JPH0876325A - Processing composition for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To enhance smoothness and gloss, and strength at the time of tabletting the solid processing agent and restraining the occurrence of precipitates in a fixing bath and the like by incorporating one of 3-amino-4- homoisotwistane and the like. CONSTITUTION: The processing composition contains at least one of the compounds represented by formulae I-III and the 3-amino-4-homoisotwistane derivatives, and In the formulae I-III, each of R1 and R2 is an H atom or a 1-3 C alkyl group; R<1> is an H atom or a 1-4 C alkyl or -COR<4> or acyl group; R<4> is a 1-4 C alkyl or alkoxy or chlorophenyl group; R<2> is a 1-4 C alkyl or alkenyl or cyclopentyl group; R<3> is a 1-4 C alkyl group; each of R and R11 -R13 , is, independently, an H atom or a 1-8 C alkyl group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material processing composition (hereinafter also simply referred to as a processing composition), and more specifically, it has excellent smoothness and strength and influences on the photographic characteristics of the light-sensitive material. A solid processing agent for silver halide photographic light-sensitive materials that does not cause scratches on the light-sensitive material during processing, does not cause contamination even during long-term storage, and does not stain the roller part of the automatic processor. The present invention relates to a composition obtained and a processing composition for a silver halide photographic light-sensitive material capable of preventing accidents caused by accidental ingestion.

[0002]

2. Description of the Related Art Color light-sensitive materials for photographing are usually subjected to color development, bleaching, fixing, washing with water and / or stabilization after exposure, and color paper light-sensitive materials are subjected to color development after exposure.
It is processed by bleach-fixing (bleaching, fixing), washing and / or stabilizing steps, and the black-and-white light-sensitive material is usually processed by developing, fixing and washing steps after exposure. Further, in the case of a reversal type photosensitive material, a reversal process is added to these processes.

In recent years, the processing of such a light-sensitive material is carried out by an automatic developing machine (hereinafter, also referred to as an automatic processor) to sequentially convey the processing solution containing the processing solution.

At this time, a replenisher replenishment system is generally used for the purpose of keeping the activity of the treatment liquid in the treatment layer constant.
As a result of liquid replenishment, a large amount of overflow liquid is usually discharged.

Conventionally, these replenishers are composed of various components (hereinafter referred to as "part agents" or "part agents") so as to exhibit good performance in photographic processing. These parts agents are in contact with each other. When it is placed, it reacts and deteriorates for a long time, impairing its function as a photographic processing agent. In particular, since many treatment agents easily react with each other due to redox reaction, they are generally made into a kit by dividing them into one or two or more parts agents, and these are dissolved in a certain amount of water when used. Are used for.

The above-mentioned kitted parts agent is, for example,
Each is put in an inner container such as a bottle or a bag, and these are put together in an outer bag (for example, a cardboard box) and sold as a unit.

In recent years, there has been a strong demand for environmental conservation and resource saving mainly in Europe and the United States, and a plastic container for a processing agent has become a particularly serious problem in photography. That is, although a plastic container for photography is cheap and convenient for storage and transportation and has excellent chemical resistance, an empty container is landfilled as industrial waste, discarded, or incinerated. The plastic container has almost no biodegradability, and when it is accumulated and incinerated, a large amount of carbon dioxide gas is generated, which causes a problem such as global warming. Further, as a user's problem, it has been pointed out that a large number of plastic containers are piled up in a narrow working space to further reduce the space.

On the other hand, the movement toward the regulation of the dumping of photographic waste liquid into the ocean is also increasing worldwide, and the reduction of photographic waste liquid,
Furthermore, the development of a new system for zeroization is required.

In a rapidly increasing minilab store, due to lack of manpower, accidents due to erroneous dissolution occurred one after another during dissolution or dilution of the replenishing solution, and many complaints about the conventional replenishing system have come to be made.

Therefore, in the photographic industry, there is a strong demand for the development of a new replenishing system that produces almost no photographic waste liquid, does not use a processing agent bottle, and does not require any dissolving operation.

As a method for responding to this demand, JP-A-5-11
Japanese Patent Publication No. 9454 discloses a method in which almost all processing agent components are tableted and directly charged into a processing tank. In addition,
4-213454 discloses a method in which a powdery processing agent is set for each part in an automatic developing machine and directly charged into a processing tank while weighing a necessary amount out of the processing agent. Further, see JP-A-2-09042. A method of using a granular treatment agent is disclosed,
Instead of the liquid treatment agents that have been used conventionally,
Although they are common in that they use solid chemicals, the former is different in that the solid processing agent is directly added to the processing layer, whereas the latter is dissolved as a replenisher.

Generally, in order to produce a solid processing agent, for example, in the case of a granular processing agent, the processing agent is pulverized, granulated while adding water or the like, and the resulting granulated product is dried to obtain a desired processing agent. A granular treatment agent can be obtained, and a tablet can be produced by compression-molding the obtained granular treatment agent or powdered treatment agent, and it is described in the above-mentioned publication that it is produced by the same method. ing.

Conventionally, generally, when continuously molding tablets,
Lubricants are used to prevent defective molding due to friction between powder particles and between powder and the formulation machine. Various kinds of such lubricants are known, and among them, magnesium stearate and talc are widely used because of their excellent lubricating effect.

However, when a tableting photographic processing agent is produced by tableting using magnesium stearate or talc as a lubricant, the lubricity is very excellent, but the obtained tablets are It has the drawback of low strength.

Further, when a silver halide photographic light-sensitive material is processed using a processing solution obtained from a photographic processing agent solidified with magnesium stearate or talc as a lubricant, scratches or stains on the light-sensitive material are obtained. It has been found that there is a problem in that there is a possibility that problems may occur in the circulation path due to the occurrence of stains, stains on the roller portion of the automatic processor, or deposits in the processing tank.

[0016] In general, a measure such as increasing the amount of lubricant is often used to improve the lubricity, but this causes not only the problems such as the above-mentioned precipitation but also the problem of affecting the photographic characteristics. Therefore, a compound having an effect on lubricity has been particularly required.

[0017]

Therefore, an object of the present invention is not only excellent in lubricity but also high in strength when used as a tablet-type solid processing agent, and moreover in processing a light-sensitive material,
Precipitation in the fixing tank, bleach-fixing tank or stabilizing tank does not affect the photographic characteristics of the photosensitive material, does not damage the photosensitive material, does not stain the roller part of the automatic processor. It is an object of the present invention to provide a processing composition for a silver halide photographic light-sensitive material, in which the generation of matter is improved.

[0018]

The above object of the present invention can be achieved by the following constitutions.

1. A halogenation containing a compound represented by the following general formula [1], general formula [2], or general formula [3] or at least one compound selected from 3-amino-4-homoisotwistane Processing composition for silver photographic light-sensitive material.

