JP3022009B2 - 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 particularly to a processing agent for a silver halide photographic light-sensitive material having improved processing stability, social environment suitability, work environment suitability and the like. .

[0002]

BACKGROUND OF THE INVENTION Silver halide photographic materials (hereinafter sometimes referred to as photographic materials or photographic materials) are usually
After exposure, the film is processed by processes such as development, desilvering, washing, and stabilization. Bleach, bleach-fix, fixer, tap water or ion-exchanged water for washing, and stabilizing solution for stabilization. Is done. The photosensitive material is immersed and processed in each of these processing solutions whose temperature is usually controlled at 30 to 40 ° C.

[0003] Such processing is usually carried out by an automatic developing machine (hereinafter, referred to as an automatic developing machine).
This is performed by sequentially transporting the processing liquid between the processing tanks storing the processing liquids by using an automatic developing machine. In this case, conventionally, in order to keep the activity of the processing solution in the processing tank constant, a method of replenishing the replenishing solution of each processing solution has been adopted. The processing operation is performed while supplying the material into the tank.

In such a case, the replenisher itself stored in the replenishment tank is usually prepared in another place and supplied to the replenishment tank as needed. Has adopted the following manual method. That is, a processing agent for a silver halide photographic light-sensitive material (hereinafter sometimes referred to as a photographic processing agent) is supplied to a user in the form of a powder or a concentrated liquid. In the case of a thick liquid, it is used by mixing, dissolving and diluting to a certain amount with water.

[0005] The replenishment tank may be installed beside the automatic machine, and it is necessary to secure a considerable space. Also,
Even in the minilabs, which have been increasing rapidly in recent years, the replenishment tank is built in the main body of the automatic processing machine.

[0006] Replenishers are divided into several parts to obtain good and stable performance in photographic processing. For example, a replenisher of a color developing solution is divided into various concentrated parts, which are mixed and added to a certain amount of water for use.

[0007] The above-mentioned concentrated parts are put in a container such as a plastic container, and these are put together and put in an outer bag (for example, a cardboard box), and are sold as one unit.

The replenishing agent prepared by dissolving, diluting and mixing the above-mentioned parts agent is used after finishing in a fixed amount. However, the replenishing agent has the following disadvantages.

That is, each part agent is individually placed in a container, and depending on the replenishing agent, the number of parts agent is several, and the number of containers is considerably large when one unit is used, and the number of containers is considerably large in storage and transportation. In addition to requiring a lot of space, there are problems in disposing of empty containers. If the replenishment agent consists of several types of parts, each part is separately placed and scattered, so it takes time to find each part, and the work efficiency of liquid preparation Was significantly reduced.

In recent years, there has been a strong demand for environmental conservation and resource saving mainly in Europe and North America, and a plastic container containing the above-mentioned concentrated processing solution has become a particular problem in photography. In other words, although plastic containers for photographic processing agents are inexpensive, convenient for storage and transportation, and excellent in chemical resistance,
Empty containers can be landfilled as industrial waste,
Although discarded or incinerated, the plastic container has little biodegradability and accumulates. When incinerated, there is a problem that a large amount of carbon dioxide gas is generated, which contributes to global warming and the like. In addition, it has been pointed out that the user of the automatic developing machine has a problem that a large amount of plastic containers are piled up in a narrow working space to further reduce the space.

[0011] Therefore, there is a demand for the development of a technology for reducing pollution that does not substantially use plastic bottles.

For this reason, for example, Japanese Patent Application Laid-Open No. 51-61837 discloses a photographic tablet containing a disintegrant, and a technique for improving solubility is proposed. JP-A-2-109042, JP-A-2-109043, JP-A-3-39735 and JP-A-3-39939 disclose a method using a granulated photographic processing agent having a certain average particle size. Therefore, improvement of powder scattering prevention has been proposed.

However, in the above method, an insoluble substance is easily generated, which causes clogging of a filter portion in a processing tank of an automatic developing machine, or the insoluble substance adheres to a photographic light-sensitive material being processed, thereby causing a development. There are problems such as affecting the processability and processability.

Further, in the tablet-type processing agent described in the above-mentioned publication, the color developing agent is a part agent (also referred to as a part agent), and when these tablets are used, stirring and dissolving operations with a replenishment tank or the like provided are indispensable. In addition, there are problems that it takes a long time to dissolve and erroneous dissolution during operation. Therefore, in order to prevent erroneous dissolution, we examined the use of a part agent component as a single component and made it into a tablet-type treatment agent. The obtained tablets were treated as one agent per treatment. However, it was found that the solubility was still poor, and when the treatment was carried out using a solution obtained by further dissolving, the stain was large, and it was found to be unsuitable for actual use.

As a method of eliminating the dissolving operation, a paste-like part agent in an amount corresponding to the mixing ratio of the part agent is extruded from each unit container as disclosed in JP-A-3-11344.
A technique for precisely adjusting and supplying the extruded parts to a predetermined concentration by diluting the same is disclosed,
Certainly, the melting work is reduced or eliminated, but equipment such as a device for extruding parts, nozzles, supply equipment, etc. are required, and maintenance and management of the equipment are required, which places a heavy burden on workers . Another drawback is that the stability of the treating agent is poor.

On the other hand, in recent years, for the protection of the global environment and for economic reasons, there has been a tendency to use a rich and low replenishment treatment.
It has been found that there are some problems in performing these rich and low replenishment treatments. That is, one of the problems is that the solubility of the replenisher determines the activity (processing performance) of the processing solution, and a concentration exceeding the limit solubility of the replenisher cannot be obtained. More recently, the need for rapid processing has increased, and in this case, methods for obtaining a concentration exceeding the limit solubility of the replenisher have been increasing. As another problem, due to the low replenishment, the residence time of the replenisher in the replenisher tank is prolonged, and the deterioration of the performance in the replenisher tank cannot be ignored. In particular, this is a serious problem in a minilab with a small amount of processing or a smaller minilab (microlab).

[0017]

Accordingly, an object of the present invention is to provide a solid photographic processing agent which has excellent storage stability, solubility and processing stability, and has a work environment suitability without using polyvin. An object of the present invention is to provide an excellent solid processing agent for a silver halide photographic material.

[0018]

The solid processing agent for a silver halide photographic light-sensitive material that achieves the above object is characterized by being obtained by compressing at least the following two types of granules.

Granules containing at least one bleaching agent Granules containing at least one fixing agent In a preferred embodiment of the present invention, the fixing agent is a thiosulfate salt. In a preferred embodiment, the bleaching agent is a ferric aminopolycarboxylic acid salt.

In still another preferred embodiment, at least 2 mol% of the cations in the fixing agent are sodium ions. In another preferred embodiment, at least 10 mol% of the cations in the bleaching agent are sodium ions. Sodium ions and / or potassium ions.

