JPH08297355A - Solid processing agent for silver halide photographic sensitive material and processing method for silver halide photographic sensitive material using the same - Google Patents

Abstract

PURPOSE: To obtain a solid processing agent excellent in productivity and handleability and capable of ensuring stable fixability even in a system in which processing is carried out with a very small amt. and to provide a processing method using the processing agent. CONSTITUTION: This solid processing agent contains at least one of normal and hydrogen salts of ammonium salt of an org. acid represented by the formula (where A is an org. group, n1 is an integer of 1-6, each of n2 and n3 is an integer of 0-3 and n1 +n2 +n3 >=2). A silver halide photographic sensitive material is processed with a processing soln. prepd. by dissolving this solid processing agent.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art In recent years, there has been a movement in the photo processing industry to adopt a solid processing agent which is effective for reducing the waste liquid for photo processing and the waste amount of plastic containers for packaging in consideration of the global environment. , Has a great effect.

Compared with liquid treatment agents, solid treatment agents have great advantages such as easy container simplification, easy handling, low replenishment and low waste liquid. On the other hand, however, there are problems peculiar to solid processing agents such as maintaining the shape.

[0004]

In the process of producing a solid processing agent, especially a solid processing agent containing an aminopolycarboxylic acid ferric complex salt as a bleaching agent, the product form is a granulated product such as granules. , Granulate in a large-scale batch, package after temporary storage accompanying transfer to packaging process, store for a long time in a product warehouse, and solidify by storing under a load. It turns out that there is a tendency to fall. Further, when tableting the granulated product into tablets, variations in the hardness of the tablets, which are presumed to be due to the difference in the time elapsed until tableting, are observed, which may cause a problem in production stability. I understand.

On the other hand, a solid processing agent containing an organic acid as a buffering agent is an alkaline agent (for example, an alkali hydroxide such as NaOH or KOH or a carbonate) for neutralizing the acid in order to bring it to a predetermined pH. , Hydrogen carbonate, etc.) is required, but in order to increase the buffer capacity, a large amount of organic acid and alkaline agent are required, and care should be taken when handling due to the hygroscopicity and poor storage stability of the alkaline agent. There is a problem that it costs.

Further, when such a treating agent containing an organic acid and an alkaline agent is used, particularly when an extremely small amount of processing is carried out by an automatic developing machine, spot-like fixing defects occur on the processed light-sensitive material. It turns out that there are cases.

The present invention has been made in view of the above circumstances, and an object thereof is a silver halide photograph which is excellent in productivity and handleability and which can obtain stable fixing property even in a system of processing a very small amount. It is to provide a solid processing agent for a light-sensitive material and a processing method using the same.

[0008]

[In the formula, x1 to x4 are 0 or more, x5 is 1 or more, and x1+x2+x3+x4+x5=m, 2≤m≤6. ]

This is achieved by a method of processing a silver halide photographic light-sensitive material using a processing solution obtained by dissolving this solid processing agent, and by directly introducing the solid processing agent into a processing tank for processing.

That is, the present inventor can not only improve the coagulability and hardness of the granulated product by adding an organic acid ammonium salt or an organic acid hydrogen salt to the solid processing agent,
The present invention has been made based on the findings that the variation in weight can be improved and that the amount of use can be reduced by using the salt of an organic acid rather than the form of an organic acid and an alkaline agent. As a result, the amount of processing agent required for processing per unit area of photosensitive material can be reduced, so that individual processing agents in product form can be downsized, and production equipment can be downsized and packaging containers can be downsized. It also has the advantage that

Regarding the spot-like fixing failure, the bleaching solution carried out by the light-sensitive material is concentrated on the transition roller from the bleaching bath to the fixing bath and is treated as a viscous syrup-like liquid. The syrup-like liquid adheres to the photographic material and delays the penetration of the fixer, which delays the fixing reaction. It was found that sodium ions and potassium ions in the liquid were involved, and the salt of the organic acid of the present invention reduced the sodium ions and potassium ions to solve this problem.

The present invention will be described in detail below.

The solid treating agent of the present invention comprises at least one selected from the normal salts of ammonium salts of organic acids represented by the above general formula (1) (hereinafter also simply referred to as organic acid ammonium salts) and hydrogen salts. The organic acid represented by the general formula (1) is HOOC(CH ₂ )m ₁ COOH (m ₁
Represents an integer of 1 to 6. ) Or a compound represented by the general formula (2). Further, these hydrous salts are also included in the organic acid ammonium salt and the organic acid hydrogen salt of the present invention.

The ammonium normal salt of an organic acid in the present invention is a salt in which all the hydrogen ions that are acidic from the free acid of an organic acid are replaced with ammonium ions. For example, the ammonium normal salt of citric acid of a tribasic acid is , (NH ₄ ) ₃ C ₆ H ₅
It is a salt represented by O ₇ .

The hydrogen salt of an organic acid refers to a salt produced when an organic acid of a polybasic acid is neutralized by a base, which contains hydrogen of an acid which can be replaced with a metal ion. , For example, as an acid salt of citric acid, Na ₂ HC ₆ H _{5
O 7, NaH 2 C 6 H} 5 O 7, (NH 4) 2 HC 6 H 5 O 7, (NH
₄ ) There are H ₂ C ₆ H ₅ O _{7 and the} like.

In the present invention, a plurality of kinds of the above organic acid ammonium normal salts are used, or a plurality of kinds of organic acid hydrogen salts are used, or an organic acid ammonium normal salt and an organic acid hydrogen salt are combined. It is also preferable to use.

Further, it is also a preferable use form to use in combination with the organic acid represented by the general formula (1). In this case, the molar ratio of the organic acid salt to the total amount of the organic acid and the organic acid salt is 2 mol% or more, and more preferably 3 to.
The content of 80 mol% is preferable because the effect of suppressing the variation in weight of each tablet at the time of tablet production is increased and the replenishment accuracy of the processing liquid is improved.

Specific examples of the organic acid, organic acid ammonium normal salt, organic acid hydrogen salt and free acid thereof are shown below, but the invention is not limited thereto.

