkaline agent and the developing principal chemical is contained as an individual component particle and the tablet type processing agent for development formed by pressurizing and compressing the mixture of the component particles has Z value of 0.3 to 4.0 given by an equation, (Z value)=(compression breaking strength (kg))/(length (mm) of the tablet in the major axis direction).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a solid processing agent for developing a tablet type silver halide photographic light-sensitive material.

[0002]

BACKGROUND OF THE INVENTION Silver halide photographic light-sensitive materials are usually used in black and white developing solutions, fixing solutions, color developing solutions, bleaching solutions, bleach-fixing solutions,
Development processing is performed using a processing solution such as a stabilizing solution to obtain an imagewise image. Each treating agent used here is put in a plastic bottle in the form of one or a plurality of concentrated liquid parts for ease of use and supplied to the user as a treating agent kit. The user dilutes these treatment agent kits with water and uses them (starting solution and replenishing solution).
Created and used.

In recent years, in the photographic processing industry, there has been a rapid increase in the number of small-scale developing laboratories called minilabs that use small automatic processors, and the amount of processing agent kits used in minilabs has also increased. Although the treatment agent kit is a concentrated liquid, it still requires a lot of space to store the treatment agent kit,
Also, the transportation cost is not ridiculous. In addition, the amount of discarded plastic bottles has been increasing year by year, and it is necessary to collect and dispose of these discarded plastic bottles, but since it is difficult to recover and dispose of these plastic bottles, they are discarded. It is desired to develop a processing agent containing a small amount of plastic.

In order to reduce the space required for storage, to reduce the transportation cost, and to reduce the amount of discarded plastic, it is conceivable to powderize and supply the photographic processing agent. When the processing agent dissolves, fine powder may fly up and be inhaled by workers, which not only raises concern about the effect on health, but also causes the flying up processing agent components to mix into another photographic processing solution, which There arises a problem that a trouble occurs in the developing process.

To solve this problem, JP-A-5-119454, JP-A-5-113646, JP-A-5-107696 and the like disclose granulated color developing agent components and granulated alkali. There is described a tablet type color photographic processing agent which is prepared by mixing and compressing agent components. Although the generation of fine powder of the solid processing agent is certainly reduced by the technology of the above-mentioned patent, it was found that when the solid processing agent was stored at a high temperature with time, the oxidation of the developing agent in the solid processing agent became severe. .

Considering the transportation of the solid treatment agent to Southeast Asia, the Middle East and Africa by ship, the treatment agent is 50 ° C.
It has also been found that it is exposed to moderate environmental conditions.

[0007]

DISCLOSURE OF THE INVENTION As a result of intensive studies, the present inventors have found that at least one of carbonate, phosphate and borate is used.
A seed-type developing treatment agent containing a seed and a developing agent as separate component particles, which is produced by compressing and compressing a mixture of the component particles.
The present invention has been completed by finding that the value greatly affects the above problem.

Therefore, an object of the present invention is to provide a solid processing agent for developing a tablet type silver halide photographic light-sensitive material which has stable storage properties over time for a long period of time and has improved generation of fine powder after storage. To provide. Other purposes will be clarified in the following description.

[0009]

The above object of the present invention is to provide at least one selected from carbonates, phosphates and borates.
In a solid developing agent for developing a silver halide photographic light-sensitive material containing an alkaline agent and a developing agent, the alkaline agent and the developing agent are contained as separate component particles, and a mixture of the component particles is added. Z of the tablet type processing agent produced by pressure compression is given by the following formula:
It is achieved by a solid processing agent for developing a silver halide photographic light-sensitive material, which has a value of 0.3 or more and 4.0 or less.

Z value = compressive breaking strength of tablet (kg) / longitudinal length of tablet (mm) The component particles containing the alkali agent or the developing agent are granulated products, or the component particles are different from each other. In the case of the granulated product, the more remarkable effect is exhibited.

Preferably, the solid processing agent for development has a specific volume of 0.3 to 0.95 cm ³ / g and a water content of 0.
1 to 15% by weight.

The present inventors have found the following facts by experiments with regard to a solid processing agent for developing a silver halide photographic light-sensitive material.

The present invention relates to a silver halide photographic light-sensitive material characterized in that at least one or more alkali agents selected from carbonates, phosphates and borates and developing agents are separate component parts. Although it is a developing tablet type processing agent, when the Z value of the developing tablet type processing agent becomes large, the granules containing the alkali agent and the granules containing the developing agent are the solid processing agents. In the solid processing agent, the contact between the alkaline agent and the developing agent is increased, resulting in oxidation of the developing agent during high temperature storage of the solid processing agent. It will be easier. As a result of the experiment, it was found that when the Z value of the developing solid processing agent exceeds 4.0, the developing agent is violently oxidized.