Hereinafter, the present invention will be described.

The solid processing agent for a silver halide photographic light-sensitive material according to the present invention comprises two types of granules containing at least one bleaching agent and granules containing at least one fixing agent. It is obtained by compressing different granules under pressure, and this solid processing agent functions as a bleach-fixing agent. In the following description, a solid processing agent means a bleach-fixing agent unless otherwise specified.

In the present invention, a method for producing a granulated product includes known methods such as rolling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation. Can be used.

The average particle size of the obtained granules is 100 to 80.
It is preferable to use one having a thickness of 0 μm, and more preferably 200 to 750 μm. When the average particle size is smaller than 100 μm or larger than 800 μm, when the above granulated material is mixed and compressed under pressure, the components become non-uniform,
So-called segregation or weight deviation occurs, which is not preferable. Furthermore, the particle size distribution is such that 60% or more of the granulated particles are ± 100.
Those having a deviation of １５０150 μm are preferred.

Next, when compressing the obtained granules under pressure, a known compressor, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a briquetting machine may be used. it can. The solid processing agent obtained by pressurizing and compression can take any shape, but from the viewpoint of productivity and handling, a cylindrical type, so-called tablet, is preferable.

The apparent density (bulk density) of the solid processing agent obtained by compression is 1.0 to 2.5 g / cm ^3.
And more preferably 1.1 to 2.0 g / cm ³
When it is less than 1 g / cm ³ , the strength of the obtained solid is insufficient, and when it exceeds 2.5 g / cm ³ , the solubility of the obtained solid is deteriorated.

The bleaching agent used in the solid processing agent for a silver halide photographic light-sensitive material according to the present invention is preferably a ferric aminopolycarboxylate, and more preferably a bleaching agent represented by the following general formula [A] -I] to [A-VI]
And a ferric complex salt of the compound represented by I].

[0028]

[Image Omitted] Formula [AI] [Wherein, A _{1 to} A ₄ may be the same or different, and each represents a hydrogen atom, a hydroxy group, —COOM, —PO
₃ (M ₁ ) ₂ , —CH ₂ COOM ₂ , —CH ₂ OH or a lower alkyl group. However, at least one of A _{1 to} A ₄ is -COOM, -PO ₃ (M ₁ ) ₂ , -CH ₂ CO
It is OM _2. M, M ₁ and M ₂ each represent a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. ]

[0029]

Formula (A-II) [Wherein, A _{11 to} A ₁₄ may be the same or different, and each represents —CH ₂ OH, —COOM _3, or —PO ₃ (M ₄ )
₂ is represented. M ₃ and M ₄ each represent a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. X
Alkylene or 2 to 6 carbon atoms is _{- (B 1 O) n-} B 2
Represents-. n represents an integer of 1 to 8, and B ₁ and B ₂
May be the same or different and each represents an alkylene group having 1 to 5 carbon atoms. ]

[0030]

Formula [A-III] [Wherein, A _{21 to} A ₂₄ may be the same or different, and each represents —CH ₂ OH, —COOM _5, or —PO ₃ (M ₆ )
₂ is represented. M ₅ and M ₆ each represent a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. X ₁
Is a linear or branched alkylene group having 2 to 6 carbon atoms, a saturated or unsaturated organic group forming a ring, or-(B
₁₁ O) n ₅ -B ₁₂ - represents a. n ₅ is an integer of 1-8, and B ₁₁ and B ₁₂ may be the same or different,
Represents an alkylene group having 1 to 5 carbon atoms. n _{1 to} n ₄ each represent an integer of 1 or more, and may be the same or different. ]

[0031]

Formula [A-IV] [Wherein, R ₁ and R ₂ each represent a hydrogen atom, an optionally substituted alkyl group or an aryl group. L is

[0032]

Embedded image Wherein Y _{1 to} Y ₃ each represent an alkylene group or an arylene group, X ₂ and X ₃ each represent an oxygen atom or a sulfur atom, and R _{3 to} R ₇ each represent a hydrogen atom, an alkyl group, Represents an aryl group. ]

[0033]

Embedded image General formula [A-V] [Wherein, R _{1 to} R ₃ each represent a hydrogen atom, an optionally substituted alkyl group or an aryl group. L is the general formula [A
-IV]. W represents a divalent linking group. ]

[0034]

Formula [A-VI] [Wherein, R _{1 to} R ₃ and R _{6 to} R ₉ each represent a hydrogen atom, an alkyl group or an aryl group which may be substituted,
R ₄ and R ₅ are each a hydrogen atom, a halogen atom, a cyano group, a nitro group, an acyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, a sulfonyl group, a sulfinyl group, and an alkyl group which may be substituted. Or, it represents an aryl group, and R ₄ and R ₅ may together form a 5- or 6-membered ring. A represents a carboxy group, a phosphono group, a sulfo group, a hydroxy group, or an alkyl metal salt or an ammonium salt thereof. Y represents an alkylene group or an arylene group, and may have a substituent. t and u are 0 or 1 respectively
Represents ]

[0035]

Formula [A-VII][Where A₁~ A_FourIs -COOM₁, -OH, -PO_ThreeM₁
M_Two, -CONH_TwoAnd even if they are the same
It may be different. M₁, M_TwoIs hydrogen atom, alkali gold
Represents a genus or other cation. n₁~ N_FourIs 0, 1 or
Represents an integer of 2. R₁~ R_FourIs hydrogen atom, lower alkyl
Group, a hydroxy group (however, n₁+ N_Two= 1 and n
_Three+ N_Four= 1 when R ₁~ R_FourDoes not become a hydrogen atom).

X represents a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms or — (B ₁ O) _m —B ₂ —. m is 1
And B ₁ and B ₂ may be the same or different and each represents a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms. The following general formula [A-
The compounds represented by I] to [A-VII] will be described in detail.

First, the compound represented by the formula [AI] will be described. Specific examples of the compound represented by the general formula [AI] are shown below, but are not limited thereto.

[0038]

Embedded image

[0039]

Embedded image The compound represented by the general formula [AI] is disclosed in
Nos. 267750 and 63-267751, JP-A-2-
It can be synthesized by a general synthesis method described in, for example, JP-A-115172 and JP-A-2-295954.

Among these, those preferably used in the present invention include the exemplified compounds [AI-1], [AI-2],
[AI-13] and [AI-15]. Next, the compound represented by Formula [A-II] will be described.

In the general formula [A-II], examples of the alkylene group representing X include groups such as ethylene, propylene, and butylene. -(B ₁ O) n-B ₂ representing X
In the above, examples of the alkylene group represented by B ₁ and B ₂ include methylene, ethylene, trimethylene and the like. These alkylene groups may have, as a substituent, a lower alkyl group such as a methyl group or an ethyl group, a hydroxy group, or the like.