[0018]

[Chemical 3]

[0019]

[Chemical 4]

[0020]

[Chemical 5]

Preferred among these compounds are:
(1-1), (1-3), (1-4), (1-5),
(1-6), (1-10), (1-14), (1-15),
(1-21), (1-22), (1-23), (1-26),
(1-27), particularly preferably (1-5), (1-
6), (1-14), (1-15), (1-21), (1-2
3).

Examples of ammonium salts of organic acids include the following.

[0023]

[Chemical 6]

As the hydrogen salt of the organic acid, it is preferable that the organic acid represented by the general formula (1) is m basic acid (H _m L) and the hydrogen salt is represented by the general formula (3). .. Specifically, ammonium hydrogen succinate, potassium hydrogen succinate, sodium hydrogen succinate, lithium hydrogen succinate, ammonium hydrogen adipate, potassium hydrogen adipate, sodium hydrogen adipate, lithium hydrogen adipate, ammonium hydrogen maleate, Examples thereof include potassium hydrogen maleate, sodium hydrogen maleate, lithium hydrogen maleate and the like, and particularly preferable are ammonium hydrogen succinate, ammonium hydrogen adipate, and ammonium hydrogen maleate.

In the present invention, the salt of an organic acid is preferably used in an amount of 70% by weight or less, more preferably 1 to 50% by weight, particularly preferably 2 to 40% by weight based on the solid processing agent.

The effect of the present invention is remarkable when the solid processing agent contains a ferric aminopolycarboxylic acid complex salt as a bleaching agent and has a bleaching ability, particularly when it is used in the bleaching step.

In the present invention, known aminopolycarboxylic acids and ferric aminopolycarboxylic acids can be used, for example, the general formula [I] described on pages 12 to 40 of JP-A-7-28213. , [A-I], [A-II], [A-II
I], [A-IV], [A-V], [A-VI], [A-VI]
I], [A-VIII] and compounds represented by the compound [A′] group. Specific examples of particularly preferable aminopolycarboxylic acids and ferric aminopolycarboxylic acid complex salts are shown below.

[0028]

[Chemical 7]

[0029]

[Chemical 8]

[0030]

[Chemical 9]

[0031]

[Chemical 10]

[0032]

[Chemical 11]

When containing an ammonium salt of an organic acid,
The molar ratio to the aminopolycarboxylic acid ferric complex salt is 0.
05-3.0, preferably 0.10-1.5, when containing a hydrogen salt of an organic acid, the molar ratio to the ferric aminopolycarboxylic acid complex salt is about 0.05-4.0, preferably 0.10-3.0, more preferably 0.20-1.5. The range is.

The ratio of ammonium ion to the total amount of alkali metal ion and ammonium ion in the raw material components contained is 55 mol% or more, which is not only excellent in bleaching property and fixing property, but also the bleaching solution is concentrated to make starch syrup. It is preferable because it can prevent the phenomenon of the occurrence of the state.

When used as a bleaching treatment agent, it may further contain an organic acid represented by the general formula (1). in this case,
When the organic acid ammonium normal salt is used, the ratio of the organic acid ammonium normal salt to the total amount of the organic acid and the salt of the organic acid is 2 mol% or more, preferably 3 to 80 mol %, particularly 10 to 60 mol. % Is preferable.

As the fixing agent used as a fixing agent or a bleach-fixing agent, thiosulfates and thiocyanates can be preferably used, and thiosulfates are particularly preferable. Also, both can be used in combination. The fixing agent is preferably used in the form of sodium salt, potassium salt, or ammonium salt, but two or more kinds of salts can be used in combination. The content of these thiosulfates is preferably 20 to 70% by weight in the solid processing agent in the case of a bleach-fixing agent and 50 to 95% by weight in the case of a fixing agent.

In the present invention, when thiosulfate is used, it is preferable to use a preservative, and sulfite, bisulfite and metabisulfite are particularly preferable. These preservatives are usually used as sodium salt, potassium salt and ammonium salt. These preservatives may be used alone or in combination of two or more. The preferred content is 2 to 30% by weight in the solid processing agent.

If desired, a buffering agent may be used in the solid processing composition of the present invention.

When used as a bleaching agent, it is preferable to use a halide such as chloride, bromide or iodide as a rehalogenating agent for promoting the oxidation of silver. As the halide, an alkali metal salt (lithium, sodium, potassium salt, etc.), an onium salt (ammonium salt, etc.), or a salt of guanidine, amine, etc. is preferably used. Bromide is more preferable, and ammonium bromide is particularly preferable. The preferred amount used is 0.05 to 2.0 mol/l, more preferably 0.1 to 1.5 mol/l, as the concentration in the bleaching solution.

As the bleaching agent, in addition to the above-mentioned ferric iron complex salt, a known inorganic oxidizing agent such as persulfate, bromate or chlorate may be used in combination.

When used as a bleaching agent, a bleach-fixing agent or a fixing agent, the compound represented by the general formula (F) described on page 56 of JP-A-1-295258 can be used.
It is preferable to add the compound represented by A) from the viewpoint of not only the effect of the present invention but also that sludge generated in the processing liquid can be extremely reduced when a small amount of the light-sensitive material is processed for a long time.

When used as a bleaching agent, a bleach-fixing agent or a fixing agent, it should contain a compound selected from the imidazole derivatives described in JP-A-1-295258 and the compounds represented by the general formulas [I] to [IX]. This is advantageous for speeding up the process. In addition to these accelerators, JP-A-62-123459, 51-115.
The compounds described on pages 22 to 25 of JP-A-63-17445, the compounds described in JP-A-53-95630 and JP-A-53-28426, and the like can also be used in the same manner.

Further, the aminopolycarboxylic acid is added to the second
About 0.1 to 15 mol% with respect to the iron complex salt (preferably 1 to 10)
Mol %), preferably used as a chelating agent.

For the purpose of the present invention, it is preferable that the proportion of the organic acid salt is as large as possible, but carbonates (potassium carbonate, sodium carbonate, ammonium carbonate, lithium carbonate, etc.),
Hydrogen carbonate (potassium hydrogen carbonate, sodium hydrogen carbonate,
Known alkali agents such as ammonium hydrogen carbonate), alkali metal hydroxides (potassium hydroxide, sodium hydroxide, lithium hydroxide, etc.), phosphates, borates and the like can also be used. In this case, from the viewpoint of stability of the aminopolycarboxylic acid iron complex salt and solubility of the solid processing agent, carbonates and hydrogen carbonates are preferable, and ammonium salts and potassium salts are preferable to sodium salts from the viewpoint of the viscosity of the treatment liquid. preferable.