[0020]

[Chemical 4]

[In the formula, R ₁ and R ₂ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

[0022]

[Chemical 5]

[Wherein, R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a —COR ⁴ group (wherein R ⁴ is an alkyl group having 1 to ⁴ carbon atoms, an alkoxy group or a chlorophenyl group))
R ² is an alkyl group having 1 to 4 carbon atoms,
It is an alkenyl group or a cyclopentyl group, and R ³ is an alkyl group having 1 to 4 carbon atoms. ]

[0024]

[Chemical 6]

[In the formula, R, R ₁₁ , R ₁₂ , and R ₁₃ are each a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and may be the same or different. ] 2. 2. The processing composition for silver halide photographic light-sensitive materials as described in 1 above, which is composed of a solid.

3. It occupies the entire processing composition for silver halide photographic light-sensitive material of at least one compound selected from the general formula [1], the general formula [2], the general formula [3] or 3-amino-4-homoisotwistane. 3. The processing composition for silver halide photographic light-sensitive materials as described in 2 above, wherein the ratio is 5 × 10 ^{−6 to} 4.0% by weight.

4. The solid is a form selected from granules and tablets, and the solid is at least one compound selected from the general formula [1], the general formula [2], the general formula [3] or 3-amino-4-homoisotwistane. The processing composition for silver halide photographic light-sensitive materials as described in 2 or 3 above, which is localized on the surface of the granules or tablets.

5. Contain at least one selected from water-soluble polymers and saccharides and at least one compound selected from the general formula [1], the general formula [2], the general formula [3] or 3-amino-4-homoisotwistane 5. The processing composition for silver halide photographic light-sensitive material as described in 4 above, which is a granule or tablet whose surface is coated with the composition.

6. 1 to 3, which contains at least one developing agent selected from para-phenylenediamine color developing agents and hydroquinone type developing agents.
5. The processing composition for silver halide photographic light-sensitive materials according to any one of 5,

That is, the present inventor has conducted various studies on a wide variety of compounds, and as a result, when the processing composition for a silver halide photographic light-sensitive material has a solid form, the general formula [1] and the general formula [ 2], general formula [3] or 3-amino-4-
At least one compound selected from homoisotwistane functions as an excellent lubricant for any form of powder, granules and tablets without impairing the strength when it is used as a tablet-type solid processing agent, The present invention has been made by finding that it does not affect the photographic performance and the processing performance, and the present invention has been achieved. However, this compound is used for so-called "emetics", and this compound is used smoothly. When used as an agent, it is preferable because it has an accompanying effect that it can prevent accidental ingestion and accidental ingestion of the processing composition for a light-sensitive material. Regarding the function of preventing accidental ingestion, it can be naturally adopted even if the treatment composition is a liquid.

Next, the general formulas [1] to [3] will be described.

In the formula, R ₁ and R ₂ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may have a substituent. R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or a —COR ⁴ group (wherein R ⁴ represents 1 to 1 carbon atoms).
4 alkyl group, alkoxy group or chlorophenyl group, each of which may have a substituent), R ² is an alkyl group having 1 to 4 carbon atoms, an alkenyl group or a cyclopentyl group, each of which is substituted. R ³ , which may have a group, is an alkyl group having 1 to 4 carbon atoms and optionally having a substituent. R, R ₁₁ , R ₁₂ and R ₁₃ are each a hydrogen atom or an optionally substituted alkyl group having 1 to 8 carbon atoms, which may be the same or different. Good.

Specific examples of the compound represented by the general formula [1] are shown below.

[0034]

[Chemical 7]

Specific examples of the compound represented by the general formula [2] are shown below.

2-1: 2-amino-6-methyl-4-n-propyl
-5-oxo-4,5-dihydro-S-triazolo- [1,5-a] pyrimidine 2-2: 2-acetamido-6-methyl-4-n-propyl-5-oxo-4,5-dihydro -S-triazolo- [1,5-a] pyrimidine 2-3: 6-methyl-4-n-propyl-2-n-propylamino-5
-Oxo-4,5-dihydro-S-triazolo- [1,5-a] pyrimidine 2-4: 2-amino-6-methyl-4-n-butyl-5-oxo-4,5-
Dihydro-S-triazolo- [1,5-a] pyrimidine 2-5: 2-amino-6-methyl-4-allyl-5-oxo-4,5-
Dihydro-S-triazolo- [1,5-a] pyrimidine 2-6: 2-amino-7-methyl-4-n-propyl-5-oxo-4,
5-Dihydro-S-triazolo- [1,5-a] pyrimidine 2-7: 2-dimethylamino-6-methyl-4-n-propyl-5-
Oxo-4,5-dihydro-S-triazolo- [1,5-a] pyrimidine 2-8: 2-di-n-propylamino-6-methyl-4-n-propyl-5-oxo-4,5 -Dihydro-S-triazolo- [1,5-a] pyrimidine 2-9: 2-isopropylamino-6-methyl-4-n-propyl
-5-oxo-4,5-dihydro-S-triazolo- [1,5-a] pyrimidine 2-10: 2-p-chlorobenzamido-6-methyl-4-n-propyl-5-oxo-4, 5-Dihydro-S-triazolo- [1,5-a] pyrimidine 2-11: 2-ethoxythiocarbonylamino-6-methyl-4-
n-Propyl-5-oxo-4,5-dihydro-S-triazolo- [1,
5-a] pyrimidine 2-12: 2-ethoxycarbonylamino-6-methyl-4-n-propyl-5-oxo-4,5-dihydro-S-triazolo- [1,5-
a] Pyrimidine 2-13: 2- (3-phenylureido-)-6-methyl-4-n-propyl-5-oxo-4,5-dihydro-S-triazolo- [1,5-a]
Pyrimidine 2-14: 2-Amino-4,6-di-n-propyl-5-oxo-4,5-dihydro-S-triazolo- [1,5-a] pyrimidine 2-15: 2-N, N -Diacetylamino-6-methyl-4-n-propyl-5-oxo-4,5-dihydro-S-triazolo- [1,5-a] pyrimidine 2-16: 2-N-ethoxycarbonyl-N-α -Phenylethylamino-6-methyl-4-n-propyl-5-oxo-4,5-dihydro-S
-Triazolo- [1,5-a] pyrimidine 2-17: 2-amino-6-methyl-4-s-butyl-5-oxo-4,5-
Dihydro-S-triazolo- [1,5-a] pyrimidine 2-18: 2-amino-6-methyl-4-cyclopentyl-5-oxo-4,5-dihydro-S-triazolo- [1,5-a ] Pyrimidine 2-19: 2-amino-6-n-butyl-4-n-propyl-5-oxo-
4,5-Dihydro-S-triazolo- [1,5-a] pyrimidine Specific examples represented by the general formula [3] are shown below.

[0037]

Embedded image

The compound structure of 3-amino-4-homoisotwistane is shown below.