Specific examples of the compound represented by the formula [A-II] are shown below, but the invention is not limited thereto.

[0043]

Embedded image

[0044]

Embedded image The compound represented by the general formula [A-II] can be synthesized by a generally known method.

Among these, a particularly preferred compound is [A
-II-1], [A-II-3], [A-II-14]
It is.

The compound represented by formula [A-III] will be described below.

In the general formula [A-III], X₁
Represents-(B₁₁O ) N_Five-B₁₂In, B₁₁And B₁₂
Examples of the alkylene group represented by methylene, ethylene,
Trimethylene and the like. These alkylene groups are
As a substituent, a lower alkyl such as a methyl group or an ethyl group
And a hydroxy group.

Specific examples of the compound represented by the above formula [A-III] are shown below, but it should not be construed that the invention is limited thereto.

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image The above [A-III-16], [A-III-17],
[A-III-18], [A-III-19], [A-
III-20] includes both a trans form and a cis form.

Among the specific examples, a particularly preferred compound is [A
-III-1], [A-III-2], [A-III-
6], [A-III-35], [A-III-36],
[A-III-37] and [A-III-38].

The compound represented by the formula [A-IV] will be described below.

In the general formula [A-IV], R ₁ ,
The alkyl group represented by R ₂ has 1 to 1 carbon atoms.
Examples thereof include linear, branched, and cyclic groups of 0, and a methyl group and an ethyl group are particularly preferable. The aryl group represented by R ₁ and R ₂ is preferably a phenyl group. When R ₁ and R ₂ are an alkyl group or an aryl group, they may have a substituent. Examples of the substituent of R ₁ and R ₂ include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, an acylamino group, a sulfonylamino group, a ureido group, a urethane group, and an aryloxy group. , A sulfamoyl group, a carbamoyl group,
Alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group,
Sulfo group, carboxy group, phosphono group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, carbonamide group, sulfonamide group,
Nitro groups and the like, but preferably,

[0059]

Embedded image Is a substituent represented by Where Ra, Rb, Rc, R
d and Re represent a hydrogen atom, an alkyl group or an aryl group.

In the general formula [A-IV], Y ₁ to
Examples of the alkylene group represented by Y ₃ include a methylene group, an ethylene group, and a propylene group, and examples of the arylene group include a phenylene group. These Y _1-
The alkylene group and the arylene group represented by Y ₃ may have a substituent. As the substituent may be those raised as a substituent, for example R _1, R _2, is _{preferably, -OH -COOH -CH 2 COOM -CH 2} OH -CONH 2 -CH 2 CONH 2 -CONHCH 3 (M represents a hydrogen atom, an alkali metal, or an ammonium group).

Among the compounds represented by the general formula [A-IV], preferred are the following general formulas [BI] or [BI]
I].

[0062]

Embedded image General formula [BI] [Wherein, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group,
Or an aryl group; L ₁ and L ₂ each represent an alkylene group or an arylene group; and M represents a hydrogen atom, an alkali metal, an ammonium group, or an organic ammonium group. ]

[0063]

Embedded image General formula [B-II] [R ₁ in the formula, R ₁ to R ₄ each formula [B-I],
It is synonymous with R ₂ , and L _{1 to} L ₃ and M also have the general formula [BI]
Are synonymous with those of The following general formula [AI]
V], but are not limited thereto.

[0064]

Embedded image

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image Particularly preferred compounds among these are [A-IV-
1], [A-IV-8], [A-IV-13], [A-
IV-19], [A-IV-20], [A-IV-2]
1] and [A-IV-22].

Hereinafter, the compound represented by formula [AV] will be described.

In the general formula [A-V], the alkyl group and the aryl group represented by R _{1 to} R ₃ include the general formula [A
-IV], the same groups as those for R ₁ and R ₂ can be mentioned, and the same applies to these substituents. In the general formula [A-V], the alkylene group represented by Y ₁ to Y _3, as the arylene group include the same groups as Y ₁ to Y ₃ in general formula [A-IV], of The same applies to the substituent.

In the general formula [A-V], the divalent linking group represented by W is preferably an alkylene group having 2 to 8 simple primes (including a cyclohexylene group and the like),
An arylene group having 6 to 10 carbon atoms,

[0071]

Embedded image (B ₁ and B ₂ represent an alkylene group or an arylene group,
n represents 1-3. ),

[0072]

Embedded image (Z is a hydrogen atom, unsubstituted or -COOM, -SO
₃ represents an alkyl group or an aryl group substituted with M or -OH, and M represents a hydrogen atom, an alkali metal, or an ammonium group), and may be a combination thereof.

Among the compounds represented by the general formula [A-V], preferred are the following general formulas [B-III] or [B
-IV].

[0074]

Embedded image The general formula [B-III] [Wherein, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group or an aryl group, L _{1 to} L ₄ each represent an alkylene group or an arylene group, and M ₁ and M ₂ each represent a hydrogen atom, an alkali metal, Represents an ammonium group or an organic ammonium group. ]

[0075]

Embedded image General formula [B-IV] [Wherein, R _{1 to} R ₄ each represent R _{1 of the} general formula [B-III]
₁ and R ₂ , and L _{1 to} L ₄ and M ₁ and M ₂ have the same meanings as those in formula [B-III]. Specific examples of the compound represented by the general formula [AV] are shown below, but it should not be construed that the invention is limited thereto.

[0076]

Embedded image

[0077]

Embedded image

[0078]

Embedded image

[0079]

Embedded image

[0080]

Embedded image Particularly preferred compounds among these are [AV-1],
[AV-4], [AV-6], [AV-13],
[AV-16], [AV-20], [AV-2]
3], [AV-26], [AV-27], [AV]
-29], [AV-30], and [AV33].

Next, the compound represented by formula [A-VI] will be described.

Hereinafter, specific examples of the compound represented by the formula [A-VI] are shown, but the invention is not limited thereto.

[0083]

Embedded image

[0084]

Embedded image

[0085]

Embedded image Among these compounds, particularly preferred is [A-VI-
1], [A-VI-3], [A-VI-4], [A-V
I-16].

The compound represented by the formula [A-VII] will be described below.

In the formula, A _{1 to} A ₄ may be the same or different, and are represented by —COOM ₁ , —OH, —PO ₃ M
₁ M ₂ represents —CONH ₂ . M ₁ and M ₂ represent a hydrogen atom, an alkali metal (eg, sodium, potassium, lithium) or another cation (eg, an ammonium group, a methyl ammonium group, a tetramethyl ammonium group, etc.).

