JPH08339054A - Manufacture of processing tablets for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide the processing tables for the silver halide photographic sensitive material improved in problems due to bulking with the lapse of time from their manufacturing to their use, such as trouble in setting them into a solid tablet feeder, pulverizing, breaking, and cracking in a package caused by vibration and the like during their conveyance, and breaking, chipping, and shaving and the like of the tablets. CONSTITUTION: (1) the manufacturing method of the processing photosensitive material is subjected to compression molding of grains or granules containing at least one kind of the following (a)-(e) with a pressure of 400-4500kg/cm<3> in >=2 times; (a) a p-phenylenediamine type color developing agent; (b) hydroxylamine or its derivative; (c) an alkali metal carbonate; (d) a ferric complex salt of an aminopolycarboxylic acid; and (e) a thiosultate; and (2) the balance of the compression molding pressure (kg/cm<2> ) satisfy the following expression: 0.5<= the molding pressure of No.(n-1) (kg/cm<2> )}/ that of No. (n) (kg/cm<2> )}<=1.5, and (n) is 2-5, where (n) is the repeating number of the compression molding cycles.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a tablet processing agent 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 by an automatic processor, and in that case, a replenisher replenishing system is generally widely used, and the activity of the processing solution in the processing tank is controlled to be constant. In the case of the replenisher replenishing system, the purpose is to dilute the eluate from the light-sensitive material, correct the evaporation amount, and replenish the consumption component. As a result of replenishing the liquid, a large amount of overflow liquid is usually discharged.

On the other hand, in recent years, there has been a worldwide increase in regulations regarding the dumping of photographic waste liquids into the ocean and regulations on the disposal of plastic materials. A new system that eliminates photographic waste liquids and does not use bottles for liquid processing agents Development is required. In addition, safety regulations for packaging materials have been strengthened in order to ensure the safety of transportation of liquid dangerous substances, resulting in an increase in cost. Further, in the minilab store, which has been rapidly increasing in number in recent years, the development of printing exposure control technology has progressed, and a system in which anyone can easily print has been introduced. Therefore, workers are covered by parts and part-time jobs. However, it is still difficult to dissolve the replenisher and to manage the treatment liquid, and it is easy to make a very serious mistake such that the treating agent is mistakenly dissolved and replenished.
There have been many complaints about this conventional replenishment system.

Therefore, there has been a strong demand in the art for the development of a solid chemical that does not use a treating agent bottle and does not require any manual dissolution work.

As a method for responding to this demand, Japanese Patent Laid-Open No. 5-11
Japanese Patent Publication No. 9454 and the like disclose a method of solidifying almost all the treating agent components and directly charging them into a treating tank. However, this system proved to have serious problems. The tablet processing agent is manufactured, packed, stored in a warehouse, then transported by various methods and used in a minilab store, but if the period from its manufacture to its use is long, the tablets will expand. The problem is that it ends up.

It has been found that the diameter and thickness of the tablet increase, so that the solid processing agent cannot be set in the apparatus, or fine powder is generated during the setting. In addition, when the storage period is long, the product expands during storage in the warehouse, and vibration and transportation between the tablets after expansion expand the powder, which causes fine powder to be generated when the packaging material is opened, and the powder to be scattered during handling. Was found. As described above, in the case of a color developer, for example, in the case of a color developing agent, fine tared powder and / or tablets enter the processing tank, and tar adheres to the photosensitive material to be processed, resulting in an accident. In the case of bleach-fixing or a fixing agent, sulfurized fine powder and / or tablets stick to the processing tank and damage the photosensitive material to be processed, which is a fatal problem depending on the film for photography. A storability problem due to the swelling of tablets was also found.

There has been an urgent need to solve the above problems and develop a method for producing a tablet processing agent for a solid chemical replenishing system that does not use a processing agent bottle and does not require any dissolving work.