On the contrary, the physical strength Z of the solid processing agent is 0.3.
It has also been found that when the particle size is smaller, many voids are formed on the surface and inside of the solid processing agent, so that the surface area of the solid processing agent which comes into contact with air is increased and the developing agent is easily oxidized.

In the present invention, Z of the solid processing agent for development is used.
The value may be in the range of 0.3 or more and 4.0 or less, but from the viewpoint of the effect of the present invention, it is preferably in the range of 0.8 or more and 3.5 or less.

The compressive fracture strength of a tablet is a direction perpendicular to the compression molding direction of the tablet (that is, a direction parallel to the compression surface of the tablet), and is a value when it is fractured by applying pressure in that direction. is there. The measurement conditions are room temperature 25 ° C, humidity 50% RH, Speed Checker TS-50N (Okada Seiko Co., Ltd.), compression speed 5
To 78 mm / min. The optimum compression speed is selected according to the size and shape of the tablet. What is the long direction of tablets?
When the tablet is disk-shaped, it means the diameter of the circle, and when it is polygonal, it is the compression surface of the hardness tester (different from the compression surface of the tablet).
And a surface which is in contact with the surface parallel to, and the distance to the farthest point or surface in the compression direction of the hardness meter. Oval, circle,
The deformed shape in which polygons are combined refers to the distance from the point in contact with the compression surface of the hardness tester to the longest point in the compression direction.

In the present invention, as means for controlling the Z value, control of pressure (tabletting pressure) during compression and compression, control of water content of solid component to be compressed and compressed, compression by compression Control of time (compression stagnation time) ・ Control of average particle diameter of solid component to be compressed under pressure can be used.

In the present invention, the water content of the developing tablet type processing agent is controlled within the range of 0.1 to 15% by weight, and the specific volume of the tablet type processing agent is controlled within the range of 0.3 to 0.95 cm ³ / g. Thereby, the effects of the present invention described above can be further enhanced, and further, a decrease in the binding force between solid components due to storage over time can be suppressed, and solid processing agents or solid processing agents that occur during transportation of the solid processing agent It has been confirmed from experiments that it is possible to suppress the generation of powder due to friction with the packaging material.

The water content of the developing tablet type processing agent described above is the water content of the mixture of granulated products before compression under pressure, using a commercially available electronic moisture meter, 105 ° C
It is a value calculated by calculating the reduced weight by heating to a constant weight by heating to obtain the reduced weight and calculating the reduced weight as the water content.

In the present invention, the water content of the solid processing agent is obtained by heating the granules before compression molding at 105 ° C. to a constant weight using a commercially available electronic moisture meter, and determining the reduced weight. It refers to the content rate calculated with the reduced weight as the water content. The water content of the present invention may be in the range of 0.1 to 15% by weight, but from the viewpoint of the effect of the present invention, it is preferably in the range of 0.3 to 10% by weight.

The specific volume of the present invention is determined from the specific volume (cm ³ / g) = volume (cm ³ ) / weight (g) by measuring the volume from the thickness and diameter size of the tablet processing agent. In the case of the tablet-type treatment agent of the present invention,
The range is 0.3 to 0.95 cm ³ / g, preferably 0.4 to
It is in the range of 0.7 cm ³ / g.

The solid processing agent of the present invention is a solid processing agent containing at least one alkali agent and at least one developing agent as separate component particles all together.
That is, in the developing solid processing agent of the present invention, in order to further exert the effects of the present invention, at least one of the alkaline agent and the developing agent is in order to minimize contact between the alkaline agent and the developing agent. The granulated product is preferable because the effect of the present invention is more remarkably exhibited. Further, it is preferable that both the alkali agent and the developing agent are granulated products. This is because, when at least one of the alkali agent and the developing agent is a granulated product, not only the above-mentioned effect but also another effect that an increase in the amount of fine powder generated due to the storage of the solid processing agent is further prevented. .

The alkaline agent of the present invention is a compound exhibiting an alkalinity of pH 8 or more when made into an aqueous solution, and preferred specific examples thereof include sodium carbonate and potassium carbonate.
Examples thereof include sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate and the like.

