JPH06130571A - Bleaching-fixer for tableted silver halide photographic sensitive material and its treatment - Google Patents

Abstract

PURPOSE:To improve the processing stability and adaptability to social and working environments by compacting a bleaching agent part and a fixer part in multiple layers and covering the compact with a water-soluble polymer. CONSTITUTION:A silver halide color photographic sensitive material is color- developed and then bleach-fixed. In this case, a bleaching-fixer for the tableted silver halide photographic sensitive material obtained by laminating a part contg. a bleaching agent and a part contg. a fixer in layers, compacting the laminate and coating the compact with a water-soluble polymer with at least a compd. expressed by the formula as the constituent is used. In this case, R1 is hydrogen atom or 1-4C alkyls, and R2 is hydrogen atom or 1-3C alkyls. The ratio of the ammonium ion to the total cation in the constituent in the bleaching-fixer is preferably controlled to <=50mol%. Besides, an intermediate layer may be provided between the bleaching agent part and the fixer part to prevent the contact catalytic reaction between the bleaching agent and fixer when the parts are laminated.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing agent for silver halide photographic light-sensitive materials and a processing method using the same, and more specifically, silver halide photography having improved processing stability, social environment suitability, work environment suitability and the like. The present invention relates to a photosensitive material processing agent and a processing method.

[0002]

BACKGROUND OF THE INVENTION A silver halide photographic light-sensitive material (hereinafter sometimes referred to as a light-sensitive material or a photographic material) is subjected to processes such as development, desilvering, washing and stabilization after exposure. Black-and-white developer, color developer for development, bleaching solution, bleach-fixing solution, fixing solution for desilvering, tap water or ion-exchanged water for washing, and stabilizing solution for stabilization. To be done. The temperature of each processing solution is usually adjusted to 30 to 40 ° C., and the light-sensitive material is dipped in these processing solutions for processing.

Such processing is usually carried out by an automatic processor (hereinafter,
It may be referred to as an automatic processing machine) or the like, and is sequentially carried between the processing tanks containing the processing liquid. In such a case, conventionally, a method of replenishing the replenisher for each treatment liquid is used in order to keep the activity of the treatment liquid in the treatment tank constant. Specifically, the processing operation is performed while supplying the replenishing liquid from the replenishing tank into the processing tank at appropriate times. In this case, the replenishing liquid itself stored in the replenishing tank is usually prepared in another place and supplied into the replenishing tank as needed. The manual method is adopted.

That is, the processing agent for silver halide photographic light-sensitive material (hereinafter sometimes referred to as photographic processing agent) is supplied to the user in the form of a powder or a concentrated liquid. It is prepared by dissolving in a certain amount of water, and when it is in a liquid state, it is mixed with water in a certain amount,
Used after dissolving and diluting.

Replenishment processing agents are divided into several parts for good and stable performance during photographic processing. For example, the replenisher for the color developing solution is divided into various concentrated parts, which are mixed and added with a fixed amount of water before use.

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

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

That is, each parts agent is individually put in a container, and depending on the replenishment treating agent, several parts agents are included, and the number of containers is considerably large when it becomes one unit. Not only does it take a lot of space, but there was a problem with the disposal of empty containers. Also, when the parts agents that make up the replenishment treatment agent consist of several types, it is necessary to find each parts agent separately because each parts agent is individually put and scattered. Was significantly reduced.

In recent years, there has been a strong demand for environmental protection and resource saving mainly in Europe and North America, and the plastic container for storing the above-mentioned concentrated processing liquid has become a particular problem in relation to photography. That is, although the plastic container for the photographic processing agent is low in cost, convenient for storage and transportation, and excellent in chemical resistance,
Will empty containers be landfilled as industrial waste,
Although discarded or incinerated, the plastic container has almost no biodegradability and accumulates, and when incinerated, a large amount of carbon dioxide gas is generated, which causes a problem such as global warming. Further, as a problem on the user side of the developing machine, it is pointed out that a large number of plastic containers are piled up in a narrow working space to further reduce the space.

Therefore, it is desired to develop a technology for reducing pollution, which does not substantially use plastic bottles.

Therefore, for example, Japanese Patent Laid-Open No. 51-61837 discloses a photographic tablet containing a disintegrant, and proposes a technique for improving the solubility. In addition,
2-109042, 2-109043, 3-39735 and 3-39739
The method of using a granulated photographic processing agent having an average particle size is disclosed in Japanese Patent Laid-Open Publication No. 2004-242242, and improvement of scattering prevention of powder is proposed.

However, in the above method, an insoluble substance is easily produced, which causes clogging of the filter portion in the processing tank of the automatic developing machine, and the insoluble substance adheres to the photographic light-sensitive material being processed to develop. There is a problem that it affects performance and processability.

Further, in the tablet type processing agent described in the above publication, the color developing agent is a part agent (also referred to as a part agent), and when these tablets are used, it is necessary to stir and dissolve them in a replenishing tank provided. In addition, there are problems that it takes a long time to dissolve and that it is erroneously dissolved during work. Therefore, in order to prevent erroneous dissolution, it was examined to use the parts agent component as a single component into a tablet-type treatment agent, and the tablets obtained were one treatment / one agent, which was effective in preventing erroneous dissolution. However, it was found to be unsuitable for actual use, such as being unsuitable for long-term storage due to its poor solubility and insufficient resistance to humidity.

As a method of eliminating the need for a melting operation, Japanese Patent Laid-Open No. 11344/1999 describes extruding an amount of paste-like parts agent from each unit container according to the mixing ratio of the parts agent, and extruding the extruded parts agent in a predetermined manner. Although a technology to accurately prepare and supply by diluting to the concentration of is disclosed, although the dissolution work will certainly decrease or disappear, equipment such as a device for extruding parts agent, a nozzle, a supply device is required. In addition, maintenance and management of the device are required, and the load on the operator is large. Further, there is a drawback that the stability of the treating agent is poor.

On the other hand, in order to protect the global environment and for economic reasons, there has been a tendency in recent years to adopt a concentrated and low replenishment treatment.
It has been found that there are some problems in carrying out these concentrated and low replenishment treatments. One of them is that the solubility of the replenisher determines the activity (treatment performance) of the treatment solution, and it is not possible to obtain a concentration exceeding the limit solubility of the replenisher. More recently, the need for rapid processing has increased, and in this case, a method for obtaining a concentration exceeding the limit solubility of the replenisher is desired. As another problem, due to the low replenishment rate, the retention time of the replenishment solution in the replenishment tank becomes long, and the deterioration of the performance of the replenishment solution in the replenishment solution tank has become a problem that cannot be ignored. This is a big problem especially in minilabs with a small amount of processing and even smaller minilabs (microlabs).

[0016]

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is to provide a processing agent for silver halide photographic light-sensitive material which is excellent in long-term storage stability of solid photographic processing agent, solubility in continuous processing and processing stability. To provide. Secondly, to provide a processing agent for a silver halide photographic light-sensitive material, which has a working environment without using a plastic bottle and has less waste.

[0017]

The present inventor has conducted extensive studies and as a result, in a method of bleach-fixing a silver halide color photographic light-sensitive material after color development, a part containing a bleaching agent and a part containing a fixing agent are stacked in layers. After compression molding, a tablet-shaped bleach-fixing agent for silver halide photographic light-sensitive materials is used, which is coated with a water-soluble polymer containing at least a compound represented by the general formula (I) as a constituent. It has been found that the object of the invention is achieved.

[0018]

[Chemical 2]

In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₂ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

That is, according to the present invention, in the bleach-fixing agent for color photographic light-sensitive material, the bleaching agent part and the fixing agent part are solidified in a multilayer form and coated with a specific water-soluble polymer. Not only does it maintain its shape even after long-term storage, it also does not deteriorate the active ingredient, does not affect the processability even if it is added to the processing tank during continuous processing, and is also problematic in terms of solubility. It was surprising that no waste and very little waste could be achieved.

The present invention will be described in detail below.

First, the bleach-fixing agent in the present invention will be described in detail.

The multi-layered tablet of the present invention can be produced by stacking two or more kinds of powder or granules having different components in layers and compression-molding them.

For compression under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a briquetting machine can be used. The solid processing agent obtained by compression under pressure can have any shape, but a cylindrical type, so-called tablet is preferable from the viewpoint of productivity and handleability. The apparent density (bulk density) of the solid processing agent obtained by compression under pressure is 1.0 g / cm ^{3 to} 2.0 g / cm ³
By weight, more preferably ^{1.1g / cm 3 ~1.5g / cm 3} . If it is less than 1.0 g / cm ³ , the strength of the obtained solid is insufficient, and if it exceeds 2.0 g / cm ³ , the solubility of the obtained solid is deteriorated.