The organic acid ammonium salt and the organic acid hydrogen salt of the present invention are the most effective and preferred forms when used in a solid processing agent used as a bleaching solution, but they can also be used in other processing agents. ..

Other preferred examples include use in solid processing agents for bleach-fixing, fixing, stabilizing and rinsing processing steps. Further, an organic acid hydrogen salt containing no ammonium ion as a cation can be used as a solid processing agent for color development and black and white development.

In the present invention, the solid processing agent means a powder processing agent, tablets, pills, granules and the like, which may be optionally subjected to moisture-proof treatment. In the present invention, the powder means an aggregate of fine grain crystals. The granules are preferably granulated powder and have a particle size of 50 to 5000 μm. The tablet in the present invention refers to a powder or granules compression-molded into a certain shape. Among the above-mentioned solid processing agents, those in the form of granules or tablets are preferable because they are less likely to generate dust during handling and have a good feeding accuracy. Furthermore, among them, the tablet form has a high replenishment accuracy and is easy to handle, and the concentration does not change rapidly due to rapid dissolution,
It is preferably used because the effects of the present invention are well exhibited.

To solidify the photographic processing agent, a concentrated solution or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or a water-soluble binding agent is formed on the surface of the temporarily molded photographic processing agent. Arbitrary means such as forming a coating layer by spraying can be adopted (JP-A-4-29136 and JP-A-4-85533).
(See the respective gazettes of 4-85536 and 4-172341).

A preferred method for producing tablets is a method in which a solid processing agent in powder form is granulated and then a tableting step is performed. There is an advantage that the solubility and storability are improved and the photographic performance becomes stable as compared with the solid processing agent formed by the tableting process by simply mixing the solid processing agent components. The granulation method for forming tablets or granules is rolling granulation, extrusion granulation,
Known methods such as compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation can be used. Further, when granulating, 0.01 to 20% by weight of a water-soluble binder (more preferably
0.1 to 10% by weight) is preferable because it has the effects of preventing the generation of fine powder of the solid processing agent and improving the tablet strength. As the water-soluble binder, celluloses, dextrins, sugar alcohols, polyethylene glycols, cyclodextrins and the like are preferable.
The compounds described in the right column on page to the left column on page 31 are particularly preferably used. In the case of a solid, pretreatment such as crushing (or directly) in the case of solid, and then mixing with other raw materials to granulate, in the case of liquid, directly used as a granulating liquid, solid and liquid Regardless, a method in which a solution dissolved in a solvent such as water or alcohol is added at the time of granulation is preferable because a better effect can be obtained.

Next, when the obtained granules are compressed by pressure to form tablets, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine, a pre-ketching machine is used. Can be used. More preferably, during granulation, the above-mentioned effects become more remarkable by separately granulating each component, such as an alkali agent and a preservative.

A method for producing a tablet treating agent is described in, for example, Japanese Patent Laid-Open No.
51-61837, 54-155038, 52-88025, British patent
It can be produced by a general method described in the specification such as 1,213,808, and the granule treating agent is, for example, JP-A-2-09042.
No. 2-09043, No. 3-39735, No. 3-39739, and the like. Further, the powder processing agent is described in, for example, JP-A-54-133332 and British Patent 7
It can be produced by a general method as described in the specifications such as 25,892, 729,862 and German Patent 3,733,861.

In the present invention, as the supply means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet, Japanese Utility Model Laid-Open Nos. 63-137783 and 63-97522,
Although there is a known method such as Japanese Utility Model Laid-Open No. 1-85732, any method may be used as long as it has at least a function of supplying tablets to the processing tank. Further, when the solid processing agent is granules or powders, it is disclosed in Japanese Utility Model Laid-Open Nos. 62-81964 and 63-84151, JP-A-1-
No. 292375, the gravity drop method described and No. 63-105159,
The method using screws or screws described in JP-A-63-195345 and the like is a known method, but is not limited thereto.

The solid processing agent of the present invention may be put in a processing tank, but preferably, it is communicated with a processing section for processing a light-sensitive material, and a processing solution flows between the processing section and the processing section. It is preferable that the structure is such that the dissolved components move to the treatment section because there is a certain amount of circulation of the treatment liquid between the treatment section and the treatment section. It is preferable that the solid processing agent is directly added to the temperature-controlled processing solution.

The amount of the solid processing agent added at one time is preferably 0.1 g or more from the viewpoints of the effects of the present invention, the durability of the charging device and the accuracy of the amount of one time charging. 50 g or less is preferable from the viewpoint of the effect and dissolution time. In addition, the manufacturing method of the solid processing agent, the processing apparatus and the processing method using the solid processing agent, the packaging form of the solid processing agent, etc. Reference can be made to 16935.

[0055]

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 was prepared according to the following procedure.

(Operation 1) Based on the following prescription, each compound was weighed in a humidity-controlled room and MIKRO-PULEV
Using ERIZER (manufactured by Hosokawa Micron Co., Ltd.)
It was pulverized until the weight average particle diameter became 30 μ or less.

1,3-Propanediamine iron complex salt (PDTA·Fe) Listed in the table 7.0 mol 1,3-Propanediamine tetraacetic acid (PDTA) 150 g Bromide Listed in the table 9.0 mol Organic acids, listed in the table 15 mol Carbonate Described in the table Described in the table (Operation 2) 100 g of D-sorbit was added to 150 g of water to prepare a granulation liquid having a concentration of 40%.

(Operation 3) NEW the crushed product created in operation 1
The mixture was put into SPEED KNEADER (manufactured by Okada Seiko Co., Ltd.) and mixed for 3 minutes. Then, the granulation liquid prepared in step 2 was added at a rate of 150 ml/min by a tube pump, and then kneaded for 3 minutes. The operations 1 to 3 were repeated to prepare about 10 kg of granules (granules). The rotation speed of the stirring blade at this time was 150 rpm.

