JPH08137058A - Manufacture of solid processing agent for silver halide photographic material - Google Patents

Abstract

PURPOSE: To provide a method for manufacturing a solid processing agent for a silver halide photographic material, by which high granulation yields are achieved, formation of micro and coarse powders and adhesion of powders to the can body of a granulator can be prevented, and, when compression molding is performed using the granulated powders obtained, variation in the amount of packing and capping are avoided so that wear and expansion of the agent when it is in a tablet form can be prevented effectively. CONSTITUTION: In a method for manufacturing a granular solid processing agent for a silver halide photographic material, powders containing at least one kind selected from a group of compounds which consists of thiosulfate, sulfite, bisulfite, a ferric salt of aminopolycarboxylic acid, carbonate, a paraphenylenediamine color developing agent, hydroxylamine and its derivative are held fluidized at an air speed of not less than 0.1m/sec and not more than 5.0m/sec and are spray granulated by use of bound water; the granular solid processing agent obtained by the manufacturing method is compression molded in a compression retention time of not less than 0.02sec and not more than 1.0sec.

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 granular solid processing agents and tablet solid processing agents for silver halide photographic light-sensitive materials.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials are
Processing is performed by steps such as development, desilvering, washing and stabilization.
Processing is usually carried out in an automatic processor, and in that case, a replenisher replenishment system is generally widely used to keep the activity of the processing solution in the processing tank constant. A large amount of waste liquid is generated because the product is diluted, the evaporation amount is corrected, and the consumption component is replenished.

On the other hand, in recent years, the movement to regulate the dumping of photographic waste liquid into the ocean and the regulations on the disposal of plastic materials have been strengthened worldwide, 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, transportation regulations have been increased due to tightened safety regulations for packaging materials for ensuring safety in transportation of liquid dangerous substances, and in minilab stores, which have been rapidly increasing in recent years, advances in exposure control technology for printing. With the introduction of a system that anyone can easily get prints at,
Although there are many places where workers are part-time or part-time workers, it is difficult to dissolve the replenisher and manage the treatment solution as before, and it is easy to make a very serious mistake such as mistakenly dissolving and replenishing the treatment agent. As a result, there have been many complaints about the conventional replenisher replenishment method.

Therefore, in the photographic processing industry, there has been a strong demand for the development of a solid processing agent which does not require a processing agent bottle and which can eliminate manual dissolution work. In order to meet this demand, Japanese Patent Laid-Open No. 5-119454 and the like disclose a method of solidifying almost all the processing agent components and directly charging them into a processing tank.

[0006]

However, in the production of the solid processing agent, there is a problem that productivity, production cost and stable productivity are poor.

[0007] Granules obtained by forced agglomeration granulation with a stirring granulator on a production scale (for example, 80 kg or more in batch) are likely to form coarse particles having a diameter of 5 mm or more. The coarse particles do not easily flow, and when fluidized and dried, the coarse particles become larger together with the surrounding granules. The coarse particles grown in this way have a large internal water content even if the surface is dried, and it takes a long time to dry them, but the granules obtained by performing a long drying operation are very It has been found that the tablet becomes a firm and heavy substance and its solubility deteriorates, and the tablet obtained by compression-molding it becomes too heavy and lacks hardness, resulting in deterioration of friability.

On the other hand, coarse particles can be classified or crushed during the drying process, but the addition of such a step requires a long time for production and significantly reduces the yield. Furthermore, by crushing coarse particles, fine powder unfavorable for tableting is generated and the particle size distribution is likely to vary, which is related to the performance of the solid processing agent such as capping during tableting and variation in filling amount. Problems are likely to occur.

On the other hand, JP-A-3-39739, 3-39735, and
Examples such as 2-109042 disclose a method for producing a granular solid processing agent using a fluidized bed granulator, which is an advantageous production method for controlling the particle size distribution.

However, a composition containing a thiosulfate, a sulfite, a bisulfite, a ferric aminopolycarboxylic acid salt, a carbonate, a paraphenylenediamine color developing agent, or a hydroxylamine or a derivative thereof is in a fluidized bed. When trying to granulate using a granulator, it is difficult to control the flow, and it is easy for powder to adhere to the can body or dust collecting filter of the granulator,
It was found that the obtained solid processing agent was inevitably subjected to blocking in the case of granules and abrasion and expansion in the case of compression-molded tablets, when stored for a long period of time or under high temperature and high humidity.