[0039]

[Chemical 9]

The compound represented by the general formula [1], the general formula [2] or the general formula [3] or 3-amino-4-homoisotwistane of the present invention can be synthesized by a conventionally known method, Further, for example, a commercial product can be obtained as a root-root syrup. Examples of these synthetic methods include JP-A-53-503.
There are methods described in No. 37, No. 50-135063, No. 53-101538, etc., and the above compounds of the present invention can be easily synthesized.

When the processing composition of the present invention is used as a solid processing agent, since the para-phenylenediamine color developing agent and the hydroquinone developing agent have poor fluidity in powder form, the para-phenylenediamine color developing agent and the hydroquinone developing agent are poor. It is very preferable to use a composition containing at least one selected from the main ingredients as a solid processing agent for silver halide photographic light-sensitive materials.

The present invention will be described in detail below.

The silver halide photographic light-sensitive material processing composition of the present invention is used, for example, in a color developing agent, a bleaching agent, a fixing agent, a stabilizer and a color paper light-sensitive material which are used in the processing of color photographic light-sensitive materials for photography. Color developing agents, bleach-fixing agents (bleaching agents, fixing agents), stabilizers, and further developing agents, fixing agents used in black-and-white photosensitive materials, and various processing agents used in processing reversal type photosensitive materials (film or paper). Applicable to

In the present invention, for the above reason,
Especially, it is preferably used for a color developing agent or a black and white developing agent. It is also preferable that the developing agent functions as an emetic agent because it has a higher risk of accidental ingestion / drinking than the constituents of other processing agents.

The tableted solid processing agent for photography according to the present invention can be obtained by granulating raw material powders, then mixing and tableting. For example, JP-A-51-61837,
The methods described in JP-A-54-155038, JP-A-52-88025, British Patent 1,213,808 and the like can also be adopted.

The compound represented by the general formula [1], the general formula [2], or the general formula [3] or at least one compound selected from 3-amino-4-homoisotwistane occupies the whole treating composition. The ratio is preferably 5 × 10 ^{−6 to} 4.0% by weight, and when it is a solid, it can be added before pulverization, during pulverization, during granulation of granules or tablets, or at any time before granulation. Further, it may be added after granulation of granules and before tablet formation. It may also be added so as to be localized on the surface of granules or tablets. 0.005-4.0% by weight for non-surface localized systems
It is preferably contained, and if localized on the surface, 5 ×
Even a small amount of about 10 ^-6 % by weight can be expected to be effective as a lubricant, an emetic and an antifungal agent.

From the viewpoint of the effect of the present invention, it is preferable that the solid treating agent is localized on the surface. As a method of localizing on the surface, coating is preferably used.

In the present invention, at least one compound selected from the compounds represented by the general formula [1], the general formula [2] and the general formula [3] or 3-amino-4-homoisotwistane on the surface of the solid processing agent. Examples of at least one preferable compound selected as the water-soluble polymer or saccharide to be contained in the solution in the case of coating the solution containing are shown below, but the invention is not limited thereto.

I. Water-soluble polymer Polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetal, polyvinyl acetate, aminoalkyl methacrylate copolymer,
Methacrylic acid-methacrylic acid ester copolymer, methacrylic acid-acrylic acid ester copolymer, methacrylic acid-based betaine-type polymer, etc.

II. Sugars Monosaccharides such as glucose and galactose, maltose,
Disaccharides such as sucrose and lactose, sugar alcohols such as mannitol, sorbitol and erythritol, pullulan, methyl cellulose, ethyl cellulose,
Hydroxypropyl cellulose, hydroxypropyl methyl cellulose, cellulose acetate phthalate, hydroxypropyl methyl cellulose phthalate, hydroxypropyl methyl cellulose acetate succinate, carboxymethyl ethyl cellulose, dextrins, starch hydrolyzate and the like.

Among these, a particularly preferable compound is polyethylene glycol (weight average molecular weight of 2,000 to 2).
000), methacrylic acid-methacrylic acid ester copolymers and methacrylic acid-acrylic acid ester copolymers represented by Eudragit manufactured by Rehm Pharma, erythritol, maltose, and pine flow or pa index manufactured by Matsutani Chemical Co., Ltd. Examples include dextrin and starch decomposition products, and methacrylic acid-based betaine-type polymers represented by Mitsubishi Yuka Co., Ltd. Yucaformer.

These coating materials usually account for 0.05% or more and 5% or less, and particularly 0.2% or more 2% to the weight of the solid processing agent.
% Or less is preferable. The weight ratio referred to here does not include a water-soluble polymer or saccharide in the case where the solid processing agent is contained inside, and is defined as a ratio of only the water-soluble polymer and saccharide localized on the surface as a coating material. To do. Further, it is preferable that the solid processing agent of the present invention is substantially coated on all the surfaces with these coating materials.

In the present invention, the method for coating the surface of the solid processing agent is as follows: the coating material is dissolved in a solvent or melted by heating, and the solid processing agent is dipped in this solution, applied to the surface of the solid processing agent, and dried. Examples of the method include spraying on the surface of the treatment agent and drying. Among these methods, the coating by the third spray is one of the particularly preferable methods.

The spray coating will be described in more detail. First, a coating solution is prepared by dissolving or suspending the coating material in water, an organic solvent, or a mixture of both.

As the coating method, pan coating is preferably used. Pan coating involves pouring or spraying the coating liquid onto the fluid surface of the solid processing agent while rotating the pan containing the solid processing agent, and then sending hot air into the pan to remove the solvent and dry it to the specified coating amount. Continue until. At this time, the pressure in the pan may be reduced. Further, two or more kinds of coating liquids may be sequentially changed and sprayed to form a multi-layer coating.

As another method, the solid processing agent may be aligned on a belt or the like, and the coating liquid may be sprayed from the upper surface and then dried. In this case, if a mesh belt is used, the coating liquid can be sprayed from both upper and lower directions to coat both surfaces simultaneously. The solid processing agent can be continuously produced by moving it on the belt from the spraying process to the drying process.

A plasticizer is preferably contained in the spray coating. As the plasticizer, polyethylene glycol, glycerin ester, sucrose fatty acid ester, castor oil, polyoxyethylene sorbitan ester (Kao Corporation trade name Tween), organic acid ester, carbitols, cellosolves, Examples thereof include ethylene glycol, propylene glycol and diethylene glycol. These are preferably added to the coating liquid in advance. Next, preferable specific examples of the plasticizer used in the present invention are shown.