In addition, an intermediate layer may be provided between the bleaching agent part and the fixing agent part in order to prevent a reaction due to contact between the bleaching agent and the fixing agent when forming a multi-layered structure. The intermediate layer may be a multi-component single layer or a multi-component multi-layer. Specific examples of the compound forming the intermediate layer include neutral salts, organic acids, polymer compounds, glycol compounds, aromatic sulfonic acid compounds, and the like.

The bleaching agent according to the present invention has the following general formula [A-
I], [A-II], [A-III], [A-IV],
It is preferable to use at least one ferric complex salt of the compound represented by [A-V], [A-VI] or [A-VII].

[0027]

[Chemical 3]

[In the formula, A _{1 to} A ₄ may be the same or different and each is a hydrogen atom, a hydroxy group, -COOM or -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 and —CH ₂ COOM ₂ . M, M ₁ and M ₂ each represent a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. ]

[0029]

[Chemical 4]

[In the formula, 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 . M
₃ , M ₄ each represents a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. X has 2 to 6 carbon atoms
Represents an alkylene group or — (B ₁ O) n—B ₂ —. n is 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. ]

[0031]

[Chemical 5]

[In the formula, 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 . M
₅ and M ₆ each represent a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. X ₁ has 2 to 6 carbon atoms
Linear or branched alkylene group, an organic group of a saturated or unsaturated to form a ring _{or, - (B 11 O) n} 5 -B 12 - represents a. n ₅ represents an integer of 1 to 8, and B ₁₁ and B ₁₂ may be the same or different and each represents an alkylene group having 1 to 5 carbon atoms. n _{1 to} n ₄ represent an integer of 1 or more, and may be the same or different. ]

[0033]

[Chemical 6]

[Wherein R ₁ and R ₂ are each a hydrogen atom,
It represents an alkyl group or an aryl group which may be substituted.
L is

[0035]

[Chemical 7]

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, R _{3 to} R ₇ each represent a hydrogen atom, It represents an alkyl group or an aryl group. ]

[0037]

[Chemical 8]

[In the formula, R _{1 to} R ₃ each represent a hydrogen atom, an optionally substituted alkyl group or an aryl group. L
Is synonymous with L of general formula [A-IV]. W represents a divalent linking group. ]

[0039]

[Chemical 9]

[In the formula, R _{1 to} R ₃ and R _{6 to} R ₉ each represent a hydrogen atom, an optionally substituted alkyl group or an aryl group, and R ₄ and R ₅ represent a hydrogen atom, a halogen atom, and
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, an optionally substituted alkyl group or an aryl group, and R ₄ and R ₅
May together form a 5-membered ring or a 6-membered ring.
A represents a carboxy group, a phosphono group, a sulfo group, a hydroxy group, or an alkyl metal salt or ammonium salt thereof. Y represents an alkylene group or an arylene group and may have a substituent. t and u represent 0 or 1, respectively. General formula _{(II) X 2 -A 2 -COOM} 2 [ wherein, X ₂ represents a halogen atom, an amino group, hydroxy group, methoxy group, a -COOM ₂ or -SO ₃ M _2. A ₂ represents an alkylene group or an arylene group which may form a saturated or unsaturated ring, and may have a substituent.
M ₂ represents a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. General formula _{(III) NH 2 -A 3 -SO} 3 M 3 [ wherein, A ₃ represents a saturated or rings formed alkylene group or arylene group of unsaturated, substituted Good. M ₃ represents a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. In the present invention, the solid bleaching agent is preferably a tablet consisting of one part. Furthermore, it is preferable that the solid bleaching agent contains a carbonate.

Further, the method of processing a silver halide color photographic light-sensitive material according to the present invention which achieves the above-mentioned object is the solid bleaching agent described above when the bleaching or bleach-fixing processing is carried out after color development of the silver halide color photographic light-sensitive material. Is used.

The present invention will be described in detail below.

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

[0044]

[Chemical 10]

[0045]

[Chemical 11]

The compounds represented by the above general formula [AI] are disclosed in JP-A Nos. 63-267750 and 63-267751, and JP-A-2-115172.
No. 2-295954, etc.

Of these, preferred compounds for use in the present invention are exemplified compounds [A-I-1], [A-I-2],
These are [AI-13] and [AI-15].

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

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

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

[0051]

[Chemical 12]

[0052]

[Chemical 13]

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

Of these, particularly preferred compounds are [A
-II-1], [A-II-3], and [A-II-14].

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

In the general formula [A-III], X ₁
In-(B ₁₁ O) n ₅ -B ₁₂ representing, the alkylene group represented by B ₁₁ and B ₁₂ includes methylene, ethylene, trimethylene and the like. These alkylene groups may have a lower alkyl group such as a methyl group or an ethyl group, or a hydroxy group as a substituent.

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

[0058]

[Chemical 14]

[0059]

[Chemical 15]

[0060]

[Chemical 16]

[0061]

[Chemical 17]

[0062]

[Chemical 18]

[0063]

[Chemical 19]

[0064]

[Chemical 20]

[A-III-16], [A-III]
-17], [A-III-18], [A-III-19],
[A-III-20] includes both trans isomers and cis isomers.

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 general formula [A-IV] will be described below.

In the above 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 alkyl groups or aryl groups, 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. , Sulfamoyl group, 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, carbonamido group, sulfonamide group,
A nitro group and the like can be mentioned, but preferably,

[0069]

[Chemical 21]

It is a substituent represented by: Where Ra and R
b, Rc, Rd 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, ethylene group, propylene group, and the like, and examples of the arylene group include a phenylene group. These Y ₁ ~
The alkylene group and arylene group represented by Y ₃ may have a substituent. As the substituent, for example, those enumerated as the substituents of R ₁ and R ₂ can be applied, and 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].
The compound represented by the formula [I].

[0073]

[Chemical formula 22]

[In the formula, R ₁ and R ₂ are each a hydrogen atom,
It represents 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. ]

[0075]

[Chemical formula 23]

[Wherein R _{1 to} R ₄ are each represented by the general formula [B-
I] has the same meanings as R ₁ and R ₂ , and L _{1 to} L ₃ and M also have the same meanings as those of the general formula [BI]. ] Specific examples of the compound represented by the general formula [A-IV] are shown below, but the invention is not limited thereto.

[0077]

[Chemical formula 24]

[0078]

[Chemical 25]

[0079]

[Chemical formula 26]

[0080]

[Chemical 27]

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].

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

In the general formula [A-V], the alkyl group and the aryl group represented by R _{1 to} R ₃ are represented by the general formula [A
The groups similar to R ₁ and R ₂ of —IV] 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 substituents.

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

[0085]

[Chemical 28]

(B ₁ and B ₂ represent an alkylene group or an arylene group, and n represents 1 to 3),

[0087]

[Chemical 29]

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

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

[0090]

[Chemical 30]

[In the formula, R ₁ and R ₂ are each a hydrogen atom,
It represents 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, an ammonium group or an organic ammonium group. ]

[0092]

[Chemical 31]

[Wherein R _{1 to} R ₄ are each represented by the general formula [B-
III] of R ₁ and R ₂ and L _{1 to} L ₄ and M ₁ ,
M ₂ also has the same meaning as those in formula [B-IIII]. ] Specific examples of the compound represented by the above general formula [A-V] are shown below, but the invention is not limited thereto.

[0094]

[Chemical 32]

[0095]

[Chemical 33]

[0096]

[Chemical 34]

[0097]

[Chemical 35]

[0098]

[Chemical 36]

The effect is particularly remarkable when the iron salts of the compounds represented by the general formulas [AI], [A-II] and [A-III] are contained.

Particularly preferred compounds among these are [A
-V-1], [A-V-4], [A-V-6], [A-
V-13], [A-V-16], [A-V-20], [A-V
-23], [A-V-26], [A-V-27], [A-V-
29], [A-V-30], and [A-V-33].

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

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

[0103]

[Chemical 37]

[0104]

[Chemical 38]

[0105]

[Chemical Formula 39]

Among these compounds, [A-VI-1], [A-VI-3] and [A-VI-] are particularly preferable.
4] and [A-VI-16].

The addition amount of the compounds of the above general formulas [A-I] to [A-VI] is preferably 0.01 to 1 mol / liter of the treatment liquid, and more preferably 0.05 to 0.6 mol / liter of the treatment liquid. is there.

[0108]

[Chemical 40]

[In the formula, A _{1 to} A ₄ are —COOM ₁ , —OH, and —PO ₃
M ₁ M ₂ and -CONH _{2 are} represented and may be the same or different. M ₁ and M ₂ represent hydrogen ion, alkali metal ion or other cation. n _{1 to} n ₄ represent an integer of 0, 1 or 2. R _{1 to} R ₄ represent a hydrogen atom, a lower alkyl group or a hydroxy group (provided that n ₁ + n ₂ = 1 and n
_{When 3} + n ₄ = 1, R _{1 to} R ₄ do not become hydrogen atoms).