N₁~ N_FourRepresents an integer of 0 to 2 and is the same
Or different, preferably n₁= 0
And n_Three= 0. R₁~ R_FourIs a hydrogen atom, lower
Alkyl group, hydroxy group
Although it may be present, it is preferably a hydrogen atom. Where n
₁+ N_Two= 1 and n_Three+ N_Four= 1 when R ₁~ R_FourIs hydrogen field
Not a child.

X represents a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms or — (B ₁ O) _m —B ₂ —. Also B ₁
And B ₂ may be the same or different and each represents a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms. Examples of the alkylene group represented by X include groups such as ethylene, trimethylene, and tetramethylene.
Examples of the alkylene group represented by B ₁ and B ₂ include methylene, ethylene, trimethylene and the like.

Examples of the substituent of the alkylene group represented by X, B ₁ or B ₂ include a hydroxyl group and an alkyl group having 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, etc.). m is 1
Represents an integer of 4, preferably 1 to 2.

Preferred specific examples of the compound represented by the formula [A-VII] are shown below, but it should not be construed that the invention is limited thereto.

[0092]

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[0093]

Embedded image

[0094]

Embedded image The addition amount of the compounds of the general formulas [AI] to [A-VII] is preferably 0.01 to 2 mol / l of the treatment liquid, more preferably 0.05 to 1.5 mol / l of the treatment liquid. Range.

In the present invention, besides the iron complex salts of the compounds represented by the above general formulas [AI] to [A-VII], ferric complex salts of the following compounds can be used as the bleaching agent. [A'-1] ethylenediaminetetraacetic acid [A'-2] trans-1,2-cyclohexanediaminetetraacetic acid [A'-3] dihydroxyethylglycinic acid [A'-4] ethylenediaminetetrakismethylenephosphonic acid [A'- 5] Nitrilotrismethylene phosphonic acid [A'-6] Diethylenetriamine pentakismethylenephosphonic acid [A'-7] Diethylenetriaminepentaacetic acid [A'-8] Ethylenediamine diorthohydroxyphenylacetic acid [A'-9] Hydroxyethylethylenediamine Acetic acid [A'-10] Ethylenediaminedipropionic acid [A'-11] Ethylenediaminediacetic acid [A'-12] Hydroxyethyliminodiacetic acid [A'-13] Nitrilotriacetic acid [A'-14] Nitrilotripropionic acid [ A'-15] Triethylene tet Min hexaacetic acid [A'-16] Ethylenediaminetetrapropionic acid [A'-17] 1,3-propylenediaminetetraacetic acid [A'-18] Glycoletherdiaminetetraacetic acid Further, see JP-A-4-174432, pp. 7-11. Exemplified Compounds 1 to 71 and 4-204533 described therein 25 to
Ferric complex salts of the exemplified compounds 1 to 36 described on page 30 can also be used.

In the present invention, it is preferred that at least 10 mol% of the cations in the bleach are sodium ions and / or potassium ions.

In the present invention, it is preferable that the solid processing agent does not substantially contain acetic acid from the viewpoint of the effect of the present invention and the odor.

The solid bleach-fixing agent according to the present invention includes imidazole and derivatives thereof described in JP-A-64-295258 or the general formulas [I] to [IX] described in the same.
By containing at least one of the compounds represented by the following formulas and these exemplified compounds, an effect can be exerted on the rapidity.

In addition to the above accelerators, JP-A-62-1234
No. 59, page 51 to page 115, and JP-A-63-17445, page 22 to page 25, and JP-A-53-956.
Compounds described in JP-A Nos. 30 and 53-28426 can be used in the same manner.

In addition to the above, the bleach-fixing agent may contain halides such as ammonium bromide, potassium bromide and sodium bromide, various fluorescent whitening agents, defoamers and surfactants.

Next, a thiocyanate, a thiosulfate or the like is used as a fixing agent contained in the solid processing agent according to the present invention, and a thiosulfate is preferred.

The content of the fixing agent in the solid processing agent, that is, the bleach-fixing agent is preferably at least 0.01 to 4.0 mol / l of the processing solution, more preferably 0.05 to 3.5 mol / l. .

The bleach-fixing agent may contain, alone or two or more pH buffers consisting of various salts, in addition to the fixing agent. Further, it is desirable to contain a large amount of 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 which are known to be added to a normal bleach-fixing agent such as alkylamines and polyethylene oxides can be appropriately added.

The bleach-fixing agent is described in JP-A-64-29525.
A compound represented by the following general formula [FA] described in page 8 of the specification 8 and its exemplified compound may be added.

[0105]

Embedded image

The compound represented by the general formula [FA] described in the same specification can be prepared by a general method as described in US Pat. No. 3,335,161 and US Pat. No. 3,260,718. Can be synthesized. These are represented by the general formula [F
A] may be used alone,
Also, two or more kinds may be used in combination.

Further, the compounds represented by formula (1) or (2) described in WO 91/08517, pages 5 to 10, may be used.

Good results can be obtained when the amount of the compound represented by the general formula [FA] or the compound represented by the general formula (1) or (2) is in the range of 0.1 g to 200 g / l.

It is also preferred to add a compound represented by the general formula [FA] or [FB] described in Japanese Patent Application No. 2-41549 and this exemplified compound, so that the effects of the present invention are more favorably exhibited. This is preferable for achieving ammonia-free.

The bleach-fixing agent according to the present invention is prepared by adding bisulfite to at least one compound selected from the group consisting of compounds represented by the following formulas (A), (B), (C) and (D). And / or a sulfinic acid or a sulfinic acid salt.

[0111]

Embedded image [In the formula, R ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a carboxy group, an ester group, an acyl group or a carbamoyl group, R ₂ represents a hydrogen atom, Alkyl group, alkenyl group, aralkyl group, cycloalkyl group,
Represents an aryl group or a heterocyclic group. Further, R ₁ and R ₂ may be integrated to form a ring.

However, R ₁ and R ₂ are not hydrogen atoms at the same time. ]

[0113]

Embedded image [Wherein, R ₃ , R ₄ , and R ₅ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a carboxy group,
Ester group, acyl group, halogen atom, alkoxy group,
Sulfo group, sulfinyl group, sulfonyl group, cyano group,
It represents a nitro group, a carbamoyl group or a sulfamoyl group, and R ₆ represents an electron-withdrawing group.