[0008]

SUMMARY OF THE INVENTION The first object of the present invention is to:
Secondly, it is to provide a solid chemical replenishment system that eliminates liquid chemicals that pose transport and handling risks, and that does not require complicated operations by the user. The third object is to provide a method for producing a tablet processing agent which is free from chipping or cracking of powder or tablet processing agent. Thirdly, tablet processing capable of increasing the number of tablets that can be molded per unit time and improving the production capacity. It is to provide a manufacturing method of the agent.

[0009]

Means for Solving the Problems The present inventors have found that the above problems include at least one of the following compounds (a) to (e) in a method for producing a tablet processing agent for silver halide photographic light-sensitive materials. Granules and / or granules, 400 kg / cm ² or more, 4500 kg /
It was found to be achieved by a method for producing a tablet processing agent for silver halide photographic light-sensitive materials, which is characterized by performing compression molding at least twice or more at a pressure of cm ² or less.

(A) Paraphenylenediamine color developing agent (b) Hydroxylamine and / or its derivative (c) Alkali metal carbonate (d) Ferric complex salt of aminopolycarboxylic acid (e) Thiosulfate In the method, the object of the present invention is more highly achieved when the pressure balance of compression molding satisfies the following equation.

0.5 ≦ {n-1 compression molding pressure (kg
/ Cm ² )} / {nth compression molding pressure (kg / cm ² )} ≦
1.5 However, 5 ≧ n ≧ 2

[0012]

It is presumed that the tablets formed by molding granules and / or granules containing at least one of the above (a) to (e) are caused by different transmission velocities inside the tablets by repeatedly applying pressure. Strains and strains estimated to be released after compression (because a force larger than the adhesive force between the tablet surface and the punch) is relaxed, and the tablets have good hardness, friability, and tablets that do not expand over time. Can be manufactured. Further, it was found that the physical properties (hardness, friability and swelling with time) after molding were good even when tableting at high speed because of its high relaxation ability, and it was found that the production capacity could be increased.

In particular, in the case of repeated compression molding, it has been found that the greatest effect is obtained when the balance between the front and rear pressures satisfies the above formula. It is presumed that this is because repeated compression molding has an effect of deteriorating the fragility of the tablet as opposed to the relaxation of strain.

The present invention will be described in detail below.

In the present invention, it is a preferred embodiment that the water content of the granules and / or granules is 0.05 wt% or more and 3.0 wt% or less. When the water content exceeds 3.0 wt%, the lubricity deteriorates, and when the compression molding process is completed and released, the tablet adheres to the punch, the tablet is pulled in the direction opposite to the compression direction, and distortion occurs inside the tablet. The probability of capping immediately after tableting due to the strain increases, and cracking and chipping easily occur when an impact is applied over time, and the effect of the present invention decreases. From this, it is assumed that water is required in the tablet.

In the present invention, the amount of particles having a diameter of 53 μm or less of the granules and / or granules is 10 wt% or less,
This is one of the preferable embodiments from the viewpoint of the effect of the present invention. In the case of a tablet processing agent having a weak binding force, this aspect is also preferable from the viewpoint of capping and lamination prevention.

In the present invention, it is preferable that the bulk density of the granules and / or granules is 0.4 g / cm ³ or more and 0.95 g / cm ³ or less in order to obtain a higher effect of the present invention. When the bulk density exceeds 0.95 g / cm ³ , compression molding (tabletting)
At this time, the granules are hard to break, and the effect of the present invention is 0.95 g /
cm ³ or less is good. On the other hand, when the bulk density of the granules and / or granules is less than 0.4 g / cm ³ , the bulk is too high, and the filling amount per tablet tends to vary particularly when continuously tableting. If the bulk density is 0.4 g / cm ³ or more, there will be no variation in the filling amount.