[0110] X is an alkylene group of a substituted or unsubstituted 2-6 carbon atoms - represents a _{- (B 1 O) m -B} 2. m represents an integer of 1 to 4, 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-VII]
The compound represented by will be described.

In the formula, A _{1 to} A ₄ may be the same or different and represent --COOM ₁ , --OH, --PO ₃ M ₁ M ₂ , --CONH ₂ . M ₁ and M ₂ represent hydrogen ion, alkali metal ion (eg sodium ion, potassium ion, lithium ion) or other cation (eg ammonium ion, methylammonium ion, tetramethylammonium ion etc.).

N _{1 to} n ₄ represent an integer of 0 to 2, and may be the same or different, preferably n ₁ = 0 and n ₃ = 0. R _{1 to} R ₄ represent a hydrogen atom, a lower alkyl group or a hydroxy group and may be the same or different, but are preferably a hydrogen atom. However,
n ₁ + n ₂ = ₁ and R ₁ to R ₄ when the n ₃ + n ₄ = 1 is not a hydrogen atom.

X represents a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms or-(B ₁ O) _m --B _2- . 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. X
Examples of the alkylene group represented by include ethylene, trimethylene, tetramethylene and the like. Also, B ₁
And the alkylene group represented by B ₂ is methylene,
Examples include groups such as ethylene and trimethylene.

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, methyl group, ethyl group). m is 1
It represents an integer of 4, and is preferably 1 or 2.

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

[0116]

[Chemical 41]

[0117]

[Chemical 42]

[0118]

[Chemical 43]

In the present invention, as the bleaching agent, in addition to the iron complex salts of the compounds represented by the above formulas [AI] to [A-VII], ferric iron complex salts of the following compounds can be used.

[A′-1] Ethylenediaminetetraacetic acid [A′-2] trans-1,2-cyclohexanediaminetetraacetic acid [A′-3] Dihydroxyethylglycine [A′-4] Ethylenediaminetetrakismethylenephosphonic acid [A '-5] Nitrilotrismethylenephosphonic acid [A'-6] diethylenetriaminepentakismethylenephosphonic acid [A'-7] diethylenetriaminepentaacetic acid [A'-8] ethylenediaminedioltohydroxyphenylacetic acid [A'-9] hydroxyethyl Ethylenediaminetriacetic acid [A'-10] Ethylenediaminepropionic acid [A'-11] Ethylenediaminediacetic acid [A'-12] Hydroxyethyliminodiacetic acid [A'-13] Nitrilotriacetic acid [A'-14] Nitrilotripropionic acid [A'-15] triethylenetetramine hexaacetic acid [ '-16] Ethylenediaminetetrapropionic acid [A'-17] 1,3-Propylenediaminetetraacetic acid [A'-18] Glycol etherdiaminetetraacetic acid Examples further described in JP-A-4-174432, pages 7 to 11 Compounds 1 to 71, ferric complex salts of Exemplified Compounds 1 to 36 described in Nos. 4-204533, pages 25 to 30, and the like can also be used.

In addition to the above, the bleach-fixing agent according to the present invention may contain a halide such as ammonium bromide, potassium bromide, sodium bromide, various fluorescent whitening agents, defoaming agents or surfactants. You can also

As the fixing agent used in the bleach-fixing agent according to the present invention, thiocyanate and thiosulfate are preferably used.

Further, in the present invention, the object of the present invention can be achieved more effectively by using a thiocyanate and a thiosulfate together.

In the bleach-fixing agent according to the present invention, in addition to these fixing agents, a pH buffering agent comprising various salts is used alone or 2
More than one species can be included. Further, it is desirable to add a large amount of alkali halide or ammonium halide, for example, a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide and the like.

Further, compounds known to be added to bleach-fixing agents such as alkylamines and polyethylene oxides can be appropriately added.

The bleach-fixing agent according to the present invention preferably contains a compound represented by the following general formula [II].

General formula [II] A (-COOM) n In the formula, A represents a valent organic group, n represents an integer of 1 to 6, M represents ammonium, an alkali metal (sodium, potassium, lithium, etc.). Or represents a hydrogen atom.

In the general formula [II], the n-valent organic group represented by A is an alkylene group (for example, a methylene group,
Ethylene group, trimethylene group, tetramethylene group, etc.),
Alkenylene group (eg ethenylene group), alkynylene group (eg ethynylene group etc.), cycloalkylene group (eg 1,4-cyclohexanediyl group etc.), arylene group (eg o-phenylene group, p-phenylene group etc.), alkane Examples thereof include a triyl group (eg, 1,2,3-propanetriyl group etc.) and an arenetriyl group (eg, 1,2,4-benzenetriyl group etc.).

The n-valent group represented by A described above is a substituent (for example, hydroxy group, alkyl group, halogen atom, etc.).
(For example, 1,2-dihydroxyethylene, hydroxyethylene, 2-hydroxy-1,2,3-propanetriyl, methyl-p-phenylene, 1-hydroxy-2-chloroethylene, chloromethylene, chloro) Ethenylene etc.). Preferred specific examples of the compound represented by the general formula [II] are shown below.

[0130]

[Chemical 44]

[0131]

[Chemical formula 45]

Of the above-exemplified compounds, particularly preferable are the exemplified compounds (II-1), (II-3), (II-4) and (II-
5), (II-16) and (II-18), with (II-5) being particularly preferred.

In the bleach-fixing agent according to the present invention, a sulfite adduct is preferably used from the viewpoint of the effect of the object of the present invention.

Examples of the compound capable of forming a stable and stable adduct with sulfite ion include a compound having an aldehyde group, a compound containing a cyclic hemiacetal,
Examples thereof include compounds having an α-dicarbonyl group, compounds having a nitrile group, and the like. The compounds of the general formulas [BI] to [B
-II] is particularly preferably used.

[0135]

[Chemical formula 46]

A ₂ , A ₃ , A ₄ , and A ₅ are hydrogen atoms and have 1 carbon atom.
Represents an alkyl group, a formyl group, an acyl group or an alkenyl group of -6. The alkyl group having 1 to 6 carbon atoms includes linear or branched ones, for example, methyl group, ethyl group, propyl group, iso-propyl group, butyl group, barrel group, iso-barrel group, hexyl group, isohexyl group. Groups and the like, which may be substituted, specifically, formyl groups (eg, formylmethyl, 2-formylethyl, etc. groups), amino groups (eg, aminomethyl, aminoethyl groups, etc.), Hydroxyl groups (eg hydroxymethyl,
Substituents such as 2-hydroxyethyl, 2-hydroxypropyl, etc.), alkoxy groups (eg, methoxy, ethoxy, etc.), halogen atoms (eg, chloromethyl, trichloromethyl, dibromomethyl, etc.) Can be mentioned.

The alkenyl group includes substituted and unsubstituted groups, the unsubstituted group includes groups such as vinyl and 2-propenyl, and the substituted group includes, for example, 1,2-dichloro-2- Examples include groups such as carboxyvinyl and 2-phenylvinyl.

Specific examples of the compound which forms a stable sulfite adduct with the sulfite ion are described above, but the compounds are not limited to these.

[0139]

[Chemical 47]

[0140]

[Chemical 48]

[0141]

[Chemical 49]

Further, in carrying out the present invention, when the ratio of ammonium ion to all cations in the bleach-fixing agent of the present invention is 50 mol% or less, the effect of the present invention is better exhibited. The ratio is more preferably 30 mol% or less, and most preferably 10 mol% or less.

Next, the general formula (I) will be described.

[0144]

[Chemical 50]

In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₂ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

Examples of the monomer represented by formula (I) of the present invention are given below.

[0147]

[Chemical 51]

[0148]

[Chemical 52]

The polymer of the present invention can be obtained by a known polymerization method. For example, a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, etc. can be mentioned.

The polymer of the present invention comprises the compound represented by the general formula (I) as a constituent. Copolymerization is preferably 5 to 100 mol%, more preferably 10 to 90 mol%.

The monomers copolymerizable with the compound represented by the general formula (I) of the present invention include acrylic acid, methacrylic acid, itaconic acid, maleic acid, acrylamide, acrylic acid ester, methacrylic acid ester, styrene and styrene. Examples thereof include derivatives, olefins, vinyl acetate, and trimethylammonium ethyl methacrylate.

The weight average molecular weight of the polymer of the present invention is 10
It is from 00 to 100,000, preferably from 3000 to 500000, particularly preferably from 1000 to 100000.

Examples of preferred polymers of the present invention are given.

