JPH0635151A - Solid bleaching agent for silver halide color photosensitive material and its processing method - Google Patents

Abstract

PURPOSE:To obtain the solid bleach-processing agent superior in solubility and storage stability by incorporating the ferric complex salt of a specified compound. CONSTITUTION:This bleach-processing agent contains at least one of the ferric complex salts of the compounds represented mainly by formulae I and II in which each of A1-A4 is H, OH, -COOM, -PO3(M1)2, or the like; each of A11-A14 is -CH2OH, -COOM3, or the like; each of M, M1, and M3 is H, ammonium, or the like; X is 2-6 C alkylene or -(B1O)n-B2-; n is an integer of 1-8; and each of B1 and B2 is 1-5 C alkylene. This agent also contains the compounds represented by formulae III and IV which X2 is halogen, amino, hydroxy, methoxy, or the like; each of A2 and A3 is H, ammonium, an alkali metal, or organic ammonium.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a processing agent and processing method for silver halide color photographic light-sensitive materials,
Specifically, it is a silver halide color with excellent solubility and bleaching performance.
The present invention relates to a solid bleaching agent for a photographic light-sensitive material and a method for processing a silver halide color photographic light-sensitive material suitable for global environment, occupational safety and health.

[0002]

BACKGROUND OF THE INVENTION The processing of a silver halide color photographic light-sensitive material basically comprises two steps of color development and desilvering, and desilvering comprises a bleaching and fixing step or a bleach-fixing step.
In addition to this, rinsing treatment, stabilizing treatment, and the like are added as additional treatment steps.

The exposed silver halide is reduced to silver in the color development process, while the oxidized aromatic primary amine developing agent reacts with the coupler to form a dye. In the desilvering step, the silver reduced in the color developing step is oxidized and eluted as silver ions in the processing liquid.

In the bleaching solution, the color developing solution in the previous tank is brought in as the light-sensitive material is continuously processed, and the processing solution becomes fatigued. Therefore, in the case of continuous processing by an ordinary automatic developing machine, a method of replenishing a replenisher for keeping the processing performance constant is adopted. Since the replenishment of the replenisher inevitably causes a large amount of overflow and is discarded, it is a serious economic and pollution problem. Therefore, in order to reduce the overflow, a method of adding a regenerant to the overflow solution and using it again as a replenishing solution, a method of replenishing the concentrated solution in a small amount, and the like have been proposed and put into practical use.

Of these methods, the method of regenerating the overflow solution has a drawback that it requires a space such as a stock tank and is complicated for a developing station. Especially, it is difficult to introduce the over-the-counter processing (so-called mini-lab), which has been increasing in recent years, to small-scale developing laboratories. On the other hand, the concentrated low replenishment method is space-saving and does not require a special device, so it can be said that it is extremely suitable for a small-scale developing laboratory such as a minilab. However, this method also has some drawbacks.

That is, when a concentrated replenishing solution is prepared, the solubility of the bleaching agent is low, so that the bleaching component is precipitated when dissolved in a small amount of dissolved water, and not only a certain processing performance is not obtained but also circulation is not performed. There is a problem that the filter provided in the line is clogged and the refill pump is damaged.

Further, in the conventional replenishing method, since the replenishing liquid is supplied in a plastic bottle or the like, the disposal of the used plastic bottle is a serious problem. In Europe and the United States, legal regulations have become active, such as the prohibition of recycling and use of plastics, and the obligatory use of degradable plastics.

With respect to these problems, JP-A-3-397
No. 39 discloses a bleach granulation technique. However, there is a high possibility that caking (agglomeration) will occur and the solubility will deteriorate due to storage over time, or that fine powder will fly up and be inhaled by an operator during dissolution, and there is a concern that it may affect health.

Therefore, tableting is a preferable form of the treating agent which takes advantage of the advantage of the dry state.
Proposed in No. 7. Although tablets originally have the drawback of being inferior in solubility compared to granules and the like, this technology discloses a method of incorporating an expansive-disintegrating aqueous colloid for the purpose of increasing the solubility of tablets in water. ing. However, it has been found that these high molecular weight polymeric colloids lead to a decrease in bleaching performance under the rapid processing conditions that are being used today. Therefore, a solid processing agent having excellent solubility and rapid bleaching performance has been difficult to realize with conventional techniques.

Another problem is that the above-mentioned conventional solid bleaching agents are extremely weak against moisture, and in order to store them for a long period of time, it is necessary to seal them by blocking moisture with vinyl, plastic or aluminum foil. However, in such a case, there are still problems that the disposal problem of the packaging material after use is not solved, and that special air conditioning equipment is required for the manufacturing and packaging processes.

[0011]

Accordingly, an object of the present invention is to firstly provide a solid bleaching agent having excellent solubility and storability, and secondly to provide a solid bleaching agent having excellent bleaching performance. is there. Third is the provision of processing technology suitable for global environment conservation. The fourth point is to provide treatment technology suitable for occupational safety and health.

[0012]

The above-mentioned objects are achieved by the following general formulas [AI], [A-II], [A-III] and [AI].
V], [A-V] or [A-VI] and at least one ferric complex salt of the compound represented by the following general formula (I
At least one of the compounds represented by I) or (III)
It has been found to be achieved by a solid bleaching agent for a silver halide color photographic light-sensitive material characterized by containing a seed.