The color developing agent of the present invention is preferably a p-phenylenediamine compound having a water-soluble group. Examples of the p-phenylenediamine-based compound having a water-soluble group include those having at least one water-soluble group in the amino group of the p-phenylenediamine-based compound or on the benzene nucleus. Specific water-soluble groups include-(CH ₂ ) nCH
_{2 OH, - (CH 2)} mNHSO 2 (CH 2) nCH 3, - (CH 2) mO (CH 2) nCH 3,
Preferred examples include — (CH ₂ CH ₂ O) nCmH _{2m + 1} , —COOH, —SO ₃ H group (m and n each represent an integer of 0 or more) and the like.

Specific examples of the color developing agent preferably used in the present invention include compounds described in JP-A No. 4-86741, 26-31.
(C-1) to (C-16), 4-amino described on page
-3-Methyl-N- (3-hydroxypropyl) aniline and the like can be mentioned.

The color developing agent can usually take the form of hydrochloride, sulfate, p-toluenesulfonate and the like.

As the method for producing the granulated product, known methods such as tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, spray drying granulation and the like can be used. Can be used.

Further, the effect of the present invention is more effectively exhibited by compressing the above-mentioned solid processing agent for development to form a tablet-type solid processing agent, and the amount of fine powder generated is increased by storage. It becomes possible to prevent it more effectively.

The tablet-type solid processing agent can be produced using a known compressor. For manufacturing, for example, a hydraulic press machine, a single-shot tableting machine, a rotary tableting machine, or a briquetting machine can be used. The tablet-type solid processing agent can have any shape, but a cylindrical one is preferable in terms of productivity and handleability.

Further, the solid processing agent of the present invention contains at least one compound selected from polyethylene glycols, polyvinylpyrrolidones, polyvinyl alcohols and saccharides, so that the components in the solid processing agent are bound to each other. The force can be increased, and the effect of preventing the generation of powder of the solid processing agent due to friction after storage with time is further enhanced.

In the present invention, the polyethylene glycols are preferably compounds represented by the following general formula [I].

[0032] Formula (I) _{HO- (A) n 1 - (} B) n 2 - (D) n 3 -H wherein, A, B, D each _{-CH 2 CH 2 O -, -} CH 2 CH (R) O
_{-, - CH 2 CH 2 CH} 2 O- or -CH ₂ CH (R) represents a CH ₂ O-. R represents a substituted or unsubstituted lower alkyl group (methyl group, ethyl group, propyl group, etc.) or a hydroxyl group. n ₁ , n ₂ and n
₃ represents 0 or an integer of 1 to 500, respectively. However, the average molecular weight of this compound is preferably in the range of 2000 to 20000.

The particularly preferable exemplified compounds in the above formula [I] are shown below.

[0034]

[Chemical 1]

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

In the present invention, the saccharides mean monosaccharides and polysaccharides in which a plurality of these are glycosidic-bonded to each other.

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

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

Specific examples of the monosaccharide of the present invention are shown below.

[Exemplified Compounds] B- (1) 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-deoxypho D-ribose B- (20) D-allose B- (21) L-allose B- (22) D-altrose B- (23) L- Altrose B- (24) D-glucose B- (25) L-glucose B- (26) D-mannose B- (27) L-ma N-Nose B- (28) D-Growth B- (29) L-Growth 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-quinobose 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-galactosamine B- (52) D-mannosamine B -(53) D-glycero-D-galactoheptose B- (54) D-glycero-D-mannoheptose B- (55) D-glyce -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-glucuronic acid B- (65) N-acetyl-D-glucosamine B- (66) Glycerin B- (67) D-Tray B- (68) L-Trait B- (69) Elitret B- (70) D -Arabite B- (71) L-Arabite 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 Among these exemplified compounds, B- is preferably used.
(66) to (83), more preferably B- (74) to
(83).