The present invention has been made under the above circumstances, and its object is to provide a thiosulfate, a sulfite, a bisulfite, a ferric aminopolycarboxylic acid salt, a carbonate, a paraphenylenediamine-based color developing agent. , Or when a composition containing hydroxylamine or a derivative thereof is granulated using a fluidized bed granulator, the yield is good and the generation of fine powder or coarse particles and the powder to the can body of the granulator Can be prevented from adhering to
Production of solid processing agents for silver halide photographic light-sensitive materials that does not cause variations in filling amount or capping when using the obtained granules and can effectively prevent abrasion and expansion when formed into tablets. To provide a method.

[0012]

The above object of the present invention is to provide a compound group {thiosulfate, sulfite, bisulfite, ferric aminopolycarboxylic acid salt, carbonate, para-phenylenediamine color developing agent, Hydroxylamine and derivatives thereof}, a powder containing at least one selected from
A method for producing a granular solid processing agent for silver halide photographic light-sensitive materials, in which a fluid state is maintained at a wind speed of 0.1 m / sec or more and 5.0 m / sec or less, and combined water is used for spray granulation. If the gas-liquid ratio of the two-fluid system is defined as (volume of atomized air supplied per unit time) / (volume of combined water supplied per unit time), the gas-liquid ratio is 10
It is 0 or more and 10000 or less, the compound selected from the compound group is contained in an amount of 5% by weight or more based on the total weight of the granular solid processing agent, and the weight average particle diameter is 20 μm or more and 350 μm.
Granulation using a granule having a particle size of m or less, providing a rectifying plate with an opening ratio of 1.0 to 20% in an apparatus used for granulation, and an air supply amount with respect to a spray rate of combined water of 1 m ³ / g or more, 20m ³ /
g or less, the total amount of the bound water sprayed with respect to the amount of the granular material to be sprayed is 1 wt% or more and 50 wt% or less, and the concentration of the additive in the bound water is 1 wt% or more and 60 wt% The following is achieved, and the granular solid processing agent obtained by these production methods is compression-molded with a compression stagnation time of 0.02 seconds or more and 1.0 seconds or less.

That is, the present inventors contain thiosulfates, sulfites, bisulfites, ferric aminopolycarboxylic acids, carbonates, paraphenylenediamine color developing agents, or hydroxylamine and its derivatives. When the system is supplied with bound water and granulated in a fluidized bed, it is difficult to control the fluid state due to the fact that these compounds are water-soluble and the humidity during granulation is high. Particles are generated, and the adhesion of powder to the can body of the granulator and the clogging of the dust collection filter are not electrostatic, and it is considered that they are due to the affinity of these compounds. As a result of repeated studies, it was found that the above problems can be overcome by setting conditions in a specific wind speed range, and the present invention has been achieved.

The present invention will be described in detail below.

The method for producing the granular solid processing agent of the present invention comprises:
It is based on the fluidized bed granulation method. That is, the granular material is kept in a fluid state by wind pressure, and a solution containing a binder and the like is sprayed here to agglomerate by the binding force of the powder particles to granulate, and mixing of raw materials, granulation, and drying. The feature is that they can be performed in the same container that is closed. The obtained granules are very porous and have excellent solubility, and are suitable as tablet-forming granules.

In the present invention, the term "powder or granule" refers to a simple substance selected from powder, crystals or granules and a mixture thereof. Granules are granules of powder or fine crystals with a particle size of 53-28.
It refers to 30 μm particles.

The weight average particle diameter of the granular solid processing agent obtained in the present invention is preferably 100 to 600 μm in view of its use.
Here, the weight average particle diameter D uses a plurality of JIS standard sieves,
D = (Σn · d) / Σn, where d is the median of the openings and n is the weight frequency of the particles.

The weight-average particle size of the granules before granulation is 20 to
It is about 350 μm, preferably 50 to 150 μm. That is, 20μ
If it is less than m, the raw material of the photographic processing agent tends to absorb moisture, so that it may not flow uniformly due to blocking or may cause clogging of the filter of the apparatus. If it exceeds 350 μm, the effect of the present invention is deteriorated. When coarse particles are contained in the raw material, it is preferable to pulverize or regulate the size in advance, and a crusher such as a hammer mill, a pin mill, a roll mill or a screen mill or a sizing machine can be used.

FIG. 1 is a schematic view of an example of a fluidized bed granulator, and the process of the manufacturing method of the present invention will be described with reference to this.

The air sucked by the blower fan F is cleaned by an air supply filter E made of chemical fiber or the like, and then heated to a predetermined temperature by a heat exchanger D,
It is sent to the fluid tank body 1 through the flow straightening plate 4. The hot air keeps the particles in a suspended state and makes them uniformly contact with the compressed air B, the liquid feeding device C, and the liquid droplets atomized by the spraying device 3, and at the same time, it is a heat source for the evaporation and drying of the fluidized bed spray-moistened. Acts as. The fine powder scattered on the upper part is collected by the dust collecting filter 2 and is discharged into the fluidized bed. The air filtered here is discharged to the outside of the system by the exhaust fan A.