[0013]

Embedded image General formula [A-I] [In the formula, A _{1 to} A ₄ may be the same or different and each represents a hydrogen atom, a hydroxy group, —COOM, —PO
_{3 represents} (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 , or —CH ₂ CO.
OM ₂ . M, M ₁ and M ₂ each represent a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. ]

[0014]

Embedded image General formula [A-II] _Wherein, A 11 _{to A 14} may each be the same or _different, -CH 2 _OH, -COOM ₃ or _-PO 3 _(M 4)
Represents ₂ . M ₃ and M ₄ each represent a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. X
Is an alkylene group having 2 to 6 carbon atoms or-(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. ]

[0015]

Embedded image General formula [A-III] [In the formula, A _{21 to} A ₂₄ may be the same or different and each is —CH ₂ OH, —COOM ₅ or —PO ₃ (M ₆ ).
Represents ₂ . 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 represents an integer of 1 to 8, and B ₁₁ and B ₁₂ may be the same or different,
It 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. ]

[0016]

Embedded image General formula [A-IV] [In the formula, R ₁ and R ₂ each represent a hydrogen atom, or an optionally substituted alkyl group or aryl group. L is

[0017]

[Chemical 14] , 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. ]

[0018]

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

[0019]

Embedded image General formula [A-VI] [Wherein, 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,
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, or an alkyl group which may be substituted. Alternatively, it represents 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 are 0 or 1 respectively
Represents 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 having one part. Further, the ratio of ammonium ions to all cations in the solid bleaching agent is preferably 50 mol% or less, more preferably 20 mol% or less. 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 object, is a solid bleaching agent as 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 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.

[0022]

[Chemical 20]

[0023]

[Chemical 21] The compound represented by the above general formula [AI] is disclosed in JP-A-63-
267750, 63-267751, JP-A-2-
It can be synthesized by a general synthetic method described in the specifications of Nos. 115172 and 2-295954.

Of these, the preferred compounds used in the present invention are exemplified compounds [AI-1], [AI-2],
These are [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 represented by X include groups such as ethylene, propylene and butylene. Representing X- (B ₁ O) n-B ₂
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 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.

[0027]

[Chemical 25]

[0028]

[Chemical formula 26] The compound represented by the general formula [A-II] can be synthesized by a generally known method.

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

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

In the above general formula [A-III], X₁
Represents-(B₁₁O ) N_Five-B₁₂At B₁₁And B₁₂
The alkylene group represented by methylene, ethylene,
Examples include trimethylene and the like. These alkylene groups are
As a substituent, lower alkyl such as methyl and ethyl
It may have a group, a hydroxy group or the like.

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

[0033]

[Chemical 30]

[0034]

[Chemical 31]

[0035]

[Chemical 32]

[0036]

[Chemical 33]

[0037]

[Chemical 34]

[0038]

[Chemical 35]

[0039]

[Chemical 36] [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],
They are [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,

[0043]

[Chemical 40] 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 above 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 mentioned as the substituents of R ₁ and R ₂ can be applied, but —OH—COOH—CH ₂ COOM —CH ₂ OH —CONH ₂ —CH ₂ CONH ₂ —CONHCH ₃ is preferable. (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].

[0046]

Embedded image General formula [BI] [Wherein R ₁ and R ₂ are each a hydrogen atom, an alkyl group,
Alternatively, it represents 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. ]

[0047]

Embedded image General formula [B-II] [R ₁ in the formula, R ₁ to R ₄ each formula [B-I],
It has the same meaning as R ₂ and L _{1 to} L ₃ and M are also represented by the general formula [BI].
Is synonymous with those of. ] Specific examples of the compound represented by the above general formula [A-IV] are shown below, but the invention is not limited thereto.

[0048]

[Chemical 43]

[0049]

[Chemical 44]

[0050]

[Chemical formula 45]

[0051]

[Chemical formula 46] Of these, particularly preferred compounds 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 above general formula [A-V], the alkyl group and 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 above 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,

[0055]

[Chemical 50] (B ₁ and B ₂ represent an alkylene group or an arylene group,
n represents 1 to 3. ),

[0056]

[Chemical 51] (Z is a hydrogen atom, unsubstituted or -COOM, -SO
₃ M represents an alkyl group or an aryl group substituted with —OH, 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] and [B].
-IV].

[0058]

Embedded image General formula [B-III] [In the formula, 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, It represents an ammonium group or an organic ammonium group. ]

[0059]

Embedded image General formula [B-IV] [Wherein R _{1 to} R ₄ are each R of the general formula [B-III].
₁ and R ₂ have the same meanings, and L _{1 to} L ₄ and M ₁ and M ₂ have the same meanings as those of the general 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.

[0060]

[Chemical 54]

[0061]

[Chemical 55]

[0062]

[Chemical 56]

[0063]

[Chemical 57]

[0064]

[Chemical 58] In particular, the compounds of the general formulas [A-I], [A-II] and [A-II]
The effect is remarkable when the iron salt of the compound represented by the formula [I] is 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-2]
7], [A-V-29], [A-V-30], [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.

[0068]

[Chemical 60]

[0069]

[Chemical formula 61]

[0070]

[Chemical formula 62] Among these compounds, [A-VI-
1], [A-VI-3], [A-VI-4], [A-V
I-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.
/ It is within the range of 1 liter of the treatment liquid.

Specific examples of the compounds represented by formulas (II) and (III) are shown below, but the compounds are not limited to these.