Specific examples of compounds of the polysaccharide 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) α-dextrin C- (22) β-dextrin C- (23) γ-dextrin C- (24) δ-dextrin C- (25) ε-dextrin C- (26) α-limit dextrin C- (27) β-limit dextrin C- (28) phosphorylase limit dextrin C- (29) Soluble Starch C- (30) Thin Nori Starch C- (31) White Dextrin C- (32) Yellow Dextrin C- (33) British Gum C- (34) Pine Flow (trade name, Matsutani Chemical Industry Co., Ltd. C- (35) Paindex 100 (trade name, manufactured by Matsutani Chemical Co., Ltd.) C- (36) Paindex 1 (product name, manufactured by Matsutani Chemical Co., Ltd.) C- (37) Paindex 2 (trade name, manufactured by Matsutani Chemical Co., Ltd.) C- (38) PA index 3 (product name, manufactured by Matsutani Chemical Co., Ltd.) C- (39) PA index 4 (trade name, Matsutani Chemical Co., Ltd.) C- (40) Paindex 6 (trade name, manufactured by Matsutani Chemical Co., Ltd.) C- (41) Foodtex (trade name, manufactured by Matsutani Chemical Co., Ltd.) C- (42) Max 1000 ( Product name, Matsutani Chemical Industrial Co., Ltd.) C- (43) Glister P (trade name, manufactured by Matsutani Chemical Co., Ltd.) C- (44) TK-16 (trade name, manufactured by Matsutani Chemical Co., Ltd.) C- (45) MPD (product name, manufactured by Matsutani Chemical Co., Ltd.) C- (46) H-PDX (product name, manufactured by Matsutani Chemical Co., Ltd.) C- (47) Stacodex (product name, manufactured by Matsutani Chemical Co., Ltd.) C- (48) Mabit (trade name, manufactured by Hayashibara Shoji Co., Ltd.) C- (49) Pullulan (trade name, manufactured by Hayashibara Shoji Co., Ltd.) C- (50) Methylcellulose C- (51) Dimethylcellulose C- ( 52) Trimethyl cellulose C- (53) Ethyl cellulose C- (54) Diethyl cellulose C- (55) Triethyl cellulose C- (56) Carboxymethyl cellulose C- (57) Carboxyethyl cellulose C- (58) Amino Chill Cellulose C- (59) Hydroxymethyl Cellulose C- (60) Hydroxyethyl Methyl Cellulose C- (61) Hydroxypropyl Cellulose C- (62) Hydroxypropyl Methyl Cellulose C- (63) Hydroxypropyl Methyl Cellulose Acetate Succinate C- (64) Carboxy Methyl hydroxyethyl cellulose Among these exemplified compounds, the one preferably used is C-
(21) to (64), more preferably C- (21) to
(48).

In the present invention, the addition amount of these saccharides is 0.5% (W / W) to 30 per unit weight of the solid developing agent.
% (W / W), more preferably 1.0% (W / W)
~ 20% (W / W).

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.

The above-mentioned compound represented by the general formula [I], polyvinylpyrrolidones, polyvinyl alcohols and saccharides may be in the form of powdery raw materials or mixed in a granulated state, or The effect of the present invention can be exhibited even when used in the state of being granulated with the alkaline agent of the present invention.

The average particle size of the granulated product of each of the alkali agent and the developing agent is preferably in the range of 150 to 1500 μm, more preferably 300 to 1000 μm.

[0047]

EXAMPLES The present invention will be described in more detail with reference to the following examples.

Example 1 A tablet-type color developer was prepared according to the following procedure.

Solid processing agent (1-1) Hydroxylamine sulfate 3500 g, potassium bromide 350 g,
Average particle size of 150 g of 1,2-dihydroxybenzene-3,5-disulfonic acid disodium salt monohydrate (hereinafter referred to as Tyrone), 5800 g of sodium sulfite, and 2500 g of diethylenetriamine pentaacetic acid 5 sodium salt using a commercially available hammer mill.
After crushing to 50 μm, add 5500 g of polyethylene glycol # 6000 (manufactured by NOF CORPORATION) and 7500 g of Mannitol and mix evenly in a commercially available mixer, and use 200 ml of commercial agitated granulator for about 7 minutes. Granulated by spraying with water. The obtained granulated product was dried at 55 ° C. for 3 hours with a commercially available fluidized bed drier, and the granulated product was sieved to obtain 149 μm.
Granules were prepared by removing those of less than 1410 μm or more (JIS standard).

The above-mentioned granulated product and a developing agent manufactured by Konica Chemical Co.
4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate 6000 g, commercially available potassium carbonate 270 mol 25
Mix for 10 minutes using a commercially available cross rotary mixer in a room temperature-controlled and humidity-controlled at 50 ° C and 0.5% by weight.
Myristoyl-N-methyl-β-alanine sodium salt was added, and then the obtained mixture was loaded using a tablet machine modified from Tough Press Collect (1527HU) manufactured by Kikusui Seisakusho Co., Ltd. Is compressed to 12 g and compressed,
A cylindrical tablet type treating agent (1-1) having a diameter of 30 mm was prepared.

Regarding the solid processing agents (1-2) to (1-8), the amount of water added during the preparation of the granulated product, the control of the drying time, the tableting pressure during the tableting of the solid component, The Z value was adjusted as shown in Table 1 by controlling the compression stagnation time.

Solid Processing Agent (1-9) Operation (A) Developing Agent (4-Amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline Sulfate) (Konica Chemical Co., Ltd.)
Called CD-4. ) Weigh 6000 g.

