JP3393264B2 - Solid processing agents for silver halide photographic materials - Google Patents

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 a silver halide photographic light-sensitive material, and more specifically, it has excellent solubility and practically sufficient strength, and the chemical stability is dramatically improved. The present invention relates to a solid processing agent for silver halide photographic light-sensitive materials.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material (hereinafter sometimes referred to as a light-sensitive material or a photographic material) is
Processing is performed by steps such as development, desilvering, washing and stabilization.
The black-and-white silver halide photographic light-sensitive material is developed and fixed after exposure. Black-and-white developer, color developer, bleaching solution for desilvering process, bleach-fixing solution, fixing solution for fixing process, tap water or ion-exchanged water for washing, stabilizing solution for anhydrous washing, and dye stabilization Stabilizers are used for each treatment.

A liquid having a processing function for performing each of these processing steps is called a processing liquid. Each treatment liquid is usually 30 ~
The temperature is adjusted to 40 ° C., and the light-sensitive material is dipped in these processing solutions and processed.

Such processing is usually carried out by sequentially conveying the inside of a processing tank containing the above processing liquid by an automatic developing machine (hereinafter referred to as an automatic processor) or the like.

When referred to as an automatic developing machine, it has a developing section, a fixing section, a desilvering section, a washing or stabilizing section and a drying section, and means for automatically conveying the photographic light-sensitive material through the respective processing sections. It generally refers to the developing machine that it has.

In the case of processing with such an automatic developing machine, a method of replenishing the processing agent is generally widely used in order to keep the activity of the processing solution in the processing tank constant.

As a method for replenishing the treating agent, a method of preparing a replenishing solution in which the treating agent is dissolved is widely used.

[0008] Specifically, the replenishing solution prepared in advance is supplied from the replenishing tank to the processing tank at appropriate time to perform the processing operation.

In this case, the replenishing liquid itself stored in the replenishing tank is generally prepared and prepared in another place, but in a minilab or the like, the replenishing tank is installed in a constant amount in a replenishing tank installed close to the developing machine. It is usually adjusted all at once, but in its production, dissolution by hand or dissolution and mixing by a mixer has been performed.

That is, a processing agent for silver halide photographic light-sensitive materials (hereinafter sometimes referred to as a photographic processing agent) is commercially available in the form of powder or liquid.
In the case of a powder, it is prepared by manually dissolving it in a fixed amount of water, and in the case of a liquid, it is concentrated so that a fixed amount of water is added and the mixture is simply stirred and diluted before use.

The replenishment tank may be installed next to the automatic machine, and it is necessary to secure a considerable space. In addition, even in the minilab, which has been increasing rapidly in recent years, a replenishment tank is built in the machine itself, but at least 5-10L
It is necessary for each liquid and it is necessary to secure the space for this replenishment tank.

Replenishing processing agents are divided into several parts in order to obtain good and stable performance during photographic processing. The color developing solution for color is divided into 3 to 4 parts, and the replenisher for the bleach-fixing solution for color is divided into a ferric salt of organic acid which is an oxidizing agent and a thiosulfuric acid part which is a reducing agent. When the replenisher is prepared, the concentrated part of the ferric salt of organic acid and the concentrated part containing thiosulfate are mixed and a certain amount of water is added for use.

The concentrated parts are put in a container such as a plastic container, and these are put together in an outer bag (for example, a cardboard box) and sold as a unit.

The replenishing treatment agent in which the above-mentioned part agent is made into a kit is used after dissolving, diluting, mixing and finishing to a fixed amount, but the replenishing treatment agent has the following problems.

First, most of the conventional kits are concentrated and concentrated aqueous solutions for improving workability, and most of them are extremely dangerous aqueous solutions with a pH of 2.0 or less or 12.0 or more. Many of them are very dangerous and are often strong oxidizers or reducing agents, and they have extremely dangerous corrosiveness when transported by ship or aircraft. Further, since it is an aqueous solution, its solubility is limited, and its weight and volume are larger than those of a solid. As described above, since the concentrate is a dangerous substance, it is necessary that the container does not break even when dropped from a certain height and the liquid does not spill. Therefore, most of the containers are made of polyethylene or polyvinyl chloride, and disposal of these poly containers is a problem.

Secondly, each part agent is placed in a container,
Depending on the replenishment processing agent, the number of part agents is several, and the number of containers is considerably large when it becomes one unit, which requires a lot of space for storage and transportation. For example, the color developing replenisher for CPK-2-20QA, which is a processing solution for color paper, is 10
The preservative-containing kit is divided into Part A, the color-developing agent-containing kit is divided into Part B, and the alkaline agent is divided into Part C with 1 as 1 unit, and each of A, B and C is contained in a 500 ml poly container. Similarly, the bleach-fixing solution has 8 l as a unit, and the parting agent is divided into 3 bottles, and the stabilizing solution has 10 l as a unit, and the parting agent is divided into 2 bottles. Each of these replenishers will be stored and transported in outer boxes of various sizes.At this time, the required volume is about 17 cm × 14 cm × 16.5 cm, which is a stable solution with a small outer box. A large bleach-fixing agent measures approximately 18.5 cm x 30.5 cm x 22.5 cm, and can only be stacked with the same type of replenisher during storage, transportation, or in a store, requiring a lot of space.

The third problem is the disposal of empty containers after use. In recent years, there has been a strong demand for environmental protection and resource saving mainly in Europe and the United States, and the disposal of the above-mentioned plastic containers has become a problem particularly in the photographic field. Although the plastic containers for photographs are cheap and convenient for storage and transportation, and have excellent chemical resistance, the plastic containers have little biodegradability and accumulate a large amount of carbon dioxide gas when incinerated. It is one of the causes of global warming and acid rain, and another problem is that a large number of empty plastic containers are piled up in a narrow work space and they cannot be crushed due to their strength. , The user's work space is narrowed.

Fourth, the chemical is very unstable.

Generally, the life of the replenisher is 2 weeks even if a floating lid is used in the replenisher tank. Further, recently, the replenishment amount of each processing solution has been lowered, and 10 L of the replenishing solution is often used for more than one month in a minilab that receives an average of 30 color films per day.

In such a case, the replenishing solution in the replenishing tank has a much higher rate of contact with air than the treating solution in the processing tank, so that the deterioration is remarkable and it is often meaningless to replenish it. ing. Therefore, the replenishment tank has been reduced to 5 L and the accommodation unit of the replenishment kit has been reduced to 5 L. However, in this case, there is a drawback that a packaging material is further required.

Further, when preparing a color developing replenisher for color paper, after a certain amount of water is put into a replenishing tank, a preservative-containing concentration kit A is added and stirred, and then a color developing agent is contained. Concentration kit B is added and stirred, then alkali agent-containing concentration kit C is added and stirred, and finally water is added to a certain amount. At that time, some problems are likely to occur. For example, if the stirring is insufficient or if the first water is forgotten to be added, crystals of the color developing agent tend to precipitate, which accumulates in the bellows pump and is not replenished, resulting in unstable photographic performance. Or the bellows pump may be damaged. Further, the concentration kit is not used immediately after the production but may be used one year or more after the production, and in some cases, the color developing agent and the preservative may be oxidized and the performance may become unstable.