[Exemplified Compounds] (1) Polyethylene glycol (2) Triacetin (3) Polyoxyethylene sorbitan monolaurate (Tween 20 manufactured by Kao Corporation) (4) Polyoxyethylene sorbitan monopalmitate
(Tween 40 manufactured by Kao Corporation) (5) Polyoxyethylene sorbitan monostearate
(Tween 60 manufactured by Kao Corporation) (6) Polyoxyethylene sorbitan monooleate (Kao
Tween 80 Co., Ltd. (7) Triethyl citrate (8) Dibutyl phthalate (9) Diisopropyl succinate (10) Carbitol (11) Butyl carbitol acetate (12) Dibutyl carbitol (13) Ethyl cellosolve ( 14) Phenylcellosolve (15) Ethylene glycol (16) Propylene glycol (17) Diethylene glycol Of these, (1),
Examples include (2), (3), (7), and (16). The polyethylene glycol of (1) has a weight average molecular weight of 200 or more 1
It is preferably at most 0000.

The amount of these plasticizers added is preferably 0.01 to 50%, particularly preferably 0.1 to 30%, based on the weight of the coating material.

Further, the compound represented by the general formula [1], the general formula [2] or the general formula [3] of the present invention or 3-amino-4
-At least one compound selected from homoisotwistane may be used in combination with a known water-soluble lubricant.

Specific examples of the method for dissolving the solid processing agent include a method in which the solid processing agent is once dissolved in water stored in a replenishing tank or the like and then replenished in the processing tank, and a method in which the solid processing agent is directly charged into the processing tank to be dissolved. . In the former case, a replenishment tank is required separately from the processing tank, so the latter is preferable in that it can be dissolved without taking up space.

In order to supply the processing composition of the present invention to the automatic developing machine, the area of the processed photosensitive material is integrated by a detecting device attached to the photosensitive material insertion port of the automatic developing machine, and when a predetermined unit is reached, A method can be used in which the replenishing treatment agent is replenished in a predetermined amount in the form of tablets, one by one or several in number, directly into the processing tank of the developing machine.

The area detecting device for the photosensitive material to be processed may be any of the conventionally used microswitch system, infrared system and ultrasonic system, as long as the photosensitive material to be processed can be reliably detected.

Regarding the method of replenishing the solid photographic processing agent, a preferable result is obtained by directly replenishing it to the processing tank portion of the developing machine, for example, the processing liquid tank, the processing liquid circulation system or the temperature control tank and the processing liquid filtration filter portion. Is obtained.

When a tablet-shaped photographic processing agent is used, it is possible to freely change the size and shape of the tablet in accordance with the replenishing unit. From the upper part of the system, the temperature control tank, the processing liquid filtration filter section, etc., the signal sent from the area detecting device of the photosensitive material processed in a predetermined amount is supplied through the replenishing mechanism and replenished for each unit. preferable.

Further, the solid photographic processing agent replenishing section is devised so that the processing tank section of the developing machine, the temperature of the outside air, and the scattered processing solution due to the photosensitive material to be processed do not come into contact with the solid photographic processing agent before replenishment. It is more preferable that

Hereinafter, a treatment liquid with the treatment composition of the present invention and a treatment method using the treatment liquid will be described.

The processing steps adopted in the preferred processing method include, but are not limited to, the following steps.

Color development → bleach-fixing → stable Color development → bleaching → fixing → stable Color development → bleaching → bleaching fixing → stable color development → bleaching fixing → fixing → stable color development → fixing → bleaching fixing → stable color development → bleaching → Bleaching-fixing-fixing-stability The processing liquid used in the above processing step will be described below. In the following description, the processing liquid used is referred to as a tank liquid or simply a processing liquid.

As the color developing agent used in the color developing treatment agent, a p-phenylenediamine compound having a hydrophilic group is preferably used because the effect of the object of the present invention is excellent and the fog is small. .

The p-phenylenediamine-based compound having a hydrophilic group is compared with a p-phenylenediamine-based compound having no hydrophilic group such as N, N-diethyl-p-phenylenediamine.
It has advantages that the light-sensitive material is not contaminated and that the skin is not easily fogged.

Examples of the hydrophilic group include those having at least one amino group or a benzene ring of a p-phenylenediamine compound, and specific hydrophilic 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}

[0073]

[Chemical 10]

(M and n each represent an integer of 0 or more and 5 or less), —COOH, —SO ₃ H, etc. are preferred.

Specific examples of the color developing agent preferably used in the present invention are shown below.

[0076]

[Chemical 11]

[0077]

[Chemical 12]

[0078]

[Chemical 13]

[0079]

Embedded image

Examples of hydroquinone type developing agents include hydroquinone, methylhydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, and 2,5-dimethylhydroquinone.

The effect of the present invention is better exhibited when the color developing agent contains the compound represented by the following general formula (II).

[0082]

[Chemical 15]

In the general formula (II), R ₄ and R ₅ are each a hydrogen atom, an alkyl group, an aryl group,

[0084]

Embedded image

Although R ₄ and R ₅ do not represent hydrogen atoms at the same time. The alkyl groups represented by R ₄ and R ₅ may be the same or different and are preferably alkyl groups having 1 to 3 carbon atoms. Further, these alkyl groups may have a carboxylic acid group, a phosphoric acid group, a sulfonic acid group or a hydroxyl group.

R'represents an alkoxy group, an alkyl group or an aryl group. The alkyl group and aryl group of R ₄ , R ₅ and R ′ include those having a substituent, and R ₄ and R ₅ may combine to form a ring, and examples thereof include piperidine, pyridine, triazine and morpholine. You may comprise such a heterocycle.

Specific examples of the hydroxylamine compound represented by the general formula (II) are shown in US Pat.
3,293,034 and 3,287,124, etc.,
Particularly preferred specific exemplified compounds include JP-A-4-8674.
No. 1 (I-1) to (I-39) described on pages 36 to 38 and (1) to (53) described on pages 3 to 6 of JP-A-3-33845 and JP-A-3-63646 No. 5 Up to (7) to (52).

The compounds represented by the general formula (II) are
It is usually used in the form of free amine, hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate, acetate and the like.

In the color developing agent, a sulfite salt can be used as a preservative, and a buffering agent can be used.

Further, as a development accelerator, Japanese Patent Publication No. 37-16088
No. 37, No. 37-5987, No. 38-7826, No. 44-12380, No. 45-9
No. 019 and U.S. Pat.
No., JP-B-44-30074, JP-A-56-156826 and 52-43
Quaternary ammonium salts represented by 429, US Pat.
P-aminophenols described in 10,122 and 4,119,462, U.S. Patents 2,494,903, 3,128,182 and 4,230,79
No. 6, No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Patent No. 2,48
Amine compounds described in 2,546, 2,596,926 and 3,582,346 etc., Japanese Patent Publication Nos. 37-16088, 42-25201, U.S. Pat. If necessary, polyalkylene oxide represented by Patent 3,532,501 and the like, other 1-phenyl-3-pyrazolidones, hydrozines, mesoionic compounds, ionic compounds, imidazoles, etc. can be added.

It is preferable that the color developing agent contains substantially no benzyl alcohol.

Chlorine ions and bromine ions are preferably contained in the color developing tank solution for the purpose of preventing fog and the like.