In the present invention, the strength of the granule is 100 g.
Be / mm ² or more 4000 g / mm ² is preferred from the viewpoint of the effect of the present invention can be obtained higher. Granule strength is 4000g /
Beyond mm ^2, it is preferable from the viewpoint of the effect of the compression molding (tableting) during that granules become less fragile and present invention is 4000 g / mm ² or less. Also, the strength of the granules is 100 g / mm ²
If it is less than 100 g / mm ² , it is preferable from the viewpoint of the effect of the present invention that the tablet processing agent is liable to be chipped or cracked and fine powder is generated, resulting in higher frequency of compression molding failure. As described above, the strength of the granule is a value represented by the strength of the granule = 0.7 P / A (g / mm ² ), where A = πd ² × 1/4, A is the cross-sectional area of the granule. (Mm ² ),
P is the load (g) when the granules are broken, and d is the diameter (mm) of the average particle size of the granules. For this granular strength, refer to Yoshio Hiramatsu, Yukitoshi Seki, Nikko, 81,1024 (1965).

In the present invention, the above P is Okada Seimitsu
The measurement was performed using Grano manufactured by Co., Ltd. The measurement was performed in an environment of 25 ° C. and a relative humidity of 45%.

Further, it is preferable that the weight average particle diameter of the granules and / or granules is 100 μm or more and 600 μm or less in order to obtain the effects of the present invention more favorably. The granules and /
Alternatively, when the weight average particle diameter of the granules is within this range, the physical properties during continuous tableting are less likely to vary, and the tablet treatment agent of the present invention can be stably produced.

Further, as an environmental condition at the time of compression molding, the absolute humidity in the room is 0.021 kg / dry air 1 kg or less, and the effect of the present invention is satisfactorily exhibited. There is also an effect that the expansion of the tablet is small.

In the production method of the present invention, the granular material containing the photographic processing agent used for compression to form tablets may be in the form of granules or granules. Granules are preferred because the effect of the present invention is high. The granules break during compression molding, creating new fresh surfaces that have not been exposed to air, contributing to increased cohesion.

In the present invention, the term "granule" refers to granulated powder, which means a granular material having a particle size of 53 to 2830 μm.
Preferably, the weight average particle diameter is 100 to 600 μm. In the present invention, the weight average particle diameter means a numerical value obtained by a sieving method. That is, if a plurality of JIS standard sieves are used and the median of each opening is d and the weight frequency of particles is n, the weight average particle diameter (D) is D = (Σn · d)
It is represented by / (Σn). The powder means an aggregate of fine particle crystals. The powder means a powder having a large particle diameter, and means an aggregate of particle crystals having a weight average particle diameter of 2830 μm or less.

The granulation method for forming the granules is known means such as tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation and spray drying granulation. Can be used. From the viewpoint of the effect of the present invention, it is preferable that the strength of the produced granules takes a method such that 100 g / mm ² or more 4000 g / mm ² or less as described above.

To produce tablets from granules and / or granules by compression, it is possible to use, for example, a compression device having a pestle that moves up and down and compresses the granules and / or granules from above and below. As long as it has a compressing action, either one of the upper and lower punches may be fixed, and the state may be a so-called "mortar". In addition, the compression direction is preferably from the vertical direction from the viewpoint of workability, but the granular material and //
Alternatively, the method can be arbitrarily selected as long as the granules can be compression molded into a predetermined tablet shape.

As means for compressing the granules and / or granules twice or more at a pressure within the above pressure range to form tablets, for example, a plurality of units arranged concentrically with the rotating shaft on a horizontally rotating turntable can be used. In a rotary tableting machine in which granules or granules are put into an individual mortar from a hopper, and the granules or granules are put into the mortar and compressed into a tablet by being sandwiched between two upper and lower punches and compressed into tablets, the tablets are compression-molded. A method of using a rotary tableting machine having a mechanism in which compression molding is carried out twice or more before being taken out.

The tablet treating agent produced by the present invention is
It is a photographic processing agent such as a color developing agent, a black and white developing agent, a bleaching agent, a fixing agent, a bleach-fixing agent and a stabilizer.

Among the para-phenylene type color developing agents which are color developing agents, examples of the compounds which exhibit the effect of the present invention favorably include the compounds described in paragraph Nos. 0083 to 0086 of JP-A-5-232656. Of these, the following compounds are particularly preferable.