The air to be supplied may be nitrogen or an inert gas, but is preferably air from the viewpoint of cost, and further, a dehumidifying means should be provided so as not to be affected by the season and weather. preferable. Preferably the air volume of the air supply air is 1-20 m ³ / g to spray rate of bound water, more preferably from 5 to 15 m ³ / g.

The wind speed according to the present invention means a value obtained by dividing the air flow rate of air supplied per unit time by the area of the straightening vane, that is, the speed of air passing through the straightening vane. The wind speed of the present invention is 0.
It is 1 to 5.0 m / sec, preferably 1.0 to 3.0 m / sec. If the wind speed is 0.1 m / sec or less, the flow may deteriorate during spraying, and coarse particles may increase or the flow may stop. On the other hand, if the wind speed exceeds 5.0 m / sec, the granulated particles will be destroyed, and fine powder will be deposited on the can wall and the dust collection filter, resulting in extremely poor yield. The powder may affect the tableting property.

When the opening ratio of the straightening vane is 1 to 20%, good fluidity can be obtained, and preferably 5 to 15%. The dust collecting filter is preferably separated into two so that the flow does not have to be stopped during granulation.

The fluidized bed granulator can be easily obtained as a commercial product, specifically, manufactured by Paulec Co .; Multiplex series, GPCG series, WST / WSG series, Fuji Paudal Co., Ltd .; New Malmo Riser series, Inc.
Okawara Seisakusho; Mixgrad series, Freund Sangyo Co., Ltd .; Spiraflow series, Flowcoater series, etc.

To spray the bound water on the flowing granules,
A pressure nozzle, a rotating disk, a two-fluid nozzle or the like can be used. The pressurizing nozzle applies pressure to the bound water and ejects it as a high-speed fluid into the atmosphere to obtain fine droplets by the relative speed with the atmosphere. The rotating disk is one in which a liquid is poured into the center of a disk that is rotating at high speed, and the liquid is atomized into droplets around the disk by centrifugal force. The two-fluid nozzle utilizes the fact that a high-speed air flow can be obtained at a relatively low pressure with a compressible gas such as air, nitrogen gas, or water vapor.
Liquid is dispersed to obtain fine droplets.

In the present invention, a method of spraying bound water with a two-fluid nozzle is preferable because the droplets dry quickly and granules suitable for compression molding are easily obtained. In this case, the ratio of the atomized air capacity discharged from the nozzle per unit time to the combined water capacity, that is, (atomized air capacity per unit time) / (combined water capacity per unit time) is defined as the gas-liquid ratio. Then, the gas-liquid ratio is 100 or more, preferably 10000 or less, particularly
It is preferably 1000 or more and 5000 or less.

In the present invention, the bound water may be a solvent alone, but is preferably a solution containing a binder and the like. As the solvent, water or a mixed solvent of water and alcohols can be adopted, but water is preferred for reasons such as influence on the processing performance of the light-sensitive material, safety and cost. As alcohols, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol,
Butyl alcohol and the like can be mentioned. The binder has a function of binding powders and granules, and for reasons such as solubility and photosensitive material processing performance, sugars, water-soluble polymers, etc., specifically sugar alcohols, monosaccharides, disaccharides, dextrins. Preferred are celluloses, celluloses, polyalkylene glycols, polyvinylpyrrolidones and the like, and particularly preferred are dextrins and polyalkylene glycols.
Further, an oxidizing agent, a reducing agent, an alkaline agent, a buffer agent, etc. may be added to the extent that the effects of the present invention are not impaired. Various additives to be contained in the bound water are easily available as commercial products.

The concentration of the additive in the bound water is preferably 1 to 60% by weight, particularly 5 to 30% by weight for reasons such as mist and granule uniformity and nozzle clogging.
Further, the total amount of the bound water sprayed is preferably 1 to 50% by weight, and particularly 5 to 25% by weight based on the charged amount of the powdery or granular material in order to obtain desired granules.

Next, the compound group contained in the solid processing composition according to 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 bisulfites are ammonium bisulfite, sodium bisulfite, potassium bisulfite, ammonium metabisulfite, sodium metabisulfite and potassium metabisulfite.

Preferred carbonates are potassium carbonate and sodium carbonate.