Operation (B) Hydroxylamine sulfate 3500 g, potassium bromide 350 g,
150 g of 1,2-dihydroxybenzene-3,5-disulfonic acid disodium salt monohydrate (hereinafter referred to as Tyrone) was crushed with a commercially available hammer mill until the average particle size became 50 μm, and then pine flow (Matsutani (Manufactured by Kagaku Co., Ltd.), 200 g was added and mixed, and 150 ml of water was sprayed for about 7 minutes in a commercially available stirred granulation to granulate. The obtained granules were dried with a commercially available fluidized bed dryer at 55 ° C for 3 hours, and the obtained granules were sieved in the same manner as when the solid processing agent (1-1) was prepared. (B) was created.

Operation (C) 5800 g of sodium sulfite, 270 mol of potassium carbonate, and 2500 g of diethylenetriamine pentaacetic acid 5 sodium salt are operated (B).
Milled as in. To this fine powder, 5500 g of polyethylene glycol # 6000 (made by NOF CORPORATION) and 75 of Mannit
00 was added and uniformly mixed in a commercially available mixer. Then the operation
Granulation was carried out in the same manner as in (B) with the amount of water sprayed to 1400 ml. After granulation, it was dried at 55 ° C. for 4 hours, and the obtained granulated product was sieved in the same manner as in the operation (B) to prepare a granulated product (C).

Operation (D) Granules (B) and (C) and (A) prepared in operations (B) and (C)
Was mixed for 10 minutes using a commercially available cross rotary mixer in a room where the temperature was adjusted to 25 ° C and 50% RH and the humidity was adjusted, and this mixture was solid treated in the same manner as solid treating agent (1-1). Agent (1-
9) was created.

Regarding the solid processing agents (1-10) to (1-16), the solid processing agents (1-
The Z value was adjusted as shown in Table 1 in the same manner as in 2) to (1-8).

Solid Processing Agent (1-17) Operation (E) Granulation product of developing agent (4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate) (manufactured by Konica Chemical Co.) (Hereinafter, referred to as CD-4.) 6000 g was sized using a commercially available speed mill. The obtained granules were sieved with a sieve to remove granules (E) of less than 149 μm and 1410 μm or more (JIS standard).

Operation (F) Hydroxylamine sulfate 3500 g, potassium bromide 350 g,
150 g of 1,2-dihydroxybenzene-3,5-disulfonic acid disodium salt monohydrate (hereinafter referred to as Tyrone) was crushed with a commercially available hammer mill until the average particle size became 50 μm, and then pine flow (Matsutani (Chemical) 200 g was added and mixed, and granulated by spraying 150 ml of water in a commercially available stirring granulator for about 7 minutes. The obtained granulated product was dried at 55 ° C. for 3 hours with a commercially available fluidized bed dryer, and the granulated product was sieved in the same manner as in the operation (E) to obtain a granulated product (F). Created.

Operation (G): Operation (F): sodium sulfite 5800 g, potassium carbonate 270 mol, diethylenetriamine pentaacetic acid 5 sodium 2,500 g
Milled as in. To this fine powder, 5500 g of polyethylene glycol # 6000 (made by NOF CORPORATION) and 75 of Mannit
00 g was added and uniformly mixed in a commercially available mixer. Then, in the same manner as in the operation (F), the amount of water sprayed was set to 1400 ml and granulation was performed. After granulation, dry at 55 ℃ for 4 hours,
The obtained granulated product was sieved in the same manner as in the operation (E) to prepare a granulated product (G).

Operation (H) The granules (E) to (G) prepared in the operations (E) to (G) were heated at 25 ° C. and 50 ° C.
% RH was mixed in a room temperature-controlled and humidity-controlled for 10 minutes using a commercially available cross rotary type mixer, and this mixture was treated in the same manner as the solid treatment agent (1-1). )made.

Regarding the solid processing agents (1-18) to (1-24), the solid processing agents (1-
The Z value was adjusted as shown in Table 1 in the same manner as in 2) to (1-8).

Further, the obtained 1-1 to 1-17 were sealed in an aluminum packaging material, and a cycle of 50 ° C. and −20 to 60 ° C. (8 hours: −20 ° C. → 60 ° C. over 4 hours → 8 hours: 60 ° C. → stored in an environment room controlled at −20 ° C. over 4 hours) for 1 month, and evaluate the coloring showing that the sample after storage was oxidized.
The following evaluation was performed according to the following evaluation criteria.

<Evaluation Criteria> ⊚: Not colored at all ◯: Colored slightly but no problem Δ: Partially colored ×: Almost entirely colored

The results obtained are shown in Table 1.