When directly added to the color developing agent, sodium chloride, potassium chloride, chlorine chloride,
Ammonium chloride, nickel chloride, magnesium chloride,
Examples thereof include manganese chloride and calcium chloride, of which sodium chloride and potassium chloride are preferable. Examples of the bromide ion supplying substance include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cerium bromide, and thallium bromide. Of these, preferred are potassium bromide and sodium bromide.

Further, these may be supplied in the form of a salt against the optical brightener added to the color developer.

If desired, the color developer used in the present invention may contain any antifoggant in addition to chlorine ion and bromine ion. As the antifoggant, an alkali metal halide such as potassium iodide and an organic antifoggant can be used. Examples of the organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2
Typical examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

The color developing agent used in the present invention may contain a triazinyl stilbene type optical brightening agent.

Further, an auxiliary developing agent may be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminophenol hexaulfate (methol), phenidone, N, N'-diethyl-p-aminophenol hydrochloride, N, N, N ', N'-tetra Methyl-p-phenylenediamine hydrochloride and the like are known.

Furthermore, various other additives such as stain inhibitors, sludge inhibitors, and multi-layer effect accelerators can be used.

Further, the color developing agent is described in JP-A-4-118649.
It is preferable to add a chelating agent represented by the general formula [K] described on pages 69 to 74 and its exemplified compounds K-1 to K-22.

Next, regarding the automatic developing machine and the supplying apparatus in the case of the solid processing agent which are preferably used in carrying out the processing using the composition of the present invention, the apparatus described in JP-A-5-119454 is used. be able to.

[0101]

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

Example 1 A color developing replenishing tablet for a color negative film was prepared according to the following procedure.

Operation (1) CD-4 (4-amino-3-methyl-N-ethyl- (β
655 g of (hydroxyethyl) aniline sulfate) is ground in a commercially available bandam mill to an average particle size of 11 μm. This fine powder was mixed with 81 g of mannitol and granulated by spraying 10 ml of water at room temperature for about 7 minutes in a commercially available stirring granulator, and then the granulated product was dried at 40 ° C. in a fluid bed dryer. And dried for 2 hours to almost completely remove the water content of the granulated product.

Operation (2) 360 g of hydroxylamine sulfate, 39 g of potassium bromide, 3,5
20 g of disulfocatechol was pulverized in the same manner as in the operation (1), and then 20 g of Pine Flow (manufactured by Matsutani Chemical Co., Ltd.) was added and mixed to granulate. The amount of water sprayed was 50 ml, and the granulated product was 58 ° C.
At 50 minutes, the granulated product is dried for about 50 minutes to completely remove water.

Operation (3) Operation (1) with sodium sulphite 580g, potassium carbonate 3750g and diethylenetriamine pentaacetic acid 5 sodium 240g.
After pulverizing in the same manner as above, 480 g of polyethylene glycol having a weight average molecular weight of 6000 and 800 g of mannitol are uniformly mixed with this fine powder in a commercially available mixer. Next, in the same manner as in operation (1), the amount of water sprayed is set to 100 ml and granulation is performed. After granulation, it is dried at 65 ° C. for 2 hours to remove water almost completely.

Operation (4) The granules prepared in the above operations (1) to (3) were treated at 25 ° C and 45 ° C.
Mix evenly for 10 minutes using a mixer in a room conditioned to below% RH. Next, the compounds of the present invention and comparative compounds shown in Table 1 are added and mixed for another 3 minutes.

Using a modified rotary tableting machine (Tough Press Collect H18, Kikusui Seisakusho Co., Ltd.), the mixture thus obtained was filled with 12.0 g of each tablet at a compression pressure of 1000 kg / cm ^2. Continuously tableting was carried out at a rotation speed of 5 rpm and a diameter of 30 mm to prepare tablet samples for color development replenishment for color negative film.

Experiment 1 Five tablet samples obtained by the above operation were dissolved in 1 liter of water and the dissolution state of the solution was observed.

Experiment 2 In the above operation, the shape of the tablet sample in continuous tableting and the state of adhesion of the mixture to the tableting machine were observed.

Experiment 3 The mixture obtained by the above operation was compression-molded using a commercially available hydraulic press and a die having a diameter of 30 mm at a filling amount of 12 g per tablet and a compression pressure of 1000 kg / cm ² , and then, The molded tablet was extracted, and the pressure necessary for extraction at this time was measured as a discharge pressure using a load cell. Perform this operation 10
Repeated times, the average value was used as the discharge pressure.

Experiment 4 Ten tablet samples each obtained by the above operation were measured for hardness in the diametrical direction using a hardness tester (speed checker manufactured by Okada Seiko Co., Ltd.), and the average value was used to determine the hardness of the tablet sample. (Strength)
And

Experiment 5 One of the tablet samples obtained by the above-mentioned operation was used to remove almost completely the fine powder generated at the time of production, and then a square case made of styrene with a lid (length 45 mm × width 45 mm × height 22) was used.
mm), and then VIBRATION TESTER BF-UA manufactured by IDEX Co., Ltd.
A vibration test was performed for 10 minutes and 3 hours under a vibration condition of 5 to 67 Hz / 210 sec, and the state of the treatment agent adhering to the inner wall of the case after the test was visually confirmed.

The results are shown in Table 1.

[0114]

[Table 1]

In Table 1, AHI represents 3-amino-4-homoisotwistane.

[Evaluation Criteria] Solubility of Dissolved Solution ◯: No precipitate or suspended matter is observed Δ: Slight precipitate or suspended matter is observed ×: Many precipitates or suspended matter are observed

Tabletability: sample shape ◯: No defect in shape of tablet sample such as cracking or chipping is observed at all Δ: Defect in shape of tablet sample such as cracking or chipping is about 5 to 5 in total
10% can be seen. ×: Many defective tablet sample shapes such as cracks and chips are observed.

Tabletability; Adhesion ◯: No adhesion of powder to the tablet machine is observed. X: Adhesion of powder to the tablet machine is observed.

Vibration test ◎: Almost no adhesion of fine powder to inner wall of case ○: Slight adhesion of fine powder to inner wall of case ×: Adhesion of fine powder to inner wall of case almost all over × : Adhesion of fine powder to the inner wall of the case is seen almost all over,
A large amount of fine powder also exists in the case.

As is apparent from Table 1, when the compound represented by the general formula [1], the general formula [2] or the general formula [3] or AHI of the present invention is not used, the discharge pressure is large and the lubricity is high. Is low and the tabletability is poor. Further, although magnesium stearate has a small discharge pressure and a large lubricity, the strength of the obtained tablet is small, the solubility is poor, and a precipitate is generated, which cannot be put to practical use. On the other hand, it can be seen that the tablet of the present invention has a large lubricity and an excellent tableting property and a large strength, and further, the generation of fine powder during transportation and handling of the tablet is reduced.