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

[0035]

Embedded image

[In the formula, A _{1 to} A ₄ are each a hydrogen atom, a hydroxy group, —COOM, —PO ₃ (M ₁ ) ₂ , —CH ₂ COOM ₂ , —CH ₂ O
Represents H 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. ]

[0037]

Embedded image

[In the formula, A _{11 to} A ₁₄ are each —CH ₂ OH,
It represents —COOM ₃ or —PO ₃ (M ₄ ) ₂ and each of M ₃ and M ₄ represents a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. X represents an alkylene group having 2 to 6 carbon atoms or — (B ₁ O) nB ₂ —, n represents an integer of 1 to 8, and B ₁ and B ₂ each represent an alkylene group having 1 to 5 carbon atoms. . ]

[0039]

Embedded image

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

[0041]

[Chemical 4]

[Wherein R ₁ and R ₂ are each a hydrogen atom,
It represents an alkyl group or an aryl group, and the alkyl group and the aryl group may be substituted. L is

[0043]

Embedded image

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 group. Represents a group or an aryl group. ]

[0045]

[Chemical 6]

[In the formula, R _{8 to} R ₁₀ are each a hydrogen atom,
It 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 [A-I
V] is synonymous with L. W represents a divalent linking group. ]

[0047]

[Chemical 7]

[In the formula, 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 represents 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-membered ring or a 6-membered ring. A represents a carboxy group, a phosphono group, a sulfo group, a hydroxy group, or an alkyl metal salt or ammonium salt thereof.
Y represents an alkylene group or an arylene group and may have a substituent. t and u represent 0 or 1, respectively. ]

[0049]

Embedded image

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

[0051]

[Chemical 9]

As a para-phenylenediamine compound
Is preferably a compound having a water-soluble group. Has a water-soluble group
Paraphenylene diamine compounds
At the amino group of phenylenediamine compounds or as a benzene nucleus
Those having at least one water-soluble group above
It Specific water-soluble groups include-(CH₂)_nCH₂OH, − (CH
₂)_mNHSO₂(CH₂)_nCH₃,-(CH₂)_mO (CH₂)_nCH₃,-(CH₂CH₂O)
_nC_mH_{2m + 1}, --COOH group, --SO₃H group (m and n are each 0 or less
Represents the upper integer. ) And the like are preferred.
It

Specific examples of the para-phenylenediamine compound preferably used in the present invention are described in JP-A No. 4-86741, pages 7 to 9 (C-1) to
(C-16), (1) to (26) described in No. 3-246543, pages 6 to 10, and the like. The color developing agent is usually used in the form of hydrochloride, sulfate, p-toluenesulfonate, or the like. The compounds preferably used are shown below.

[0054]

[Chemical 10]

[0055]

[Chemical 11]

[0056]

[Chemical 12]

[0057]

[Chemical 13]

Of these, those particularly preferably used are (C-1), (C-3), (C-17) to (C-2).
0), and more preferred are (C-1) and (C-
3).

In the present invention, the preferred hydroxylamine derivative is represented by the following general formula [B].

[0060]

Embedded image

[In the formula, R ₂₀ and R ₂₁ each represent a hydrogen atom or an alkyl group which may have a substituent. ] The alkyl group represented by R ₂₀ and R ₂₁ is preferably
It represents a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, and particularly preferably 1 to 5 carbon atoms. As the substituent, a carboxy group, a sulfo group, a phosphono group, a sulfinic acid residue, a hydroxy group, a cyano group, an alkoxy group, an amino group which may be alkyl-substituted, an ammonio group which may be alkyl-substituted, and an alkyl-substituted group. Optionally carbamoyl group, optionally substituted alkyl sulfamoyl group, optionally substituted alkylsulfonyl group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonyl group, arylsulfonyl group, nitro group, cyano group Alternatively, it represents a halogen atom. There may be two or more substituents. R ₂₀ and R ₂₁ are hydrogen atom, methyl group, ethyl group, propyl group, carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, methoxyethyl group, A cyanoethyl group or a hydroxyethyl group can be mentioned as a preferable example, and a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a sulfoethyl group,
A sulfopropyl group, a phosphonomethyl group, a methoxyethyl group, a cyanoethyl group or a phosphonoethyl group can be mentioned as a particularly preferable example. R ₂₀ and R ₂₁ may combine to form a ring.

The compound represented by the general formula [B] is used in the form of a usual free amine, hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate or acetate. You can When it has an anionic substituent such as a carboxyl group, a sulfo group or a phosphono group, it may be in the form of an alkali metal salt or an ammonium salt.