It is known that the color developing replenisher prepared from the concentration kit or the powder also has some problems in the replenishing tank. For example, if the replenisher is not used for a long period of time, crystals may adhere to the wall of the refill tank,
In addition, the replenisher may be easily oxidized and tar may be generated. In addition, depending on the storage conditions, there is a problem that components that easily crystallize in the replenisher, such as color developing agents, will precipitate at low temperatures.Therefore, depending on the manufacturer, the storage conditions of the replenisher may be specified and managed by the user. It is the actual situation that I am instructing.

As described above, the method for preparing a replenishing solution using a commonly used concentration kit or the method for preparing a replenishing solution using a dusting agent is exemplified by a color developing solution for color paper. There are the above-mentioned problems, and there are similar problems with bleach-fixing solutions, bleaching solutions and fixing solutions. For example, the bleach-fixing solution has a characteristic that storage stability is extremely poor. Because the bleach-fixing process is a process immediately after the color developing solution having a high pH, and since this alkaline color developing solution is usually brought in by the paper to be processed, the acidity is high and the pH is remarkably low for the purpose of neutralization. Is customary. At a low pH, it is said that a bleach-fix solution composed of thiosulfate and an oxidizer has a markedly poor storability and a replenisher is prepared to make low replenishment impossible. In addition to this, the same applies to the fixing solution and the stabilizing solution.

Another problem is that the replenisher solution is only thickened as the replenishment rate is lowered and speeded up, and the recent replenisher solution is usually concentrated to the solubility limit.

This means that the storability of the replenisher is only poor, and it has many practical problems such as crystal precipitation.

On the other hand, in addition to the method of preparing a replenisher using the concentration kit or powder as described above, a method of directly replenishing the concentration kit is known.

In this method, in order to improve the inefficiency of the dissolving work, the concentration kit is directly replenished in the treatment tank by using a supplying means such as a bellows pump, and a certain amount of replenishing water is independently supplied. is there. Certainly, this method does not require a liquid preparation operation as compared with the method of adjusting the replenisher solution from the above-mentioned concentration kit or powder. Alternatively, since a replenisher is not prepared, the problem of storability is eliminated.

However, the above method also has many problems. That is, in order to supply the concentration kit, a tank for the concentration kit and a pump as a supply means are newly required, which is a problem that the automatic developing machine becomes large. For example, taking CPK-2-20 which is a processing solution for color paper as an example, there are 3 parts of a color development replenisher replenisher concentration kit, a bleach-fix replenisher replenisher concentration kit 3 parts, and a stable replenisher concentration The kit is in 2 parts, and when it is supplied, there are 8 tanks for the concentration kit and 8 pumps.
I need a stand. In the case of the conventional replenishment system, it is sufficient to have a tank and a pump for each replenisher, so that three replenishers are sufficient. Looking only at the case of supplying the concentration kit like this, more tanks and pumps are required than the conventional method,
Furthermore, a pump for adjusted water is also required. Further, the accuracy of the bellows pump is not so high, and it is difficult to simultaneously discharge a plurality of liquids with high accuracy, and there is a drawback that the components are crumpled.

Furthermore, since the concentration kit is a concentrated liquid, crystals are likely to precipitate near the outlet of the replenishing nozzle, which makes maintenance difficult. Further, there is a problem that the bellows pump does not have such a high supply accuracy, and when replenishing the concentrated liquid, the replenishment accuracy is likely to be significantly different, resulting in a large variation in photographic performance. As another problem, the conventional replenishment method and the amount of the waste poly container do not change even if the waste poly container is provided with the concentration kit.

Other than the above methods, some proposals have been made for solid photographic processing agents for eliminating the plastic container and improving the chemical stability of the replenisher.

For example, JP-A-54-133332 and JP-A-54-155038 disclose powdery photographic processing agents, and JP-A-2-09042.
Nos. 2-109043, 3-39735 and 3-39739 disclose methods of using granulated photographic processing agents having a certain average particle size. Since the method described in the above publication does not use a liquid photographic processing agent and therefore has the effect of improving the stability of the replenisher without using a poly container, the aforementioned processing agent is in the case of a powder. However, there are drawbacks such as blocking during storage to cause poor dissolution, and powder scattering during preparation of the treatment liquid, deteriorating the working environment.

Also, in the case of the granular treatment agent, although the phenomenon such as blocking is improved to some extent, the scattering of dust cannot be completely prevented.

In order to solve these problems, tabletized photographic processing agents are known from WO92 / 200B and the like.

Although this tableted photographic processing agent is a solution to the above-mentioned dust scattering problem, it has a drawback that its solubility becomes extremely poor as compared with powdery or granular photographic processing agents. is doing. Therefore, in order to increase the solubility,
No. 51-61837 discloses a photographic processing tablet containing a disintegrant. However, since the disintegrant described in the above publication uses a water-swellable colloid, when the processing liquid is adjusted from the tablet containing the colloid, the colloid adheres to the rack or the transport roller of the developing machine, and the photosensitive material is processed. It turned out that there is a serious drawback that it causes stains on the. Further, effervescent tablets are known as means for promoting dissolution of tablets, for example, in pharmaceutical products. This is a method of promoting dissolution by internal disintegration of tablets by utilizing the foaming action during dissolution. However, this method requires a foaming agent in order to produce a foaming effect, and if the content of the main active ingredient per tablet is low like pharmaceutical products, a large amount of foaming agent can be added to maintain the foaming effect. However, in the case of a photographic processing agent, if a component other than the essential components for photographic processing is contained, the processing capacity per tablet decreases, and there is a drawback that more than the originally required processing component is required.

As another problem, for example, in the case of a color developing tablet, when it is sealed in a moisture-proof packaging material and stored for a long period of time,
The tablets may be colored depending on the storage conditions, and although there is no problem in terms of processing performance, the commercial value may be significantly reduced.

Therefore, as a result of intensive studies on the solubility of the photographic processing tablets, the present inventors have found that the solubility can be controlled by adjusting the strength of the tablets without adding a special additive such as a disintegrant or a foaming agent. I found a thing.

This is not described in the above publication, and the invention of the present application was completely unexpected.

[0038]

SUMMARY OF THE INVENTION The first object of the present invention is to:
In addition, it is to achieve the practical application of an automatic developing machine that eliminates liquid chemicals that pose transport and handling hazards and enables solid chemicals to be used without complicated operations for users.

Secondly, to supply a solid processing agent having excellent solubility and practically sufficient strength.

Thirdly, it is necessary to supply a solid processing agent which is excellent in long-term storability and is easy to approach.

[0041]

In order to solve the above problems, the present inventors have found that the above problems can be solved by the following constitution.

(1) A tablet obtained by press-compacting a granulated product containing at least one treating agent component, wherein the strength Z of the tablet is in the following range. Solid processing agent for photosensitive materials.

0.5 ≦ Z ≦ 3.5 where Z = compressive breaking strength of tablet (kg) / length of tablet in longitudinal direction (mm) (2) The above tablet is a disk-shaped tablet The solid processing agent for silver halide photographic light-sensitive materials as described in 1) above.