[0073]

[Chemical 65]

[0074]

[Chemical formula 66]

[0075]

[Chemical formula 67] Of these, those preferably used in the present invention are exemplified compounds (II-3), (II-5), (II-6),
(II-10), (II-11), (II-12),
(II-16), (II-17), (II-18),
(II-19) and (III-4), particularly (II-
5), (II-6) and (II-16) are preferred. The compounds represented by the general formulas (II) and (III) are preferably used in combination of two or more in order to maintain the bleaching agent according to the present invention at a desired pH.
Is one. The above compounds are used in the form of acid, sodium salt and potassium salt, preferably potassium salt.

The addition amount of the compounds of the above general formulas [II] and [III] is preferably 0.05 to 1 mol / liter of the treatment liquid, more preferably 0.1 to 0.6 mol / liter of the treatment liquid. Is.

The bleaching agent of the present invention preferably contains substantially no acetic acid or acetate from the viewpoint of the effect of the present invention.

The bleaching agent of the present invention has the general formula [A
-I], [A-II], [A-III], [A-I]
V], [A-V] and [A-VI], in addition to the ferric complex salts of the compounds represented by the formulas [1] to [5], [A-V] and [A-VI].
An agent can be included. In this case, the free chelating agent may be any one of the above general formulas [AI], [A-II],
[A-III], [A-IV], [AV] and [A
-VI] is preferable, but other commonly known chelating agents may be used.

In addition to the above, the bleaching agent of the present invention includes halides such as ammonium bromide, potassium bromide and sodium bromide, nitrates such as ammonium nitrate and potassium nitrate, various fluorescent whitening agents, defoaming agents or interfaces. An activator can be included.

The solid bleaching agent of the present invention consists of one part containing all the components necessary for the bleaching treatment of a silver halide color photographic light-sensitive material in one tablet. It is preferable in handling. At this time, it is also possible to form a layered form in which compounds that react easily among the respective components are partitioned by a compound or a film that is inactive to both.

In the present invention, it is preferable that the ratio of ammonium ion to the total cations in the solid bleaching agent is 50 mol% or less from the viewpoint of aging of the solid treating agent and odor when dissolved as a treating solution. , And more preferably 20 mol% or less.

Further, the solid bleaching agent of the present invention can further improve the solubility by containing a carbonate. When the solid bleaching agent according to the present invention is prepared by granulating in advance, it is preferable to granulate the compounds represented by the general formulas (II) and (III) and the carbonate separately.

The color developing agent used in the processing method according to the present invention preferably contains a para-phenylenediamine type color developing agent. Specific examples of the color developing agent preferably used in the present invention include Japanese Patent Application No. 2-2
03169, pages 26-31 (C-1)
To (C-16), JP-A-61-289350, 29-3.
(1) to (8) described on page 1 and JP-A-3
No. 246543, pages 5 to 9 (1) to
(26), particularly preferably, Japanese Patent Application No. 2-20
No. 3169 (C-1), (C-3),
Exemplified compound (2) described in JP-A-61-289350 and exemplified compound (1) described in JP-A-3-246543 may be mentioned.

The color developing agent according to the present invention may contain a hydroxylamine derivative, a hydrazine derivative or a reducing saccharide as a preservative. Further, it is more preferable to use a sulfite such as sodium sulfite, potassium sulfite and sodium bisulfite together. In addition, known chelating agents, fluorescent whitening agents, surfactants, and halides may be contained.

In the fixing agent according to the present invention, thiosulfates and thiocyanates are preferably used as the main fixing agent, and both can be used in combination. The fixing agent can contain known pH buffering agents, chelating agents, sulfites and sulfite releasing compounds.

From the viewpoint of environmental suitability, the ratio of ammonium ion to all cations in the bleaching agent is preferably 50% or less, more preferably 20% or less.

The stabilizer according to the present invention may contain formaldehyde, but instead of this, an aldehyde amine condensate such as hexamethylenetetramine,
It is preferable to contain an N-methylol compound, hydroxybenzaldehyde and its derivative, formaldehyde-releasing compound and the like. In addition, known chelating agents,
It may contain a surfactant, an optical brightener, and an antifungal agent.

These color developing agent, fixing agent and stabilizer are
Like the bleaching agent of the present invention, it is preferably replenished to the developing machine as a solid processing agent, and the effect of the present invention becomes more remarkable by being a tablet.

In the present invention, when the silver halide color photographic light-sensitive material is imagewise exposed and continuously processed by using an automatic processor, the solid processing agent of the present invention is added to the tank solution. It is preferable to add it to a dissolving portion provided in a portion that comes into contact with to dissolve and replenish it. 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 dissolution section (sub-tank) for dissolving a solid processing agent. And the dissolution section communicate 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 dissolving device in the dissolving section for positively dissolving the supplied solid processing agent. Further, it is preferable to have a filtering means in the dissolving section so that impurities, insoluble matter or undissolved matter mixed in the supplied solid processing agent do not flow into the processing tank.

When the solid processing agent is added to the dissolution section,
Replenishing the minimum evaporation amount of water is a preferred mode for carrying out the present invention. That is, the processing liquid tank at a certain temperature is always accompanied by evaporation, and if the water is not replenished, the liquid surface is lowered and becomes thicker, which causes problems such as deterioration of photographic performance and precipitation of components. Therefore, a minimum amount of water replenishment is necessary to maintain the tank liquid level. Furthermore, in addition to the amount of evaporation, it is necessary to replenish water in consideration of taking out the liquid by the photosensitive material and diluting the waste products that are eluted from the photosensitive material and accumulate in the processing liquid. However, if the amount of replenishing water is too large, the amount of waste liquid will increase, which is not preferable for the effect of the present invention.