Those with a rating of X have a low commercial value.

[0066]

[Table 1]

As is clear from Table 1, Z of the solid processing agent is
It was confirmed that by controlling the value within the range of the present invention, it is possible to suppress the oxidation of the developing agent when the solid processing agent is stored at high temperature.

Further, in the present invention, by using at least one of the alkaline agent and the main agent as granules, the above-mentioned effects of the present invention can be enhanced, and by using both the alkaline agent and the main agent as granules. Therefore, the effects of the present invention can be further exerted.

Further, when the above experiment was carried out by changing the above-mentioned potassium carbonate to potassium triphosphate and potassium metaborate, the same effect of the present invention was confirmed.

Example 2 Solid Treatment Agent (2-1) Bis (sulfoneethyl) hydroxylamine disodium
8000g, sodium p-toluenesulfonate 16000g, Chinopearl SFP (Ciba Geigy) 2500g, sodium sulfite 370g, diethylenetriamine pentaacetic acid 5 sodium 330
0 g, 14000 g of sodium p-toluenesulfonate and 3400 g of lithium hydroxide monohydrate were crushed with a bandam mill to an average particle size of 10 μm, and then 60000 g of mannitol and 5000 g of polyethylene glycol (# 4000) were added and mixed.
Then, in the same manner as in the operation (B), 3500 ml of water was added to carry out granulation and drying was carried out at 60 ° C. The obtained granulated product was sieved in the same manner as in the operation (E) to remove large and small particles to prepare a granulated product.

A developing agent (4-amino-3-methyl) was added to the granulated product.
-N-ethyl-N-β-methanesulfonamidoethyl-aniline 3/2 sulfuric acid monohydrate) (manufactured by Konica Chemical Co., Ltd.) 15000g, commercially available potassium carbonate 33000g at 25 ° C, 50% temperature and humidity control Using a commercially available cross rotary mixer in a controlled room
Mix for minutes, 0.5% by weight of the total weight of myristoyl-
After adding N-methyl-β-alanine sodium,
Using a mixer in a room whose temperature and humidity have been adjusted to 25 ℃ and 50% RH
Mix for 10 minutes. Then, the resulting mixture is Kikusui Seisakusho
Using a tableting machine modified from Tough Press Collect (1527HU) manufactured by Co., Ltd., compression tableting was performed with the filling amount per tablet being 12 g, to prepare a cylindrical tablet type treatment agent having a diameter of 30 mm.

Regarding the solid processing agents (2-2) to (2-8), the amount of water added during the preparation of the granulated product, the control of the drying time, and the tableting pressure during the tableting of the solid component were The Z value was adjusted as shown in Table 2 by controlling the compression stagnation time.

Solid Processing Agent (2-9) Operation (I) Developing Agent (4-Amino-3-methyl-N-ethyl-N-β-methanesulfonamidoethyl-aniline 3/2 sulfuric acid monohydrate) (Konica Weigh 15000 g (Chemical Co., Ltd.).

Procedure (J) Bis (sulfoethyl) hydroxylamine disodium 80
00g, sodium p-toluenesulfonate 16000g, Chinopearl SFP (manufactured by Ciba Geigy) 2500g were crushed with a bandam mill to an average particle size of 10μm, and then pine flow 2500g was added at room temperature in a commercial stirring granulator. After mixing for 5 minutes, the mixture was granulated by adding 2000 ml of water. The obtained granulated product was dried at 60 ° C. in a fluidized bed dryer. The obtained granulated product was sieved in the same manner as in the operation (E) to remove large and small particles to prepare a granulated product (J).

Operation (K): Potassium carbonate 33000 g (239 mol), sodium sulfite 370
g, diethylenetriamine pentaacetic acid 5 sodium 3300 g,
After crushing 14000 g of sodium p-toluenesulfonate and 3400 g of lithium hydroxide monohydrate in the same manner as in the operation (J), 60000 g of mannitol and polyethylene glycol # 4
000 5000g was added and mixed. Then, in the same manner as in the operation (J), 3500 ml of water was added and granulation was performed.
Drying was performed at ° C. The obtained granulated product was sieved in the same manner as in the operation (E) to remove large and small particles to prepare a granulated product (K).

Operation (L) Granules (J), (K) and (I) prepared in operations (J) and (K)
Was mixed for 10 minutes using a commercially available cross rotary type mixer in a room where the temperature was adjusted to 25 ° C and 50% RH and the humidity was adjusted, and this mixture was solid treated in the same manner as solid treating agent (2-1). Agent (2-
9) was created.

