JPH1039458A - Methods for manufacturing and conveying solid processing agents for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To eliminate adhesiveness from the surfaces of granules and to enable stable operation of a system by mixing the granules obtained by granulating ferric aminopolycarboxylate with the ones obtained by granulating a thiosulfate each by using an aqueous solution of a polyethylene glycol binder. SOLUTION: The granules obtained by granulating a powder containing the ferric aminopolycarboxylate by using the aqueous solution of the polyethylene glycol and the sprayers of the 2-fluid system are mixed with the granules obtained by granulating a powder containing the thiosulfate by using the same solution and the same system in order to prevent the granules of the ferric aminopolycarbonate from absorption of water and moisture from the thiosulfate and to prevent the granules of the thiosulfate from absorption of water and moisture.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a granular solid processing agent and a tablet solid processing agent for a silver halide photographic light-sensitive material and a method for transporting the same.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material is
Processing is performed by steps such as development, desilvering, washing, and stabilization.
Processing is usually performed in an automatic processor. In this case, a replenisher replenishment method is generally widely used to maintain the activity of the processing solution in the processing layer constant. A large amount of waste liquid is generated to dilute the substance, correct the amount of evaporation, and replenish the consumed components.

On the other hand, in recent years, there has been a worldwide movement to regulate the marine waste of photographic waste liquid and the disposal of plastic materials, and the development of a system that eliminates photographic waste liquid and avoids the use of plastic bottles for liquid processing agents. Is required.

Further, safety regulations on packaging materials for ensuring safety in transporting liquid hazardous materials have been strengthened, which has raised transportation costs. In recent years, minilab stores have been rapidly increasing. Because a system that allows anyone to easily obtain prints has been introduced,
In many cases, workers are part-time workers or part-time workers.However, dissolution of replenishers and management of processing liquids are as difficult as before, and extremely serious mistakes such as incorrectly dissolving and replenishing processing agents are likely to occur. As a result, complaints about the conventional replenishment method have increased.

Accordingly, in the photographic processing industry, there has been a strong demand for the development of a solid processing agent which does not require a bottle for the processing agent and can eliminate the dissolving operation by humans. To meet this demand, Japanese Patent Application Laid-Open No. 5-119454 discloses a method in which almost all photographic processing components are solidified and directly charged into a processing layer.

[0006]

However, it has been found that this system has the following problems. When tablets are ejected from the cartridge and pass through the chute and fall into the treatment layer, the problem that the tablets adhere to the chute and do not fall occurs.If the feeding interval is shifted or in the worst case the next tablet falls, it will not fall at the same time. As a result, the tablets accumulated in the shooter portion and destroyed the charging module, and the photographic processing solution was diluted too much, causing problems in photographic performance.

When the cause is analyzed, the chute portion is wetted and fine powder due to the abrasion of the tablet adheres thereto and serves as an adhesive. Further, it was found that the tablet absorbed moisture and the wettability of the surface was increased, so that the tablet adhered to the shooter portion. In particular, it was found that when the ferric salt of aminopolycarboxylic acid and the thiosulfate were present in one tablet, the wettability of the surface of the tablet was increased and the adhesion was increased. Further, it was found that the adhesion of the fine powder was increased due to the abrasion. The highly hygroscopic thiosulfate absorbs moisture first, and this water moves to the ferric salt of aminopolycarboxylic acid, and the hygroscopic aminopolycarboxylic acid has extremely high adhesion and adheres to the shooter in the shooter portion. Can be estimated. Further, it can be estimated that the adhesiveness of the fine powder increases.

It has also been found that the same problem as described above occurs in the granule cutting system disclosed in JP-A-6-208215 as a technique developed for the same purpose. In particular, in the case of this method, it was found that not only the granules were blocked and a fixed amount could not be cut out, but also that in the worst case, the cutting machine was broken. The cause can be similarly estimated.

It has been found that such a solid processing agent also affects the physical properties of the solid processing agent during use depending on transportation conditions.