Example 2 N-myristoyl-N-methyl-β-alanine sodium 4 was added to the granules prepared in steps (1) to (3) of Example 1 above.
Add 0 g and mix for 10 minutes as in procedure (4) of Example 1 above.

The mixture thus obtained is used in Example 1.
Continuous tableting was carried out in the same manner as in the operation (4) to prepare a tablet sample for color development replenishment for color negative film.

On the other hand, the coating agent shown in Table 2 was dissolved in water to prepare an aqueous solution having a solid content concentration of 30%, and the compound represented by the general formula [1] shown in Table 2 was added to the tablet sample. Was added so that the weight% with respect to the weight of 1 was the value shown in Table 2, and this was stored for 1 week in an open state at a temperature of 25 ° C and a humidity of 50%.

[0124] The tablet sample produced by the above operation was put into an Aqua Coater AQC-48T type manufactured by Freund Sangyo Co., Ltd., heated at an air supply temperature of about 60 ° C for 5 minutes, and then the number of revolutions of the pan was set to 15 rpm. , At an air supply temperature of 60 to 65 ° C and an exhaust temperature of 35 to 40 ° C, spray the coating solution prepared previously and stored,
A spray amount and a spray time were adjusted, and coating was performed so that the total weight of the coating material as a solid content with respect to the tablet weight was 1.0% to prepare a tablet sample for color development replenishment for color negative film.

[0125] The tablet sample obtained by the above-mentioned operation was heated at a temperature of 25
After being left for 1 day in an environment of ° C and humidity of 50%, the appearance of the tablet sample surface was visually observed. Further, the same vibration test as in Experiment 5 of Example 1 was performed.

The results are shown in Table 2.

[0127]

[Table 2]

In the table, PEG6000 of the coating agent indicates polyethylene glycol having a weight average molecular weight of 6000, Pine Flow is manufactured by Matsutani Chemical Co., Ltd., and Yucaformer AM-75, 510 and AM-75W are both Mitsubishi Petrochemicals. It is manufactured by Co., Ltd.

[Evaluation Criteria] Surface Appearance ⊚: No contamination of the surface of the tablet sample ∘: Slight black-green contamination is observed on the surface of the tablet sample ×: Black-green in a considerable area of the surface of the tablet sample The evaluation criteria for the vibration test are the same as in Example 1.

As is clear from Table 2, when the compound represented by the general formula [1] of the present invention is used by being localized on the surface by coating, even when the addition amount is small, when handling tablets, etc. The effect of preventing the generation of fine powder can be made equal or more, and further, even in a coating solution stored for a long period of time by the addition of the compound, due to coating unevenness or the like which is considered to be the effect of solution spoilage. It is possible to obtain a stable tablet without generation of fine powder and contamination of the tablet surface. In addition, the exemplified compound 1-3 used in this experiment was replaced with the exemplified compounds 2-1 and 3-2 and AH.
As a result of carrying out the same experiment and evaluation by substituting for I, respectively, almost the same result as above was obtained.

Example 3 CD-4 (4-amino-3-methyl-N-ethyl- (β
-Hydroxyethyl) aniline sulfate) 660 g of Example 1
In the same manner as in the operation (1), the compound of the present invention shown in Table 3 was mixed with the amount shown in Table 3 (powder addition amount) and 81 g of mannite. Furthermore, disulfoethylhydroxylamine disodium salt was dissolved in water to obtain a solid content concentration.
A 30% coating aqueous solution was prepared, and the compound of the present invention shown in Table 3 was added thereto in an amount to give the amount shown in Table 3 (coating addition amount), and the coating material as a solid content relative to the weight of the solid processing agent. The coating solution was sprayed onto the mixture using a commercially available fluidized bed granulator so that the ratio of the total weight of ) Got.

The obtained granule sample was subjected to a temperature of 25 ° C. and a humidity of 50%.
After standing for 2 weeks in an RH environment, the surface of the granule sample was visually observed.

[0133] Further, the granule sample after the standing was 149 μm.
(JIS standard) sieve is used to remove particles with a particle size smaller than 149 μm, and 10 g of each is alternately transferred 5 times and 20 times by 2 cases made of styrene, and the state of the treatment agent adhering to the inner wall of the case Was visually confirmed.

The results are shown in Table 3.

[0135]

[Table 3]

The evaluation criteria for the appearance of the surface were the same as in Example 2, and the evaluation criteria for the transfer test were the same as those for Experiment 5 in Example 1.

As is clear from Table 3, by using the compound represented by the general formula [1] of the present invention, the surface of the solid processing agent is not contaminated and the generation of fine powder during handling is small. A stable solid processing agent can be obtained. Moreover, this effect is obtained by localizing the compound of the present invention on the surface by coating.
It can be more remarkably obtained by adding a small amount. Further, the same experiment was carried out by replacing Exemplified Compounds 1-3 and 1-2 used in this experiment with Exemplified Compounds 2-1, 3-2 and AHI, respectively.
As a result of the evaluation, almost the same result as the above was obtained.

Example 4 (Color development replenishing tablet for color paper) Operation (A) CD-3 (4-amino-3-methyl-N-ethyl-N-) as a developing agent
(β- (methanesulfonamido) ethyl) aniline sulfate) 1
Grind 523 g in a Van Dam mill until the average particle size is 10 μm. This fine powder is granulated by spraying 50 ml of water at room temperature for about 5 minutes in a commercially available stirring granulator, and then the granulated product is dried at 40 ° C for 1 hour 40 minutes in a fluidized bed dryer. Then, the water content of the granulated product is almost completely removed.

Operation (B) Disulfoethylhydroxylamine disodium salt 410
g, 1690 g of sodium p-toluenesulfonate and 310 g of Tinopearl SFP (manufactured by Ciba Geigy) are pulverized and granulated in the same manner as in the operation (A). The amount of water sprayed was 60 ml, and after granulation,
The granulated product is dried at 50 ° C. for 2 hours to almost completely remove water.

Procedure (C) 35 g of sodium sulfite, 3310 g of potassium carbonate, 320 g of diethylenetriamine pentaacetic acid 5 sodium salt and 340 g of lithium hydroxide monohydrate were crushed in the same manner as in the procedure (A), and then 600 g of mannitol and polyethylene having a weight average molecular weight of 6000 were used. Add 1010 g of glycol and mix evenly with a commercially available mixer.

Then, in the same manner as in the operation (A), the amount of water sprayed is set to 100 ml and granulation is carried out. 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.

Operation (D) The compound of the present invention and the comparative compound are added to the granules prepared in the above operations (A) to (C) and mixed as in Example 1. The obtained mixture was subjected to continuous tableting in the same manner as in Example 1 to prepare a tablet sample for color development replenishment for color paper.

When the above samples were used and evaluated in the same manner as in Example 1, the same results were obtained, and the effect of the present invention was confirmed.