Further, the automatic processing machine has means for detecting the processing amount of the silver halide color photographic light-sensitive material, and an apparatus for automatically supplying a solid processing agent to the dissolving portion according to the processing amount and the water replenishment. It is preferable to have a water replenishing device for performing.

The solid bleaching agent and treatment method of the present invention make it possible to substantially eliminate the melting work which has conventionally been done manually, and the parting agent scatters during the work, so Do not inhale or contaminate hands, clothes or peripherals. In addition, it is possible to supply an environmentally compatible treatment agent that does not require the use of a plastic bottle. Moreover, it is possible to even eliminate the replenishment tanks and replenishment pumps that occupy about half of the automatic processing machine, and the equipment can be made significantly compact.

The solid processing agent in the present invention means not only tablets, granules and powders but also the tablets, granules and powders which are packaged or covered with a soluble film such as an alkali-soluble film or a water-soluble film. Including things.

The powder in the present invention refers to an aggregate of fine crystal grains. The granules referred to in the present invention are obtained by adding a granulation step to powder, and mean granules having a particle size of 50 to 5000 μm.

The term "tablet" as used in the present invention means one obtained by compression-molding powder into a certain shape, or one obtained by once granulating and then compression-molding into a certain shape.

Of the above solid processing agents, tablets are preferably used because the effects of the present invention can be more remarkably exhibited.

To solidify the photographic processing agent, a concentrated solution or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the surface of the temporarily molded photographic processing agent is mixed with a water-soluble binder. Arbitrary means, such as forming a coating layer by spraying, can be adopted (Japanese Patent Application No. 2-135887,
No. 203165, No. 2-203166, No. 2-203
No. 167, No. 2-203168, No. 2-300409.
No.).

A preferable tablet manufacturing method is a method in which a solid processing agent in powder form is granulated and then a tableting step is performed to form the tablet. There is an advantage that solubility and storability are improved as compared with a solid processing agent formed by a tableting process by simply mixing solid processing agent components, and as a result, photographic performance becomes stable.

The granulation method for tablet formation includes rolling granulation,
Known methods such as extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation and spray drying granulation can be used. The obtained granules preferably have an average particle size of 100 to 800 μm, more preferably 200 to 800 μm.
750 μm. When the average particle size is smaller than 100 μm or larger than 800 μm, when the above granules are mixed and compressed under pressure, nonuniformity of components, so-called segregation occurs, which is not preferable.

Further, the particle size distribution is preferably such that 60% or more of the granulated product particles have a deviation of ± 100 to 150 μm.

When the obtained granulated product is compressed under pressure, a known compressor such as 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 compression under pressure can have any shape, but a cylindrical type, a so-called tablet is preferable from the viewpoint of productivity and handleability.

More preferably, at the time of granulation, the above-mentioned effect becomes more remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a bleaching agent and a preservative.

The method for producing the tablet treating agent is described in, for example, JP-A Nos. 51-61837, 54-155038 and 52-52.
-88025, British Patent No. 1213808, and the like, which can be produced by a general method described in the specification. Further, the granule treating agent is, for example, JP-A Nos. 2-109042 and 2-109.
043, 3-39735, and 3-39739.
It can be produced by a general method described in the specification such as No.
Further, the powder processing agent is, for example, JP-A-54-13333.
No. 2, British Patent No. 725892, No. 729862, and German Patent No. 3733861.

[0104] The bulk density of the solid processing agent, and in view of its solubility, when the solid processing agent from the viewpoint of the desired effect of the present invention is a tablet 1.0g / cm ³ ~2.5g / cm ³ Is preferably more than 1.0 g / cm ^3, and in terms of strength of the obtained solid, less than 2.5 g / cm ³ is preferable in terms of solubility of the obtained solid. When the solid material treating agent is granules or powder, the bulk density is 0.40 to 0.95 g / cm ^3.
Are preferred.

[0105]

【Example】

Example 1 A color negative drift supplement tablet was prepared according to the following procedure. Operation (1) 0.30 mol of a ferric potassium salt of a compound represented by the general formulas [AI] to [A-VI] shown in Table 1, the general formula (II) or (III) shown in Table 1 60 g of organic acid represented by
Grind to m. The fine powder is granulated by spraying 2.5 ml of water in a commercial fluidized bed spray granulator at room temperature for about 6 minutes, and then the granulated product is dried at 65 ° C. for 7 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 (2) 40 g of potassium bromide and about 30 g of potassium carbonate are pulverized and granulated in the same manner as in operation (1). Water spray amount is 0.5m
After granulating, it is dried at 65 ° C. for 5 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. The amount of potassium carbonate was adjusted according to the organic acid added in step (1) so that the pH of the produced tablet when dissolved in water was about 4. Operation (3) The granulated product granulated in the above operations (1) and (2) is placed at 25 ° C. for 4 hours.
Uniformly mix for 10 minutes with a mixer in a room whose humidity is adjusted to 0% RH or less. Next, the mixture was compressed into tablets having a diameter of 3 cm with a solid processing tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho, and compression-pressed, and 50 color negative bleaching supplement tablets were prepared by evenly distributing the mixture.