[0010] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a solid in which a ferric salt of aminopolycarboxylic acid and a thiosulfate are present in the same tablet and the same granule. A method for producing a solid processing agent capable of providing a solid processing agent capable of stably operating the above-mentioned system (a method of solidifying a photographic processing agent component and directly putting it into a processing layer) while preventing surface adhesion due to the hygroscopicity of the processing agent. Is to provide.

It is still another object of the present invention to provide transportation conditions when the solid processing agent is transported so that the above problem does not occur.

[0012]

The above objects of the present invention have been attained by the following constitutions.

(1) Granules obtained by granulating at least ferric salt of aminopolycarboxylic acid with an aqueous solution of polyethylene glycol using a two-fluid spray device using a fluidized bed granulator, and a fluidized bed granulator. A method for producing a solid processing agent for silver halide photographic light-sensitive materials produced by mixing at least thiosulfate with granules granulated with an aqueous solution of polyethylene glycol using a two-fluid spray device.

(2) The preparation of a solid processing agent for a silver halide photographic light-sensitive material according to (1), wherein the thiosulfate-containing granules are produced by spraying polyethylene glycol and a polysaccharide as a binder. Method.

(3) The content of the polyethylene glycol is 1.0% by weight or more and 6.0% by weight of the solid processing agent.
(1) The method for producing a solid processing agent for a silver halide photographic light-sensitive material according to (1) or (2), wherein

(4) The powder temperature during the fluidized-bed granulation is 30 ° C.
The method for producing a solid processing agent for a silver halide photographic light-sensitive material according to any one of (1) to (3), wherein the temperature is 65 ° C. or lower.

(5) The solid processing agent is prepared using a rotary tableting machine to produce a tablet-like solid processing agent at a tableting pressure of 850 to 1700 kg / cm ² . The method for producing a solid processing agent for a silver halide photographic material according to claim 1.

(6) 100 L of the tablet-like solid processing agent
A method of transporting a solid processing agent for a silver halide photographic light-sensitive material, wherein a cushion material is spread on the bottom when transported in the above-mentioned closed container.

(7) The method for transporting a solid processing agent for a silver halide photographic light-sensitive material according to (6), wherein the oxygen permeability and the moisture permeability of the closed container satisfy the following conditions.

Water permeability: 1 g / m ² · 24 hours or less That is, the object of the present invention is to use a two-fluid spraying device using at least a ferric salt of aminopolycarboxylic acid using a fluidized bed granulator. Achieved by mixing granules granulated with an aqueous solution of polyethylene glycol combined with granules granulated with an aqueous solution of polyethylene glycol combined using a fluidized bed granulator and at least thiosulfate using a two-fluid spray device. You.

That is, a ferric salt containing aminopolycarboxylic acid is granulated with a fluidized bed granulator using a two-fluid spraying device to form a polyethylene glycol-bound aqueous solution, and the granules transfer water from thiosulfate. It is possible to use a fluidized bed granulator to granulate the lead thiosulfate-containing powder with a polyethylene glycol-bonded aqueous solution using a two-fluid system to prevent the water from being absorbed easily. The present invention was able to solve the problem in total by reducing the adhesiveness of the generated fine powder when absorbing moisture and improving the wettability of the surface of the solid processing agent. In addition, it was surprising that the generation of fine powder could be prevented.

It is preferable from the viewpoint of the effect of the present invention that the thiosulfate-containing granules are produced by spraying polyethylene glycol and a polysaccharide as a binder. Particularly, the effect of preventing generation of fine powder is great.

It is preferable that the content of the polyethylene glycol is 1.0% by weight or more and 6.0% by weight or less of the solid processing agent from the viewpoint of the effect of the present invention. In addition, the solubility is improved.

The powder temperature during the fluidized-bed granulation is preferably 30 ° C. or more and 65 ° C. or less from the viewpoint of the effect of the present invention. Particularly, coarse particles are not formed and the yield of granulation is good.

It is preferable from the viewpoint of the effects of the present invention that the solid processing agent is prepared by using a rotary tableting machine to produce a tablet-like solid processing agent at a tableting pressure of 850 to 1700 kg / cm ² . Particularly, the stability of tablet properties (hardness, friability) during continuous tableting is good.