(Operation 4) The granulated product was used as a fluid bed dryer MDD-400N type manufactured by Fuji Paudal Co., Ltd., and the granule temperature was 55.
The water content is 1.5 while adjusting the supply temperature so that it does not exceed ℃.
It was dried to below wt%. At this time, while maintaining the temperature of the granules at 50° C. or lower, 1 hour after the start of drying, the particles were sized (primary sized) using NEW SPEED MILL (made by Okada Seiko Co., Ltd.) with a screen opening of 5.0 mm. At the end of drying, a 2.0 mm screen was used for sizing (secondary sizing). After sizing, the powder was placed in a cylindrical moisture-proof plastic container having a diameter of 30 cm.

(Operation 5) To the granules obtained by the above operation
After adding 1.0% by weight of sodium N-lauroyl sarcosine sun and mixing for 3 minutes using a commercially available cross rotary mixer, a rotary tablet press modified from Kikusui Seisakusho's Clean Press Collect 18K was used. Continuous tableting was performed. However, the tableting conditions are 9 cylindrical punches and a main pressure of 1400.
Kg / cm ^2, the preload force 140 kg / cm ^2, the rotation number of the turntable 1
The setting was 0 rpm, a compression stagnation time of 0.05 seconds, and a filling amount of 10.7 g.

<Evaluation method> Based on the following operations, the coagulability of the granules, the variation and hardness of the tablet weight, and the viscous property upon concentration of the treatment liquid were evaluated.

(Coagulability of Granules) The granule samples obtained by the above (Operation 1) to (Operation 4) were placed in a bag having a thickness of 70 μm made of a laminated film of polyethylene/vinylidene chloride coated nylon/polyethylene. After sealing without leaving excess air, apply a load of 300 kg/100 cm ² and
The granules were stored at 5°C for 1 week, and the coagulability of the granules after storage was evaluated according to the following criteria.

◎: Excellent in fluidity without solidifying ○: A small amount of small lumps are observed, but there is no problem at all △: Partially solidified and collapsed if lightly crushed by hand, Practically problematic level ×: Practically problematic level due to large lumps that cannot be easily crushed by hand XX: Practically problematic level when the entire bag is solidified (tablet hardness ) Time from preparation of granules to tableting (time from the end of (Operation 4) to the start of (Operation 5))
The prepared tablet samples were sampled once every 10 tablets for a total of 30 tablets for 24 hours and 120 hours.

Regarding the obtained sample, a tablet hardness measuring device "Speed Checker NT-50" (manufactured by Okada Seiko Co., Ltd.)
The hardness was measured using and the average value of 10 tablets was obtained.

The hardness measured was the maximum value of the load applied to the load cell (the load when the tablet cracked), and the measurement was performed so that the load was applied in the diameter direction of the tablet.

(Viscosity and Fixability during Concentration of Treatment Liquid) An aqueous solution (treatment liquid) was prepared by dissolving the obtained 5 tablet samples in 100 ml of water, and developed in 20 ml on a petri dish having a diameter of 10 cm, and released. The mixture was allowed to stand at room temperature for 1 week at room temperature to spontaneously evaporate and concentrate.

Next, the unexposed Konica Color Negative Film LV400 was developed in the following processing step (I), and the emulsion surface of the processed film sample was pressed against the processing solution concentrate on the petri dish and separated. At that time, the state of the treatment liquid adhered to the film surface was observed.

After completion of the observation, the adhered portion was marked, and the film sample was immediately subjected to the development treatment in the following processing step (II) to observe how the adhered material on the film surface was melted in the fixing bath. After the treatment step (II) was completed, the red light transmission densities of the portion where the adhered matter was adhered to the treated film and the portion where the adhered matter was not adhered were measured, and the density difference (ΔD _min R) was obtained and the fixability was evaluated.

ΔD _min R=D _min R (attached portion)-D _min R (non-attached portion) Treatment step (I) Treatment step (II) Treatment step Treatment time Temperature Treatment step Treatment time Temperature Current image 3 minutes 15 seconds 38 ℃ settling 1 min 00 sec 38 ℃ Bleach 45 sec 45 ℃ Water wash 1 min 00 sec 38 ℃ water wash 1 min 00 sec 30 ℃ Dry 1 min 00 sec 55 ℃ Dry 1 min 00 sec 55 ℃ For The treatment liquid used was as follows.

(Developer) Diethylenetriamine pentaacetic acid 1.0 g Potassium sulfite 3.6 g Potassium carbonate 30.0 g Sodium bromide 1.2 g Potassium iodide 1.8 mg Hydroxylamine sulfate 2.5 g 4-Amino-3-methyl-N-ethyl-N-( β-Hydroxyethyl)aniline sulphate 4.2g Add water to make 1 liter and adjust to pH 10.01 with sulfuric acid or potassium hydroxide solution.

(Bleach) Water 500 ml 1,3-Propanediamine tetraammonium iron acetate monohydrate 120 g 1,3-Propanediamine tetraacetic acid 7 g Ammonium bromide 100 g Succinic acid 100 g Maleic acid 30 g Ammonia water (25%) Adjust to pH 4.40 using and add water to make 1 liter.

(Fixer) Ammonium thiosulfate 150.0 g Ammonium thiocyanate 170.0 g Ammonium bisulfite 12.0 g Sodium metabisulfite 2.5 g Ethylenediaminetetraacetic acid disodium 0.5 g Water was added to make 1 liter and pH was adjusted to 7 with acetic acid and ammonia water. Adjust to 0.

Evaluation Criteria (Viscosity) State of Condensate Adhesion to Film Solubility in Fixing Solution ◎ Almost dry Almost no dissolution, no problem at all (does not become viscous even in the drying process) ○ Some Moist but slightly adhered Immediately dissolves (within 3 seconds), almost no stickiness No problem at all △ Wet and sticks a little stickiness Some time (less than 5 seconds is required) to dissolve However, there is some problem. × Wet and sticky. Adhesion considerably adheres. It takes a long time (less than 10 seconds is quite a long time) to dissolve, and there is a problem. × × Wet, sticky and sticky. 10 seconds to dissolve. Table 1 to 5 show the above results and the formulation of each sample, which requires much time to pull the thread and is very problematic.