Regarding the solid processing agents (2-10) to (2-16), the solid processing agents (2-
The Z value was adjusted as shown in Table 2 in the same manner as in 2) to (2-8).

Solid Processing Agent (2-17) Procedure (M) Preparation of developing agent (4-amino-3-methyl-N-ethyl-N-β-methanesulfonamidoethyl-aniline 3/2 sulfuric acid monohydrate) Granules (manufactured by Konica Chemical Co., Ltd.) 15,000 g were sized using a speed mill. The obtained granules were sieved with a sieve having openings of 149 μm and 1410 μm (JIS standard) to remove large and small particles to prepare a granulated product (M).

Operation (N) Bis (sulfonethyl) hydroxylamine disodium salt
8000 g, sodium p-toluene sulfonate 16000 g, Chinopearl SFP (manufactured by Ciba Geigy) 2500 g were crushed with a bandam mill to an average particle size of 10 μm, and then pine flow 2500 g was added at room temperature in a commercial stirring granulator. After mixing for 5 minutes, the mixture was granulated by adding 2000 ml of water. The obtained granulated product was dried at 60 ° C. in a fluidized bed dryer. The obtained granulated product was sieved in the same manner as in the operation (M) to remove large and small particles to prepare a granulated product (N).

Procedure (O): Potassium carbonate 33000 g (239 mol), sodium sulfite 370
g, diethylenetriamine pentaacetic acid 5 sodium 3300 g,
After crushing 14000 g of sodium p-toluenesulfonate and 3400 g of lithium hydroxide monohydrate in the same manner as in the operation (N), 60000 g of mannitol and polyethylene glycol # 4
000 5000g was added and mixed. Then, in the same manner as in the operation (N), 3500 ml of water was added and granulation was performed.
Drying was performed at ° C. The obtained granulated product was sieved in the same manner as in the operation (M) to remove large and small particles to prepare a granulated product (O).

Operation (P) The granules (M) to (O) prepared in the operations (M) to (O) are heated at 25 ° C. and 50 ° C.
% RH was mixed in a room temperature-controlled and humidity-controlled for 10 minutes using a commercially available cross rotary type mixer, and this mixture was treated in the same manner as the solid processing agent (2-1). )made.

Regarding the solid processing agents (2-18) to (2-24), the solid processing agent (2-
The Z value was adjusted as shown in Table 2 in the same manner as in 2) to (2-8).

The same experiment as in Example 1 was conducted using the above solid processing agent. The results are shown in Table 2.

[0084]

[Table 2]

As is clear from Table 2, the solid processing agent Z
It was confirmed that by controlling the value within the range of the present invention, it is possible to suppress the oxidation of the developing agent when the solid processing agent is stored at high temperature.

Furthermore, in the present invention, by using at least one of the alkaline agent and the main agent as granules, the above-described effects of the present invention can be enhanced, and by using both the alkaline agent and the main agent as granules. Therefore, the effects of the present invention can be further exerted. Further, when the above experiment was carried out by changing the above-mentioned potassium carbonate to tripotassium phosphate and potassium metaborate, the same effect of the present invention was confirmed.

Example 3 Solid Processing Agent (3-1) The granulated products (E) to (G) prepared by the operations (E) to (G) of the solid processing agent (1-17) of Example 1 were used. The mixture was mixed for 10 minutes using a commercially available cross rotary type mixer in a room controlled at 50 ° C and 50% RH, and this mixture was treated in the same manner as the solid treatment agent (1-1). )made.

Regarding the solid processing agents (3-2) to (3-26), the amount of potassium carbonate in step G replaced with potassium carbonate 1.5 hydrate, the granulation time, the amount of water added, and the control of the drying time were controlled. By adjusting the specific volume and the water content of each solid treating agent as shown in Table 3, Z was prepared in the same manner as in Example 1.
The values were adjusted and prepared as shown in Table 3. The water content referred to here indicates the water content of the granulated product mixture, and the water content and the specific volume were measured by the methods described above.

Using the above solid processing agent, a storage experiment similar to that of Example 1 was conducted. In addition to the evaluation of the colorability of each solid processing agent similar to that of Example 1, the solid processing agent after storage at 50 ° C. was subjected to IDEX.
Vibration test was performed using the vibration tester BF-UA manufactured by the same company, and the powder generation rate (%) was calculated from (before vibration test-weight of solid processing agent after vibration test) / weight of solid processing agent before vibration test x 100. The results are shown in Table 3.