(3) Length of the above tablet in the longitudinal direction: X (m
m) and thickness: H (mm) ratio: X / H is in the range of 1.0 to 6.0. The solid processing agent for silver halide photographic light-sensitive materials as described in (1) or (2) above.

(4) The solid processing for silver halide photographic light-sensitive material as described in any one of the above items (1) to (3), wherein the tablet contains at least one para-phenylenediamine type color developing agent. Agent.

(5) The above-mentioned tablet is obtained by compressing a granule containing at least one para-phenylenediamine color developing agent and a granule containing at least one alkali agent. (1)-
The solid processing agent for silver halide photographic light-sensitive materials as described in any one of (4).

(6) The solid for a silver halide photographic light-sensitive material as described in any of the above items (1) to (3), wherein the tablet contains at least one ferric aminopolycarboxylic acid complex salt. Processing agent.

(7) The solid processing agent for a silver halide photographic light-sensitive material as described in any one of the above items (1) to (3), wherein the tablet contains at least one thiosulfate salt.

(8) The tablet is obtained by compressing a granule containing at least one ferric aminopolycarboxylic acid complex salt and a granule containing at least one thiosulfate salt. The solid processing agent for a silver halide photographic light-sensitive material according to any one of the above items (1) to (3).

The present invention will be described in more detail below.

As a method for compressing the photographic processing agent under pressure to form a tablet, a known method can be used, but a preferable method for forming a tablet is to granulate a powdery solid processing agent and then compress it into tablets. This is a method of forming by performing steps. 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.

As the granulation method for forming tablets, known methods such as rolling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation and spray drying granulation are used. Can be done.
For tablet formation, the average particle size of the obtained granules is 100-800 μm in that when the granules are mixed and compressed under pressure, the components become nonuniform, so-called segregation does not easily occur. It is preferable to use one, more preferably 200 to 750 μm
Is. Furthermore, the particle size distribution is ± 10 for 60% or more of the granulated particles.
Those within a deviation of 0 to 150 μm are preferred. More preferably, at the time of granulation, the above-mentioned effects become more remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a bleaching agent, a preservative and the like. When compressing the obtained granulated product under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a briquetting machine can be used.

The physical strength Z of the solid processing composition of the present invention is 0.5.
Between 3.5 and 3.5, preferably between 0.8 and 3.0. When the strength is less than 0.5, the solid treatment agent obtained is extremely brittle and cannot be put to practical use. Also, if it exceeds 3.5, the elasticity of the solid processing agent is lost, and it becomes easier to chip, or
This is because the solubility of itself deteriorates extremely. The physical strength in the present invention is defined by the following formula.

Z = compressive breaking strength of tablet (kg) / length of tablet in longitudinal direction (mm) The above compressive breaking strength is perpendicular to the compression molding direction of the tablet (parallel to the compression molding surface of the tablet). That is, the value when a pressure is applied in the direction to break. The measurement conditions are a room temperature of 25 ° C. and a humidity of 50% RH, and a tablet hardness meter: Speed Checker TS-50N (Okada Seiko Co., Ltd.) is used, and the compression rate of the hardness meter is 5 to 78 mm / min. The compression speed can be arbitrarily set within the above range depending on the size and shape of the tablet to be measured.

Next, the length of the tablet in the longitudinal direction refers to the diameter of the circle when the tablet has a disk shape, and when the tablet has a polygonal shape, the surface in contact with the compression surface of the hardness tester in parallel with the surface. On the other hand, it means the distance to the farthest point or plane in the compression direction of the hardness tester.
A deformed shape in which an ellipse, a circle, a polygon, etc. are combined refers to the distance from the point of contact with the compression surface of the hardness tester to the longest point in the compression direction.

The tablet of the present invention can have any shape, but a disk-shaped tablet is preferable from the viewpoint of productivity and handleability. In the case of the disk-shaped tablet, the length in the longitudinal direction of the tablet refers to the diameter of the tablet, but the diameter at this time can be any value depending on the purpose of use. From the viewpoint of productivity, it is preferably 5 to 50 mm, more preferably 7 to 30 mm.
Is. On the other hand, the ratio x of the length x in the oblong direction of the tablet and the thickness h
/ H is preferably in the range of 1.0 to 6.0, more preferably 2.5 to 5.0. When the above ratio is less than 1.0, the thickness of the obtained tablet increases, the solubility deteriorates and the productivity also deteriorates. If it exceeds 6.0, the desired strength cannot be obtained.

From the viewpoint of productivity, the tablet of the present invention preferably has a weight of 0.1 to 30 g per tablet. The use form of the solid processing agent according to the present invention can be any method depending on the purpose, but from the viewpoint of downsizing of the automatic developing machine, reduction of processing waste liquid, etc., a replenishing agent for the processing tank of the automatic developing machine. The direct injection method is preferred.

As the color developing agent used in the color developing agent in the present invention, a p-phenylenediamine compound having a water-soluble group is preferably used because the effect of the present invention is excellent and the fog is small. To be

The p-phenylenediamine-based compound having a water-soluble group has less contamination of the light-sensitive material and skin than the para-phenylenediamine-based compound having no water-soluble group such as N, N-diethyl-p-phenylenediamine. As for the above, not only has the advantage that the skin is not easily fogged, but the object of the present invention can be achieved more efficiently by combining it with the color developing solution of the present invention.

Examples of the water-soluble group include those having at least one amino group of the p-phenylenediamine compound or on the benzene nucleus, and specific water-soluble groups include-(CH ₂ ) _n -CH ₂ OH. ,-(CH ₂ ) _m -NHSO _2- (CH ₂ ) _n CH ₃ ,-(CH
_{2) m -O- (CH 2)} n -CH 3, - (CH 2 CH 2 O) n C m H 2m + 1 (m and n
Each represents an integer of 0 or more. ), --COOH group, --SO ₃ H
A group and the like can be mentioned as preferable ones.

Specific examples of the color developing agent preferably used in the present invention include, but are not limited to, the following compounds.

[0062]

[Chemical 1]

[0063]

[Chemical 2]

[0064]

[Chemical 3]

[0065]

[Chemical 4]

The color developing agent is usually used in the form of a salt such as hydrochloride, sulfate or p-toluenesulfonate.

Further, in the present invention, the effect of the object of the present invention is better exhibited by containing the compound represented by the following general formula [A] in the color developer according to the present invention.

That is, when it is made into a solid processing agent, it is effective in that not only the storage stability of the solid processing agent such as tablets is improved but also the strength can be maintained as compared with other compounds, and moreover, it is stable in photographic performance. There is also an advantage that less fog occurs in the exposed area.

[0069]

[Chemical 5]

In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group.

The compound represented by the above general formula [A] according to the present invention is preferably a compound represented by the following general formula [A '] from the viewpoint of the present invention.

[0072]

[Chemical 6]

In the formula [A '], L has 1 to 1 carbon atoms.
It represents a straight or branched alkylene group of 0, preferably 1 to 5, and may be substituted. Examples thereof include methylene, ethylene, trimethylene, propylene, etc., and the substituents are a carboxyl group, a sulfone group, a phosphon group, a phosphinic acid residue, a hydroxy group, a cyano group, and a carbon number of 1 to 5
Examples thereof include an ammonio group which may be alkyl-substituted to some extent.