[0154]

[Chemical 53]

These are Eudragit L30D-55, L100-55, L100, S100, RS100L, RSPO manufactured by Rohm Pharma.
It is also possible to purchase as L, RS30DL, RS100, RSPO, RS30D, NE30D.

The film thickness of the film formed on the surface of the tablet by the water-soluble polymer of the present invention is preferably 10 to 120 μ, particularly preferably 15 to 80 μ, particularly preferably 20 to 60 μ. It is preferably used. If it is less than 10μ, the storage stability of the solid processing agent becomes poor, and if it exceeds 120μ, it takes too much time to dissolve the water-soluble polymer, and depending on the type of treatment liquid, the water-soluble polymer does not completely dissolve. Is also generated.

Further, the tensile strength of the water-soluble polymer of the present invention is preferably 0.5 × 10 ⁶ to 50 × 10 ⁶ kg / m ² , and particularly 1 × 10 ⁶
〜25 × 10 ⁶ kg / m ² is preferred, especially 1.5 × 10 ⁶ 〜
10 × 10 ⁶ kg / m ² is preferred. These tensile strengths are JIS
It is measured by the method described in Z-1521.

In the present invention, for coating a tablet-type treating agent with a water-soluble polymer, for example, JP-A-51-61837 can be used.
No. 54-155038, No. 52-88025, British Patent 1,213,808
Any means such as spraying a water-soluble polymer on the surface of a tablet produced by a general method as described in No. etc. in a coating pan or the like can be adopted.

The coating amount of the water-soluble polymer used for coating is 0.01 g in view of storage stability, abrasion resistance and solubility.
/ Treatment agent solution is preferably 1000ml or more, more preferably 0.5-3.0g
/ About 1000 ml of treatment agent solution is more preferable. In the tablet-type photographic processing agent of the present invention, all the constituent components may be tableted into one tablet, or may be tabletted separately into a plurality of tablets. In addition, one or more tablets may be used as a part of the components and one or more liquids or powders may be used as the rest, and any composition may be selected according to the properties of the treating agent and the required performance. Can be taken.

When processing a silver halide photographic light-sensitive material using the bleach-fixing agent of the present invention, a color developing agent is used as a pre-process. As the color developing agent used in the color developing agent, a p-phenylenediamine compound having a water-soluble 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 water-soluble group has less contamination of the photosensitive material than the para-phenylenediamine-based compound having no water-soluble group such as N, N-diethyl-p-phenylenediamine, and As for the skin, not only has the advantage that the skin is less prone to rash, but the object of the present invention can be achieved more effectively by using the treated tablet of the present invention.

Examples of the water-soluble group include those having at least one on the amino group of the p-phenylenediamine compound or on the benzene nucleus. Specific water-soluble groups include-(C
_{H 2) nCH 2 OH, -} (CH 2) mNHSO 2 (CH 2) nCH 3, - (CH 2) mO (CH 2) n
_{CH 3, - (CH 2 CH} 2 O) nCmH 2 m +1 (m and n each represents an integer of 0 or more.), - COOH group, and as -SO ₃ H group and the like.

Specific examples of the color developing agent preferably used in the present invention include Japanese Patent Application No. 2-203169, 26 to 31.
(C-1) to (C-16) described on page, and the following compounds (C'-1), (C'-2), (C'-3) and the like.

[0164]

[Chemical 54]

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

The color developing agent may be used alone or in combination with 2.
One or more kinds in combination, and if desired, a black and white developing agent such as phenidone, 4-hydroxymethyl-4-methyl-1-phenyl
It may be used in combination with -3-pyrazolidone or metol.

Further, in the present invention, when the color developer according to the present invention contains the compounds represented by the following general formulas [A] and [B], not only the effects of the present invention are exhibited but also This is one of the preferred embodiments because it also produces the effect of less fog on the exposed portion.

[0168]

[Chemical 55]

In the formula, R ₁ and R ₂ each represent an alkyl group, an aryl group, an R ₃ CO— group or a hydrogen atom. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. Also, R ₁
And R ₂ may form a ring.

In the general formula [A], the substituted and unsubstituted alkyl groups represented by R ₁ and R ₂ may be the same or different and each is preferably an alkyl group having 1 to 3 carbon atoms.
Further, these alkyl groups may have a carboxyl group, a phosphoric acid group, a sulfo group or a hydroxyl group. R ₃ is a substitution,
It represents an unsubstituted alkoxy group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Examples of the ring which may be formed by R ₁ and R ₂ include heterocycles such as piperidine, pyridine, triazine and morpholine.

[0171]

[Chemical 56]

In the formula, R ₁₁ , R ₁₂ and R ₁₃ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group or a heterocyclic group, and R ₁₄ represents a hydroxyl group, a hydroxyamino group, a substituted or unsubstituted group. It represents a substituted alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, carbamoyl group or amino group. The heterocyclic group is a 5- or 6-membered ring, is composed of C, H, O, N, S and a halogen atom, and may be saturated or unsaturated. R ₁₅ is -CO -, - SO ₂ -
Or a divalent group selected from -C (= NH)-, and n is 0
Or 1. Particularly when n = 0, R ₁₄ represents a group selected from an alkyl group, an aryl group and a heterocyclic group, and R ₁₃ and R ₁₄
May together form a heterocycle.

Specific examples of the hydroxylamine compound represented by the general formula [A] are shown in US Pat. No. 3,287,125.
Although described in 3,329,034 and 3,287,124, etc.,
Particularly preferred specific exemplified compounds include Japanese Patent Application No. 2-2031
(A-1) to (A-39) described in No. 69, pages 36 to 38, and JP-A
3-33845 (1) to (53) described on pages 3 to 6 and JP-A-3-6
(1) to (52) described in No. 3646, pp. 5-7.

Next, specific examples of the compound represented by the general formula [B] are described in Japanese Patent Application No. 2-203169, pages 40 to 43 (B-1) to
(B-33) and (1) to JP-A-3-33846, pages 4 to 6
(56) is mentioned.

The compounds represented by the general formula [A] or the general formula [B] are usually free amines, hydrochlorides, sulfates,
It is used in the form of p-toluene sulfonate, oxalate, phosphate, acetate and the like.

A hydroxylamine compound represented by the following general formula [A '] is also preferably used as a preservative for the color developing solution.

[0177]

[Chemical 57]

In the formula, L represents a substituted or unsubstituted alkylene group, A represents a carboxyl group, a sulfo group, a phosphono group, a phosphino group, a hydroxyl group, an amino group which may be alkyl-substituted, an ammonio group, or a carbamoyl group. Or, it represents a sulfamoyl group, and R represents a hydrogen atom or a substituted or unsubstituted alkyl group.

Specific examples of the compound represented by the general formula [A '] include (1) to (54) described in JP-A-3-84044, page 4, lower left column to page 6, lower right column. But above all (1)
And the following compounds represented by (7) are preferable.

(1) HON (CH ₂ CH ₂ COOH) ₂ (7) HON (CH ₂ CH ₂ SO ₃ H) _{2 The} compound represented by the general formula [A ′] is obtained by alkylating a commercially available hydroxylamine with an alkyl group. It is obtained by a chemical reaction. For example, West German Patent 1,159,634 and Inorganica Chimica Acta., 93
(1984) 101 to 108 and the like according to the synthesis method.

A slight amount of sulfite can be used as a preservative in the color-developed tablet and the black-and-white developed tablet according to the present invention. Examples of the sulfite include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite and the like.

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

As the development accelerator, Japanese Examined Patent Publication No. 37-16088,
37-5987, 38-7826, 44-12380, 45-9019
And thioether compounds represented by U.S. Pat. No. 3,813,247, p-phenylenediamine compounds represented by JP-A-52-49829 and 50-15554, and JP-B-44-30074.
No. 5, JP-A-50-137726, JP-A-56-156826 and JP-A-52-43429
Quaternary ammonium salts represented by U.S. Pat.
0,122 and 4,119,462 described p-aminophenols, U.S. Patents 2,494,903, 3,128,182, 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. Patents 3,128,183, 41-11431, 42-23883, and U.S.A. Polyalkylene oxide typified by Patent 3,532,501 and the like, 1-phenyl-3-pyrazolidones,
Hydrazines, mesoionic compounds, ionic compounds,
Imidazoles and the like can be added as necessary. Chloride ions and bromine ions may be used in the color developer for the purpose of preventing fog and the like. In the present invention, preferably, chlorine ions are 1.0 × 10 ^{-2 to} 1.5 × 10 ^-1.
Mol / l, more preferably 3.5 × 10 ^{-2 to} 1.0 × 10 ^-1 mol / l
Contains l. When the chloride ion concentration is more than 1.5 × 10 ^-1 mol / l, it is not preferable to delay the development and quickly obtain a high maximum concentration. On the other hand, if it is less than 3.5 × 10 ^-2 mol / l, stain is generated and photographic characteristic variation (particularly minimum density) due to continuous processing becomes large, which is not preferable.