[0029]

Embedded image

Among hydroxylamine and its derivatives, compounds that can effectively exhibit the effects of the present invention are disclosed in
Examples thereof include the compounds described in paragraph numbers 0100 to 0130 of JP-A-5-232656, and among them, bis (sulfoethyl) hydroxylamine disodium salt and hydroxylamine are preferable.

Among the alkali metal carbonates, the compounds exhibiting the effect of the present invention favorably include the compounds described in paragraph No. 0105 of JP-A-5-232656. A particularly preferred compound is potassium carbonate.

Of the ferric iron complex salts of aminopolycarboxylic acids, the compounds exhibiting the effects of the present invention well are disclosed in Japanese Patent Application No. 5-10.
Examples thereof include the compounds described in paragraph numbers 0040 to 0110 of 6278. Particularly preferred compounds are ferric complex salts of ethylenediaminetetraacetic acid, 1,3-propylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, respectively.

[0033]

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

Example 1 A color developing replenisher for color paper was prepared as shown below.

Operation (A) The developing agent CD-3 (4-amino-3-methyl-N-ethyl-N-)
[Β- (Methanesulfonamide) ethyl] aniline 3/2 sulfate monohydrate 1450 g in a commercial Van Dam mill with an average particle size of 30
It was pulverized to a size of μm. After granulating this fine powder in a commercial stirred granulator at room temperature by adding 50 ml of water, the granulated product is dried in a fluid bed dryer at 40 ° C for 2 hours to remove the water content of the granulated product. The particles were removed to 0.05 wt% to prepare color developing granules for color paper. The color-developing granules had a weight average particle diameter of 250 μm, a bulk density of 0.60 g / cm ³ , and a granule strength of 500 g / mm ² .

Operation (B) 800 g of bis (sulfoethyl) hydroxylamine disodium salt, 1700 g of sodium p-toluenesulfonate and Tinopearl (trade name, Ciba Geigy as a fluorescent whitening agent)
Ltd.) 30 g of the operation (A ₁₎ and respectively a similarly comminuted, PINEFLOW (trade name as a binder, Matsutani Chemical Co., a Ltd.)
After adding 24 g and mixing, the mixture was stirred and granulated with 240 ml of water. The granulated product is dried at 60 ° C for about 2 hours, and the moisture content of the granulated product is 1.0 wt%.
The color-developing granules for color paper were made to have a weight-average particle size of 240μ.
m, the bulk density was 0.70 g / cm ³ , and the strength of the granules was 800 g / mm ² .

Operation (C) Diethylenetriamineacetic acid 5 sodium salt 330 g, sodium p-toluenesulfonate 130 g, sodium sulfite 3
5g, 350g lithium hydroxide monohydrate and anhydrous potassium carbonate
3300 g was pulverized in the same manner as in the operation (A ₁ ). PE
1500 g of G # 4000 (Mw = 4000) (manufactured by NOF CORPORATION) and 600 g of Mannit (manufactured by Kao Corporation) were mixed, and 260 ml of water was added for granulation. The granulated product was dried at 55 ° C for about 2 hours, and the water content of the granulated product was removed to 0.9 wt% to prepare color developing granules for color paper. The particle size was 140 μm, the bulk density was 0.71 g / cm ³ , and the strength of the granules was 3800 g / mm ² .

All of the granules prepared in each of the above operations (A), (B) and (C) were 25 ° C., relative humidity 45% and absolute humidity 0.
Under the environment of 013 kg / dry air 1 kg, the mixture was mixed for 10 minutes using a commercially available cross rotary type mixer, and 50 g of n-myristoylalanine sodium was added thereto and further mixed for 3 minutes. The weight of particles of 53 μm or smaller in the mixed granules was 1 wt%.