A is a carboxy group, a sulfone group, a phosphonic group, a phosphinic acid residue, a hydroxy group, an amino group having about 1 to 5 carbon atoms which may be substituted with an alkyl group, or an alkyl group having about 1 to 5 carbon atoms which may be substituted. Good ammonio group, carbon number 1 ~
It represents a carbamoyl group which may be alkyl-substituted with about 5 carbon atoms, a sulfamoyl group which may be alkyl-substituted with about 1 to 5 carbon atoms, and an alkylsulfonyl group which may be substituted.

Examples of A-L- include carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, hydroxyethyl group and the like.

R ₃ represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and may be substituted. As a substituent, a carboxy group, a sulfone group, a phosphone group, a phosphinic acid residue, a hydroxy group, a cyano group, a carbon number of 1 to 1
Examples thereof include an ammonio group which may be substituted with about 5 alkyl groups. Further, L and R may be connected to each other to form a ring.
These compounds are used not only as free amines but also as salts such as hydrochlorides, sulfates, oxalates, p-toluenesulfonates, alkali metal salts and ammonium salts.

Next, specific compounds represented by the general formula [A] will be exemplified, but the compounds are not limited to these compounds.

[0078]

[Chemical 7]

Compounds A-12 to A-20 and A-27
Can be used in the form of an alkali metal salt (sodium salt, potassium salt, lithium salt, etc.).

Among these, particularly preferable compounds are the following compounds.

[0081]

[Chemical 8]

A small amount of sulfite may be used as a preservative in the color developing agent used in the present invention. Examples of the sulfite include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite and the like.

It is necessary to use a buffering agent in the color developing agent used in the present invention. Examples of the buffering agent include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate and triphosphate. Potassium, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), o-
Examples thereof include potassium hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like.

The color developing agent used in the present invention preferably contains a triazinyl stilbene type optical brightening agent from the viewpoint of the effect of the object of the present invention. As such a fluorescent whitening agent, a compound represented by the following general formula [E] is preferable.

[0085]

[Chemical 9]

In the above formula, X ₂ , X ₃ , Y ₁ and Y ₂ are each a hydroxyl group, a halogen atom such as chlorine or bromine, an alkyl group, an aryl group,

[0087]

[Chemical 10]

Or represents --OR ₂₅ . Where R ₂₁ and R ₂₂
Each represents a hydrogen atom, an alkyl group (including a substituent), or an aryl group (including a substituent), R ₂₃ and R ₂₄ represent an alkylene group (including a substituent), and R ₂₅ represents a hydrogen atom or an alkyl group ( (Including a substituent) or an aryl group (including a substituent), and M represents a cation.

The details of each group of the general formula [E] or the substituents thereof are the same as those described in JP-A No. 4-118649, from the lower left of page 16 to the ninth line to the upper right of page 17. .

Specific examples of the compound represented by the general formula [E] will be given below.

[0091]

[Chemical 11]

[0092]

[Chemical 12]

[0093]

[Chemical 13]

[0094]

[Chemical 14]

[0095]

[Chemical 15]

[0096]

[Chemical 16]

The above compound can be synthesized by a known method. Among the above-exemplified compounds, particularly preferably used are E-4, E-24, E-34, E-35, E-36 and E-.
37, E-41. The addition amount of these compounds is preferably adjusted such that the solid processing agent is in the range of 0.2 to 10 g per liter of the color developing solution, and more preferably 0.4 to 5 g.

Further, the color developing agent of the present invention is described in JP-A-4-11.
In the present invention, it is preferable to add a chelating agent represented by the following general formula [K] and its exemplified compounds K-1 to K-22 described in the 8th line to the 20th line from the upper right of page 19 of Japanese Patent No. 8649. It is preferable from the viewpoint of effectively achieving the purpose.

[0099]

[Chemical 17]

Among these chelating agents, K
-2, K-9, K-12, K-13, K-17, and K-19 are preferably used, and especially K-2 and K-9 exhibit the effect of the present invention.

The main bleaching agent preferably used in the bleaching agent or bleach-fixing agent according to the present invention is a ferric iron complex salt of an organic acid represented by the following general formula [C].

[0102]

[Chemical 18]

[In the formula, A _{1 to} A ₄ may be the same or different and each represents —CH ₂ OH, —COOM or —PO ₃ M ₁ M ₂ . M,
M ₁ and M ₂ each represent a hydrogen atom, an alkali metal or ammonium. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms. The compound represented by formula [C] will be described in detail below.

In the formula, A _{1 to} A ₄ are Japanese Patent Application No. 1-260628 12
Since it has the same meaning as A _{1 to} A ₄ described from line 15 to page 15 to line 3 from page 15, detailed description will be omitted.

Since the ferric iron complex salt of the organic acid represented by the general formula [C] has a high bleaching ability, the amount used when solidifying is small, and the solidification of weight reduction and size reduction can be achieved. It has the effect of improving the preservability of the solidifying agent, and is preferably used in the present invention.

Preferred specific examples of the compound represented by the above general formula [C] are shown below.

[0107]

[Chemical 19]

[0108]

[Chemical 20]

As the ferric iron complex salts of these compounds (C-1) to (C-12), sodium salt, potassium salt or ammonium salt of these ferric iron complex salts can be optionally used.

Of the above-mentioned compound examples, those which are particularly preferably used in the present invention include (C-1), (C-3),
(C-4), (C-5) and (C-9), and particularly preferred is (C-1).

In the present invention, the bleaching agent or the bleach-fixing agent may contain, as the main bleaching agent, a ferric complex salt of the following compound in addition to the iron complex salt of the compound represented by the general formula [C].

[A′-1] ethylenediaminetetraacetic acid [A′-2] trans-1,2-cyclohexanediaminetetraacetic acid [A′-3] dihydroxyethylglycine acid [A′-4] ethylenediaminetetrakismethylenephosphonic acid [A′-4] A'-5] Nitrilotrismethylenephosphonic acid [A'-6] diethylenetriaminepentakismethylenephosphonic acid [A'-7] diethylenetriaminepentaacetic acid [A'-8] ethylenediaminedioltohydroxyphenylacetic acid [A'-9] hydroxy Ethyl ethylenediamine triacetic acid [A'-10] ethylenediamine dipropionic acid [A'-11] ethylenediamine diacetic acid [A'-12] hydroxyethyliminodiacetic acid [A'-13] nitrilotriacetic acid [A'-14] nitrilo-3 Propionic acid [A'-15] triethylenetetramine hexaacetic acid [A'-16 ] Ethylenediaminetetrapropionic acid [A'-17] β-alaninediacetic acid [A'-18] ethylenediaminetetrasuccinic acid [A'-19] 1,3-propanediaminetetrasuccinic acid bleaching agent or bleach-fixing agent is Besides, halides such as ammonium bromide, potassium bromide and sodium bromide, various optical brighteners, defoaming agents or surfactants may be contained.

The fixing main agent used in the fixing agent or the bleach-fixing agent in the present invention is preferably thiocyanate or thiosulfate, and particularly preferably thiosulfate.