In the present invention, the color developing solution preferably contains bromine ions in an amount of 3.0 × 10 ^{-5 to} 1.0 × 10 ^-3 mol / l. More preferably, it is 5.0 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol / l. It is particularly preferably 1.0 × 10 ^{−4 to} 3.0 × 10 ⁻⁴ mol / l. When the bromine ion concentration is higher than 1.0 × 10 ^-3 mol / l,
When the development is delayed to decrease the maximum density and the sensitivity, and the density is less than 3.0 × 10 ⁻⁵ mol / l, stain is generated, and photographic characteristic fluctuation (especially minimum density) is generated during continuous processing, which is not preferable.

When added directly to the color developing agent, sodium chloride, potassium chloride, chloride ion-providing substances,
Ammonium chloride, nickel chloride, magnesium chloride,
Examples thereof include manganese chloride, calcium chloride, and cadmium chloride, with sodium chloride and potassium chloride being preferred.

It may also be supplied in the form of a counter salt of the optical brightening agent added to the color developing agent.

As bromide ion supplying substances, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, Thallium bromide may be mentioned, of which potassium bromide and sodium bromide are preferred.

If necessary, an antifoggant may be added to the color-developing processed tablet of the present invention 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 antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole,
Typical examples include nitrogen-containing heterocyclic compounds such as 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolidine, and adenine.

It is preferable that the color-developing tablet of the present invention contains a triazinyl stilbene type optical brightening agent from the viewpoint of the effect of the object of the present invention. As the fluorescent whitening agent, a compound represented by the following general formula [E] is preferable.

[0190]

[Chemical 58]

In the above formula, X ₁ , X ₂ , Y ₁ and Y ₂ are each a hydroxyl group, a halogen atom such as chlorine or bromine,
Alkyl group, aryl group, -N (R ₂₁ ) (R ₂₂ ) group,

[0192]

[Chemical 59]

Or represents OR ₂₅ . Here, R ₂₁ and R ₂₂ are each a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, R ₂₃ and R ₂₄ are a substituted or unsubstituted alkylene group, and R ₂₅ is a hydrogen atom. Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and M represents a cation.

The details of each group of the general formula [E] or the substituents thereof are the same as those described in Japanese Patent Application No. 2-240400, from page 62 down to line 8 to page 64 down to line 3. As specific compounds, E-1 to E-45 described on pages 65 to 67 of the same item can be mentioned.

The above compound can be synthesized by a known method. Representative compounds are exemplified below, and among them, particularly preferably used are E-4, E-24, E-34,
E-35, E-36, E-37 and E-41. The amount of these compounds added is preferably in the range of 0.2 to 10 g, and more preferably 0.4 to 5 g, per 1000 ml of color developing solution.

[0196]

[Chemical 60]

[0197]

[Chemical formula 61]

Further, in the color-developed tablet and the black-and-white developed tablet used in the present invention, if necessary, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other Japanese Patent Publication No. 47-33378,
The compounds described in JP-A-44-9509 can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developing agent may be used together with the developing agent. As these auxiliary developers, for example, methol, phenidone, N, N-diethyl-p-aminophenol hydrochloride, N, N, N ′, N′-tetramethyl-p-phenylenediamine hydrochloride, etc. are known. However, the addition amount thereof is usually preferably 0.01 to 1.0 g / l.

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

Further, the color-developing processed tablets and the black-and-white developed processing tablets include chelating agents represented by the following general formula [K] described in Japanese Patent Application No. 2-240400, from page 69, line 9 to page 75, below. It is preferable to add the exemplified compounds K-1 to K-22 from the viewpoint of effectively achieving the object of the present invention.

[0202]

[Chemical formula 62]

Among these chelating agents, K-2 and K-
9, K-12, K-13, K-17, and K-19 are preferably used, and the effects of the present invention are more exerted particularly when K-2 and K-9 are added to the color developing solution.

The amount of these chelating agents added is preferably in the range of 0.1 to 20 g, more preferably 0.2 to 8 g, per 1000 ml of the color developing solution and the black and white developing solution.

Further, the color-developed tablet and the black-and-white developed tablet may contain anionic, cationic, amphoteric and nonionic surfactants. If necessary, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, aromatic carboxylic acid may be added.

As the fixing agent or the bleach-fixing agent, Japanese Patent Application No. 64-295 can be used.
It is preferable to add the compound represented by [FA] described in No. 258, page 56 and the exemplified compounds, and not only to exert the effect of the present invention but also to process a small amount of a light-sensitive material for a long time. Another effect is that the sludge generated in the processing liquid having the fixing ability is extremely small.

The compound represented by the general formula [FA] described in the above item can be synthesized by a general method as described in US Pat. Nos. 3,335,161 and 3,260,718. These compounds represented by the general formula [FA] may be used alone or in combination of two or more kinds. Good results are obtained when the amount of these compounds added is in the range of 0.1 to 200 g per 1000 ml of the treatment liquid.

In the present invention, the stabilizer preferably contains a chelating agent having a chelate stability constant for ferric ions of 8 or more. Here, the chelate stability constant is defined by LG Sillen / AEMartell, “Stabillity Consta
nts of Metal-ion Complexes ”, The Chemical Societ
y, London (1964). S.Chaberek · AEMarteel, “Orga
nic Sequestering Agents ”, Wiley (1959) and others.

As a chelating agent having a chelate stability constant for ferric ions of 8 or more, Japanese Patent Application No. 2-234776 can be used.
Nos. 1-324507 and the like. The amount of these chelating agents used is preferably 0.01 to 50 g, more preferably 0.05 to 20 g, per 1000 ml of the stabilizing solution, and good results are obtained.

Ammonium compounds are mentioned as preferred compounds to be added to the stabilizer. These are supplied by ammonium salts of various inorganic compounds. Addition amount of ammonium compound is 0.001 per 1000 ml of stabilizer.
To 2.0 mol is preferable, and more preferably 0.002 to 1.
It is 0 mol. Further, the stabilizer preferably contains sulfite.

Further, the stabilizer preferably contains a metal salt in combination with the chelating agent. Examples of such metal salts include Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb and S.
There are metal salts of n, Zn, Ti, Zr, Mg, Al or Sr, which can be supplied as inorganic salts such as halides, hydroxides, sulfates, carbonates, phosphates, acetates or water-soluble chelating agents. The amount used is preferably in the range of 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably 4 × 10 ^-4 to 2 × 10 ^-2 per 1000 ml of the stabilizing solution.
It is a mole.

Further, to the stabilizer, an organic acid salt (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), a pH adjusting agent (phosphate salt, borate salt, hydrochloric acid, sulfate salt, etc.) should be added. You can In the present invention, known antifungal agents can be used alone or in combination as long as the effects of the present invention are not impaired.

The light-sensitive material to which the processing agent of the present invention is applied will be described below.

When the light-sensitive material is a light-sensitive material for photographing, silver iodobromide or silver iodochloride having an average silver iodide content of 3 mol% or more is used as the silver halide grains, but particularly 4 mol% Silver iodobromide containing from 0.5 to 15 mol% of silver iodide is preferred. Among them, the average silver iodide content of the present invention is preferably 5 to 12 mol%, most preferably 8 to 11 mol%.
Is.

As the silver halide emulsion used in the light-sensitive material processed with the photographic processing agent of the present invention, those described in Research Disclosure 308119 (hereinafter abbreviated as RD308119) can be used. The following shows the locations.

[Item] [Page of RD308119] Iodine structure 993 IA Item Production method 993 I-A Item and 994 E Item Crystal habit Normal crystal 993 IA Item Twin 〃 Epitaxial 〃 Halogen composition Uniform 993 IB Item Not uniform 〃 Halogen conversion 994 IC Item 〃 Substitution 〃 Metal-containing 994 I-D Item Monodispersion 995 I-F Item Solvent addition 〃 Latent image forming position Surface 995 I-G Item 〃 Applied Sensitive Material Negative 995 I -H term Positive (including internal fog grains) 〃 Mix and use emulsion 995 I-J term Desalting 995 II-A term Use silver halide emulsion that has been physically ripened, chemically ripened and spectrally sensitized. To do. Additives used in such a process are Research Disclosure No. 1764
3, No. 18716 and No. 308119 (hereinafter RD17643, RD18716 and RD30, respectively)
8119).