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

[0064]

[Chemical 15]

[0065]

Embedded image

[0066]

[Chemical 17]

[0067]

Embedded image

[0068]

[Chemical 19]

[0069]

Embedded image

[0070]

[Chemical 21]

Among these, particularly preferable compounds are:

[0072]

[Chemical formula 22]

Examples include:

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

The tablet-like solid processing agent in the present invention (hereinafter,
Also called a tablet. The term “)” refers to a solid processing agent in which at least a part of the raw material is granules, which is compression-molded into a certain shape, but it is preferably molded from only the granules in order to further exert the effects of the present invention. Further, although it is preferable to mold the granules by one kind, it may be molded by two or more kinds in order to obtain storage stability. When two or more kinds of granules are mixed and compression-molded or a lubricant is mixed, it is preferable to mix them using an ordinary mixer or the like. The lubricant to be mixed is preferably a water-soluble surfactant because 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 machine, a single-shot tableting machine, a rotary tableting machine, a briquetting machine and the like. It is advantageous in terms of productivity.

In the rotary tableting machine, the upper punch and the lower punch are aligned in a cylindrical shape by the turntable, and when the granules are filled by the hopper, the upper punch and the lower punch are pressed and compressed,
Tablets can be made continuously. The step of compressing the granules into tablets is the first process in which the upper and lower punches are compressed while approaching each other along the pressure roller, and the upper and lower punches move horizontally along the lowermost and uppermost ends of the pressure roller, respectively. It consists of a second step and a third step of completing and releasing the compression. The time required for the first process is called the dynamic compression time, the time required for the second process is called the compression stagnation time, and both are called the total compression time. Here, if the rotation speed of the turntable becomes faster, the compression stagnation time becomes shorter, and the pressure strain inside the tablet may not be sufficiently relieved, and the tablet may expand over time. Depending on the physical properties of the granules, the performance to be imparted to the tablets, the tableting main pressure, the tableting preload, the compression stagnation time, the rotation speed of the turntable, and the filling amount are set, but in the present invention, problems such as capping and lamination are set. It is preferable to carry out in the following range.

[0078] Preferred ranges particularly preferable range tabletting the pressure 140~4300kg / cm ² 700~2100kg / cm ² strokes tablet preload ^{1.4~ 280kg / cm 2 14~ 140kg /} cm 2 compression dwell time from 0.02 to 1.0 seconds 0.05 to 0.80 seconds Rotational speed of turntable 1-30 rpm 5-20 rpm Filling amount 1-30 g 5-15 g Also, the shape of the tablet is arbitrary, but from the viewpoint of handling, a cylindrical shape is preferable, and its diameter is a tablet. However, in the present invention, the range of 10 to 35 mm is preferable.

[0079]

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

Example 1 A solid processing agent for fixing a color negative film was prepared according to the following procedure.

(Operation 1) Ammonium thiosulfate / sodium thiosulfate mixture (weight ratio 90/10) 60.0 kg Sodium sulfite 12.5 kg Disodium ethylenediaminetetraacetate 1.4 kg Anhydrous potassium carbonate 1.4 kg The above compounds were weight averaged by a commercially available hammer mill. It was pulverized to have a particle size of 50 μm to 150 μm. The obtained powder was put in a fluidized bed granulator (manufactured by Paulec Co., Ltd .; GPCG-60 type), the air supply temperature was set to 55 ° C, and the air speeds shown in Table 1 were adjusted while adjusting the air supply air volume. It was made to flow. At this time, the area of the current plate was 0.415 m ² , and the aperture ratio was 8%.

(Operation 2) Preheating is performed until the temperature in the layer reaches 45 ° C., and then 20% by weight of pine flow (manufactured by Matsutani Chemical Co., Ltd.)
The aqueous solution was atomized with a two-fluid nozzle. The spraying speed at this time was adjusted to 300 g / min, and the atomizing air was adjusted to have a gas-liquid ratio of 2700. Aqueous solution (bound water) is based on the amount of powder charged.
Sprayed until reaching 10% by weight. After the spraying was finished, the air supply temperature and the air flow rate were kept unchanged, and the mixture was allowed to flow for about 1 hour to be dried.

(Operation 3) Separately, ammonium thiosulfate /
100 kg of sodium thiosulfate mixture (weight ratio 90/10) was sized using a New Speed Mill (Okada Seiko Co., Ltd.) with a screen opening of 0.5 mm. This sized product, granules granulated in (Operation 1) and (Operation 2), and crushed soypon
SLP (Kawaken Fine Chemical Co., Ltd.) was mixed at a ratio of 300: 200: 1 for about 10 minutes using a commercially available cross rotary mixer.