The fixing agent or the bleach-fixing agent used in the present invention may contain, alone or in combination, two or more pH buffering agents composed of various salts, in addition to these fixing main agents. Further, it is desirable to contain a rehalogenating agent such as an alkali halide or an ammonium halide, for example, potassium bromide, sodium bromide, sodium chloride, ammonium bromide and the like. Further, compounds known to be added to ordinary fixing agents or bleach-fixing agents such as alkylamines and polyethylene oxides can be appropriately added.

In the present invention, the stabilizer preferably contains a chelating agent having a chelate stability constant with respect to ferric ion of 8 or more. Here, the chelate stability constant is defined by LG Sillen / AEMartell, “Stability Constan
ts of Metal-ion Complexes ”, The Chemical Societ
y, London (1964), S.Chaberek AEMartell, “Or
ganic Sequestering Agents ”, Wiley (1959) and the like.

Examples of the chelating agent having a chelate stability constant of 8 or more for ferric ions include those described in JP-A-3-182750.

The amount of the above chelating agent used is 1 liter of the stabilizing solution.
A preferable result is obtained in the range of 0.01 to 50 g, and more preferably in the range of 0.05 to 20 g.

Further, the stabilizer preferably contains sulfite.

Further, the stabilizer preferably contains a metal salt in combination with the chelating agent. Such metal salts include Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb,
There are metal salts of Sn, Zn, Ti, Zr, Mg, Al or Sr, which can be supplied as inorganic salts such as halides, hydroxides, sulfates, carbonates, phosphates, acetates or as water-soluble chelating agents. . The amount used is preferably in the range of 1 × 10 ^-4 to 1 × 10 ^-1 mol, and more preferably in the range of 4 × 10 ^-4 to 2 × 10 ^-2 mol, per liter of the stabilizing solution.

[0120]

【Example】

Example 1 A color developing agent tablet for color paper was prepared according to the following procedure.

Operation (1) CD-3 [4-amino-3-methyl-N-ethyl-N-] as a developing agent
1200 g of [β- (methanesulfonamido) ethyl] aniline sulfate] is ground in a commercially available hammer mill until the average particle size becomes 30 μm. This fine powder was granulated in a commercial stirred granulator at room temperature for about 7 minutes by adding 50 ml of water, and then the granulated product was dried in a fluidized bed dryer at 40 ° C. for 2 hours. The water content of the granulated product is almost completely removed. In this way, polyethylene glycol 6000 15
0 g is uniformly mixed for 10 minutes using a mixer in a room whose humidity is controlled to 25 ° C and 40% RH or less. Next, 4 g of sodium N-myristoylalanine was added and mixed for 3 minutes, and then the obtained mixture was compressed into tablets by changing the filling amount and strength per tablet with a rotary tableting machine as shown in Table 1. ,each
Color developing agent tablet sample 1-1 for 400 color papers
Created ~ 14.

Experiment-1 A speed checker TS-50N (Okada Seiko Co., Ltd.) was prepared by randomly taking 10 tablets out of the tablet samples obtained by the above operation.
Was used to measure the hardness, and the strength was calculated from the average value.
Take another 10 pieces and drop them from a height of 1 m on an iron plate.
This was repeated several times, and the state immediately after dropping was observed. Furthermore, the other 5 pieces were put into 500 ml of pure water at 25 ° C., and the time until complete dissolution was measured while stirring with a magnetic stirrer.

Experiment-2 Ten tablet samples obtained by the above operation were put in a high-density polyethylene bag, sealed, and subjected to a vibration test for 2 hours by a vibration tester of IDEX Co., then at 35 ° C. and 80% R.
The sample was stored in the H environment for 2 weeks, and the degree of coloring of the sample after storage was compared.

The results are shown in Table 1.

[0125]

[Table 1]

Evaluation of the results of the drop test × Broken into pieces at one time △ Partial chipping is seen at one time ○ Chipping is seen at 3 to 5 times ◎ No chipping is seen at 5 times Coloring Evaluation × Does not become a product because it changes to blackish brown △ Some are discolored to brown but acceptable as a product ○ Almost no discoloration ◎ No discoloration at all According to the above Table 1, if the tablet strength is less than 0.5, the drop strength is It is insufficient and cannot be put to practical use in handling or transportation.
Further, if the tablet strength exceeds 3.5, hardness will be obtained but the dissolution time will be extremely delayed. On the other hand, it can be seen that the tablets having the strength of the present invention have practically sufficient strength and are excellent in solubility and storability.

Example 2 Instead of CD-3 used in Example 1, exemplified compound C-
Similar operations and experiments were carried out using 3, C-5, C-17, C-18 and C-19. As a result, almost the same results as in Example 1 were obtained.

Example 3 A processed tablet for a color negative film was prepared according to the following procedure.

Operation (1) Potassium carbonate: 3750.0 g, sodium sulfite 580.0 g,
Diethylenetriamine pentaacetic acid pentasodium 240.0g, p-
500.0 g of sodium toluenesulfonate are ground in a commercial hammer mill until the average particle size is 10 μm. To this fine powder, 500.0 g of PEG6000 and 800.0 g of mannitol were granulated by adding 160 ml of water at room temperature for about 7 minutes in a commercially available stirring granulator, and then the granulated product was put into a commercially available fluidized bed. Dry for 120 minutes at 70 ° C. using a dryer to almost completely remove the water content of the granulated product.

Operation (2) 360.0 g of hydroxylamine sulfate, 40.0 g of potassium bromide
20.0 g of 1,2-dihydroxybenzene-3,5-disulfonic acid disodium salt is pulverized in the same manner as in the operation (1), and then pine flow (Matsuya Chemical Co., Ltd.) 20.0 g is added and mixed for granulation.
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 (3) CD-4 [4-amino-3-methyl-N-ethyl-β-] as a developing agent
(Hydroxy) ethylaniline sulphate] 650.0 g was pulverized in the same manner as in step (1) and then granulated by adding 10 ml of water at room temperature for about 7 minutes. 40
The granulated product is dried at 2 ° C for 2 hours to almost completely remove water.

Operation (4) The granules prepared in the above operations (1) to (3) were mixed at room temperature with a commercially available cross rotary mixer for 10 minutes, and 40.0 g of sodium N-myristoylalanine was added. Mix for 3 minutes. The mixed granules thus obtained were continuously tableted by a rotary tableting machine to obtain 600 tablets for color development replenishment for color negative films shown in Tables 2 and 3, respectively.

The tablet sample obtained by the above operation was evaluated in the same manner as in Example 1. Also, 5 samples of each were put in a high-density polyethylene bag and stored for 4 weeks in an environment of 35 ° C. and 80% RH. The degree of coloring of each sample after storage was compared with that of the sample before storage. The results are shown in Tables 2 and 3.

[0134]

[Table 2]

[0135]

[Table 3]

From the results shown in Table 2, it is understood that the color developing tablet of the present invention has practical strength, solubility and storability. Further, from the results of Table 3, it can be seen that the strength is particularly excellent in the ratio d / h of the tablet diameter d (mm) and thickness h (mm) d / h of 2.5 to 5.0.

Example 4 A color negative film bleaching tablet sample was prepared according to the following procedure.