When the tablet-like solid processing agent is transported in a closed container of 100 L or more, the effect of the present invention is exerted by laying a cushion material on the bottom and transporting the cushioning agent. There is no problem when transporting a small amount of tablets in a small amount of containers, but when transporting in a closed container of 100 L or more, the combination with the tablets of the present invention exhibits the effect of the present invention well.

When the oxygen permeability and the moisture permeability of the closed container satisfy the following conditions, the effect of the present invention is exhibited well.

Moisture permeability: 1 g / m ² · 24 hours or less Hereinafter, the present invention will be described in detail.

The method for producing the granular solid processing agent of the present invention comprises:
It is based on a fluidized bed granulation method. That is, the powder is kept in a fluid state by wind pressure, and a solution containing a binder or the like is sprayed here to aggregate by the binding force between the powder and granules, and the raw materials are mixed, granulated, There is a feature that drying can be performed in the same closed container. The obtained granules are very porous and excellent in solubility, and are optimal as granules for tablet molding.

The term "granules" as used in the present invention refers to simple substances selected from powders, crystals or granules, and mixtures thereof.
In addition, the granules are formed by granulating powder or fine crystals, and refer to granules having a particle size of 53 to 2830 μm. The weight average particle size of the granular solid processing agent obtained in the present invention is preferably 100 to 600 μm from the effects of the present invention. Here, as for the average particle diameter D of heavy particles, when a plurality of JIS standard sieves are used, the median value of each opening is d, and the weight frequency of the particles is D = (Σ
nd) / Σn.

The weight average particle size of the powder before granulation is 20
Approximately 350 μm, preferably 50-150 μm. That is, when the thickness is less than 20 μm, the raw material of the photographic processing agent easily absorbs moisture, so that it does not flow evenly due to blocking or clogging of the filter of the apparatus is liable to occur.
If it exceeds 350 μm, the effect of the present invention is deteriorated. If the raw material contains coarse particles, it is preferable to grind or size in advance, hammer mill, pin mill, roll mill,
FIG. 1 is a schematic view showing an example of a fluidized bed granulator, and the process of the production method of the present invention will be described with reference to FIG.

The air sucked by the blower fan F is cleaned through an air supply filter made of chemical fiber or the like, and then heated to a predetermined temperature by the heat exchanger D, and is then sent to the fluidized bed main body 1 through the rectifying plate 4. Will be sent. This hot air keeps the granules in a suspended state, and the compressed air B and the liquid feeder C
In addition, the fluidized layer is brought into uniform contact with the liquid to be atomized by the spray device 3 and also acts as a heat source for evaporating and drying the spray-humidified fluidized bed. The fine powder scattered to the upper part is repaired by the dust collecting filter 2 and blown off into the fluidized bed.
The air filtered here is exhausted out of the system by the exhaust fan A. The air to be taken in may be nitrogen or an inert gas, but is preferably air from the viewpoint of cost, and it is preferable to provide a dehumidifying means so as not to be affected by the season or the weather. Further, it is preferable that the dust collecting filter is separated into two so as not to stop the flow during granulation.

The fluidized bed granulator can be easily obtained as a commercially available product. Specifically, Powrex Co., Ltd., Multiplex Series, GPCG Series, WST / WSG Series, Fuji Paudal Co., Ltd., Nummar Melizer Series, manufactured by Ogawara Corporation, Mixgrade series, manufactured by Freund Corporation, spiral throw series, flow coater series, and the like.

In the two-particle method of the present invention, in which the binding water is sprayed on the powder, the two-particle nozzle is used. The two-grain nozzle is a device that disperses a liquid and obtains fine droplets by utilizing the fact that a high-speed airflow is obtained at a relatively low pressure with a compressible gas such as air, nitrogen gas, or water vapor. Necessary to achieve effect. Fine droplets are preferred because drying time is short and granules suitable for compression molding are easily obtained. In this case, the ratio of the volume of atomized air discharged from the nozzle per unit time to the volume of combined water, that is, (the volume of atomized air per unit time) / (the amount of combined water per unit time) is defined as the gas-liquid ratio. , Gas-liquid ratio is 100 or more, 1000
0 or less, preferably 1000 to 500
0 or less is more preferable than the effect of the present invention.