Evaluation Criteria ( Fixability ) If ΔD _min R is 0.03 or less, there is no problem in practical use, and 0.05 is a level which is an allowable limit.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

[0079]

[Table 4]

[0080]

[Table 5]

Here, for example, 1-6 (NH
_4, NH _4), the diammonium salt of an organic acid (1-6), i.e., represents _{H 4 N-00C-CH 2} CH 2 -COO-NH 4, are hereinafter similarly notation. In addition, in each sample of Table 1, Table 2 and Table 3, PDTA
・The first line of each column of the Fe complex salt, organic acid salt, bromide, and carbonate cation composition is an ammonium salt, the second line is a potassium salt,
The third line describes the sodium salt.

As is clear from the table, the addition of the organic acid ammonium salt of the present invention has a remarkable effect in preventing the coagulation of the granules. Furthermore, when the ratio of ammonium ions in all cations is 55 mol% or more,
Not only does the hardness of the tablet not decrease even after a lapse of time from granulation to tableting, an effect of increasing the hardness is recognized. Further, it can be seen that by increasing the ratio of ammonium ions (particularly by reducing sodium ions), it is possible to prevent the bleaching solution from sticking in the form of starch syrup even when it is concentrated, and to suppress the occurrence of defective fixing.

Example 2 Solid treating agents shown in Table 5 were prepared in the same manner as in Example 1 except that the formulation in (Operation 1) was changed as follows.

1,3-Propanediamine tetraironammonium acetate/monohydrate (PDTA/Fe/NH ₄ ) 5.0 mol 1,3-Propanediamine tetraacetic acid (PDTA) 0.4 mol NH ₄ Br 7.0 mol Organic acid, organic acid Salt: Total 10 mol described in Table 5 The obtained samples were evaluated for coagulability of granules and average hardness of tablets in the same manner as in Example 1. The weight variation was evaluated as follows.

(Variation in Weight of Tablet) The time from the end of preparation of granules to tableting (the time from the end of (Operation 4) to the start of (Operation 5)) was 120 hours, and 10 tablets were prepared. A total of 30 tablets were sampled one by one.

The weight of the obtained sample was measured and the coefficient of variation was determined to evaluate the variation.

The results are shown in Table 7.

[0088]

[Table 6]

[0089]

[Table 7]

From the table, it is recognized that the variation of the weight is small when the ratio of the ammonium salt of an organic acid to the total amount of the organic acid is 2 mol% or more, and further 3 to 80 mol%. It can be seen that this is preferable for improving replenishment accuracy.

Example 3 Solids shown in the table in the same manner as in Example 1 except that the formulation in (Operation 1) was changed as follows and the addition amount of the granulating liquid in (Operation 3) was changed to 35.7 g. A treating agent was prepared.

1,3-Propanediamine Tetraammonium Iron Acetate Monohydrate (PDTA•Fe•NH ₄ ) 1.0 mol 1,3-Propanediamine tetraacetic acid (PDTA) 0.05 mol NH ₄ Br 2.0 mol Demol MS (Kao Corporation) 2.5g sodium p-toluenesulfonate 10g Organic acid Listed in table Listed in table Organic acid salt Listed in table Listed in carbonate table Listed in table Solid coagulability of the obtained solid processing agent (preservation The period was 1 week and 4 weeks), and the variation in the average hardness and weight of the tablets was evaluated. The formulations and results of each sample are shown in Tables 8-11.

[0093]

[Table 8]

[0094]

[Table 9]

[0095]

[Table 10]

[0096]

[Table 11]

From this, it is understood that by using the organic acid hydrogen salt of the present invention, the coagulation of the granules can be prevented, the variation in the weight of the tablets can be reduced, and the stable production can be performed. Also, the ratio to the iron complex salt is in the range of 0.05 to 4.0 in terms of molar ratio,
Especially, a larger effect is recognized in the range of 0.10 to 2.0.

Example 4 A solid processing agent for bleaching was prepared according to the following procedure.

(Operation 4-1) 1,3-Propanediamine tetraironammonium acetate/monohydrate (PDTA/Fe/NH ₄ ) 2000 g 1,3-Propanediamine tetraacetic acid (PDTA) 100 g Organic acid Listed in Table 12 Listed in Table 12 Listed in Table 12 Listed in Table 12 NH ₄ Br 7.0 mol Carbonate or bicarbonate Listed in Table 12 Listed in Table 12 Sodium p-toluenesulfonate 30 g Each of the above compounds in a conditioned room Weigh out maleic acid
MIKRO- for bromide, hydrogencarbonate and organic acid alkali salts
Pulverizer (described above) was used to grind to a weight average particle size of 30 μm or less. For other compounds,
If necessary, make sure that the particle size distribution is such that particles with a particle size of 300 μm or less are 30% by weight or more, particles with a particle size of 500 μm or less are 80% by weight or more, and particles with a particle size of 1000 μm or more are less than 2% by weight. It was adjusted by crushing and classifying.

(Operation 4-2) D-Sorbit 7 in 160 g of water
A granulation liquid was prepared by adding 0 g.

The following are (operation 3) to (operation 5) in Example 1.
The bleaching tablet sample shown in Table 12 was prepared in the same manner as in. (Processing of photosensitive material) Color negative film processor CL-KP-50Q
The replenishing device part of A (manufactured by Konica Corp.) was modified as shown in FIG. 1, and the solid processing agent supply (input) device shown in FIG. 2 was used. Konica Color Negative Film Super DD100
After imagewise exposing (135-24 shots), set a columnar container containing tablets in the tablet loading part and treat with 10 treatments per day for 60 days using the treatment agent shown below. , Desilvering property, foaming property, and presence/absence of fixing failure were evaluated.

FIG. 1 shows solid processing agent replenishing devices 2A, 2B, 2
FIG. 3 is a view showing the mounting positions where C and 2D are mounted on the automatic developing machine, and the solid processing agent replenishing devices 2A, 2B, 2C,
2D is a color developing tank 1A, a bleaching tank 1B, a fixing tank 1C,
It is attached to the upper part of the stabilizing tank 1D at the position shown by the diagonal lines. FIG. 2 shows solid processing agent replenishing devices 2A, 2B, 2C,
In the 2D configuration diagram, a dissolution chamber 106 into which a solid processing agent 111 is charged is provided beside each tank.