Operation (1) 1,3-Propanediaminetetraacetic acid Ferric ammonium monohydrate
Example 1 175 g, 1,3-propanediamine tetraacetic acid 2 g, and pine flow (maltodextrin manufactured by Matsutani Chemical Co., Ltd.) 17 g
Pulverize and mix in the same manner as in operation (1), and granulate with the amount of water added to 8 ml. After the granulation, the granulated product is dried at 60 ° C for 30 minutes to almost completely remove the water content of the granulated product.

Operation (2) 133 g of succinic acid, 200 g of ammonium bromide and pine flow
102 g are pulverized, mixed and granulated in the same manner as in the operation (1) of Example 1. The amount of water added is 170 ml, and after granulation, the granules are dried for 60 minutes to remove water almost completely.

Operation (3) In the same manner as in the operation (1) of Example 1, 66.7 g of potassium sulfate, 60 g of potassium hydrogen carbonate and 8 g of mannite were pulverized, mixed and granulated. The amount of water added is 13 ml, and after granulation, the granules are dried at 60 ° C for 60 minutes to almost completely remove water.

Operation (4) The granules prepared in the above operations (1) to (3) were subjected to 25 ° C. and 40%
Mix evenly for 10 minutes using a mixer in a room whose humidity is adjusted to below RH. Next, 6 g of sodium N-lauroyl sarcosine is added to this mixed granulated product, and they are mixed for 3 minutes. Next, the mixture was compressed and compressed by a rotary tableting machine with the filling amount and diameter per tablet as shown in Table 4, and 80 bleaching replenishing tablet samples 4-1 to 10 for color negative films were obtained. Created.

In the same manner as in Experimental Example 1, strength measurement, drop test and dissolution test were performed.

The results are shown in Table 4.

[0144]

[Table 4]

From Table 4 above, the tablets having the strength of the present invention have practically sufficient strength even if the diameter of the tablets is changed, and
It can be seen that the solubility is excellent.

Example 5 Instead of the 1,3-propanediaminetetraacetic acid ferric ammonium salt used in Example 4, the same moles of exemplified compounds C-3 and C were used.
-5, C-9, A'-1, A'-7, A'-17, A'-
Similar operations and experiments were carried out using a ferric ammonium salt of 18, A'-19. As a result, almost the same result as in Example 4 was obtained.

Example 6 A bleach-fixing tablet sample was prepared according to the following procedure.

Operation (1) Diethylenetriamine pentaacetic acid ferric sodium trihydrate;
6000.0 g, diethylenetriamine pentaacetic acid; 300.0 g, sodium carbonate monosalt water; 500.0 g
Similar to, pulverize and polyethylene glycol 4000; 1000.0
Add g and mix to granulate. Add 200 ml of water,
The granulator is dried at 60 ° C. for 3 hours to almost completely remove the water content of the granulated product.

Procedure (2) 8000.0 g of ammonium thiosulfate; 8000.0 g of sodium metabisulfite; 3050.0 g are pulverized in the same manner as in the procedure (1), and 500.0 g of these pine flows are added and mixed to granulate. The amount of water sprayed is 170 ml, and after granulation, it is dried at 60 ° C. for 120 minutes to almost completely remove the water content of the granulated product.

Operation (3) The granule samples prepared in the above operations (1) and (2) were mixed at room temperature with a commercially available cross rotary mixer for 10 minutes, and then N-lauroylsarcosine sodium;
And mix for 3 minutes. The mixed granules thus obtained were continuously tableted with a rotary tableting machine to give a diameter of 30.
1700 bleach-fixing replenishing tablet samples (shown in Table 4) each for m color paper were obtained.

Experiment A dissolution experiment similar to that of Example 1 was conducted using 10 samples obtained by the above operation. Another 10 samples each were placed in a polyethylene bag, sealed, and subjected to a vibration test for 3 hours using a vibration tester, and then stored for 3 weeks in an environment of 35 ° C and 80% RH. It was dissolved in water and the dissolved state was observed. The results are shown in Table 5.

Preservation evaluation ×: A large amount of precipitate is generated △: A precipitate is generated ◯: A small amount of precipitate is generated but it is acceptable ⊚: No precipitate is generated

[0153]

[Table 5]

From the results in Table 5, it can be seen that, as in Example 1, the bleach-fixing tablet of the present invention is excellent in strength, solubility and storability.

Example 7 Instead of the diethylenetriaminepentaacetic acid ferric salt used in Example 6, equimolar exemplified compounds A'-1, A'-7,
The same operation experiment as in Example 6 was carried out except that the ferric sodium salts of A'-17 and A'-18 were used. As a result, the same result as in Example 6 was obtained.

Example 8 Color negative film fixing tablets and stabilizing tablets were prepared according to the following procedure.

Fixing and Filling Tablet Operation for Color Negative Film (1) Ammonium thiosulfate 2500 g, sodium sulfite 150
g, 150 g of potassium carbonate, 20 g of ethylenediaminetetraacetic acid disodium salt and 65 g of Pine Flow (manufactured by Matsutani Chemical Co., Ltd.) are pulverized, mixed and granulated in the same manner as in the operation (1) of Example 1. The amount of water added was 50 ml, and after granulation, the granules were dried for 120 minutes to almost completely remove water.

Operation (2) The granules prepared in the above operation (1) and 13 g of sodium N-lauroylsarcosine are mixed for 3 minutes using a mixer in a room where the humidity is adjusted to 25 ° C. and 40% RH or less. Then, the mixture is filled in a rotary tableting machine and the filling amount and diameter of each tablet are shown in Table 6.
The compression setting was carried out by setting as described above to prepare 100 color negative fixing replenishing tablet samples 3-1 to 3-12.

Stable replenishing tablet operation for color negative (3) m-hydroxybenzaldehyde 1500 g, sodium lauryl sulfate 200 g, ethylenediamine tetrasodium acetate 6
00g, lithium hydroxide monohydrate 650g and pine flow 100g
Are pulverized, mixed and granulated in the same manner as in the operation (1) of Example 1. The amount of water added was 10 ml, and after granulation, the granulated product was dried at 50 ° C. for 2 hours to almost completely remove the water content of the granulated product.

Operation (4) The granules prepared in the above operation (3) were subjected to a rotary tableting machine in a room whose humidity was adjusted to 25 ° C. and 40% RH or less, and the filling amount and diameter per tablet were shown in Table 7. Set as follows and perform compression tableting,
Stable replenishment tablet samples 4-1 to 4 for 200 color negatives each
-12 was created.

In the same manner as in Experimental Example 1, strength measurement, drop test and dissolution test were performed.

The results are shown in Tables 6 and 7.

[0163]

[Table 6]

[0164]

[Table 7]

Example 9 Konica QA Paper Type-5 (manufactured by Konica Corporation) was imagewise exposed, and then a modified NPS-808 machine (manufactured by Konica Corporation) having the configuration shown in FIG. 1 was used. It processed according to the following process steps. However, the replenishment water in the replenishment tank was deionized.