Prepare 1000 ml of water in a beaker and
The temperature was adjusted to 5 ° C. While stirring with a magnetic stirrer, 5 tablets of each of the tablet samples obtained by the above-mentioned operation were charged and the solubility thereof was evaluated. In addition, 2 tablets for each
Each piece was released and stored at 30 ° C. and 50% humidity for 2 weeks. The appearance of the tablets after storage was visually observed. Furthermore,
Five tablet samples were placed in a polyethylene bag and sealed, and then stored at 65 ° C. and a humidity of 35% for 2 weeks. The strength of the tablets after storage was evaluated. The results are shown in Table 1.

The solubility evaluation criteria in Table 1 are as follows.

⊚: Completely dissolved within 10 minutes. ◯: Completely dissolved within 15 minutes. Δ: Completely dissolved within 20 minutes. ×: It took 20 minutes or more to completely dissolve. The evaluation criteria for the appearance of the sample are as follows.

◯: No change in appearance from before storage was observed. Δ: Tablet swelled with moisture, but tablet shape was maintained. ×: Almost no tablet shape was maintained due to moisture absorption. The evaluation criteria for the strength of the sample after storage are as follows.

○: All tablets were not broken even when dropped on a wooden board from a height of 1 m △: Some tablets were broken when dropped on a wooden board from a height of 1 m ×: 1 m All tablets were damaged when dropped from a height onto a wooden board

[0111]

[Table 1A]

[0112]

[Table 1B]

From Tables 1A and B, the tablets of the present invention are soluble,
It can be seen that the storage stability is excellent. As another effect, it is recognized that it is strong against abrasion after storage.

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. Example 2 A color negative drift supplement tablet was prepared according to the following procedure.

Operation (1) 0.3 mol of a ferric salt bleach of the compound represented by the general formula [A-III] shown in Table 1, 30 g of succinic acid (Exemplified compound II-6), maleic acid (Exemplified compound) II-5)
35 g, average particle size 10 μm in air jet pulverizer
Crush until The fine powder is granulated by spraying 2.5 ml of water in a commercial fluidized bed spray granulator at room temperature for about 6 minutes, and then the granulated product is dried at 65 ° C. for 7 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 (2) 40 g of potassium bromide and 50 g of potassium hydrogen carbonate are pulverized and granulated in the same manner as in operation (1). Water spray amount is 0.5m
After granulating, it is dried at 65 ° C. for 5 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 (3) The granulated product granulated in the above operations (1) and (2) is uniformly mixed with a mixer for 10 minutes in a room whose humidity is controlled to 40% RH or less at 25 ° C. Next, the mixture was compressed into tablets having a diameter of 3 cm with a solid processing tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho, and compression-pressed, and 50 color negative bleaching supplement tablets were prepared by evenly distributing the mixture.

In the same manner, ethylenediaminetetraacetic acid ferric potassium monohydrate [A-III-35] or 1,3-
Propanediaminetetraacetic acid ferric potassium monohydrate [AI
II-36], potassium hydrogencarbonate and potassium bromine are sequentially equimolar, and ethylenediaminetetraacetic acid ferric ammonium dihydrate or 1,3-propanediaminetetraacetic acid ferric ammonium monohydrate, ammonium hydrogencarbonate and bromide are added. Instead of ammonium, the ratio of ammonium ion to all cations in the tablet was adjusted as shown in Table 2 to prepare a tablet.

Prepare 1000 ml of water in a beaker and
The temperature was adjusted to 5 ° C. While stirring with a magnetic stirrer, 5 tablets of each of the tablet samples obtained by the above-mentioned operation were charged and the solubility thereof was evaluated. In addition, 2 tablets for each
Each piece was released and stored at 30 ° C. and 50% humidity for 2 weeks. The appearance after storage was visually observed. The evaluation criteria are the same as in Example 1.

[0120]

[Table 2]

From Table 2, the ratio of ammonium ion is 5
It can be seen that when the content is 0 mol% or less, the solubility is particularly excellent. Further, it is understood that this effect is more remarkable than when the ratio of ammonium ions is 20 mol% or less, and the storage stability is particularly good.

Example 3 (Sample 3-1) 120 g of ferric potassium ferric potassium monohydrate [A-III-36] 1,3-propanediaminetetraacetic acid [A-III-36], 66 g of potassium maleate (II-11), and 40 g of potassium bromide.
g is pulverized and granulated in the same manner as in the operation (1) of Example 1. The amount of water sprayed is 3.0 ml, and after granulation, it is dried at 65 ° C. for 7 minutes.

(Sample 3-2) 1,3-Propanediaminetetraacetic acid Ferric potassium potassium monohydrate [A-III-36] 12
0 g, maleic acid (II-5) 40 g, potassium bromide 4
After mixing 0 g and 50 g of potassium carbonate, the mixture is pulverized and granulated in the same manner as in the operation (1) of Example 1. The amount of water sprayed is 3.0 m
After granulating, it is dried at 65 ° C. for 7 minutes.

(Sample 3-3) 1,3-Propanediaminetetraacetic acid Ferric potassium monohydrate [A-III-36] 12
0 g and 40 g of maleic acid (II-5) are pulverized and granulated in the same manner as in the operation (1) of Example 1. The amount of water sprayed is 2.5 m
After granulating, it is dried at 65 ° C. for 7 minutes. Separately, 40 g of potassium bromide and 50 g of potassium carbonate are similarly pulverized and granulated. The amount of water sprayed is 0.5 ml, and after granulation, it is dried at 65 ° C. for 5 minutes.