In the present invention, the polyethylene glycol-bound aqueous solution refers to an aqueous solution containing polyethylene glycol.

The weight average molecular weight of polyethylene glycol is preferably from 1800 to 8000 from the viewpoint of the effect of the present invention. From the viewpoint of the effects of the present invention, it is preferable to use other binders, for example, sugar alcohols, monosaccharides, and polysaccharides in combination in the aqueous polyethylene glycol binding solution. Further, an oxidizing agent, a reducing agent, an alkali agent, a buffer agent and the like can be added.

Polysaccharides are defined in the Encyclopedia of Chemistry 5 (Kyoritsu Shuppan)
The one described in the 14th printing of the reduced edition is used.

The sugar alcohol is disclosed in Japanese Patent Application Laid-Open No. 7-295262.
And the like. D-Sorbit is preferred from the viewpoint of the effects of the present invention.

Examples of the monosaccharide include those described in JP-A-102627 and the like. Among these, D-mannitol is preferable.

Most preferred among these are starch hydrolysates.

The concentration of the additive in the bound water is preferably 1 to 60% by weight, more preferably 5 to 40% by weight, for reasons of uniformity of mist and granules, nozzle clogging, and the like. In addition, the total amount of the combined water spray is 1 to 50 with respect to the charged amount of the powdery granules in order to obtain desired granules.
%, Preferably 5 to 25% by weight from the viewpoint of the effect of the present invention.

Next, a group of compounds contained in the solid processing agent of the present invention will be described.

Preferred thiosulfates are ammonium thiosulfate, sodium thiosulfate and potassium thiosulfate.

Preferred sulfites are ammonium sulfite, sodium sulfite and potassium sulfite.

Preferred as the bisulfite are ammonium bisulfite, sodium bisulfite, potassium bisulfite, ammonium metabisulfite, sodium metabisulfite and potassium metabisulfite.

Preferred as carbonates are potassium carbonate and sodium carbonate.

Preferred as aminopolycarboxylic acids are ferric salts of chelating agents represented by the general formulas [AI] to [A-VII].

[0048]

Embedded image

Wherein A _{1 to} A ₄ are each a hydrogen atom, a hydroxy group, —COOM, —PO ₃ (M ₁ ) ₂ , and —CH ₂ C
OOM ₂ , —CH ₂ OH or a lower alkyl group. However, at least one of A _{1 to} A ₄ is -COOM, -PO ₃
(M ₁ ) ₂ and —CH ₂ COOM ₂ . M, M ₁ and M ₂ each represent a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. ]

[0050]

Embedded image

Wherein A _{11 to} A ₁₄ are each —CH ₂ O
H, —COOM ₃ or —PO ₃ (M ₄ ) ₂ , M ₃ , M ₄
Represents a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group, respectively. X is an alkylene group having 2 to 6 carbon atoms _{- (B 1 O) n-} B 2 - represents, n represents 1-8
And B ₁ and B ₂ each represent an alkylene group having 1 to 5 carbon atoms. ]

[0052]

Embedded image

Wherein A _{21 to} A ₂₄ are each —CH ₂ O
H, —COOM ₅ or —PO ₃ (M ₆ ) ₂ , M ₅ , M ₆
Represents a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group, respectively. X ₁ is a linear or branched alkylene group having 2 to 6 carbon atoms, an organic group of a saturated or unsaturated to form a ring, or _{- (B 11 O) n 5} -B 12 - represents, n ₅
Represents an integer of 1 to 8, and B ₁₁ and B ₁₂ each represent an alkylene group having 1 to 5 carbon atoms. n _{1 to} n ₄ each represent an integer of 1 or more. ]

[0054]

Embedded image

[Wherein R ₁ and R ₂ are each a hydrogen atom,
Represents an alkyl group or an aryl group, wherein the alkyl group and the aryl group may be substituted; L is

[0056]