Processing step Processing time Processing temperature Tank capacity Color development 22 seconds 38.0 ° C 12l Bleach fixing 22 seconds 37.5 ° C 12l Stable-1 22 seconds 35 ° C 12l Stable-2 22 seconds 35 ° C 12l Stable-3 22 seconds 35 ° C 12l Dry Drying 50 seconds 55 ° C Stability is a countercurrent system from 3 to 1, and all the overflow liquid of Stable-1 was made to flow into the bleach-fixing tank. The carryover of the light-sensitive material per 1 m ² of light-sensitive material is 45 ml from the color developing tank to the bleach-fixing tank and 50 m from the bleach-fixing tank to the stabilizing tank.
l, stable-1 to 2, 2 to 3 and 3 to dry was 40 ml.

The opening area of each of the color developing tank, the bleach-fixing tank and the stabilizing tank was 4.5 cm ² per liter of the processing solution.

The outside air of the automatic developing machine was 27 ° C. and 60% RH, and the replenishing water was replenished when the amount of evaporation reached 100 ml.

The formula (1) of Japanese Patent Laid-Open No. 3-280042 was used for the method of calculating the supplementary water. The processed light-sensitive material was processed at 2.0 m ² per day and continuously processed for 2 months.

The composition of the processing liquid is shown below.

[0171] (Color developer)   Potassium bromide 0.02g   3.2g potassium chloride   30g potassium carbonate   0.2g potassium sulfite   Diethylenetriamine pentaacetic acid pentasodium 2g   Nitrilotrimethylenephosphonate sodium 2g   Chino Pearl SFP 2g   Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 5g   4-Amino-3-methyl-N-ethyl N- [β- (methanesulfonamide)     Ethyl] aniline sulfate 7g                   (CD-3) Water was added to make 1 liter, and the pH was adjusted to 10.10.

[0172] (Bleaching fixer)   Ethylenediaminetetraacetic acid ferric ammonium monohydrate 60g   Ethylenediaminetetraacetic acid 2g   Ammonium thiosulfate 80g   Sodium metabisulfite 15g   Sodium sulfite 18g Water was added to make 1 liter and the pH was adjusted to 7.0.

(Stabilizer) Water 800 ml 1,2-Benzisothiazolin-3-one 0.1 g 1-Hydroxyethylidene-1,1-diphosphonic acid 5.0 g Ethylenediaminetetraacetic acid 1.0 g Chinopearl SFP (manufactured by Ciba Geigy) 2.0 g Ammonium sulfate 2.5 g Zinc chloride 1.0 g Magnesium chloride 0.5 g O-phenylphenol 1.0 g Sodium sulfite 2.0 g Water was added to make 1 liter, and the pH was adjusted to 8.0 with 50% sulfuric acid or 25% aqueous ammonia.

A treated tablet for color paper was prepared according to the following procedure.

1) Tablet operation for color development replenishment for color paper (A) CD-3 [4-amino-3-methyl-N-ethyl-N- [β-
(Methanesulfonamide) ethyl] aniline sulfate] 1200
g in a commercially available hammer mill until the average particle size is 10 μm. After granulating this fine powder by adding 50 ml of water for about 7 minutes at room temperature in a commercial stirred granulator,
The granulated product is dried in a fluidized bed dryer at 40 ° C. for 2 hours to almost completely remove the water content of the granulated product. In this way, 150 g of polyethylene glycol 6000 was added to the adjusted granules.
Mix evenly for 10 minutes using a mixer in a room where the temperature is controlled to ℃ and 40% RH or less. Next, 4 g of sodium N-myristoylalanine was added and mixed for 3 minutes, and then the resulting mixture was mixed with a rotary tableting machine at a loading amount of 1.0 g
Then, compression tableting was carried out to prepare 400 tablets of color development replenishment tablet A for color paper.

Operation (B) Disulfoethylhydroxylamine disodium salt 120
Then, g is pulverized and granulated in the same manner as in the operation (A). How much water is added
After granulating to 6.0 ml, the granulated product is dried for 30 minutes at 50 ° C. to almost completely remove water from the granulated product. In this way, 4 g of sodium N-myristoylalanine is added to the prepared granulated product, and mixed for 3 minutes using a mixer in a room where the humidity is adjusted to 25 ° C. and 40% RH or less. Next, the resulting mixture was compressed into tablets using a rotary tableting machine at a filling amount of 1.0 g per tablet to prepare 100 tablet B agents for color development replenishment for color development.

Operation (C) 30.0 g of Tinopearl SFP (manufactured by Ciba Geigy), 3.7 g of sodium sulfite, 0.3 g of potassium bromide, 25 g of diethylenetriamine-5-acetic acid, sodium p-toluenesulfonate 28
After crushing 0 g, 20 g of potassium hydroxide and 10.6 g of mannitol in the same manner as in (A), they are uniformly mixed with a commercially available mixer. Then, in the same manner as in (A), the amount of water added is adjusted to 20 ml and granulation is performed. After the granulation, the granulated product is dried at 60 ° C for 30 minutes to almost completely remove the water content of the granulated product. In this way, 4 g of sodium N-myristoylalanine was added to the prepared granules.
Is added, and the mixture is mixed for 3 minutes by using a mixer in a room whose humidity is controlled to 25 ° C. and 40% RH or less. Next, the obtained mixture was compressed into tablets by a rotary tableting machine at a filling amount of 3.2 g per tablet to prepare 100 tablet C agents for color developing replenishment for color paper.

Operation (D) 350 g of potassium carbonate is ground and granulated in the same manner as in the operation (A). The amount of water added is 20 ml, and after granulation, the granules are dried for 30 minutes to remove water almost completely. In this way, polyethylene glycol 6000 was added to the adjusted granules.
15 g is uniformly mixed for 10 minutes using a mixer in a room whose humidity is controlled to 25 ° C and 40% RH or less. Next, 4 g of N-myristoylalanine sodium was added and mixed for 3 minutes, and then the resulting mixture was compression-pressed by a rotary tableting machine to a filling amount shown in Table 1 for 110 color papers. A tablet D agent for replenishing color development was prepared.

2) Tablet operation for replenishing bleach-fix for color paper (E) 1250 ethylenediaminetetraacetic acid ammonium ferric acetate monohydrate
g, ethylenediaminetetraacetic acid 100 g, sodium carbonate 1
100 g of water salt and 121 g of Pine Flow (Matsuya Chemical Co., Ltd.) are pulverized, mixed and granulated in the same manner as in the operation (C). The amount of water added is 80
After the granulation, the granulated product is dried at 60 ° C. for 2 hours to almost completely remove the water content of the granulated product. In this way, 15 g of sodium N-lauroylsarcosine was added to the prepared granules,
Mix for 3 minutes using a mixer in a room where the temperature is controlled to 40 ° C and 40% RH or less. Next, the obtained mixture was compressed into tablets with a rotary tableting machine at a loading amount of 5.8 g per tablet to prepare 170 tablets of bleach-fixing supplement tablet A for color paper.

Operation (F) Ammonium thiosulfate 1640 g, sodium metabisulfite
750 g and pine flow 90 g are crushed in the same manner as in operation (C),
Mix and granulate. The amount of water sprayed is 100 ml, and after granulation, 60
The granules are dried at 120 ° C for 120 minutes to almost completely remove water. In this way, 20 g of sodium N-lauroylsarcosine is added to the prepared granulated product, and the mixture is mixed for 3 minutes using a mixer in a room whose humidity is adjusted to 25 ° C. and 40% RH or less. Next, the obtained mixture was compressed into tablets with a rotary tableting machine at a filling amount of 9.2 g per tablet to prepare 180 bleach-fixing replenishing tablet B agents for color paper.