(Operation 4) Using a tableting machine modified from Kikusui Seisakusho Co., Ltd. Clean Press Collect 18K, the filling amount of each mixture was 11 g, and the corner angle of 30 mm was used. Using a flat cylindrical mortar, tableting pressure 1400 kg /
cm ² , turntable speed 10 rpm, compression stagnation time 0.05
The tablets were produced by compression molding in seconds.

At this time, the following evaluations were carried out.

<< Granule Yield >> The weight of the granules obtained at the end of drying was measured, and the yield was calculated by comparing with the charged amount.

<< Frequency of Fine Powder >> 150 from the obtained granules
g was collected, classified with a JIS standard sieve having an opening of 149 μm, and the generation rate of fine powder was calculated from the weight of the particles that passed through.

<< Adhesion to Can Body >> After completion of drying, the state of adhesion to the inside of the can body was visually confirmed. The evaluation criteria are shown below.

⊚: No adhesion at all ◯: A slight amount of adhered matter was observed on the upper part of the can body, but all were dropped when tapped Δ: Adhered matter was observed on the upper and lower parts of the can body, and remained slightly even after being beaten ×: Adhered matter was observed on the upper and lower parts of the can body and was not peeled off at all when hitting ×: A considerable amount of adhered matter was deposited on the entire can body and adhered to the dust collecting filter. Amount >> 150g from the obtained granules and opening 4
After classification with a JIS standard sieve of 000 μm, the amount of coarse particles was calculated from the weight on the sieve.

<< Variation in Filling Amount >> Tablets discharged from the tablet machine were sampled every 50 tablets, and the weight was measured to obtain the variation width with respect to the target value.

The above results are shown in Table 1.

[0092]

[Table 1]

Thus, in the production method of the present invention, the yield of granules, the generation rate of fine powder, the amount of coarse particles, the adhesion to the can body,
Excellent in any variation during filling, especially with a wind speed of 0.5
It can be seen that the effect is remarkable at ~ 3.0 m / sec.

Example 2 The same evaluation was performed on the obtained granules and tablets in the same manner as in Example 1 except that atomizing air was not used and a pressure nozzle that did not use atomizing air was used for spraying. Also, the experiment with all wind speeds showed that the amount of coarse particles and the variation at the time of filling were large.
It was found that the production method of the present invention was very advantageous because it deteriorated by 40% or more.

Example 3 In the operation of Experiment No. 1-5 of Example 1, the atomizing air was adjusted and the gas-liquid ratio was set as shown in Table 2, and the following evaluations were carried out. Table 2 shows the results.

<< Capping Rate >> 500 tablets thus prepared were rotated with a Doria Coater DRC500 (manufactured by Powrex Co., Ltd.) at a peripheral speed of 10 rpm for 15 minutes, and then the number of peeled tablets was counted.

[0097]

[Table 2]

From the results in Table 2, it can be seen that the production method of the present invention exhibits excellent capping performance, and is particularly advantageous when the gas-liquid ratio is 100 to 10,000.

Example 4 The weight ratio of the mixture of ammonium thiosulfate / sodium thiosulfate (90:10 by weight) and ethylenediamine disodium disodium dihydrate was changed, and the solid weight of the granular solid treating agent was shown in Table 3. Example 1 was repeated except that sodium sulfite and anhydrous potassium carbonate were removed so that the values were as described.
Table 3 shows the results of the following evaluations performed in the same manner as in Experiment No. 1-5.

<< Expansion Rate of Tablets >> 20 tablets thus prepared were sealed in an aluminum packaging material laminated with polyethylene on the inside and stored for 1 month at 50 ° C. and 80% RH. Was measured.

<< Rate generation rate by vibration test >> 40 tablets that were made were manufactured by Konica Co., Ltd .; stored in an eco-jet chemical storage cartridge, and the inside was sealed with an aluminum packaging material laminated with polyethylene, then at 50 ° C. , 80% RH
The sample was stored for 2 weeks under the conditions. Using a vibration tester BF-UA (made by IDEX), this sample is 5 to 67Hz / 210se
A vibration test was performed at c for 30 minutes, and the powder generation rate was calculated from the weight loss rate before and after the test.

[0102]

[Table 3]

As a result, a tablet containing 5% by weight or more of the compound of the present invention and compression-molded using the granules obtained by the production method of the present invention has almost no generation of powder due to expansion and vibration after storage. I understand.

Example 5 In Experiment No. 1-5 of Example 1, the number of revolutions of the hammer mill was adjusted and crushed, and the same operation was performed by using the powder and granules shown in Table 4 to collect the granules. Table 4 shows the results of the same evaluation of the rate, the adhesion to the can body, and the expansion coefficient of the tablet.
The weight average particle diameter was calculated by the sieving method.