Using a rotary tableting machine (Kikusui Seisakusho Co., Ltd., modified Clean Press Collect H18), the mixture thus prepared was filled with a mortar and pestle having a diameter of 30 mm and a thickness of 10 mm to a filling amount of 10.8 per piece. g, the compression molding pressure, the number of times of compression molding, and the number of rotations of the turntable in which a plurality of mortars are arranged were changed as shown in Table 1 to prepare tablets. The diameter and thickness of the produced tablets were measured, and a vibration test and a drop test were performed by the following methods.
In addition, 20 tablets of which the diameter and thickness were measured were placed in an aluminum vapor deposition packaging material, sealed, and stored at a temperature of 50 ° C for 4 weeks, after which the packaging material was opened and the diameter and thickness were measured. The amount of change in thickness was determined. Table 1 shows the results. In the table below, Δ diameter (or Δ thickness) = (diameter (or thickness) after storage) − (diameter (or thickness) before storage).

Drop test: 18 tablets in total, 1000 tablets each
The sample was naturally dropped from a height of 0 cm, and the frequency of cracking and chipping was evaluated according to the following evaluation criteria.

Evaluation Criteria A: No chipping or cracking occurs.

B: One out of 1,000 tablets had cracks or cracks of 0.10 wt% or less based on the total tablet weight.

C: 0.50 wt% or less of chippings or cracks was generated at a ratio of 10 to 1000 tablets based on the total weight of the tablet.

D: Chips or cracks occurred at a rate of 50 out of 1,000 pieces.

DD: Chips or cracks occurred at a rate of 100 out of 1000 pieces.

Vibration test: Vibration tester BF made by IDEX Co., Ltd., using a sample wrapped with aluminum vapor deposition packaging material.
Vibration test was performed for 10 minutes using UA. After the vibration test is completed, the sample is opened and the aluminum vapor-deposited sample that has not been subjected to the vibration test and the sample that has been subjected to the vibration test are each opened, and the conditions in which the powder adheres to the packaging material are visually compared, and the following evaluation criteria are used. evaluated.

Evaluation Criteria A: There is almost no difference from the one not subjected to the vibration test, and there is almost no adhesion of powder to the packaging material.

B: A slight amount of powder adhering to the packaging material is observed, but it is at a level that does not pose a problem during work.

C: Adhesion of powder to the packaging material was clearly observed, and generation of powder by vibration test was observed.

D: The powder adheres strongly to the packaging material, and a considerable amount of powder flies when opened.

DD to DDD: The larger the number of D, the more the powder adheres, and the larger the amount of the powder flies when opened.

The results of this evaluation are shown in Table 1 below.

[0053]

[Table 1]

From Table 1, the compression pressure is 400 to 4500 kg / cm.
^2, and that the compression molding count is more than 2 times, is effective on reducing the swelling of the tablet during storage, it can be seen that the transport suitability is excellent. Moreover, the results of the vibration test and the drop test immediately after tableting show that the tablets having a reduced degree of expansion due to storage are excellent in strength and friability. Also, by making the compression molding a plurality of times in one rotation of the turntable, the rotation speed of the turntable can be increased without deteriorating the quality, that is, the number of tablets molded per unit time is increased. I see that I can do it. Example 2 A tablet was prepared in the same manner as in Example 1 except that the compression molding pressure under the tablet forming conditions of a rotary tableting machine was changed as shown in Table 2 below. However, the rotation speed of the turntable was 30 rpm. These tablets were evaluated in the same manner as in Example 1. The results are shown in Table 2 below.

[0055]

[Table 2]

It can be seen from Table 2 that the object of the present invention can be achieved to a higher degree when the compression molding pressure balance between the first time and the second time satisfies the above expression (1).

Example 3 A fixing replenishing tablet for a color negative film was prepared as shown below.

Operation (D) 2500 g of ammonium thiosulfate was pulverized in the same manner as in the above operation (A), and 180 g of sodium sulfite, 2 g of ethylenediaminetetraacetic acid disodium, 20 g of potassium carbonate and 70 g of oil Q (manufactured by Nippon Starch Chemical Co., Ltd.) Is added with water and granulated with a commercially available stirring granulator. The weight average particle diameter is 300 μm and the bulk density is 0.66.
Granules having g / cm ³ and a strength of 1000 g / mm ² were prepared, and compression molded in the same manner as in Example 1 to prepare tablets. The results of evaluating these tablets in the same manner as in Example 1 are shown in Table 3 below.