In FIG. 2, the solid processing agent 111 is contained in a container (cartridge) 101 divided into a plurality of chambers and sealed by a slide type cap 102. When this cartridge is set on the cartridge support base 103 of the solid processing agent automatic supply device installed in the upper part of the processing tank of the automatic processor, the cap 102 is opened, and the tablet is cut from the cartridge fixed obliquely and the rotary cylinder 104 is cut. Rolls into mouth 105. The slits 105 of the rotating cylinder 104 are staggered so that a plurality of tablets stored in different chambers of the cartridge do not roll down at the same time.

Treatment process Treatment temperature Treatment time Tablet replenishment amount Replenishment water amount Tank capacity Color development 38.0°C 3 minutes 15 seconds 8.48m/tablet 16.6ml/m 21l Bleach 38.0°C 45 seconds *1 2.7ml/m 6l Fixing-1 38.0 ℃ 45 seconds − − 5l Fixing − 2 38.0° C. 45 seconds 2.75m/tablet (18.0ml/m) *2 5l stable − 18.0°C 20 seconds − − 3l stable − 2 38.0°C 20 seconds − − 3l stable − 38.0 ℃ 20 seconds 110m/tablet 30.0ml/m ² *3 3l dry 40-70℃ − − − *1 PDTA, Fe, NH ₄ contained in the bleaching solution is the photosensitive material. The value was set such that 1.8 g was replenished per 1 m. The bleaching tank was aerated with an air pump.

*2 The fixing bath is a countercurrent system from Fixing-2 to Fixing-1, and the amount of replenishing water to the fixing tank is stable-1 and is supplied by a bellows pump as a dissolved water instead of replenishing water. It is the amount that is done.

*3 Stabilization bath is stable-3 → stable-2 → stable-
This is the countercurrent method of 1.

Evaporation correction is color development, bleaching, fixing-1, fixing-2, stable-1, stable-2, stable- during temperature control.
10ml, 6.5ml, 7ml, 7ml, 8.6ml in 1 hour each in 3 tanks
Evaporation correction was performed using a program that replenishes 8.6 ml and 9.3 ml of water. When not in operation, the non-operation time is added up, and color development, bleaching, fixing-1, fixing-2, stable-1, stable-2,
Stable -3 with evaporation-corrected water 7.5 ml/hour, 5 m each
A total of 1, 6 ml, 5 ml, 5 ml and 5 ml were replenished with water at the start of operation. The following tank liquid was used at the start.

<<Color development tank liquid>> (per 11) Potassium carbonate 30.0 g Potassium bicarbonate 4.2 g Sodium sulfite 4.5 g Diethylenetriamine pentaacetic acid 5 sodium 2.6 g Polyethylene glycol #6000 (manufactured by Tokyo Kasei KK) 5.0 g p-toluene Sodium sulfonate 3.0 g Mannitol 3.0 g Hydroxylamine sulfate 4.0 g Potassium bromide 1.7 g Potassium iodide 4 mg Procatechol-3,5-disodium disodium salt 0.2 g Pine Flow (Matsuya Chemical Co., Ltd.) 0.32 g CD-4 [4 -Amino-3-methyl-N-ethyl-β-(hydroxy)ethylaniline sulphate] 5.0 g N-myristoylalanine sodium 0.3 g Sulfuric acid or potassium hydroxide is used to adjust the pH to 10.0±0.05.

<<Bleaching Tank Liquid>> (per 11) 1,3-Propanediamine 4 Acetic Acid Policy 2 Iron Ammonium Monohydrate 140.0 g 1,3-Propanediamine 4 Acetic Acid 6.7 g Ammonium Bromide 60.0 g Succinic Acid 80.0 g Demol MS (Manufactured by Kao Corporation) 2.1 g Sorbitol 3.5 g N-lauroyl sarcosine sodium 7.2 g Ammonia water is used to adjust the pH to 4.35±0.5.

<Fixing tank liquid> (per 11) Ammonium thiosulfate 225.0 g Sodium thiosulfate 25.0 g Sodium sulfite 18.0 g Ethylenediaminetetraacetic acid disodium 3.5 g Pine flow (Matsuya Chemical Co., Ltd.) 10.0 g N-lauroyl sarcosine sodium 1.5 g Potassium carbonate PH=7.0±0.5.

<Stable tank liquid> (per 11) m-Hydroxybenzaldehyde 1.5 g Megafac F116 (Dainippon Ink and Chemicals, Inc.) 0.05 g Lithium hydroxide monohydrate 0.16 g Ethylenediaminetetraacetic acid disodium 0.2 g Pine flow (Matsuya Chemical Co., Ltd.) 0.1g Potassium hydroxide is used to adjust the pH to 8.5±0.5.

A solid processing agent for replenishment was prepared as follows.

(1) Tablets for color development Tablet preparation operation (A) Potassium carbonate 375 g, sodium sulfite 58.0 g, diethylenetriamine pentaacetic acid 5 sodium salt 24.0 g, PEG#600
00.0 g and 80.0 g of Mannitol are crushed in a commercially available bandam mill to an average particle size of 10 μm. This fine powder was granulated by adding 100 ml of water for about 7 minutes at room temperature with a commercially available stirring granulator, and then the granulated product was dried at 70° C. for 60 minutes using a commercially available fluidized bed dryer. The granules are dried to almost completely remove water.

Operation (B) Hydroxylamine sulfate 36.0 g, potassium bromide 4.3 g,
2.0 g of disulfocatechol disodium and 2.0 g of pine flow (manufactured by Matsutani Chemical Co., Ltd.) are pulverized in the same manner as in the operation (A), then mixed and granulated. The amount of water added is 3.5 ml, and after granulation, it is dried at 60° C. for 60 minutes to almost completely remove the water content of the granulated product.

Operation (C) CD-4 [4-amino-3-methyl-N-ethyl-β-]
(Hydroxy)ethylaniline sulfate] 150 g was pulverized in the same manner as in step (A) and then granulated by adding 10 ml of water at room temperature for about 7 minutes.
The granulated product is dried at 2°C for 2 hours to almost completely remove water.