3) Tablet operation for stable replenishment of color paper (G) Sodium carbonate monohydrate 10 g, 1-hydroxyethane-1,1
-Trisodium diphosphonate 200g, Tinopearl SFP15
In the same manner as in the operation (C), 0 g, 300 g of sodium sulfite, 20 g of zinc sulfate heptahydrate, 150 g of ethylenediaminetetraacetic acid disodium, 200 g of ammonium sulfate, 10 g of o-phenylphenol, and 25 g of pine flow are pulverized, mixed and granulated. The amount of water added is 60 ml, and after granulation, it is dried at 70 ° C. for 60 minutes to almost completely remove the water content of the granulated product. In this way, 10 g of sodium N-lauroyl sarcosine was added to the granules prepared.
Is added, and the mixture is mixed for 3 minutes by using a mixer in a room whose humidity is controlled to 25 ° C. and 40% RH or less. Next, the obtained mixture was compressed into tablets with a rotary tableting machine at a filling amount of 3.1 g to give 360 stable replenishing tablets for color paper.

The strength of these tablets was adjusted as shown in Table 8.

[0183]

[Table 8]

As shown in FIGS. 2 and C, the color developing replenishing replenishing tablets are each A to D, and the bleach-fixing replenishing replenishing tablets are A and B, one each. Each tablet was sealed with a laminated polymer resin film made of PET / polyvinyl alcohol / ethylene copolymer / polyethylene, and 20 minutes of continuous packaging was used as one cartridge. Next, each of the above replenishing tablet cartridges was shaken for 6 hours using a commercially available shaker, and then charged using the processing agent supply device of the automatic processor shown in FIGS. 1 and 2. The above tablets are added one by one when 1 m ² of color paper is processed, and at the same time, replenishment water is supplied from the replenishment water tank to the color developing tank.
ml, 42 ml to the bleach-fixing tank, and 247 ml to the stabilizing tank.

Then, continuous treatment was carried out until the treatment amount of the color paper reached 20 m ² , and the above-mentioned tablet supply device and the state of tablet dissolution in each treatment were observed.

(For the automatic processor shown in FIG. 1,
Treatment tank 1, treatment unit 2, filter 3, circulation pipe 4, circulation pump 5, drainage pipe 6, heater 7, treatment amount information detection means and treatment agent supply control means 8, solid treatment agent feeding section 11, partition wall 12. , Solid treated tablets 13, filtration section (division) 14, pipe (for water replenishment) 41, replenishment water supply means 42, replenishment water tank 43, treatment agent cartridge 150, package 152, peel open cylinder 153,
A package winding shaft 156 is shown.

2A and 2B, the solid processing agent 151, the package 152, the peel open cylinder 153, the charging port 154, the charging section 155, and the coiling shaft of the packing body. 1
56, a knob 157, a clamper 158, and a winding shaft drive motor M are shown. Further, FIG. 2C shows an example of a divided (continuous) seal packaging. ) The results are shown in Table 9.

[0188]

[Table 9]

According to Table 9 above, when a tablet having a strength Z of less than 0.5 is used in an automatic developing machine equipped with a charging device, the strength against vibration is insufficient and the tablet is broken. If this is used as it is, the broken pieces of the tablet adhered to the packaging material may interfere with the tablet supply device, causing a problem that the supply device stops. On the other hand, if the strength Z exceeds 3.5, it has strength against vibration, but the solubility is significantly deteriorated, and undissolved tablets accumulate in the dissolution tank.

As a result, undissolved tablets are clogged in the circulating pump of the treatment liquid, and a serious trouble occurs that the automatic developing machine is stopped. However, when the tablet having the strength of the present invention is used, it is strong against vibration and, even in the dissolution tank, only 1 or 2 pieces always remain, and continuous treatment can be performed without causing any trouble. .
The photographic properties were all satisfactory when processed using the tablet of the present invention.

[0191]

According to the present invention, firstly, there is provided an automatic developing machine which eliminates liquid chemicals which are dangerous in transportation and handling and which enables solid chemicals to be used without complicated operations for users. Practical application can be achieved.

Secondly, it is possible to supply a solid processing agent having excellent solubility and practically sufficient strength.

Thirdly, it is possible to supply a solid processing agent which has excellent long-term storability and is easy to use.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a processing agent input unit and a processing agent supply device to which a replenishing water supply unit of an automatic processor is added.

FIG. 2 is a plan view and a perspective view of a supply device and a plan view of a package.

[Explanation of symbols]

1 processing tank 2 processing section 3 filters 4 circulation pipe 5 circulation pumps 6 drainage pipe 7 heater 8 Processing amount information detection means and processing agent supply control means 11 Solid processing agent injection section 12 partition walls 13 Solid processed tablets 14 Filtering section (classification) 41 Pipe (for water replenishment) 42 Means for supplying supplementary water 43 Water tank 150 treatment agent cartridge 151 Solid treatment agent 152 Package 153 Peel open cylinder 154 Input port 155 Input 156 Package winding shaft 157 knob 158 Clamper M winding shaft drive motor

Front page continued (58) Fields surveyed (Int.Cl. ⁷ , DB name) G03C 5/26 520 G03C 5/00 G03C 7/407 G03C 7/42

Claims (8)

(57) [Claims] 1. A structure comprising at least one treating agent component.
A solid processing agent for a silver halide photographic light-sensitive material, which is a tablet obtained by compressing granules under pressure, and the strength Z of the tablet is in the range shown below. 0.5 ≤ Z ≤ 3.5 where Z = compressive breaking strength of tablet (kg) / length of tablet in longitudinal direction (mm) 2. The solid processing agent for silver halide photographic light-sensitive materials according to claim 1, wherein the tablets are disk-shaped tablets. 3. The tablet according to claim 1 or 2, wherein the ratio of the length of the tablet in the longitudinal direction: X (mm) and the thickness: H (mm): X / H is in the range of 1.0 to 6.0. The solid processing agent for a silver halide photographic light-sensitive material as described above. 4. The solid processing composition for silver halide photographic light-sensitive materials according to claim 1, wherein said tablet contains at least one para-phenylenediamine color developing agent. 5. The tablet is obtained by compressing a granule containing at least one paraphenylenediamine color developing agent and a granule containing at least one alkaline agent. The solid processing agent for silver halide photographic light-sensitive materials according to claim 1. 6. The solid processing agent for silver halide photographic light-sensitive materials according to claim 1, wherein said tablet contains at least one ferric aminopolycarboxylic acid complex salt. 7. The solid processing composition for silver halide photographic light-sensitive materials according to claim 1, wherein said tablet contains at least one thiosulfate. 8. The tablet is obtained by compressing a granule containing at least one ferric aminopolycarboxylic acid complex salt and a granule containing at least one thiosulfate salt. The solid processing agent for silver halide photographic light-sensitive materials according to claim 1.