[0105]

[Table 4]

As a result, the weight average particle size of the granules to be granulated is 20 to 350 μm, so that the yield of granules is good,
It can be seen that the adhesiveness can be remarkably improved, the expansion of the tablet after storage can be prevented, and the effect of the present invention is excellent.

Example 6 The same as Experiment No. 1-5 of Example 1 except that the charged amount was increased by 20% by weight and the aperture ratio was adjusted to the value shown in Table 5 according to the number of holes in the straightening vane. Table 5 shows the results of the same evaluations as above.

[0108]

[Table 5]

From the results shown in Table 5, almost the same results were obtained despite the increase of the charging amount by 20% by weight, and the effect of the present invention was excellent when the opening ratio of the straightening vane was 8 to 20%. Understand.

Example 7 In Experiment No. 1-5 of Example 1, the air supply amount was kept constant and the spraying speed was adjusted so that (supply air amount) / (spraying speed).
The same operation was performed except that the value of was adjusted to the value described in Table 6, and the results of the same evaluation are shown in Table 6.

[0111]

[Table 6]

As a result, (air flow rate) / (spraying speed)
By setting the value of 1.0 to 20 m ³ / g, it is understood that the generation of fine powder and the amount of coarse particles are reduced, and the effect of the present invention is excellent.

Example 8 In Experiment No. 1-5 of Example 1, the same operation was performed except that the amount of bound water relative to the charged amount of powder was adjusted to the value shown in Table 7 to generate fine powder. Rate, adhesion to cans, amount of coarse particles and expansion coefficient of tablets were evaluated in the same manner,
The following evaluation was also performed.

<< Blocking of granules >> 1 kg of prepared granules
Was sealed in a polyethylene bag, further sealed in a Toslon container, and stored for 2 weeks under the conditions of 50 ° C and 80% RH, then classified with a JIS standard sieve having an opening of 4000 μm, and aggregates on the sieve ( The amount of (blocking) was measured.

The results are shown in Table 7.

[0116]

[Table 7]

As is clear from the results shown in Table 7, generation of fine powder, amount of coarse particles, and adhesion to the can body were prevented by setting the amount of bound water to 1.0 to 50% by weight relative to the charged amount of powder. In addition, the tablets can be prevented from swelling after storage and the granules can be prevented from blocking, and the effects of the present invention can be further exerted.

Example 9 In Experiment No. 1-5 of Example 1, the same operation was performed except that the pine flow concentration in the bound water to be sprayed was adjusted to the value shown in Table 8, and the adhesion to the can body was performed. Table 8 shows the results of similar evaluations regarding the amount of coarse particles, the expansion coefficient of tablets, and the blocking of granules.

[0119]

[Table 8]

Thus, by controlling the additive concentration in the binding water to be sprayed to 1.0 to 60% by weight, generation of coarse particles, adhesion to the can body, blocking of granules due to storage and expansion of tablets are effectively prevented. I know what I can do.

Example 10 In Experiment No. 1-5 of Example 1, the same operation was performed except that the rotation speed of the turntable was adjusted during tableting and the compression stagnation time was adjusted to the value shown in Table 9. Table 9 shows the results of the same evaluations for the capping rate, the tablet expansion rate, and the generation of powder by the vibration test.

[0122]

[Table 9]

Thus, by controlling the compression stagnation time during tableting of the granules obtained by the granulation method of the present invention to 0.02 to 1.0, tablet capping, granule blocking by storage and tablet swelling are effectively performed. It turns out that it can be prevented.

Example 11 A color paper bleach-fixing treatment agent was prepared according to the following procedure.

(Operation 5) 5.0 kg of sodium carbonate monohydrate
With a commercially available hammer mill, the weight average particle size is 50 μm or more 1
It was crushed until it became 50 μm or less. This and 75.0 kg of ferric monosodium ethylenediaminetetraacetate trihydrate were put into a fluidized bed granulator; GPCG-60 type manufactured by Paulec Co., Ltd., and the same conditions as in (Operation 1) to (Operation 3). Granulated and dried.

This is designated as Bleach-fixing agent granule A.

(Operation 6) Ammonium thiosulfate / sodium thiosulfate mixture (weight ratio = 90: 10) 57.0 kg Sodium metabisulfite 21.0 kg Sodium carbonate monohydrate 0.7 kg Each of the above compounds was weight averaged with a commercially available hammer mill. It was pulverized until the diameter became 50 μm or more and 150 μm or less.
The obtained powder is fluidized bed granulator; GPCG manufactured by Paulec Co., Ltd.
-60 type, it granulated and dried on the conditions similar to (operation 1)-(operation 3).