Operation (D) The granule samples prepared in the above operations (A) to (C) were mixed at room temperature with a commercially available cross rotary mixer for 10 minutes, and 0.3 g of sodium N-myristoylalanine was added. And mix for 3 minutes. The mixed granules thus obtained were continuously tableted by a rotary tableting machine (Kikusui Seisakusho Co., Ltd., Clean Press Collect H18) to obtain a diameter of 30 mm,
600 color negative film color developing tablet samples having a thickness of 10.0 mm and a weight of 10.3 g were obtained.

Tablet coating 6 kg of the color-developing tablet for color negative described above was put in a Doria Coater 500 type manufactured by Paulec Co., Ltd., and the intake temperature was adjusted to about 6
Adjust the exhaust temperature to 0℃ and the exhaust temperature to 40-45℃, and adjust the pan rotation speed to 8
set to rpm.

In this state, polyethylene glycol #600
0: Bis(sulfoethyl)hydroxylamine disodium salt: Erythrosin (Daiwa Kasei Co., Ltd.): Vitrex (Macfarlan Smith Limited)=3500:1500:1:1
To prepare an aqueous solution in which these solid components are 50%. Spray pressure of this aqueous solution 2.0 kg/c
The amount of m ^{2 was} sprayed at 5 g/min, and coating was performed until the solid content weight of the coating substrate was 1.0% based on the total weight of the tablet.

(2) Tablet for Bleaching Tablet coating 6 kg of the bleaching tablet was placed in a Doria Coater 500 type manufactured by Paulec Co., Ltd., and the intake temperature was about 60° C. and the exhaust temperature was 40.
The temperature was adjusted to ˜45° C., and the rotation speed of the pan was set to 8 rpm.

In this state, erythrosine (Daiwa Kasei Co., Ltd.): quinoline yellow (Daiwa Kasei Co., Ltd.): erythritol: Vitrex (Macfarlan Smith Limite)
d)=5:5:30000:10 at the ratio of mixing to prepare an aqueous solution in which these solid components are 30%. This aqueous solution was sprayed at a spraying pressure of 2.0 kg/cm ² and an amount of spraying of 5 g/min, and coating was performed until the solid content weight of the coating substrate was 0.5% based on the total weight of the tablet.

(3) Fixing tablets Preparation of tablets (E) Ammonium thiosulfate 1350 g, sodium thiosulfate 150
g, sodium sulfite 350 g, 3-mercapto-1,
10 g of 2,4-triazole, 40 g of potassium carbonate, 40 g of ethylenediamine tetraacetic acid disodium salt and 40 g of Pine Flow (Matsuya Chemical Co., Ltd.) were crushed and mixed in the same manner as in the operation (A).
Granulate. The amount of water added is 50 ml, and after granulation, 120 at 60°C.
The granules are dried for a minute to almost completely remove the water content. This operation was repeated to produce about 5 kg of granules.

Operation (F) 0.5% by weight of the granulated product of N-lauroylsarcosine sodium was added to the granulated product prepared in the above operation (E), and the mixture was mixed at 40°C at 25°C.
Mix for 3 minutes with a mixer in a room conditioned below %RH. Next, the mixture was compressed into tablets with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. with a filling amount of 11.0 g per tablet to form fixing tablets.

(4) Stabilized tablets Preparation of tablets Operation (G) 1500 g of hydroxybenzaldehyde, Megafac F11
6 (manufactured by Dainippon Ink and Chemicals, Inc.), 50.0 g of ethylenediaminetetraacetic acid disodium, 160 g of lithium hydroxide monohydrate and 100 g of pine flow are pulverized, mixed and granulated in the same manner as in the operation (A).

Water is added to 100 ml, and after granulation, the granulated product is dried at 50° C. for 2 hours to almost completely remove the water content of the granulated product.

Operation (H) The granules prepared in the above operation (G) were continuously tableted in a room where the humidity was adjusted to 25° C. and 40% RH or less in the same manner as in the operation (A) to obtain a diameter of 30 mm and a thickness of 10.0. A stable tablet sample for color negative film having a size of 8 mm and a weight of 8.9 g was prepared.

Coating of Tablets 6 kg of the above-mentioned stabilized tablets for color negative are supplied by Paulec Co., Ltd.
Put in the Doria Coater 500 type manufactured by the company, the air supply temperature is about 60 ℃,
Adjust the exhaust temperature to 40-45℃ and adjust the pan rotation speed to 8 rpm.
Set to.

In this state, Brilliant Blue (Daiwa Kasei Co., Ltd.): Quinoline Yellow (Daiwa Kasei Co., Ltd.): Erythritol: Vitrex (Macfarlan Smith Limite)
d)=4:8:30000:10 were mixed to prepare an aqueous solution in which these solid components were 30%. This aqueous solution was sprayed at a spraying pressure of 2.0 kg/cm ² and an amount of spraying of 5 g/min, and coating was performed until the solid content weight of the coating substrate was 0.5% based on the total weight of the tablet.

The evaluation was performed as follows.

(Desilvering property) After completion of the 60-day running process, the Konica Color Negative Films LV400 (ISO400) and GX3200 (ISO3200) manufactured by Konica Co., Ltd. were subjected to wedge exposure to obtain the maximum exposed area. Evaluation was made by the difference in infrared absorption density from the unexposed area.

(Fixing failure) Further, the above-mentioned negative film (LV400, GX3200) that had not been exposed was processed and the state of occurrence of spot-like fixing failure was visually observed.

Evaluation Criteria ⊙ No spotted fixing defects are observed at all × Spotted fixing defects are slightly observed × × Spotted fixing defects are clearly observed

Incidentally, it was confirmed that these spots were eliminated by reprocessing with a new solution of the pre-fixing solution.

(Effervescent) The appearance of the bleaching tablet when it was added to the bleaching start solution was observed.

Evaluation Criteria ◎ Foaming is hardly observed and there is no problem. ○ Slight foaming is recognized, but there is almost no problem. △ Some foaming is recognized, but there is almost no problem. × Considerable foaming is observed and tablets are added. The liquid splashes up to the part, which hinders tablet loading.

Table 12 shows the above results.