Further, 35 g of sodium N-myristoyl-N-methyl-β-alanine was added to the granules prepared in the above operations (A) to (C), and tableting was carried out in the same manner as in Example 2, When the same coating as in Example 2 was performed using the compound of the present invention and the same evaluation was performed, almost the same results were obtained, and the effect of the present invention was confirmed.

Further, with the same coating as in Example 2,
First, the surface of the tablet was coated with 0.5% by weight of the coating solution containing no compound of the present invention, and then the surface of the tablet was further coated with 0.5% by weight of the coating solution containing the compound of the present invention. Results similar to those of Example 2 were obtained, confirming the effect of the present invention.

Example 5 A color negative film bleaching tablet was prepared according to the following procedure.

Operation (5) 1,3-Propanediaminetetraacetic acid Ferric ammonium monohydrate
1910 g, 1,3-propanediamine tetraacetic acid 95.0 g, potassium bromide 850.0 g, succinic acid 96.0 g, and disodium succinate hexahydrate 420 g were pulverized in the same manner as in the operation (1) of Example 1, and demolition MS ( 30.0 g (manufactured by Kao Corporation) and 15.0 g of mannitol were added and mixed, and the amount of water added was adjusted to 90 ml for granulation. After the granulation, the granulated product is dried at 60 ° C. for 120 minutes to almost completely remove the water content of the granulated product.

Operation (6) β-Cyclodextrin 5 was added to the granules prepared in operation (5).
After adding 0.0 g and mixing, 50 g of sodium N-lauroyl sarcosine was added and mixed for 3 minutes. Next, the mixture was subjected to continuous tableting in the same manner as in Example 2, the same coating as in Example 2 was performed using the compound of the present invention, and the same evaluation was carried out. It was confirmed.

Example 6 A color negative film fixing tablet was prepared according to the following procedure.

Operation (7) Ammonium thiosulfate 2400.0 g, sodium sulfite 155.
0g, potassium carbonate 20.0g, ethylenediamine tetraacetic acid 2
20.0 g of sodium was crushed in the same manner as in the operation (1) of Example 1, and 65 g of Pine Flow (manufactured by Matsutani Chemical Industry Co., Ltd.) was added thereto and mixed and granulated. The amount of water added was 50 ml, and after granulation,
The granules were dried at 60 ° C for 120 minutes to almost completely remove water.

Operation (8) The granules prepared in operation (7) were mixed with 15 g of sodium N-lauroylsarcosine at 25 ° C. in a room whose humidity was controlled to 40% RH or less for 3 minutes using a mixer. The obtained mixture was subjected to continuous tableting in the same manner as in Example 2, and the same coating as in Example 2 was performed using the compound of the present invention. The same evaluation was carried out. confirmed.

Example 7 A color negative film stabilizing tablet was prepared according to the following procedure.

Operation (9) m-Hydroxybenzaldehyde 1450.0 g, Megafac F116 (manufactured by Dainippon Ink and Chemicals) 38.0 g, ethylenediamine tetraacetic acid disodium 210.0 g, lithium hydroxide monohydrate 1
00.0 g was pulverized in the same manner as in the operation (1) of Example 1, and 100.0 g of Pine Flow (manufactured by Matsutani Chemical Industry Co., Ltd.) was added and mixed to granulate. The amount of water added is 80 ml, and after granulation, at 50 ℃
The granules were dried for 120 minutes to almost completely remove water.

Operation (10) The granules prepared in operation (9) were mixed for 3 minutes using a mixer in a room where the humidity was controlled to 40% RH or less at 25 ° C. The obtained mixture was subjected to continuous tableting in the same manner as in Example 2, and the same coating as in Example 2 was performed using the compound of the present invention. The same evaluation was carried out. confirmed.

Example 8 Color paper bleach-fixing tablets were prepared according to the following procedure.

Operation (E) Diethylenetriamine pentaacetic acid ferric ammonium monohydrate
5980.0 g, diethylenetriamine pentaacetic acid 290.0 g and sodium carbonate monohydrate 490.0 g are pulverized in the same manner as in the operation (1) of Example 1, and 2010.0 g of polyethylene glycol having a weight average molecular weight of 6000 is added and mixed to granulate. The amount of water added is 20
After granulating to 0 ml, the granulated product is dried at 60 ° C. for 3 hours to almost completely remove water from the granulated product.

Operation (F) Ammonium thiosulfate 7900.0 g, sodium sulfite 195
0.0 g was pulverized in the same manner as in the operation (1) of Example 1, and 500.0 g of pine flow was added thereto and mixed to granulate. The amount of water sprayed was 150 ml, and the granulated product was dried at 60 ° C. for 120 minutes to almost completely remove the water content of the granulated product.

Operation (G) The granule samples prepared in operations (E) and (F) were mixed at room temperature with a commercially available cross rotary mixer for 10 minutes, and then 100 g of sodium N-lauroylsarcosine was added, Mix for 3 minutes. The obtained mixture was subjected to continuous tableting in the same manner as in Example 2, the same coating as in Example 2 was performed using the compound of the present invention, and the same evaluation was carried out. confirmed.

Example 9 Color paper stabilizing tablets were prepared according to the following procedure.

Operation (H) 500.0 g of sodium carbonate monohydrate, 1-hydroxyethane-1,
1-diphosphonic acid trisodium 3050.0g, ethylenediamine tetraacetic acid disodium 160.0g, o-phenylphenol 6
5.0 g was crushed in the same manner as in the operation (1) of Example 1, and 500.0 g of polyethylene glycol having a weight average molecular weight of 6000 was crushed.
Was added, mixed and granulated. The amount of water added was 60 ml, and the granulated product was dried at 70 ° C. for 120 minutes to almost completely remove the water content of the granulated product.

Operation (I) The granules prepared in operation (H) and 50 g of sodium N-lauroylsarcosine were mixed at 25 ° C. in a room whose humidity was adjusted to 40% RH or less for 3 minutes using a mixer. The obtained mixture was subjected to continuous tableting in the same manner as in Example 2, and the same coating as in Example 2 was performed using the compound of the present invention. The same evaluation was carried out. confirmed.

Example 10 (Evaluation by automatic developing machine) The developer for color negative obtained by the same operation as in Example 1 was used, and the other processing solutions were the same as those in Example 2 in JP-A-5-119454. The Konica Color XG400 film (Konica Color) that has been exposed to the automatic developing machine prepared using the tablets obtained by the method described
(Manufactured by Co., Ltd.) were continuously treated for 100 days each for 30 days.

After the continuous processing is completed, Konica CONTROL ST
RIPS PROCESS CNK-4 (manufactured by Konica Corp.) was processed and the state of scratches on the film was observed.

After the continuous treatment, the condition of contamination of each tank roller of the automatic developing machine was observed.

Furthermore, the generation of precipitates in the processing tank was observed.