The granulated product granulated by the above operation was used in Example 1 respectively.
The mixture was tableted uniformly by the method described in the operation (3) to prepare 50 color negative bleaching supplement tablets.

Prepare 1000 ml of water in a beaker and
The temperature was adjusted to 5 ° C. While stirring with a magnetic stirrer, 5 tablets of each of the tablet samples obtained by the above-mentioned operation were charged and the solubility thereof was evaluated. The results are shown in Table 3. The evaluation criteria are the same as in Example 1.

[0127]

[Table 3] From Table 3, it can be seen that the solubility of the tablet is improved by adding the carbonate. Further, it can be seen that the solubility is further improved by separately granulating the organic acids represented by the general formulas (II) and (III) and the carbonate and then mixing them. Example 4 A processed tablet for color negative film was prepared according to the following procedure. 1) Color development replenishing tablet operation for color negative (1) CD-4 [4-amino-3-methyl-N-ethyl-β- (hydroxy) ethylaniline sulfate] 60 g of developing agent
Is pulverized in an air jet fine pulverizer until the average particle size becomes 10 μm. After granulating the fine powder in a commercial fluidized bed spray granulator for about 7 minutes at room temperature with 5.0 ml of water, the granulate is dried at 63 ° C. for 8 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove water.

Operation (2) 60 g of hydroxylamine sulfate is pulverized in the same manner as in the operation (1), and the amount of water sprayed is adjusted to 2.6 ml for granulation. After the granulation, the granulated product is dried at 65 ° C for 7 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove water.

Operation (3) 58 g of disodium 1-hydroxyethane-1,1-diphosphonate, 70 g of sodium sulfite, 6 potassium carbonate
18 g, sodium hydrogen carbonate 30 g, sodium bromide 6
g and 40 g of diethylenetriamine pentaacetic acid are pulverized in the same manner as in the operation (1) and then uniformly mixed with a commercially available mixer. Next, in the same manner as in the operation (1), the amount of water sprayed is set to 200 ml and granulation is performed. After granulation, the granulate is dried at 65 ° C for 15 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove water.

Operation (4) The granulated product prepared in the above operations (1) to (3) was subjected to 4 hours at 25 ° C.
Uniformly mix for 10 minutes using a mixer in a room whose humidity is adjusted to 0% RH or less. Next, the mixture was compressed into tablets using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho, with the filling amount per tablet being 5.0 g,
Individual color negative replenishing tablets for color development were prepared. 2) Bleaching Replenishing Tablet for Color Negative Operation (5) 237 g of 1,3-propanediaminetetraacetic acid ferric potassium monohydrate [A-III-36], general formula (I) shown in Table 4
The organic acid represented by I) and (III) and 10 g of 1,3-propanediaminetetraacetic acid are pulverized and granulated in the same manner as in the operation (1). The amount of water sprayed is 5.0 ml, and after granulation, the granulated product is dried at 60 ° C. for 7 minutes. Then granulate in vacuum
Dry at 2 ° C. for 2 hours to remove water almost completely.

Operation (6) Operation (1) with 60 g of potassium bromide and 60 g of potassium carbonate
Grind and granulate in the same manner as in. The amount of water sprayed is 1.0 ml, and after granulation, the granulated product is dried at 70 ° C. for 3 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 120 minutes to almost completely remove water. The amount of potassium carbonate was increased or decreased according to the organic acid added in the operation (5) so that the pH of the prepared tablet was constant when dissolved in water.

Operation (7) The granules prepared in the above operations (5) and (6) were heated at 25 ° C. for 4 hours.
Uniformly mix for 10 minutes using a mixer in a room whose humidity is adjusted to 0% RH or less. Next, the mixture was compressed into tablets with a tableting machine modified from Tough Press Collect CO., LTD. 3) Fixing replenishing tablet operation for color negative (8) Potassium thiosulfate 950 g, sodium thiocyanate 2
020g, sodium sulfite 120g, potassium carbonate 1
50 g, ethylenediamine tetraacetic acid disodium salt 10 g
Is pulverized and granulated in the same manner as in the operation (1). The amount of water spray is 3
After granulating to 0.0 ml, it is dried at 65 ° C. for 60 minutes.
Next, the granulated product is dried in vacuum at 40 ° C. for 480 minutes to almost completely remove water.

Operation (9) The granulated product prepared in the above operation (8) was subjected to 40% RH at 25 ° C.
Mix evenly for 10 minutes using a mixer in a conditioned room. 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 13.0 g, and 200 fixing fixing tablets for color negatives were prepared. 4) Stable replenishing tablet for color negative (10) M-hydroxybenzaldehyde (200 g), Emulgen 985 (10 g) and potassium carbonate (45 g) are pulverized and granulated in the same manner as in the operation (1). The amount of water sprayed is 3.0 ml, and after granulation, the granulated product is dried in vacuum at 30 ° C. for 8 hours to almost completely remove water.

Operation (11) The granulated product prepared in the above operation (10) was subjected to 40% R at 25 ° C.
Mix evenly for 10 minutes using a mixer in a room whose humidity is controlled to H or less. Next, the mixture was compressed into tablets using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho, with the filling amount per tablet being 0.2 g, to prepare 1060 stable supplement tablets for color negative.

By repeating the above operation, the number of each processing tablet required for the following running experiments was prepared.

Next, a method of processing a light-sensitive material using an automatic developing machine in the present invention will be described. The Konica Color Negative Film Processor CL-KP-50QA was provided with the following tablet supply function, liquid level detection function, and water supply function by modification.