[0090]

[Table 3]

As is clear from Table 3, the solid processing agent Z
By controlling the value within the range of the present invention and further controlling the specific volume and the water content of the solid processing agent within the ranges of the present invention, the oxidation of the developing agent during high temperature storage of the solid processing agent is further suppressed. It was confirmed that it was possible to further suppress the powder generation degree of the solid processing agent after storage with time.

Example 4 Solid Treatment Agent (4-1) The solid treatment agent (2-17) of Example 2 was used to prepare granules (M) to (O) prepared in steps (M) to (O) of 25. The mixture was mixed for 10 minutes using a commercially available cross rotary type mixer in a room where the temperature and humidity were adjusted to 50 ° C and 50%, and this mixture was treated in the same manner as the solid treatment agent (2-1). -1) was created.

Further, solid treating agents (4-2) to (4-26) were prepared in the same manner as in (3-2) to (3-26) of Example 3, and the same experiment as in Example 3 was conducted. The results obtained are shown in Table 4.

[0094]

[Table 4]

As is clear from Table 4, Z of the solid processing agent
By controlling the value within the range of the present invention and further controlling the specific volume and the water content of the solid processing agent within the ranges of the present invention, the oxidation of the developing agent during high temperature storage of the solid processing agent is further suppressed. It was confirmed that it was possible to further suppress the powder generation degree of the solid processing agent after storage with time.

Example 5 Solid Treatment Agent (5-1) The granulated products (E) to (G) prepared in steps (E) to (G) of the solid treatment agent (1-17) of Example 1 were used. The mixture was mixed for 10 minutes using a commercially available cross rotary type mixer in a room where the temperature and humidity were adjusted to ℃ and 50% RH, and this mixture was treated in the same manner as the solid treatment agent (1-1). 5-1) was created.

The polyethylene glycol # 6000 (manufactured by NOF CORPORATION) of 5000 g in the operation (G) was replaced as shown in Table 5.

For the solid processing agents (5-1) to (5-8), the Z value, the specific volume and the water content were controlled as shown in Table 5 in the same manner as in Example 3, The same experiment was performed.

The results are shown in Table 5.

[0100]

[Table 5]

As is clear from Table 5, by adding the above-mentioned compound to the solid processing agent of the present invention, oxidation of the developing agent during high temperature storage of the solid processing agent, and the solid processing after storage with time. It was confirmed that the powder generation rate of the agent was further suppressed.

Example 6 Solid Treatment Agent (6-1) The solid treatment agent (2-17) of Example 2 was used to prepare granules (M) to (O) prepared in steps (M) to (O) of 25. The mixture was mixed for 10 minutes using a commercially available cross rotary type mixer in a room where the temperature and humidity were controlled to 50 ° C and 50%, and this mixture was treated in the same manner as the solid treatment agent (2-1). -1) was created.

A sample was prepared by further adding the compounds shown in Table 6 in the operation (O).

For the solid processing agents (6-1) to (6-8), the Z value, the specific volume and the water content were controlled as shown in Table 6 in the same manner as in Example 4. The same experiment as in 4 was performed.

The results are shown in Table 6.

[0106]

[Table 6]

As is clear from Table 6, by adding the above compound to the solid processing agent of the present invention, oxidation of the developing agent during high temperature storage of the solid processing agent and the solid processing agent after storage over time. It was confirmed that the degree of powder generation of the above was further suppressed.

[0108]

EFFECT OF THE INVENTION A tablet-type solid processing agent for developing a silver halide photographic light-sensitive material having a long-term stable storage performance and improved generation of fine powder after storage was obtained.

Claims (4)

[Claims] 1. A solid processing agent for developing a silver halide photographic light-sensitive material, which comprises at least one alkali agent selected from carbonates, phosphates and borates and a developer, wherein the alkali agent and the developer are used. Are contained as separate component particles, and the tablet-type developing agent produced by compressing and compressing the mixture of the component particles has a Z value of 0.3 or more and 4.0 or less given by the following formula. A solid processing agent for developing a silver halide photographic light-sensitive material, comprising: Z value = compressive breaking strength of tablet (kg) / length of tablet in longitudinal direction
(mm) 2. The solid processing agent for developing a silver halide photographic light-sensitive material according to claim 1, wherein the component particles containing the alkali agent or the developing agent are granulated products. 3. The solid processing agent for developing a silver halide photographic light-sensitive material according to claim 1, wherein the component particles containing the alkali agent or the developing agent are different granules. 4. The specific volume of the solid processing agent for development is 0.3 to
4. The solid processing agent for developing a silver halide photographic light-sensitive material according to claim 1, 2 or 3, wherein the solid content is 0.95 cm ³ / g and the water content is 0.1 to 15% by weight.