After the continuous processing, the exposed Konica Color XG400 film (manufactured by Konica Corp.) is processed, and the processed film is treated under an environment of a temperature of 40 ° C. and a humidity of 80% RH for 30 days.
After standing for a day, the state of contamination of the emulsion surface of the film after standing was visually observed.

The results are shown in Table 4.

[0168]

[Table 4]

[Evaluation Criteria] Scratches on the film ◯: No scratches are observed ×: Many scratches are observed The larger the number of scratches, the more scratches are generated.

Dirt on the roller part ◯: No deposits or deposits were found Δ: Some deposits were seen ×: Many deposits or deposits were found The larger the number of ×, the more deposits or deposits Indicates a lot.

Occurrence of Precipitates ◯: No precipitates are seen Δ: Some precipitates are seen ×: Many precipitates are seen The larger the number of ×, the larger the amount of precipitates.

Contamination status of processed photosensitive material ⊚: No contamination of the photosensitive material is observed. ◯: Fine black stains are slightly observed. ×: Fine black stains are observed at several places xx: Fine Black stains were considerably observed and the gloss of the light-sensitive material was deteriorated. Incidentally, the stains and precipitates on the roller portion without addition of the compound of the present invention were different from those using magnesium stearate. .

From Table 4 above, in the continuous processing using the processed tablet of the present invention, there was no generation of scratches on the processed light-sensitive material, there was little roller stain in the processing tank, and there was no precipitation in the processing tank. Further, it can be seen that when the compound of the present invention is used in a processing liquid, it is excellent without causing contamination even when the processed light-sensitive material is stored for a long period of time.

Example 11 Using the color negative film processing tablets prepared in the same manner as in Examples 2, 5, 6 and 7, the light-sensitive material was processed by the same automatic developing machine as in Example 10, and the same evaluation was carried out. As a result, the effect of the present invention could be obtained without causing contamination of the light-sensitive material even if the amount of the compound of the present invention added was small.

Example 12 Using the tablets for color paper treatment prepared in the same manner as in Examples 4, 8 and 9, the conventional method was carried out in the same automatic developing machine as in Example 3 in JP-A-5-119454. The exposed Konica Color QA Paper Type A5 (manufactured by Konica Co., Ltd.) was continuously treated for 7.5 days by 7.5 m ² every day.

After the continuous processing, Konica Color QA Paper Type A5 which had been subjected to normal exposure was further processed, and the state of scratches on the photosensitive material was observed. Furthermore, when the contamination of the roller portion, the precipitate, and the contamination due to the storage of the processed photosensitive material were evaluated in the same manner as in Example 10, almost the same results were obtained, and it was found that the effect of the present invention was obtained. .

Example 13 1-5, 2-3, 2-8, 2-16, 3-1, 3-3 and 3 were used in place of the additive compound 2-1 used in the sample No. 11 of Example 1. Experiments and evaluations were carried out in the same manner as in Example 1 except that the values were changed to −10, respectively, and substantially the same results as in sample No. 11 of example 1 were obtained.

Example 14 Instead of the additive compound 1-2 used in the sample No. 6 of Example 1, the additive compound 1-2 (addition amount 0.05% by weight) and the additive compound 2-1 (addition amount 0.05% by weight) , Added compound 2-1 (added amount 0.05) instead of the added compound 2-1 used in sample No. 11.
Wt%) and added compound 3-2 (addition amount 0.05% by weight),
Instead of the additive compound 3-2 used in the sample No. 12, the additive compound 3-2 (addition amount 0.05% by weight) and the added compound AHI (addition amount 0.05% by weight), instead of the AHI used in the sample No. 13 Added compound AHI (added amount 0.05% by weight) and added compound 1-2
Experiments and evaluations were carried out in the same manner as in Example 1 except that the addition amount was changed to 0.05% by weight. Sample No. 6, Sample No. 11, Sample No. 12 and Sample No. 13 of Example 1 were obtained. It was found that the same results as in Example 1 were obtained, and that the effect of the present invention was obtained even when the compound of the present invention was used in combination.

[0179]

INDUSTRIAL APPLICABILITY According to the present invention, a processing agent which is excellent not only in tableting property and lubricity but also in high strength can be obtained, and further, the photosensitive material is not scratched during the processing of the photosensitive material. The silver halide photographic light-sensitive material not only does not stain the roller part of the automatic developing machine, but also does not cause precipitation in the fixing tank, the bleach-fixing tank or the stabilizing tank, and has good storability of the processed light-sensitive material. It is possible to provide a composition for obtaining a solid processing agent for use in silver halide and a processing composition for a silver halide photographic light-sensitive material capable of preventing accidents due to accidental ingestion.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G03C 7/413

Claims (6)

[Claims] 1. A compound represented by the following general formula [1], general formula [2], general formula [3] or at least one compound selected from 3-amino-4-homoisotwistane is contained. A characteristic processing composition for a silver halide photographic light-sensitive material. Embedded image [In the formula, R ₁ and R ₂ are each a hydrogen atom or a carbon number of 1 to
3 represents an alkyl group. ] [Chemical 2] [Wherein R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a —COR ⁴ group (wherein R ⁴ is an alkyl group having 1 to ⁴ carbon atoms,
An acyl group of the alkoxylated is a group or chlorophenyl group), R ² is an alkyl group, an alkenyl group or a cyclopentyl group having 1 to 4 carbon atoms, R ³ is an alkyl group having 1 to 4 carbon atoms. ] [Chemical 3] [In formula, R, R < ₁₁ >, R < ₁₂ >, R < ₁₃ > is a hydrogen atom and a C1-C8 alkyl group, respectively, and each may be same or different. ] 2. The processing composition for a silver halide photographic light-sensitive material according to claim 1, which is composed of a solid. 3. A treatment for a silver halide photographic light-sensitive material with at least one compound selected from the general formula [1], the general formula [2], the general formula [3] or 3-amino-4-homoisotwistane. The processing composition for a silver halide photographic light-sensitive material according to claim 2, wherein the proportion of the whole composition is 5 × 10 ^{-6 to} 4.0% by weight. 4. The solid is in a form selected from granules and tablets, and is selected from the general formula [1], the general formula [2], the general formula [3] or 3-amino-4-homoisotwistane. 4. The processing composition for silver halide photographic light-sensitive materials according to claim 2, wherein at least one compound is localized on the surface of the granules or tablets. 5. At least one selected from a water-soluble polymer and a saccharide and at least one selected from the general formula [1], the general formula [2], the general formula [3] or 3-amino-4-homoisotwistane. The processing composition for silver halide photographic light-sensitive materials according to claim 4, which is a granule or a tablet whose surface is coated with a composition containing two compounds. 6. A compound containing at least one developing agent selected from a para-phenylenediamine color developing agent and a hydroquinone developing agent.
A processing composition for a silver halide photographic light-sensitive material according to any one of claims 5 to 7.