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

When the color negative film is carried in from the photosensitive material inserting portion 13 and passes through the photosensitive material area detecting sensor 7 and a certain amount of area is detected, the solid photographic processing agent replenishing device 8, the replenishing water tank 10 and the replenishing water supply are supplied. The means 12 operates in response to a signal from the control unit 11, and the solid photographic processing agent and the liquid make-up for preparing the liquid are supplied to the respective processing tanks 1, 2, 3, 5 in the 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 5 evaporates, and when the temperature becomes lower than a certain level, the liquid level detection sensor 9 operates and the control unit Replenishment water is replenished until the replenishment tank 10 and the replenishment water supply means 12 are operated in response to the signal of 11, and the upper limit detection mechanism of the liquid level detection sensor 9 operates. In addition, it is preferable that the wash warm water 14 that is the makeup water supplied by the makeup water supplement pipe 15 is temperature-controlled for both the liquid preparation makeup water and the evaporation correction makeup water. In addition, each processing tank 1 to 5, 1 is a color developing tank, 2 is a bleaching tank,
3 is a fixing tank, 4 is a washing tank, and 5 is a stabilizing tank.
Further, 6 is a drying section.

FIG. 2 is a schematic explanatory view showing an example of the solid photographic processing agent replenishing device 8 in the case where a solid photographic processing agent solidified into a tablet is used.

In response to the signal from the photosensitive material area detection sensor 7, the control unit 11 operates to activate the solid / solid photographic processing agent replenishment cam 2
When 2 is operated, the solid solid photographic processing agent pushing claw 23 is stored in the cartridge 25 and is in the solid state solid photographic processing agent 24.
1 to several are replenished inside the filtering device 21 in the sub-tank 20 which is the solid photographic processing agent dissolving part of each processing tank 1, 2, 3 and 5.

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

The whole or most of the circulating flow of the processing liquid 17 which circulates between the main processing tank 16 and the sub tank 20 by the circulation pump 18 is used for the filtering device 21 in the sub tank 20.
If it is configured to directly pass through the solid photographic processing agent 24
The solubility of is increased.

In the figure, 19 is a temperature control heater, 26
Is a push 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 and the sub tank 20 of each processing tank 1, 2, 3, 5 and 28 is an overflow port. Is.

In addition, the processing tank 1 to
When the treatment liquid 17 of 5 causes the liquid level to drop due to evaporation, the liquid level detection sensor 9 detects the lowered liquid level, transmits a signal to the control unit 11, and activates the replenishment water supply means 12.
Add evaporation correction make-up water to the normal liquid level.
When the liquid reaches 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 supplementary water supply means 12. The table below shows the standard processing conditions for the automatic processing machine.

[0146]

[Outer 1] The fixer is replenished in the second tank, the overflow liquid flows into the first tank, the stabilizer is replenished in the third tank, and the overflow liquid sequentially flows into the second tank and the first tank in a cascade system.

The processing liquid for the automatic processing machine was prepared by the following method. Color developing tank liquid (21.0 liters) 15 liters of warm water at 35 ° C. was placed in the automatic developing machine color developing tank, and 399 color developing film replenishing tablets for color negative film were added and dissolved. Next, a starter having the following formulation, which was separately tabletted as a starter component, was used.
After individually pouring and completely dissolving, warm water was added up to the tank mark to complete the tank solution.

Color negative color development starter Sodium bromide 0.8 g Sodium iodide 2.0 mg Sodium hydrogen carbonate 3.0 g Potassium carbonate 0.5 g

Bleaching solution (5.0 liters) 3.0 liters of warm water at 35 ° C. was placed in the bleaching tank of the developing machine, and 3 bleaching replenishing tablets for color negative film were prepared.
50 pieces were charged and dissolved. Next, 10 starters of the following formulation, which had been tabletted separately, were added as starter components and completely dissolved, and then warm water was added up to the tank mark to complete the tank solution.

Bleach Starter for Color Negative Potassium Bromide 10 g Sodium Bicarbonate 1.5 g Potassium Carbonate 3.5 g

Fixing solution (4.5 liters for the first tank, 4.5 liters for the second tank) Fixing tank for color negative film prepared by adding 3.0 liters of warm water at 35 ° C. to the first tank and the second tank, respectively. 112 supplement tablets were added and dissolved. Next, warm water was added up to the tank mark to complete the tank solution.

Stabilizer (3.2 liters for 1 to 3 tanks) Develop machine stabilizing tanks 35 ° C. for 1st tank, 2nd tank and 3rd tank, respectively
40 liters each of the prepared stable negative replenishing tablets for color negative film were added and dissolved.
Next, warm water was added up to the marked line to complete the tank solution.

It should be noted that 1 liter of the same composition as the color developing solution was provided in the overflow liquid storage tank, and when 1 liter or more of overflow liquid was collected, it overflowed from the storage tank side and was introduced into the waste liquid recovery tank. .

During the temperature control of the automatic developing machine, 20 tablets for each supplemental tablet prepared by the above-mentioned operation were set in the supplemental tablet supplying device provided to the automatic machine. This refill tablet is 135 size 24
When two pieces of film are processed, they are put into the overflow storage tank one by one, and at the same time, supplemental hot water is supplied from the hot water supply device to the color developing tank at 40 ml, the bleaching tank at 10 ml, and the fixing tank at 40 ml in the stabilizing tank. It was set so that 80 ml was supplied.