[0136]

[Table 12]

According to the table, by using the bleaching treatment agent containing the organic acid ammonium salt or the organic acid hydrogen salt of the present invention, even in the case of an extremely small amount of treatment, spot-like defects due to poor fixing are also observed. It can be seen that stable processing can be performed without any occurrence. Further, by using the organic acid salt of the present invention, the amount of carbonate used for pH adjustment can be reduced to suppress the foaming property of the treating agent, and the treating agent charging section can be used for treating liquid bubbles, mist, etc. It can be seen that the automatic operation of a stable processing agent can be ensured without being soiled with and that it is also useful for preventing the bleaching solution from contaminating the color developing tank.

Example 5 A tablet sample prepared in the same manner as in Example 4 except that the formulation of the solid bleaching treatment agent was changed as follows, and the results of the same evaluation as in Example 4 were shown in Table 13. Show.

Aminopolycarboxylic acid ferric complex salt shown in Table 13 10 mol Free acid of aminopolycarboxylic acid constituting the ferric aminopolycarboxylic acid complex salt 0.5 mol Ammonium bromide 13 mol Succinic acid Table 13 Listed in 13 Ammonium adipate Listed in Table 13 Listed in Table 13 Ammonium hydrogen succinate Listed in Table 13 Listed in Table 13 Carbonate Listed in Table 13 Listed in Table 13

[0140]

[Table 13]

As described above, the same effect can be observed with ferric aminopolycarboxylic acid complex salts other than PDTA.Fe.NH ₄ .

Example 6 Example 1 was repeated except that the amount of N-lauroyl sarcosine sodium added during mixing was changed to 0.5% by weight and distilled water was changed to 250 ml instead of the granulating liquid according to the following formulation. Performing the same operation, a tablet sample of the solid fixing agent (1 tablet 10
g) was prepared and evaluated for coagulation of the granules, tablet hardness, and fixability.

Ammonium thiosulfate 6500 g Sodium thiosulfate 700 g Potassium metabisulfite 500 g Organic acid salt As described in Table 14 Ethylenediamine tetraacetic acid 80 g 3-Mercapto-1,2,4-triazole 50 g Pine flow (Matsuya Chemical Co., Ltd.) The results are shown in Table 14.

[0144]

[Table 14]

[0145]

EFFECTS OF THE INVENTION According to the present invention, the solid treatment agent can be stably produced since it does not cause the coagulation of the granules, the tablet hardness, and the variation in the filling degree, and the solid treatment agent can be used in a system for a small amount treatment. Can also supply a solid processing agent with stable processing performance.

[Brief description of drawings]

FIG. 1 is a configuration diagram showing a mounting position of a solid processing agent replenishing device to an automatic developing device.

FIG. 2 is a configuration diagram of a solid processing agent supply (input) device.

[Explanation of symbols]

1A-1D processing tank 2A-2D Solid processing agent replenishing device 101 Cartridge 102 Sliding cap 103 Cartridge support 104 Rotating cylinder 105 Notch 106 Dissolution chamber 107 Filter 108 Shutter 109 Processing tank 110 Canopy 111 Solid processing agent (tablets)

Claims (14)

[Claims] 1. A silver halide photographic light-sensitive material containing at least one selected from a normal salt of an ammonium salt of an organic acid represented by the following general formula (1) and a hydrogen salt of the organic acid. Solid treatment agent for. [Chemical 1] Wherein, A represents an organic group, n ₁ is an integer from 1 to 6, n _2,
n ₃ represents an integer of 0 to 3, and n ₁ +n ₂ +n ₃ ≧2. ] 2. The solid processing agent for a silver halide photographic light-sensitive material according to claim 1, which is formed by granulation. 3. The solid processing agent for a silver halide photographic light-sensitive material according to claim 1, which is a tablet. 4. A solid processing agent for a silver halide photographic light-sensitive material according to claim 3, which is formed by tableting the granulated product according to claim 2. 5. The solid processing agent for a silver halide photographic light-sensitive material according to claim 1, 2, 3, or 4, which has a bleaching ability. 6. A bleaching agent, which is a bleaching agent.
The solid processing agent for silver halide photographic light-sensitive materials as described in 1. 7. A ferric amino acid complex containing iron(III) complex salt, 1, 2, 3, 4, 5 or 6.
The solid processing agent for silver halide photographic light-sensitive materials as described in 1. 8. The silver halide photographic light-sensitive material according to claim 7, wherein the molar ratio of the hydrogen salt of the organic acid to the ferric aminopolycarboxylic acid complex salt is 0.05 to 4.0. Solid processing agent. 9. The ratio of ammonium ion to the total amount of the alkali metal ion and ammonium ion contained is 55 mol% or more, 1, 2.
The solid processing agent for a silver halide photographic light-sensitive material as described in 3, 4, 5, 6 or 7. 10. The organic acid represented by the general formula (1) is further contained, and the ratio of the normal salt of the organic acid ammonium salt to the total amount of the organic acid and the salt of the organic acid is 3 to 80 mol. %, Claims 1, 2, 3, 4, 5,
6. A solid processing agent for a silver halide photographic light-sensitive material described in 6, 7 or 9. 11. The organic acid represented by the general formula (1) is represented by HOOC(CH ₂ )m ₁ COOH (m ₁ represents an integer of ₁ to 6) or the following general formula (2). The compound of claim 1, 2, 3, 4, 5, 6, 7, 8, 9
Or the solid processing agent for a silver halide photographic light-sensitive material as described in 10 above. [Chemical 2] [In the formula, m ₂ and m ₃ represent an integer of 0 to 6, and m ₂ +m ₃ =0
~6. ] 12. The organic acid represented by the general formula (1) is m basic acid (H _m L), and the hydrogen salt of the organic acid is represented by the following general formula (3). Claim 1,
The solid processing agent for a silver halide photographic light-sensitive material described in 2, 3, 4, 5, 6, 7, 8 or 11. Formula _{(3) Li x1 Na x2 K} x3 (NH 4) in _x4 H _x5 L [wherein, x1 to x4 is 0 or more, x5 is at least 1, a x1 + x2 + x3 + x4 + x5 = m, 2 ≦ m ≦ 6. ] 13. A processing method for a silver halide photographic light-sensitive material, which comprises using a processing solution obtained by dissolving the solid processing agent according to claim 1. Description: 14. The method of processing a silver halide photographic light-sensitive material according to claim 12, wherein the solid processing agent is directly charged into a processing tank for processing.