Further, R ₃ and R ₄ , R ₄ and R ₅ ,
R ₅ and R ₆ , or R ₆ and R ₃ may be integrated to form a ring. ]

[0115]

Embedded image [Wherein, R ₇ , R ₈ , and R ₉ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, an amino group, a carboxy group, an ester group, an acyl group. Represents a group, an alkoxy group, a hydroxyl group or a thioether group, and X represents an anion. Further, R ₇ and R ₈ , R ₈ and R ₉ , and R ₉ and R ₇ may be integrated to form a ring. n represents 0 or 1. ]

[0116]

Embedded image [Wherein, R ₁₀ represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and R ₁₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group. , An aryl group, a heterocyclic group, a halogen atom, an alkoxy group, a carboxy group, an acyl group, a cyano group, a sulfo group, a carbamoyl group, a nitro group, a dialkylamino group or an ester group, and Z represents a carbon atom, a nitrogen atom, oxygen Represents a hetero ring composed of an atom, a sulfur atom or a selenium atom, Y represents an anion, and m represents 0 or 1. R ₁₀ may be bonded to an atom in Z to form a ring. Hereinafter, the general formulas (A), (B), (C) and (D) will be described in detail.

In the general formula (A), R ₁ is a hydrogen atom,
Each is a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, methoxyethyl group, carboxymethyl group, sulfomethyl group, sulfoethyl group, etc.), alkenyl group (eg, allyl group, etc.), aralkyl group (eg,
Benzyl group, phenethyl group, 4-methylbenzyl group, 4
-Sulfobenzyl group, etc.), cycloalkyl group (for example,
Cyclohexyl group, etc.), aryl group (for example, phenyl group, naphthyl group, 3-sulfobutoxyphenyl group, 4-
N-methyl-N-sulfopropylaminophenyl group, 3
-Sulfopropylphenyl group, 3-carboxyphenyl group, etc.), heterocyclic group (eg, pyridyl group, thienyl group, pyrrolyl group, indolyl group, furyl group, furfuryl group, morpholyl group, imidazolyl group, etc.), ester group (eg, Methoxycarbonyl group, etc.), an acyl group (eg, acetyl group, methoxypropionyl group, etc.), a carbamoyl group (eg, unsubstituted carbamoyl group, dimethylcarbamoyl group, etc.), a carboxy group or a salt thereof.

[0118] Examples of substituted or unsubstituted alkyl group, alkenyl group, aralkyl group, cycloalkyl group, aryl group or heterocyclic group represented by R ₂ are the same as those of R _1. Further, R ₁ and R ₂ are integrated into 5 to 7
It may form a saturated or unsaturated ring of the member. However, R ₁ and R ₂ are not hydrogen atoms at the same time.

In the general formula (A), R ₁ and R ₂ are preferably a hydrogen atom, a substituted or unsubstituted alkyl group,
It is an aryl group or a heterocyclic group, and more preferably, R ₁ is a hydrogen atom, and R ₂ is a substituted or unsubstituted aryl group or a heterocyclic group.

When the aryl group has a substituent, the sum of Hammett's substituent constants (σ values) of the substituent is-
It is preferably from 1.2 to 1.0 and having at least one sulfo group, carboxy group, sulfino group, phosphono group or ammonia group in the substituent. The Hammett's σ value here refers to the journal of medicinal
Chemistry (J. Med. Chem.) 16, 120
7 (1973) and 20, 304 (1977).

Next, the general formula (B) will be described in detail. The substituted or unsubstituted alkyl group, alkenyl group, aralkyl group, cycloalkyl group, aryl group, heterocyclic group, carboxy group, ester group, acyl group, carbamoyl group represented by R ₃ , R ₄ , and R ₅ are Has the same meaning as each of R ₁ , and further includes a halogen atom (eg, a chlorine atom), a sulfo group or a salt thereof, a substituted or unsubstituted alkoxy group (eg, a methoxy group, a phenoxy group, etc.), a sulfinyl group (eg, And a sulfonyl group (eg, a methanesulfonyl group, a phenylsulfonyl group, a 4-methylbenzenesulfonyl group), and a sulfamoyl group (eg, an unsubstituted sulfamoyl group, a dimethylsulfamoyl group).
Further, R ₆ is an electron-withdrawing group (hamet σ value of 0 to 0 described above).
1.0 is preferable, and represents, for example, a nitro group, a cyano group, a sulfonyl group, an acyl group, an ester group, etc.).

In the general formula (B), preferably, R ₃ , R ₄ ,
R ₅ is that hydrogen atom, a carboxyl group, a cyano group, substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, an ester group or an acyl group, R ₆
Is a nitro group, a cyano group, a substituted or unsubstituted acyl group or an ester group, respectively.

Next, the general formula (C) will be described in detail. The substituted or unsubstituted alkyl group, alkenyl group, cycloalkyl group, aralkyl group, aryl group, heterocyclic group, carboxy group, ester group, acyl group, and alkoxy group represented by R ₇ , R ₈ , and R ₉ are Has the same meaning as each of R ₃ , and further has a substituted or unsubstituted amino group (eg, an unsubstituted amino group, a dimethylamino group, a carboxymethylamino group, etc.) and a substituted or unsubstituted thioether group (eg, a methylthio group, a methylthio group) Methylthio group etc.) and a hydroxyl group.

X represents an anion (for example, chloride ion, bromine ion, p-toluenesulfonic acid ion, perchlorate ion, etc.).

In the general formula (C), preferably, R ₇ ,
R ₈ and R ₉ are a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, and an amino group, respectively.

Next, the general formula (D) will be described in detail. Substituted or unsubstituted alkyl group ,, alkenyl group represented by R _10, aralkyl group, cycloalkyl group, aryl group, heterocyclic group has the same meaning as R _1.

R ₁₁ is a hydrogen atom, each substituent of R _10, a halogen atom (for example, chlorine atom, bromine atom, etc.), a substituted or unsubstituted alkoxy group (for example, methoxy group, isopropyloxy group, butoxy group, etc.) ), Carboxy group, substituted or unsubstituted acyl group (eg, acetyl group, benzoyl group, butanoyl group, etc.), cyano group, sulfo group, substituted or unsubstituted carbamoyl group (eg, ethylcarbamoyl group, dimethylcarbamoyl group, etc.) ), A nitro group, a substituted or unsubstituted dialkylamino group (eg, dimethylamino group, dihydroxyethylamino group, etc.), and a substituted or unsubstituted ester group (eg, methoxycarbonyl group, acetoxy group, etc.).

Z is a 5- to 6-membered heterocyclic ring composed of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom (for example, a pyridinium ring, an imidazolium ring, a quinolinium ring, an oxazolium ring, a thiazolium ring, Imidazolium ring). Z may have a substituent.

Y represents an anion (for example, chloride ion, bromine ion, p-toluenesulfonic acid ion, etc.).

In the general formula (D), R ₁₀ preferably represents a substituted or unsubstituted alkyl group, R ₁₁ represents a substituted or unsubstituted alkyl group or a hydrogen atom, Z represents an imidazolium ring, benzimidazolium. And a quinolinium ring.