The places described in the table below are shown.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A Item 23 648 Spectral sensitizer 996 IV-AA, B, C, D, E, H, I , J Item 23-24 648-9 Supersensitizer 996 IV-AE, J Item 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Photographic additives are also described above. It is described in Research Disclosure. The following table shows the relevant locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 Item VII-I 25 650 Dye image stabilizer 1001 Item VII-J 25 Whitening agent 998 V 24 Ultraviolet absorber 1003 VIII C, XIII C Item 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Static inhibitor 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / coating aid 1005 XI 26-27 650 Matting agent 1007 X VI Developer (contained in light-sensitive material) 1011 XX-B Item Photographic processing agent of the present invention Various couplers can be used in the light-sensitive material, and specific examples thereof are described in Research Disclosure above. The following table shows the relevant locations.

[Item] [Page of RD308119] [RD 17643] [RD 18716] Yellow coupler 1001 Item VII-D Item VII C to G Magenta coupler 1001 Item VII-D Item VII C to G Cyan Coupler 1001 VII-D Item VII C to G DIR coupler 1001 VII-F VII F BAR coupler 1002 VII-F Other useful residue releasing coupler 1001 VII-F alkali-soluble coupler 1001 VII-E Additive is RD308119 XIV It can be added by the described dispersion method or the like.

In the present invention, the above-mentioned RD17643th
28, RD18716, pages 647-648 and RD3081
The supports described in XIX 19 can be used.

For the light-sensitive material, the above-mentioned RD308119 V is used.
An auxiliary layer such as a filter layer or an intermediate layer described in the section II-K can be provided. The photosensitive material is the RD described above.
308119 Various layer configurations such as a forward layer, an inverse layer, and a unit configuration described in the item VII-K can be adopted.

Next, the light-sensitive material for color printing which is preferable for applying the photographic processing agent of the present invention will be described.

As silver halide grains in the light-sensitive material, silver halide grains mainly containing silver chloride containing at least 80 mol% of silver chloride are used, preferably 90 mol% or more,
Particularly preferably, those containing 95 mol% or more, and most preferably those containing 99 mol% or more are used.

The silver halide emulsion mainly containing silver chloride can contain silver bromide and / or silver iodide as a silver halide composition in addition to silver chloride. In this case, the silver bromide content is 20 mol% or less. Is preferable, more preferably 10 mol% or less, further preferably 3 mol% or less, and when silver iodide is present, it is preferably 1 mol% or less, more preferably 0.5 mol%.
Below, it is most preferably zero. Such silver chloride 50
The silver halide grains mainly composed of silver chloride containing more than mol% are
It may be applied to at least one silver halide emulsion layer, but is preferably applied to all light-sensitive silver halide emulsion layers.

The crystals of the silver halide grains may be normal crystals, twin crystals or other crystals, and have a [1.0.0] plane and a [1.
Any ratio can be used for the [1.1] plane. Furthermore, even if the crystal structure of these silver halide grains is uniform from the inside to the outside, layers (phases) with different inside and outside
It may be in the shape of a core (core shell).
Further, these silver halides may be of a type that forms a latent image mainly on the surface or may be of a type that is formed inside the grain. Further, tabular silver halide grains (JP-A-58-11393)
No. 4, Japanese Patent Application No. 59-170070) can also be used.
Further, silver halides described in JP-A 64-26837, 64-26838, 64-77047 and the like can be used.

Further, the silver halide grains are prepared by an acid method,
It may be obtained by any preparation method such as a neutral method or an ammonia method.

Alternatively, for example, a method may be used in which seed particles are formed by an acidic method and further grown by an ammonia method having a high growth rate to grow to a predetermined size. When growing the silver halide grains, the pH, pAg, etc. in the reaction vessel are controlled, and the amount of silver ions corresponding to the growth rate of the silver halide grains as described in JP-A-54-48521 is used. It is preferable to sequentially and simultaneously inject and mix halide ions with halide ions.

In the present invention, when the silver halide color photographic light-sensitive material is imagewise exposed and then continuously processed by using an automatic processor, the method for replenishing the color development processing tank is as follows. Although it may be prepared and used, it is preferable that the solid color developing treatment agent of the present invention is added to and dissolved in a dissolving portion provided in a portion in contact with the color developing treatment solution.

That is, the automatic developing machine preferably used in the present invention comprises a processing tank (main tank) for processing a silver halide color photographic light-sensitive material and a dissolving section (sub-tank) for dissolving a solid processing agent, The processing tank and the dissolution section are in communication with each other, and by having a circulation means, the respective liquids circulate between the processing tank and the dissolution section.

It is preferable to have a filtering means in the dissolving section so that impurities, insoluble substances or undissolved substances mixed in the supplied solid processing agent do not flow into the processing tank.

[0232] When the solid processing agent is added to the dissolution section,
Replenishing the minimum evaporation amount of water is a preferable mode for carrying out the present invention. That is, in the processing liquid tank at a certain temperature, the liquid level is constantly lowered and thickened unless water is supplied with evaporation, which causes problems such as deterioration of photographic performance, precipitation, tar and the like. Therefore, a minimum amount of water supply is required to keep the tar liquid level.

Further, in the water supply, it is necessary to consider taking-out by the photosensitive material in addition to the evaporation, and especially in the color developing tank, it is necessary to supply water by taking out the photosensitive material in addition to the evaporation.

The automatic developing machine has a detection means for detecting the processing amount of the silver halide color photographic light-sensitive material, and a supply device for automatically supplying the solid processing agent to the dissolving part according to the processing amount,
It is preferable to have a replenishing device for replenishing the water.

In the present invention, a processing section for processing a light-sensitive material and a dissolving section for dissolving a solid processing agent are provided, and the dissolving section is arranged at a portion of the processing section which comes into contact with a processing solution,
Moreover, by using an automatic developing machine having a dissolving means, it is possible to substantially eliminate the manual dissolving work which has been conventionally performed, and a replenishing tank or a replenishing tank which occupies about half of the developing machine. It is even possible to eliminate the pumps for replenishment and liquid feeding, and it is possible to significantly reduce the cost and downsize the device or equipment. However, since the treating agent is dissolved in the dissolving portion, even the solid treating agent can be rapidly dissolved, a local increase in concentration can be prevented, and the treating agent can be made uniform throughout the treating portion.

When there is no dissolution part, for example, when tablets or granules are directly added to a tank treatment tank or a replenishment tank, the initial solubility is slightly good, but the dissolution rate is slow, and the alkali agent is hard to dissolve due to solidification. As it accumulates on the bottom of the tank, a high concentration phenomenon of the photographic processing agent occurs locally, and tar and insoluble substances are generated, which seriously affects photographic performance and clogging of the circulation system.

Further, in the present invention, since the photographic processing agent is a solid processing agent, the parts agent may scatter during the work and adhere to or be contaminated with the human body, especially hands, clothes and peripheral equipment. In addition, it is possible to supply an environmentally compatible processing agent that does not require a plastic bottle.

Furthermore, by providing the processing agent supply means in the dissolving section of the automatic developing machine, the processing agent is not manually introduced into the dissolving section, and the working efficiency is greatly improved.

Next, a preferred automatic developing machine in the present invention will be described.

FIG. 1 is a schematic explanatory view showing an example of an automatic developing machine according to the present invention, and shows a control device of a color paper processing device in a simple manner.

When the color paper is carried in from the photosensitive material insertion portion 13 and passes through the photosensitive material area detection 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 are provided. Is operated in response to a signal from the control unit 11, and the replenishment treatment tablets and the replenishment water for preparation are treated in the respective treatment tanks 1, 2, 3
Will be replenished with the required amount.

When the temperature of the automatic processing machine is adjusted for several hours, the processing liquid 17 in each of the processing tanks 1 to 3 evaporates, and when the liquid level is below a certain level, the liquid level detection sensor 9 operates and the controller 11 In response to this signal, the replenishment water replenishing device 10 and the solenoid valve 12 are operated, and the evaporation correction replenishment water is replenished until the upper limit detection mechanism of the liquid level detection sensor 9 operates. It is preferable that the temperature of the warm water for washing 14, which is the replenishing water supplied through the replenishing water replenishing pipe 15, be adjusted for both the replenishing water for liquid preparation and the replenishing water for evaporation correction. Further, in each of the processing tanks 1 to 3, 1 is a color developing tank, 2 is a bleach-fixing tank, and 3 is a stabilizing tank. Further, 4 is a drying section.

FIG. 2 shows the tablet type processing agent replenishing device 8 as a schematic explanatory view.