Embedded image

Wherein Y _{1 to} Y ₃ each represent an alkylene group or an arylene group, X ₂ and X ₃ each represent an oxygen atom or a sulfur atom, and R _{3 to} R ₇ each represent a hydrogen atom or an alkyl Represents a group or an aryl group. ]

[0058]

Embedded image

Wherein R _{8 to} R ₁₀ are each a hydrogen atom,
Represents an alkyl group or an aryl group, and the alkyl group and the aryl group may have a substituent. L is a general formula [AI
V]. W represents a divalent linking group. ]

[0060]

Embedded image

[Wherein R _{11 to} R ₁₃ and R _{16 to} R ₁₉ each represent a hydrogen atom, an alkyl group or an aryl group, and the alkyl group and the aryl group may have a substituent. R ₁₄
And R ₁₅ each represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an acyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, a sulfonyl group, a sulfinyl group, an alkyl group or an aryl group, and the alkyl group and the aryl group May have a substituent, and R ₁₄ and R ₁₅ may form a 5- or 6-membered ring. A represents a carboxy group, a phosphono group, a sulfo group, a hydroxy group, or an alkyl metal salt or an ammonium salt thereof.
Y represents an alkylene group or an arylene group, and may have a substituent. t and u each represent 0 or 1. ]

[0062]

Embedded image

Wherein A _{31 to} A ₃₅ are each —COOM
₇ , —PO ₃ M ₈ M ₉ , M _{7 to} M ₉ each represent a hydrogen atom, an alkali metal or ammonium ion, and n ₆
Represents 1 or 2. Specific examples of these aminopolycarboxylic acids include exemplified compounds AI-1 to 15, A-II-1 to 17, and A-III described in JP-A-6-35151, pages 12 to 42.
-1 to 41, A-IV-1 to 30, A-V-1 to 35, A
-VI-1 to VI-16, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, diethylenetriaminepentamethylenephosphonic acid, and the like. Particularly preferred compounds are as follows.

[0064]

Embedded image

As the paraphenylenediamine compound, a compound having a water-soluble group is preferable. Examples of the paraphenylenediamine-based compound having a water-soluble group include compounds having at least one water-soluble group in the amino group of the paraphenylenediamine-based compound or on the benzene nucleus. A specific water-soluble group is-(CH ₂ ) _n CH ₂ O
_{H, - (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 C m H
_2m + 1, -COOH group, -SO ₃ H groups (m and n each,
Represents an integer of 0 or more. ) Are preferred.

Next, the tablet manufacturing method of the present invention will be described.

The tablet-like solid processing agent of the present invention (hereinafter referred to as “the solid processing agent”)
The term “tablet” also refers to a product obtained by compression-molding a solid processing agent in which at least a part of the raw material is a granule into a certain shape, but is formed from granules alone in order to further exert the effects of the present invention. Preferably, there is. Furthermore, it is preferable to be formed by one kind of granules. In order to improve the storage stability of the tablet-like solid processing agent, it may be formed by two or more types. When two or more kinds of granules are mixed and compression-molded or a lubricant is mixed, it is preferable to mix them for about 5 to 10 minutes using a usual mixer or the like. The lubricant to be mixed is preferably a water-soluble surfactant since the tablet is a photographic processing agent.

The tablet-like solid processing agent can be produced by using a compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine, a briquetting machine, etc. This is advantageous in terms of productivity.

In a rotary tableting machine, an upper punch and a lower punch are arranged in a cylindrical shape by a turntable. When the granules are filled by a hopper, the granules are pressed and compressed by the upper punch and the lower punch, and continuously. Tablets can be made. The step of compressing the granules into tablets is a first step in which the upper and lower punches are compressed while approaching each other along the pressure roller, and a step in which the upper and lower punches move horizontally along the uppermost end and the lowermost end of the pressure roller. It consists of two steps and a third step of completing and releasing the compression. The time required for the first process is called the dynamic compression time, and the time used for the second process is called the compression stagnation time. Together, they are called the total compression time. Here, if the rotation speed of the turntable is increased, the compression stagnation time is shortened, and the pressure distortion inside the tablet is not sufficiently relaxed, and the tablet may expand over time.
According to the physical properties of the granules and the performance to be imparted to the tablet, the tableting main pressure, the compression stagnation time, and the filling amount are set.In the present invention, it is carried out in the following range from the problem of capping and lamination. Is preferred.