Hereinafter, specific examples of the compounds represented by formulas (A) to (D) are shown, but the invention is not limited thereto.

[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

Embedded image Many of these compounds are commercially available and can be used as they are. Further, other compounds can be synthesized using a known organic synthesis reaction. For example, Organic Synthesis (Org. Syn.) C
collective Vol. I 1537 (194
1), Collective Vol. II 564
(1955), Organic Reaction (Org.
Reaction) 16, 1 (1958); R. Sandler, W.S. Kalaw, Organic Functional Group Preparation (Organic)
Functional group Preparat
ion) Volume 2, p. 291 (1966);
It can be synthesized according to the method described on page 05 (1972) and the like.

The amount of the compounds represented by the above general formulas (A), (B), (C) and (D) to be added to the solid processing agent is 0.01 to 1 per liter of the liquid in which the solid agent is dissolved. 0 mol is preferable, and 0.03 to 0.5 mol is more preferable.

Among the above exemplified compounds, preferred is A-
1, A-9, B-3, B-6, B-9, C-10, D-
4, and particularly preferred are A-1, B-9 and D-4.

Next, the sulfinic acid which can be used in the present invention is a compound in which at least one --SO ₂ H group is bonded to an aliphatic group, an aromatic group or a heterocyclic group.

Here, the aliphatic group means a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group, and further has a substituent (for example, ethyl, t-butyl, sec-amyl, cyclohexyl). Benzyl). Further, the aromatic group includes a carbocyclic aromatic group (for example, phenyl and naphthyl) and a heterocyclic aromatic group (for example, furyl, thienyl, pyrazolyl, pyridyl,
Indolyl), and may be a single ring system or a condensed ring system (for example, benzofuryl, phenanthridinyl). Further, these aromatic rings may have a substituent.

The above-mentioned heterocyclic group means a carbon atom, an oxygen atom,
Consisting of nitrogen, sulfur or hydrogen atoms 3
A group having a 10- to 10-membered ring structure is preferred, and the hetero ring itself may be a saturated ring or an unsaturated ring, and further substituted with a substituent (eg, cumanyl, pyrrolidyl, pyrrolinyl, morpholinyl). You may.

Examples of the salt of sulfinic acid used in the present invention include salts of the above-mentioned sulfinic acid with alkali metals, alkaline earth metals, nitrogen-containing organic bases, or ammonia. Here, examples of the alkali metal include Na, K, and Li, and examples of the alkaline earth metal include Ca and Ba. Examples of the nitrogen-containing organic base include ordinary amines capable of forming a salt with sulfinic acid. Incidentally, when there are a plurality -SO 2 _H group in the molecule, also include those that are in the form of their whole or partial salts.

The sulfinic acid is preferably a compound in which an —SO ₂ H group is bonded to an aromatic group or a heterocyclic group from the viewpoint of preventing stain, and is preferably an alkali metal, an alkaline earth metal, a nitrogen-containing organic base, or an ammonium salt. Salts are preferred. More preferably, the compound is a compound in which a —SO ₂ H group is bonded to an aromatic group, and an alkali metal or alkaline earth metal salt thereof is preferable.

When a —SO ₂ H group is bonded to the phenyl group, the group to be substituted for the phenyl group is Ha.
A combination of substituents whose sum of σ values of mmet is 0.0 or more is preferable.

On the other hand, from the viewpoint of solubility in water, the total number of carbon atoms is preferably 20 or less, particularly preferably 1 to 15 carbon atoms, depending on the number of hydrophilic substituents.
Their salts and their precursors.

Specific examples of the sulfinic acid and its salts are shown below, but are not limited thereto.

[0151]

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[0152]

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[0153]

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[0154]

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Of the above compounds, particularly preferred sulfinic acids and sulfinates include S-1, S-2, S
-36, S-42 and S-43.

The above sulfinic acid can be synthesized by a known method.

The bleach-fixing agent according to the present invention can be used in any desired form. In particular, when performing continuous processing using an automatic processing machine, the automatic processing apparatus can be made compact, the dissolving operation can be simplified, and the like. In view of the above, a method described in Japanese Patent Application No. 4-111502, that is, a method in which a replenishing bleach-fixing agent is directly added to a processing tank of an automatic developing machine and water for dissolution is preferably used.

[0158]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the present invention.

Example 1 A bleach-fixed tablet for color paper was prepared according to the following procedure. 1) Preparation of tablet sample-1 Operation (1) 550 g of ferric ammonium ethylenediaminetetraacetate,
25 g of diammonium ethylenediaminetetraacetate and 200 g of maleic acid are pulverized in a commercially available hammer mill pulverizer until the average particle size becomes 10 μm. After granulating the fine powder by spraying 10.0 ml of water at room temperature for about 5 minutes in a commercially available fluidized bed spray granulator,
Dry for minutes. The obtained granules are sieved using a commercially available shaker to filter fine particles of less than 100 μm and excessive particles of more than 800 μm.

Operation (2) 725 g of ammonium thiosulfate, 276 g of ammonium sulfite and 140 g of ammonium bromide are pulverized and granulated in the same manner as in the operation (1). The spray amount of water is 20.0 ml,
After granulation, it is dried at 60 ° C. for 15 minutes to remove water almost completely. The obtained granules are sieved as in the operation (1).

Operation (3) The granulated product prepared in the above operations (1) and (2) was heated at 25 ° C. for 4 hours.
Mix evenly for 10 minutes using a mixer in a room humidified below 0% RH. Next, the mixture was filled with 7.66 g per tablet using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho, and the compression pressure was 800 kg.
Tableting was performed at 500 g / cm ² to prepare 500 bleach-fixing replenishing tablet samples-1 for color paper. 2) Preparation of tablet sample-2 Operation (4) 550 g of ferric ammonium ethylenediaminetetraacetate,
25 g of disodium ethylenediaminetetraacetate, 200 g of maleic acid, 725 g of ammonium thiosulfate, 276 g of sodium sulfite, and 140 g of potassium bromide are ground and granulated in the same manner as in the operation (1). Water spray amount is 40.0
After granulation, the mixture is dried at 55 ° C. for 30 minutes to remove water almost completely. The obtained granules are sieved as in the operation (1).

Operation (5) The granulated product prepared in the above operation (4) was tableted in the same manner as in the operation (3) to prepare 500 bleach-fixing replenishing tablet samples-2 for color paper. 3) Experiment Five tablet samples each obtained by the above operation were put in a glass bottle, sealed, and stored at 60 ° C. for 3 months. Then, the content of thiosulfate in one tablet after storage was measured, and the value before storage was 1
The average residual ratio was determined as 00%. Further, while stirring each of the six tablet samples before storage in 1 liter (25 ° C.) of water with a magnetic stirrer (150 rpm),
The dissolution was observed. Table 1 shows the results.