Photosensitive material area detection sensor 7 (see FIG. 1)
When the control unit 11 shown in FIG. 1 operates in response to the signal and the tablet-type processing agent supply stepping motor 95 operates, it is directly connected to it and the rack of the tablet-type processing agent supply push-out plunger 94.
The driving pinion 96 engaging with the 94A raises the plunger 94 having the rack 94A by one step, that is, the pitch length P of the thickness of the processing agent, and the replenishment tray main body of the processing agent 24.
The uppermost tablet type processing agent 24A in 91 comes to stand by at the dropping position, and the tablet type processing agent 24 stored in the tray main body 91 is a processing agent replenishing tank (hereinafter referred to as a sub tank) which is a processing agent dissolving section. That is, preparation for putting one in the filtering device 21 in 20 is completed.

In this way, the tablet type processing agent 24A waiting at the uppermost portion is moved forward and backward by the plunger 99 which horizontally reciprocates on the piston slide base 92, and the guide plate 20A above the sub tank 20 and the ceiling. The inside of the tunnel formed by the cover 20B is slid laterally so as to drop on the liquid surface of the filtering device 21 of the sub tank 20. In the plunger 99, a rack 99A, which is partially cut off, meshes with a pinion 98 directly connected to the stepping motor 97, and the stepping motor 97 is started by a command signal, whereby the reciprocating operation is performed. When the tablet type processing agent 24A is put into the sub tank 20 by the forward movement, the stepping motor 97 rotates in the reverse direction and the plunger 99 returns to the original position even if it moves back and waits until the next command signal comes. . In addition, the command signal may instruct the supply of a plurality of tablet-type treatment agents, in which case the above-described operation is repeated a predetermined number of times.

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

If all or most of the circulating flow of the processing liquid 17 circulating between the main processing tank 16 and the sub tank 20 is directly passed through the filtering device 21 in the sub tank 20 by the circulation pump 18, The dissolved portion of the mold treatment agent 24 is further increased.

In the figure, 19 is a temperature control heater, 27 is a communication pipe for connecting the main processing tank 16 and the sub tank 20, 28
Is a processing rack, and 29 is an overflow port.

Here, the tray main body 91 of the tablet type processing agent replenishing device 8 is surrounded by four vertical walls, and the plunger is inserted from the bottom.
The 94 reciprocates up and down. In this way, the tablet-type treating agent 24 is protected in the replenishing tray in an almost sealed state, and the uppermost tablet-type treating agent 24A is also almost sealed in the tunnel to the sub-tank 20 as described above. Since it is pushed out in a state, it is not contaminated due to the rebound and evaporation of each processing liquid.

Further, the forward speed of the plunger 99 is set to an appropriate value, and the injection direction of the tablet-type treatment agent is the direction shown in FIG. 2 so that the flat surface is vertical, so that the splashing is extremely high. Decrease.

In response to the signal from the photosensitive material area detection sensor 7, the control unit 11 operates, and the stepping motors 95 and 97 for replenishing the tablet type processing agent and the pinion 96 that is driven by the stepping motors 95 and 97.
A plunger 94 having a rack 94A and a plunger 99 having a rack 99A which are linearly moved by the operation of 98 actuate to replenish the tablet type processing agent 24 and at the same time, a replenishing water replenishing device.
10 and the solenoid valve 12 are activated, and the replenishment water for liquid preparation is replenished. The replenishment amount of the replenishing water for liquid preparation may be set as long as it is more than necessary to dissolve the tablet-type treating agent 24 and is solved by inputting the operation time of the solenoid valve 12 and the replenishing water replenishing device 10 to the control unit 11 in advance. it can.

When the processing liquid 17 in the processing tank evaporates and the liquid level is lowered while the temperature of the automatic processing machine is adjusted or stopped, the liquid level detection sensor 9 detects the lowered liquid level and controls the signal. Part 11
Then, the solenoid valve 12 and the replenishing water replenishing device 10 are operated to replenish the evaporation correcting replenishing water to a normal liquid level. When reaching the regular liquid level, the liquid level detection sensor 9 detects the regular liquid level, transmits a signal to the control unit 11, and stops the operation of the solenoid valve 12 and the replenishment water replenishing device 10.

Example 1 Operation (1) 550 g of ferric ammonium ammonium diamine tetraacetate, 20 g of ethylene diammonium tetraacetic acid, and 200 g of maleic acid are ground in an air jet pulverizer until the average particle size becomes 100 μm.

Operation (2) 725 g of ammonium thiosulfate, 300 g of sodium sulfite, 170 g of potassium bromide and 20 g of p-toluenesulfinic acid are ground in the same manner as in the operation (1).

Operation (3) 3.85 g of the ground product prepared in the above operation (1) and operation (2)
6.08 g of the pulverized product of 1. was thoroughly mixed to obtain a mixed pulverized product. The total amount of this was compressed into tablets with a compression pressure of 800 Kg / cm ² using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho,
Sample 1 was prepared.

Operation (4) 3.85 g of the pulverized product prepared in the above operation (1) was compressed into tablets with a compression pressure of 100 Kg / cm ² using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho, and further on top. 6.08g of the pulverized product prepared in step (2) was added to and the compression pressure was 800Kg / c.
Sample 2 was prepared by compression compression with m ² .

Operation (5) 3.85 g of the pulverized product prepared in the above operation (1) was compressed into tablets with a compression pressure of 100 Kg / cm ² using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho, and then compressed. Na-p-toluenesulfonate (1.5 g) was added, the mixture was compressed into tablets at a compression pressure of 100 kg / cm ² , and 6.08 g of the pulverized product prepared in step (2)
Was added and compressed into tablets at a compression pressure of 800 Kg / cm ² , and sample 3
It was created.

Operation (6) Samples 1 to 3 were coated with a water-soluble polymer shown in Table 1 using a high coater HCT-48 manufactured by Freund Sangyo Co., Ltd. so that the coating rate was 3 wt%. . Let this sample be 4-6.

Procedure (7) Samples 2 to 7 are coated with the water-soluble polymer shown in Table 1 in the same manner as in the procedure (6).

Five tablet samples each obtained by the above operation were placed in a glass bottle, tightly stoppered, and stored at 50 ° C. for 4 months. The shape of the tablet sample after storage was evaluated according to the following criteria 1.
The content of thiosulfate in one tablet was measured, and the value before storage was set to 100% to determine the average residual rate of these. In addition, the dissolution time and the dissolution state after 1 hour were evaluated according to Criterion 2 while stirring each of 6 tablet samples before storage in 1 L of water at 25 ° C. with magnetic stirring (150 rpm). The results are shown in Table 1.

Evaluation Criterion 1 ○ Maintain original shape △ Slightly deformed × Not retain original shape Evaluation Criteria 2 ○ Clear solution without insoluble residue △ Slight residue × Clearly insoluble component remains

[0262]

[Table 1]

As is clear from Table 1, the combination of the present invention makes it possible to provide a processing agent which is stable as a tablet and has excellent solubility even in a processing tank.

Example 2 Instead of the ferric ammonium ethylenediaminetetraacetate used in Example 1, the exemplified compounds A-I-2 and A-II- were used.
1, A-II-3, A-III-6, A-IV-8, AV-2
The same operation and experiment as in Example 1 were carried out except that the ferric ammonium salts of 0, A-VI-4 and A-4 were used. As a result, the same results as in Example 1 were obtained.

[0265]

[Chemical formula 63]

Continuous treatment experiments were carried out using the treated tablets of the present invention according to the following procedure.

5) Tablet for color development replenishment for color paper (A) Developing agent CD-3 [4-amino-3-methyl-N-ethyl-N- [β-
(Methanesulfonamide) ethyl] aniline sulfate] 120 g
Is pulverized in an air jet fine pulverizer until the average particle size becomes 10 μm. This fine powder is granulated by spraying 4.5 ml of water at room temperature for about 5 minutes in a commercially available fluidized bed spray granulator, and then the granulated product is dried at 60 ° C. for 8 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove the water content of the granulated product.

Procedure (B) Disulfoethylhydroxylamine disodium salt 120 g
Is pulverized and granulated in the same manner as in the operation (A). The amount of water spray is 3.
Adjust the volume to 0 ml, granulate and dry at 50 ° C for 10 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove the water content of the granulated product.

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 of potassium bromide
g, 25 g of diethylenetriamine pentaacetic acid, 300 g of sodium p-toluenesulfonate and 20 g of potassium hydroxide were pulverized in the same manner as in (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in (A), the amount of water sprayed is set to 200 ml and granulation is performed. After granulation, the granulate is dried at 70 ° C. for 15 minutes and then the granulate is dried in vacuum at 40 ° C. for 2 hours to remove almost completely the water of the granulate.

Operation (D) The granules prepared in the above operations (A) to (C) are subjected to 40 ° C. at 25 ° C.
Mix evenly for 10 minutes using a mixer in a room whose humidity is adjusted to below% RH. Next, the mixture was compressed into tablets with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho, with the filling amount per tablet being 7.85 g, to prepare 150 color development replenishing tablets for color paper.