Preferred range Particularly preferred range Tableting main pressure 140 to 4300 kg / cm ² 850 to 1700 kg / cm ² Tablet compression time 0.02 to 1.00 seconds 0.05 to 0.80 seconds Although it is optional, it is preferably cylindrical in terms of production in terms of handling, and its diameter is optional depending on the purpose of use of the tablet, but is preferably in the range of 10 to 35 mm from the effects of the present invention.

The closed container of the present invention only needs to have a detachable lid structure capable of shutting off the outside air. Preferably, the packing is better than maintaining the seal when receiving an accident during transportation. If the water permeation is 1 g / m ² · 24 hours or less with the lid closed, it is said to be sealed. As the material of the container, for example, among the materials described in "New Development of Functional Packaging Materials, Published by Toray Research Center Co., Ltd. (1990)", it is preferable to use a material of 1 g / m < ² >. Density polyethylene type and polypropylene type are preferred.

Any material can be used for the packing as long as it has elasticity. Rubber is preferred from the effects of the present invention. Rubber-based means natural rubber and synthetic rubber. The surface may be coated with silicon, Teflon or the like in order to improve chemical resistance.

The cushioning material of the present invention may be any generally available transportation material. It may be made of paper or plastic. An air cap is more preferable than the effect of the invention.

[0074]

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

Example 1 Preparation of processing agent for bleach-fix for color paper Preparation of Part A Granules-(1) 487.5 g of PEG # 4000 (manufactured by NOF Corporation) is added and dissolved in water so as to have a binding solution concentration of 40 wt%. A total of 1219 g of the combined aqueous solution and 5250 g of sodium diethylenetriamineferric acid were added to GPCG-5 manufactured by Powrex Corporation.
Into a fluidized bed granulator, and using a commercially available two-fluid spray device, a combined aqueous solution speed of 80 g / min and an air pressure of 1.5
It was granulated at kg / cm ² . Other conditions of the fluidized bed granulation are as follows: supply air temperature 65 ° C., supply air flow 8 m ³ / hour,
The powder temperature is 50 ° C. After completion of the spraying, the mixture was dried for 15 minutes to prepare granules A-1.

-(2) Granules A-2 were prepared in the same manner as in-(1). However, binder P
EG $ 4000 was replaced with Pine Flow (Matsuya Chemical).

[0077]. Preparation of Part B Granules-(1) Ammonium thiosulfate / sodium thiosulfate mixture (weight ratio = 90:10) 3995 g Sodium metabisulfite 296 g Sodium sulfite 540 g
Pulverization was performed until the particle size weight of μm or less exceeded 80%. The obtained granules are subjected to fluidized bed granulator: GPC manufactured by Powrex Co., Ltd.
G-5 type, using a two-fluid spray device, combined aqueous solution speed 50 g / min and air pressure 1.5 kg / cm ²
And granulated. Other conditions of the fluidized bed granulation are as follows: supply air temperature 65 ° C., supply air flow 8 m ³ / hour, powder temperature 50
° C. After completion of the spraying, the mixture was dried for 15 minutes to prepare granules B-1.

The binding aqueous solution was prepared as follows.

PEG $ 4000 (manufactured by NOF Corporation) 70.5
g was adjusted with water so as to have a concentration of 20 wt%, and pine flow was adjusted to 23.5 g with water so as to have a concentration of 20 wt%. Finally, the two liquids were mixed to prepare a total amount of 470 g.

-(2) Granules B-2 were prepared in the same manner as in-(1). However, the binding aqueous solution was not a mixed solution, but only a PEG♯4000 aqueous solution.

-(3) Granules B-3 were prepared in the same manner as in-(1). However, as the binding aqueous solution, only the pine flow aqueous solution was used without using the mixed solution.