[0163]

[Table 1] (Evaluation criteria for solution state in the table) ○: transparent ×: insoluble matter is seen from Table 1 above, it can be seen that the solid processing agent of the present invention is excellent in long-term storage stability and solubility.

Example 2 The same experiment as in Example 1 was carried out except that the ratio (mol%) of potassium ion or sodium ion to the cation of the bleaching agent and the fixing agent in the tablet sample-1 of Example 1 was adjusted as shown in Table 2 below. Was done. Table 2 shows the results.

[0165]

[Table 2] Example 3 In place of ferric ammonium ethylenediaminetetraacetate used in Example 1, exemplified compounds AI-2 and A-II-
1, A-II-3, A-III-6, A-IV-8, A
The same operation and experiment as in Example 1 were performed, except that the ferric ammonium salts of -V-20, A-VI-4, and A-VII-4 were used. As a result, the same result as in Example 1 was obtained.

Example 4 Sample No. 2 of Example 2 The same operation and experiment as in Example 2 were performed, except that the bisulfite adduct of Exemplified Compound A-VII-1 and S-2 were used in equimolar amounts instead of the sodium sulfite used in 2-13. As a result, the storability was improved in Example 2.
Sample No. Same as 2-13, but 20% strength
Improved.

Example 5 A processed tablet for color paper was prepared according to the following procedure.

1) Tablet for replenishing color development for color paper Operation (A) CD-3 [4-amino-3methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] aniline sulfate as a developing agent 120.0 g in an air jet mill to an average particle size of 10 μm. This fine powder was placed in a commercially available fluidized bed spray granulator at room temperature for about 5 minutes, 4.5 m
After granulation by spraying 1 l of water, the granulate is dried at 60 ° C. for 8 minutes. Next, the granulated product is dried at 40 ° C. for 2 hours in a vacuum to remove water almost completely.

Operation (B) Disulfoethylhydroxylamine disodium salt 12
0 g is pulverized and granulated in the same manner as in the operation (A). The spray amount of water is 3.0 ml, and after granulation, it is dried at 50 ° C. for 10 minutes. Next, the granulated product is dried at 40 ° C. for 2 hours in a vacuum to remove water almost completely.

Operation (C) 30.0 g of Tinopearl SFP (manufactured by Ciba Geigy), 3.7 g of sodium sulfite, 350 g of potassium carbonate, 0.3 g of potassium bromide, 25 g of diethylenetriaminepentaacetic acid
g, 300 g of sodium p-toluenesulfonate and 20 g of potassium hydroxide are ground in the same manner as in the operation (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in the operation (A), the spray amount of water is set to 200 ml, and granulation is performed. After granulation, the granules are dried at 70 ° C. for 15 minutes. Next, the granulated product is dried at 40 ° C. for 2 hours in a vacuum to remove water almost completely.

Operation (D) The granulated product prepared in the above operations (A) to (C) was treated at 25 ° C. for 4 hours.
Mix evenly for 10 minutes using a mixer in a room humidified below 0% RH. Next, the mixture was subjected to compression tableting using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho, with the filling amount per tablet being 7.85 g, and 15 tablets.
No color development replenishment tablets for color paper were prepared.

2) Tablet for replenishing bleach-fix for color paper The same tablet sample as tablet sample 2-13 prepared in Example 2 was prepared.

3) Tablet for stable replenishment for color paper Operation (H) 10 g of sodium carbonate monohydrate and 200 g of disodium 1-hydroxyethane-1,1-diphosphonate were pulverized and granulated in the same manner as in operation (A). I do. 1.0m water spray amount
After the granulation, the granulated product is dried at 70 ° C. for 3 minutes. Next, the granulated product is dried at 40 ° C. for 2 hours in a vacuum to remove water almost completely.

Operation (I) Tinopearl SFP 150 g, sodium sulfite 300
g, zinc sulfate heptahydrate 20 g, ethylenediaminetetraacetic acid 2
Sodium 150 g, ammonium sulfate 200 g, o-
Grind 10 g of phenylphenol as in operation (A)
Granulate. The amount of water spray was adjusted to 10.0 ml, and after granulation, the granulated product was dried at 65 ° C. for 5 minutes. Next, the granules are dried at 40 ° C. for 8 hours in a vacuum to remove water almost completely.

Operation (J) The granules prepared in the above operations (H) and (I) were mixed at 25 ° C. for 4 hours.
Mix evenly for 10 minutes using a mixer in a room humidified below 0% RH. Next, the mixture was subjected to compression tableting using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho, with the filling amount per tablet being 2.6 g, and 100 tablets.
Zero stable refill tablets for color paper were prepared.

Next, a method of processing a photographic material using a self-developing machine will be described.

The self-developing machine used was as shown in FIGS. Hereinafter, the automatic machine shown in FIGS. 1 and 2 will be described.

FIG. 1 is a schematic explanatory view showing an example of an automatic processing machine according to the present invention, and simply shows a control mechanism of a color paper processing apparatus.

When the color paper is carried in from the photosensitive material insertion section 13 and passes through the photosensitive material area detecting sensor 7 and a certain area is detected, the tablet type processing agent replenishing device 8, the replenishing water replenishing device 10, and the solenoid valve 12 Operates in response to a signal from the control unit 11, and replenishing tablets and replenishing water for liquid preparation are replenished to the respective processing tanks 1, 2, and 3 in required amounts.

When the temperature of the automatic processing machine is controlled for several hours, the processing liquid in each of the processing tanks 1 to 3 evaporates. When the processing liquid becomes lower than a certain level, the liquid level detecting sensor 9 is activated. Upon receiving the signal, the replenishing water replenishing device 10 and the solenoid valve 12 are operated, and the replenishing water for evaporation correction is replenished until the upper limit detecting mechanism of the liquid level detecting sensor 9 operates. It is preferable that the temperature of the washing hot water 14, which is the replenishing water supplied by the replenishing water replenishing pipe 15, be adjusted for both the replenishing water for adjusting the liquid and the replenishing water for evaporating correction. In addition, each of the processing tanks 1 to 3 is 1
Denotes a color developing tank, 2 denotes a bleach-fixing tank, and 3 denotes a stabilizing tank. 4 is a drying section.

FIG. 2 is a schematic explanatory view showing an example of a tablet-type processing agent replenishing device 8 when a solid photographic processing agent molded into a tablet is used.