[0059]

[Table 3]

From Table 3, it can be seen that the effects of the present invention can be obtained even if the composition of the tablet treating agent is changed.

Example 4 The same experiment as in Example 3 was carried out except that the number of compression moldings was set to 2 and the compression pressure was changed as shown in Table 4 below. Table 4 shows the results.

[0062]

[Table 4]

From Table 4, it can be seen that it is preferable that each compression molding pressure of the multiple compression moldings is within the range of the formula (1) even when the composition of the tablet treating agent is changed.

Example 5 Procedure (E) Sodium sulfite (180 g), ethylenediaminetetraacetic acid disodium (2 g), potassium carbonate (20 g) and oil Q (manufactured by Nippon Starch Chemical Co., Ltd.) (70 g) were added to the above procedure (A ₁ ). Similarly, granulation and drying were performed to prepare granule E-1. Separately, 2500 g of ammonium thiosulfate (manufactured by Hoechst Co., Ltd., crystal) was sized,
Granule E-2 was prepared as a granule having a weight average particle diameter of about 500 μm. E-1 and E-2 were mixed and tablets were prepared by changing the compression molding frequency and compression pressure in the same manner as in Example 1. However, the water content of the granules E-1 was 1.00 wt% and the water content of the granules E-2 was 0.
70 wt%, Granule E-1 has a bulk density of 0.55 g / cm ³ , Granule E
-2 has a bulk density of 0.80 g / cm ² , granules E-1 and granules E-
8.0% by weight of the particles of the mixture of 2 having a diameter of 53 μm or less
And Table 5 shows the results of the same evaluations as in Example 1 for these tablets.

[0065]

[Table 5]

From Table 5, it can be seen that the effects of the present invention can be obtained in the case of granules as in the case of granules.

Example 6 Compression molding (tabletting) under the conditions of Experiment No. 1-6 of Example 1, Experiment No. 3-7 of Example 3 and Experiment No. 5-7 of Example 5. Absolute humidity during compression molding was the same as the results except that tableting was performed under the condition that the absolute humidity at the time was more than 0.021 kg / dry air 1 kg.
In the case of 0.021 kg / dry air 1 kg or less, the expansion in the width direction was deteriorated by 20% in all cases.

[0068]

EFFECTS OF THE INVENTION According to the present invention, there is no risk of transportation and handling of liquid chemicals, and a solid used in a processing system for silver halide photographic light-sensitive materials which can be replenished by a user without complicated operations. It is a chemical that improves tablet deformation (bulk swelling) over time and tablet chipping, cracking, chipping, etc., and defects due to this deformation (unable to set in the solid processing agent feeder, vibration during transportation, etc.) Provided is a method for producing a tablet processing agent in which fine powder and generation of chips and cracks in a package are improved.

Claims (2)

[Claims] 1. A method for producing a tablet processing agent for a silver halide photographic light-sensitive material, wherein particles and / or granules containing at least one of the following compounds (a) to (e) are added in an amount of 400 kg / cm ² or more and 4500 kg. A method for producing a tablet processing agent for silver halide photographic light-sensitive materials, which comprises compression-molding at least twice at a pressure of / cm ² or less. (a) Paraphenylenediamine color developing agent (b) Hydroxylamine and / or its derivative (c) Alkali metal carbonate (d) Ferric complex salt of aminopolycarboxylic acid (e) Thiosulfate 2. The pressure balance of compression molding is expressed by the following formula (1).
2. The method for producing a tablet processing agent for silver halide photographic light-sensitive materials according to claim 1, wherein 0.5 ≦ {n-1st compression molding pressure (kg / cm ² )} / {nth compression molding pressure (kg / cm ² )} ≦ 1.5 where 5 ≧ n ≧ 2 (1)