6) Bleach-fixing replenishing tablet for color paper The same tablet sample as that prepared in Example 1 was prepared.

7) Tablet for stable replenishment for color paper (H) Sodium carbonate monohydrate 10 g, 1-hydroxyethane-1,1-
200 g of disodium diphosphonate is ground and granulated in the same manner as in the operation (A). The amount of water sprayed is 1.0 ml, and after granulation, 70 ℃
Dry for 3 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove the water content of the granulated product.

Operation (I) Tinopearl SFP 150 g, sodium sulfite 300 g, zinc sulfate heptahydrate 20 g, ethylenediaminetetraacetic acid disodium 150
g, ammonium sulfate 200 g, and o-phenylphenol 10 g are pulverized and granulated in the same manner as in the operation (A). The amount of water sprayed is 10.0
After granulating, it is dried at 65 ° C for 5 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 8 hours to almost completely remove the water content of the granulated product.

Operation (J) The granules prepared in the above operations (H) and (I) were subjected to 40 ° C. at 25 ° C.
Mix evenly for 10 minutes using a mixer in a room whose humidity is adjusted to below% RH. Next, the mixture was compressed into tablets with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho, so that the filling amount per tablet was 2.6 g, and 1000 stable supplement tablets for color paper were prepared. Next, a method of processing a light-sensitive material using the automatic developing machine of the present invention will be described below. Konica Color Paper Type QA Processor CL
-PP-718 was provided with a tablet supply function, a liquid level detection function, a hot water supply function, etc. by modification, and the following treatment experiment was performed. The standard processing conditions for the automatic processing machine are shown below.

Processing process Temperature Time Color development 38 ± 0.3 ° C. 17 seconds Bleach-fixing 35 ± 1.0 ° C. 17 seconds Stability −1 33 ± 3.0 ° C. 25 seconds Stable-2 33 ± 3.0 ° C. 25 seconds Stable-3 33 ± 3.0 ° C 25 seconds Dry 72 ± 5.0 ° C 40 seconds Stabilizer is replenished in the third tank, and the overflow solution flows in two tanks and one tank in sequence.

The automatic processing solution was prepared by the following method.

Color developing tank solution (23.0 liters) 18 l of 35 ° C. warm water was placed in the developing machine color developing tank, and 142 prepared color development replenishing tablets for color paper were charged and dissolved. Next, 23 starters having the following formulation, which had been separately tabletted, were added as starter components, and after dissolution, warm water was added to the tank drift line to complete the tank solution.

Color development starter for color paper Potassium chloride 4.0 g Potassium hydrogen carbonate 4.8 g Potassium carbonate 2.1 g Bleach-fixing solution (23.0 l) 15 l of 35 ° C. warm water was placed in the automatic bleach-fixing tank and the same as in Example 1. 460 bleach-fixing replenishing tablets for color paper prepared in the above were added and dissolved. After dissolution, warm water was added up to the tank mark to complete the tank solution.

Stabilizer (15 liters for 1st to 3rd tanks) 12 l of warm water at 35 ° C was added to each of the 1st tank, 2nd tank, and 3rd tank of the developing machine stabilizing tank, and the stable replenishing tablets for color paper were prepared. 40 pieces were added and dissolved. Next, warm water was added to the tank line to complete the tank solution.

Next, 20 replenishing tablets prepared during the temperature control of the automatic developing machine were set in the replenishing tablet supplying device provided in the automatic developing machine, respectively. When 1 m ² of color paper is processed, 1 replenishing tablet for color development, 4 replenishing tablets for bleach-fixing, and 1 stable replenishing tablet are added, respectively, and at the same time, replenishing hot water is supplied from the hot water supply device. Was set to supply 80 ml to the color developing tank, 200 ml to the bleach-fixing tank, and 250 ml to the stabilizing tank.

Next, the wedge-exposed Konica color paper QAA5 was continuously treated for 10 days at 10 m ² for 200 days in accordance with a conventional method,
The minimum reflection density (DminB) of blue and the maximum reflection density (DmaxR) of red were measured at the start of the treatment and after 200 days, and the differences before and after the treatment were designated as ΔDminB and ΔDmaxR, respectively. The degree of filter clogging of the bleach-fix processing tank was calculated as the deterioration rate of the flow rate of the circulation pump before and after the processing according to the following formula.

(Flow rate after treatment / flow rate at the start of treatment) × 100 (%) The results are shown in Table 2.

[0283]

[Table 2]

As is clear from Table 2, the use of the bleach-fixing agent of the present invention enables processing which is excellent in processing stability and which does not cause clogging of the filter and has excellent maintenance.

Example 4 The procedure of Example 3 was repeated except that the bleach-fixing solution and the bleach-fix replenishing tablet used in Example 3 were replaced by the equimolar amount of the compound used in Example 2 in place of the ferric ammonium salt of ethylenediaminetetraacetic acid. The same continuous treatment experiment as in Example 3 was conducted. As a result, it was improved by about 10% as compared with Example 3.

Example 5 The amount of hot water replenished to the automatic bleach-fixing tank used in Example 3 was changed.
The same continuous treatment experiment as in Example 3 was carried out except that the amount was changed from 200 ml / m ² to 100 ml / m ² . As a result, in the treatment using the comparative tablets, both the stain and the color reversion property were 30% at the end of continuous treatment.
Although worsened, the same results as in Example 3 were obtained with the treatment using the tablet of the present invention. This shows that the tablet of the present invention is excellent in continuous treatment stability when the amount of hot water replenishment is reduced.

Example 6 Tablets were prepared in the same manner as in Sample No. 5 except that the ratio of ammonium salt to all cations was changed as shown in Table 3 in the operations (1) and (2) of Example 1. . This was carried out in the same manner as in Example 1 except that the storage temperature was set to 60 ° C. and storage was performed for 5 months. The results are shown in Table 3.

[0288]

[Table 3]

From Table 3, it is more preferable that the ratio of the ammonium salt to the total cations of the components of the bleach-fixing agent of the present invention is 50% or less, more preferably 30% or less, further preferably 10%.
It is clear that the effect of the present invention is better achieved when the content is less than or equal to%.

Example 7 Sample No. 5-8 of Example 1 was prepared so as to contain 1% w / w of glutaraldehyde Na bisulfite in the fixing agent part, and was designated as No. 5-8. The same experiment was conducted, and the comparison was sample No. 5. As a result, in No. 5 the residual rate of thiosulfate was 80%, whereas in No. 5-8
Was 91%. From this, it is more preferable that the bleach-fixing agent of the present invention contains a compound forming a sulfite adduct from the viewpoint of the effect of the present invention.

[0291]

According to the present invention, there is provided a bleach-fixing agent for silver halide photographic light-sensitive materials, which is free from shape deterioration even in a long-term storage state and has very little deterioration of active ingredients and which is excellent in processing stability. You can

[Brief description of drawings]

FIG. 1 is a schematic explanatory view showing an example of an automatic developing machine according to the present invention.

FIG. 2 is a schematic explanatory view showing an embodiment of a solid processing agent supply device.

[Explanation of symbols]

 1 color developing tank 2 bleach-fixing tank 3 stabilizing tank 4 drying section 7 photosensitive material area detection sensor 8 replenishing tablet type processing agent replenishing device 9 liquid level detecting sensor 10 replenishing water replenishing device 11 control section 12 solenoid valve 13 photosensitive material inserting section 14 Washing warm water 15 Replenishment water supply pipe 16 Main treatment tank 17 Treatment liquid 18 Circulation pump 19 Temperature control heater 20 Sub-tank 21 Filtration device 24 Replenishment tablet type treatment agent 24A Top replenishment tablet type treatment agent 25 Supply tray 26 Push spring 39 Filtration filter 91 Supply tray main body 94,99 Plunger 94A, 99A Rack 95,97 Stepping motor 96,98 Pinion

Claims (3)

[Claims] 1. A part containing a bleaching agent and a part containing a fixing agent are stacked in layers and compression molded, and then coated with a water-soluble polymer containing at least a compound represented by the general formula (I) as a constituent. A bleach-fixing agent for tablet-shaped silver halide photographic light-sensitive materials, which is characterized in that [Chemical 1] [In the formula, R ₁ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
R ₂ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ] 2. The bleach-fixing agent for tablet silver halide photographic light-sensitive materials according to claim 1, wherein the bleach-fixing agent has a ratio of ammonium ions to all cations in the components of 50 mol% or less. . 3. A tablet-shaped silver halide photographic material, characterized in that the bleach-fixing agent according to claim 1 or 2 is used in a processing method in which a silver halide photographic light-sensitive material is imagewise exposed, and then color-developed and bleach-fixed. Method of processing photosensitive material.