Upon receiving a signal from the photosensitive material area detection sensor 7, the control unit 11 operates and the solid photographic processing agent replenishment cam 22 operates, and the solid photographic processing agent pushing claw 23 is inserted into the solid photographic processing agent stored in the cartridge 25. 24 for each treatment tank 1.2
・ A sub-tank 20 which is a section for dissolving the solid photographic processing agent in 3.4.
One or several replenishers are supplied to the inside of the filtration device 21 inside.

The replenished solid photographic processing agent 24 gradually dissolves and is supplied into the main processing tank 16 by the circulation pump 18.

It should be noted that all or most of the circulating flow of the processing liquid 17 circulating between the main processing tank 16 and the sub tank 20 by the circulating pump 18 is passed through the filtering device 21 in the sub tank 20.
, The solid photographic processing agent 24
Will be more soluble.

In the figure, 19 is a temperature control heater, 26
Is a pressing spring for pressing and holding the solid photographic processing agent 24 in the cartridge 25, 27 is a communication pipe for connecting the main processing tank 16 of each processing tank 1, 2, 3, 4 with the sub tank 20, and 28 is an overflow port. It is.

In addition, during the temperature control of the automatic processing machine or during the stop, the processing tank 1
In the case where the liquid level of the treatment liquid 4 is lowered due to evaporation, the liquid level detection sensor 9 detects the lowered liquid level, transmits a signal to the control unit 11, activates the water replenishment supply means 10, and activates the normal liquid. Replenish the water for evaporation correction to the surface level. When the liquid level reaches the normal liquid level, the liquid level detection sensor 9 detects the normal liquid level, transmits a signal to the control unit 11, and stops the operation of the rehydration supply unit 10.

The standard processing conditions of the automatic processing machine were as follows.

[0188]

[Outside 1] The stabilizer is replenished to the third tank, and the cascade system is such that the overflow liquid flows into the second tank and the first tank sequentially.

The preparation of the processing tank liquid for the automatic processing machine was performed by the following method.

Color developing tank solution (23.0 liters) 15 liters of warm water at 35 ° C. was placed in a color developing tank of an automatic developing machine, and a color developing and replenishing tablet for color paper prepared in the same manner as in the Example was prepared. 142 were charged and dissolved. Next, start
Star of the following formulation, separately tableted as a tar component
Twenty-three tars were charged, and after dissolution, hot water was added up to the tank mark to complete a tank liquid.

Color developing starter for color paper (per liter) Potassium chloride 4.0 g Potassium hydrogen carbonate 4.8 g Potassium carbonate 2.1 g

Bleach-fix solution (23.0 liters) 15 liters of warm water at 35 ° C. were put into a bleach-fix tank of an automatic developing machine, and 115 tablets for replenishing bleach-fix for color paper prepared in the same manner as in the examples were added. Dissolved. After dissolution, warm water was added up to the tank mark to complete the tank liquid.

Stabilizing liquid (15 liters for each of the first to third tanks) 12 liters of warm water at 35 ° C. were added to the first, second, and third tanks of the automatic developing machine in the same manner as in Examples. Inject 40 tablets for color paper for stable replenishment,
Dissolved. Next, hot water was added up to the tank mark to complete the tank liquid.

Next, during the temperature control of the automatic developing machine, 20 refilling tablets prepared in the examples were set in each of the refilling tablet supply devices provided to the automatic developing machine. . When 1 m ^{2 of} color paper is processed, 1 tablet (5 bleach-fixing tablets) is added to each replenishing tablet, and at the same time, 80 ml of replenishing hot water is supplied from a hot water supply device to the color developing tank and to the bleach-fixing tank. It was set to supply 200 ml and 250 ml to the stabilization tank.

Next, Konica Color Paper QA-A5, which was exposed to wedges according to a conventional method, was continuously processed at 20 m ² per day for 90 days, and the optical density and silver amount at the start and end of the processing were measured. Table 3 shows the results.

[0196]

[Table 3] From Table 3 above, it can be seen that the treatment using the tablet according to the present invention has little stain during continuous processing, has good desilvering properties, and has excellent processing stability.

Example 6 In the bleach-fixing solution and the tablet for replenishing bleach-fix used in Example 5, the compound used in Example 2 was used in place of ferric ethylenediaminetetraacetic acid in an equimolar amount.
The same continuous processing experiment was performed. As a result, the same result as in Example 5 was obtained.

Example 7 A continuous processing experiment was performed in the same manner as in Example 5, except that the amount of hot water replenished to the bleach-fixing tank of the automatic developing machine used in Example 5 was changed from 200 ml / m ² to 100 ml / m ² . . As a result, in the process using the comparative tablet, at the end of the continuous process, stain,
Although the desilvering property was deteriorated by 30%, the same results as in Example 5 were obtained by the treatment using the tablet of the present invention. This indicates that the tablet of the present invention has excellent continuous processing stability when the hot water replenishment amount is reduced.

[0199]

Industrial Applicability According to the present invention, a halogen which is excellent in storage stability, solubility and processing stability of a solid photographic processing agent, has a work environment suitability without using polyvin, and further has a work environment suitability. A solid processing agent for a silver halide photographic material can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic plan view showing an example of an automatic machine to which the present invention can be applied.

FIG. 2 is a schematic explanatory view showing an example of a replenishing section for a solidified replenishing agent.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Color developing tank 2 Bleaching and fixing tank 3 Stabilizing tank 4 Drying part 7 Photosensitive material area detection sensor 8 Solid photographic processing agent replenishing device 9 Liquid level detecting sensor 10 Replenishing water supply device 11 Control part 12 Electromagnetic valve 13 Photosensitive material insertion part 14 Rinse with water Hot water 15 Water supply pipe 16 Processing tank 17 Processing liquid 18 Circulation pump 19 Temperature control heater 20 Subtank 21 Filtration filter 22 Cam 23 Solid photographic processing agent pushing claw 24 Solid replenisher 25 Cartridge 26 Solid replenishing agent pushing spring 28 Overflow port

Claims (5)

(57) [Claims] 1. A solid processing agent for a silver halide photographic light-sensitive material obtained by compressing at least the following two types of granules under pressure. Granulated material containing at least one bleaching agent Granulated material containing at least one fixing agent 2. The solid processing agent for a silver halide photographic light-sensitive material according to claim 1, wherein said fixing agent is a thiosulfate. 3. The solid processing agent according to claim 1, wherein said bleaching agent is a ferric aminopolycarboxylic acid salt. 4. A solid processing agent for a silver halide photographic light-sensitive material according to claim 1, wherein at least 2 mol% of the cations in said fixing agent are sodium ions. 5. The method of claim 1, wherein at least 10 of the cations in the bleaching agent are present.
4. The solid processing agent for a silver halide photographic light-sensitive material according to claim 1, wherein mol% is sodium ion and / or potassium ion.