This is designated as Bleach-fixing agent granule B.

Table 10 shows the results of the same evaluations regarding the yield of these granules, the generation rate of fine powder, the adherence to the can body, the amount of coarse particles, and the blocking of granules.

[0130]

[Table 10]

From this, it is understood that the solid processing agent for bleach-fixing is also excellent in productivity when the granulating method of the present invention is adopted.

Example 12 (Operation 8) 70: 120: 10 of Granule A, Granule B, powdered polyethylene glycol # 4000, ethylenediaminetetraacetic acid and crushed Soypon SLP (manufactured by Kawaken Fine Chemicals Co., Ltd.) prepared by the above-mentioned operation : 3: 1 ratio using a commercial cross rotary mixer for about 10 minutes.

The obtained mixture was tableted under the same tableting conditions as in (Operation 4) using a tableting machine modified from Kikusui Seisakusho's Green Press Collect 18K.

Table 11 shows the results of evaluation of the obtained tablets in the same manner as in Example 10.

[0135]

[Table 11]

From this, it is understood that the bleach-fixing tablet also has excellent performance when the granule obtained by the granulation method of the present invention is compression-molded.

[0137]

According to the present invention, thiosulfates, sulfites,
Bisulfite, ferric aminopolycarboxylic acid, carbonate,
When a composition containing a paraphenylenediamine color developing agent, or hydroxylamine or a derivative thereof is granulated using a fluidized bed granulator, the yield is good and the generation of fine powder or coarse particles and the granulator The powder can be prevented from adhering to the can body, and when compression molding is performed using the obtained granules, there is no variation in the filling amount or capping, and the wear and expansion of tablets can be effectively prevented. obtain.

[Brief description of drawings]

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

[Explanation of symbols]

 1 Fluid tank 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 Blower fan

Claims (10)

[Claims] 1. At least one selected from the group of compounds {thiosulfate, sulfite, bisulfite, ferric aminopolycarboxylic acid salt, carbonate, paraphenylenediamine color developing agent, hydroxylamine and its derivative}. Granules for a silver halide photographic light-sensitive material, characterized in that a powder containing a seed is kept in a fluid state at a wind speed of 0.1 m / sec or more and 5.0 m / sec or less and is spray-granulated using bound water. Manufacturing method of solid processing agent. 2. The method for producing a granular solid processing agent for a silver halide photographic light-sensitive material according to claim 1, which is a two-fluid type spraying method. 3. When the gas-liquid ratio of the two-fluid system is defined as (volume of atomizing air supplied per unit time) / (volume of combined water supplied per unit time), the gas-liquid ratio is 100
3. The method for producing a granular solid processing agent for silver halide photographic light-sensitive materials according to claim 1, wherein the amount is 10,000 or less. 4. The silver halide photographic light-sensitive material according to claim 1, wherein the compound selected from the compound group is contained in an amount of 5% by weight or more based on the total weight of the granular solid processing agent. A method for producing a granular solid processing agent for a material. 5. The silver halide photographic light-sensitive material according to claim 1, wherein the granulation is performed using a powder or granular material having a weight average particle diameter of 20 μm or more and 350 μm or less. A method for producing a granular solid processing agent. 6. A rectifying plate having an aperture ratio of 1.0 to 20% is provided in an apparatus used for granulation.
Or the method for producing the granular solid processing agent for silver halide photographic light-sensitive materials as described in 5 above. 7. The amount of supply air with respect to the spray velocity of the combined water is 1
The method for producing a granular solid processing composition for silver halide photographic light-sensitive materials according to claim 1, 2, 3, 4, 5 or 6, characterized in that it is not less than m ³ / g and not more than 20 m ³ / g. 8. The total amount of bound water to be sprayed with respect to the charged amount of the powder and granules is 1% by weight or more and 50% by weight or less, 1, 2, 3, 4, 5, 6. Or the method for producing the granular solid processing agent for silver halide photographic light-sensitive materials as described in 7 above. 9. The concentration of the additive in the bound water is 1% by weight or more and 60% by weight or less, 1.
2. A method for producing a granular solid processing agent for a silver halide photographic light-sensitive material as described in 2, 3, 4, 5, 6, 7 or 8. 10. A tablet-like solid processing agent for silver halide photographic light-sensitive materials, characterized by compression-molding the granular solid processing agent obtained by the above-mentioned manufacturing method with a compression stagnation time of 0.02 seconds or more and 1.0 seconds or less. Manufacturing method.