Using these granules, JP-A-6-2082
The granulating apparatus of FIG. 1 described in No. 15 was installed and modified on a color paper automatic developing machine CL-PP8112B manufactured by Konica Corporation, and a running experiment was performed. The running was performed in a room at a room temperature of 25 ° C. and a relative humidity of 65% RH. The humidity was adjusted for about 12 hours a day, and the remaining 12 hours were in a standby state. After the three-day running test was performed, the test was performed in a pattern of setting a standby state for 24 hours a day. 8.4 m ² of paper was developed per day.

The following items were evaluated and the results are summarized in Table 1.

The degree of adhesion of the fine powder on the lower part of the cutting device and the operating state of the cutting device immediately before the start of the processing after the completion of the two rounds were evaluated as follows.

◎ No attachment at all, good operation of the cutout device ○ Small amount of adhesion Good operation of the cutout device △ Somewhat adhesion Not at a level where the movement of the cutout portion or the roughening is a problem × Attachment The problem is that the movement of the cutout portion is slow ×× Attachment The cutout did not work.

In order to determine whether or not the cut-out amount has been accurately performed, a control strip manufactured by Konica Corporation was processed at the end of two rounds of running, and the amount of residual silver was measured by atomic absorption.

[0087]

[Table 1]

As can be seen from the results shown in Table 1, the present invention has a small amount of fine powder adhered to the lower part of the cutting device, indicating that the cutting device is operating normally. With respect to the cutting accuracy, only the present invention is normal, and in the case other than the present invention, the cutting amount is small and the granules are blocked.

Example 2 Using the granules prepared in Example 1, granules A, B and pulverized Soypon SLP (manufactured by Kawaken Fine Chemical Co., Ltd.) were marketed at a ratio of 42.2: 57.80: 0.5. About 10 minutes using a cross rotary mixer.

Using a tableting machine modified from Clean Press Collect 18K manufactured by Kikusui Seisakusho Co., Ltd.
The filling amount per tablet was set to 10.70 g, and a tableting main pressure was about 1000 kg / cm using a 30 mm-diameter angular cylindrical punch.
^{2. A} tablet was prepared by compression molding with a compression stagnation time of 0.05 seconds.

The tablets thus prepared were subjected to a running experiment using a color paper automatic developing machine CL-PP8112B manufactured by Konica Corporation. The running conditions and method are the same as those in the first embodiment.

The following items were evaluated and the results are summarized in Table 2.

The state of adhesion of the fine powder to the shooter portion immediately before the start of the treatment after the two-round treatment and the presence or absence of adhesion of the tablet shooter portion were evaluated as follows.

◎ No adhesion ○ Small amount of adhesion △ Some adhesion × At least one tablet adhered to shooter XX Adhesion observed, two or more tablets adhered to shooter

The operating state of the module (tablet removal device) immediately after the start of the processing after the completion of the two rounds was evaluated as follows.

Good ○ Good. However, there is a slight amount of fine powder inside. Trace of fine powder inside × Dull. There are times when it moves and times when it doesn't move XX No operation.

At the end of the two rounds of running to determine whether the tablets were loaded as required, a control strip manufactured by Konica Corporation was processed and the amount of residual silver was measured by atomic absorption.

[0098]

[Table 2]

As can be seen from the results in Table 2, in the case of the present invention,
It can be seen that there was no adhesion of the granule fine powder and the tablet in the shooter part, and the module was operating normally.

Example 3 Each of the granules was prepared by changing the concentration of PEG # 4000 in the aqueous solution of the combination of the granules A-1 and B-1 in Example 1 as shown in Table 3 below. Tablets were prepared in the same manner as in Example 2 to prepare tablets as shown in Table 3. These were evaluated in the same manner as in Example 2.

Table 3 shows the results.

[0102]

[Table 3]

From the results shown in Table 3, PEG # 4000 in the tablet
It can be understood that the effect of the present invention is excellently exhibited when the content of is 1.0 wt% or more and 6.0 wt% or less.

Example 4 The granules prepared in Example 3 were evaluated in the same manner as in Example 1 without tableting. The results are summarized in Table 4.

[0105]

[Table 4]

As can be seen from the results in Table 4, PEG # in the tablets
It can be seen that when the content of 4000 is 1.0 wt% or more and 6.0 wt% or less, the effect of the present invention is favorably exhibited.

Example 5 Among the production conditions of the granules A-1 and B-1 prepared in Example 1, the granule temperature during the fluidized-bed granulation was changed as shown in Table 5, and the A-1 ′ granules were respectively obtained. Tablets were prepared in the same manner as in Example 2 except that (5-1 to 5-9) and B-1 'granules (5-1 to 5-9) were prepared, and evaluated in the same manner as in Example 2.

[0108]

[Table 5]

From the results shown in Table 5, it can be seen that the effect of the present invention is favorably exhibited when the powder temperature under the conditions of fluidized bed granulation is 30 to 65 ° C.

Example 6 Experiment No. 2 of Example 2 Tablets were prepared in the same manner except that the pressure at the time of tableting in 2-1 was changed as shown in Table 6, and evaluated in the same manner.

[0111]

[Table 6]

From the results shown in Table 6, the tableting pressure was 850-17.
It can be seen that 00 kg / cm ² exerts the effect of the present invention well.

Example 7 Experiment No. 2 of Example 2 The tablet prepared in 2-1 was placed in the following plastic drum, and subjected to a reciprocating transport test by truck to Hokkaido. Evaluation was performed in the same manner as in 2-1.

[0114]

[Table 7]

From the results shown in Table 7, it can be seen that when transported by a drum of 100 liters or more, moisture permeability of 1 g / m ² · 24 Hr or less and the use of an air cap as a cushion material can provide the effect of the present invention well. . The drum is 80
In the case of liter, there was no significant difference as described above.

[0116]

According to the present invention, the surface adhesion due to the hygroscopicity of a solid treating agent in which a ferric salt of aminopolycarboxylic acid and a thiosulfate are present in the same tablet and the same granule is prevented, A method for producing a solid processing agent capable of providing a solid processing agent capable of stably operating the above-described system (a method of solidifying a photographic processing agent component and directly charging it into a processing layer) could be provided.

In addition, it was possible to provide transport conditions for transporting the solid processing agent so that the above-mentioned problem does not occur.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a fluidized bed granulator.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Fluidized bed main body 2 Dust collection filter 3 Spray device 4 Rectifier plate A Exhaust fan B Compressed air C Liquid feeder D Heat exchanger E Air supply filter F Blast fan

Claims (7)

[Claims] Claims: 1. Use of a fluidized bed granulator to granulate at least a ferric salt of aminopolycarboxylic acid with an aqueous solution of polyethylene glycol combined using a two-fluid spraying apparatus and a fluidized bed granulator. At least two thiosulfates
A method for producing a solid processing agent for a silver halide photographic light-sensitive material, which is produced by mixing granules granulated with an aqueous solution of polyethylene glycol using a spray device of a fluid system. 2. The method according to claim 1, wherein the thiosulfate-containing granules are produced by spraying polyethylene glycol and a polysaccharide as a binder. . 3. The solid processing for a silver halide photographic light-sensitive material according to claim 1, wherein the content of the polyethylene glycol is 1.0% by weight or more and 6.0% by weight or less of the solid processing agent. Method of manufacturing the agent. 4. The powder temperature during fluidized-bed granulation is 30 ° C. or higher.
The method for producing a solid processing agent for a silver halide photographic material according to any one of claims 1 to 3, wherein the temperature is 5 ° C or lower. 5. The solid processing agent according to any one of claims 1 to 4, wherein the solid processing agent is prepared using a rotary tableting machine at a tableting pressure of 850 to 1700 kg / cm ^2. The method for producing a solid processing agent for a silver halide photographic light-sensitive material as described above. 6. A method for transporting a solid processing agent for a silver halide photographic light-sensitive material, wherein the tablet-shaped solid processing agent is transported in a closed container of 100 L or more by laying a cushion material on the bottom. 7. The method for transporting a solid processing agent for a silver halide photographic light-sensitive material according to claim 6, wherein the oxygen permeability and the water permeability of the closed container satisfy the following conditions. Moisture permeability: 1 g / m ² · 24 hours or less