Color negative film DD-100 (manufactured by Konica Corporation) was used as a photosensitive material for testing.

The light-sensitive material sample was subjected to wedge exposure according to a conventional method and then subjected to running processing according to the above-mentioned processing steps.
However, the running treatment was continuously carried out until the double amount of the bleaching tank layer was replenished (2R).

For each photographic light-sensitive material after processing, the fluorescence X
The amount of residual silver in the highest color density portion was measured by line analysis.
In addition, the processed sample was subjected to concentration measurement to obtain blue light (Blue
e) and the Dmin value of green light (Green) were read. Further, the treated sample was cut in half and one was re-treated with the following treatment liquid formulation. Treatment liquid temperature is 35 ℃
And soaked for 6 minutes and 30 seconds. (Reprocessing liquid) Ethylenediaminetetraacetic acid ferric ammonium monohydrate 100 g Water was added to make 1.0 liter, and the pH was adjusted to 6.0 with ammonia water.

Dmax red light (Re
d) was measured, and the difference from the Dmax density before reprocessing was defined as the color restoration failure (ΔDmax). Color recovery failure (ΔDmax) = (Dmax before reprocessing) −
(Dmax after reprocessing) The above results are shown in Table 4.

[0159]

[Table 4] From Table 4, it can be seen that the processing method using the bleaching agent of the present invention shows a small bleaching fog and shows a good bleaching performance.

EXAMPLE 5 1,3-Propanediaminotetraacetic acid potassium ferric acid [A-III-36], which is the main bleaching agent in Example 4, was added to [AI-
2], [A-II-1], and [A-II-3] were replaced by the same running experiment, and the amount of residual silver increased by about 20 to 30% and good processing performance was exhibited.

[A-IV-8], [A-V-1]
3] and [A-VI-4] were used, the residual silver amount and the color reversion property were slightly deteriorated, but the processability was almost good.

Example 6 Using the same photographic light-sensitive material as in Example 4, the processing conditions were changed as follows, and the same running experiment was conducted.

[0163]

[Outside 2] The bleaching agent was replenished in the bleaching tank, and the fixing agent was replenished in the fixing tank, and the overflow solution of both tanks flowed into the bleaching and fixing tank. In addition, the stabilizer is replenished in the third tank, and the overflow solution is successively flown into the second tank and the first tank in a cascade system.

Experimental level no. 4-5, 4-
When the same evaluation was performed on Nos. 8 and 4-9, good results were obtained in the same manner as in Table 4.

Example 7 Colored paper-treated tablets were prepared according to the following procedure.

1) Color development replenishing tablet for color paper Operation (A) Color developing agent CD-3 [4-amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] Aniline sulphate] 100 g is ground in an air jet mill to an average particle size of 10 mμ. This fine powder in a commercial fluidized bed spray granulator at room temperature for about 5 minutes,
After granulating by spraying with 4.5 ml water, the granulate is dried at 65 ° C. for 8 minutes. Then granulate 4 in vacuum
The granulated product is dried at 0 ° C. for 2 hours to almost completely remove water.

Operation (B) In the same manner as in the operation (A), 185 g of diethylhydroxylamine oxalate is pulverized and granulated. The amount of water sprayed is 3.0
After granulation, the mixture is dried 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, 500 g of potassium carbonate, 0.3 g of potassium bromide, 25 g of diethylenetriamine-5-acetic acid.
g, 100 g of sodium p-toluenesulfonate and 200 g of potassium hydroxide are pulverized in the same manner as in the operation (A), and then uniformly mixed with a commercially available mixer. Then, in the same manner as in the operation (A), the amount of water sprayed is set to 200 ml and granulation is performed. After granulation, the granulate is dried at 65 ° 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 granulated product prepared in the above operations (A) to (C) was mixed with a mixer in a room where the humidity was adjusted to 40% RH or less at 25 ° C.
Mix evenly for a minute. Then, the mixture was mixed with a tabletting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho,
Compressing tableting was performed with the filling amount per tablet being 5.86 g to prepare 150 color development replenishing tablets for color paper.

2) Tablet for stable replenishment for color paper (H) Potassium carbonate 10 g, 1-hydroxyethane-1,1-
200 g of sodium diphosphonate, similar to the operation (A),
Pulverize and granulate. The amount of water sprayed is 1.0 ml, and after granulation, it is dried at 70 ° C. for 3 minutes. Then granulate 4 in vacuum
The granulated product is dried at 0 ° C. for 2 hours to almost completely remove water.

Operation (I) Chinopearl SFP 150 g, sodium sulfite 300
g, zinc sulfate heptahydrate 20 g, ethylenediamine tetraacetic acid 1
50 g are pulverized and granulated in the same manner as in the operation (A). The amount of water sprayed is 10.0 ml, and after granulation, 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 mixed at 25 ° C. in a room whose humidity was adjusted to 40% RH or less by using a mixer.
Mix evenly for a minute. Then, the mixture was mixed with a tabletting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho,
The tablet was compressed into tablets with a filling amount of 0.66 g per tablet to prepare 1000 stable supplement tablets for color paper.

Next, a tablet supply function, a liquid level detection function, a hot water supply function and the like were remodeled and provided in the Konica Color Paper type QA processor CL-PP-718, and the following treatment experiment was conducted. The table below shows the standard processing conditions for the automatic processing machine.

[0174]

[Outside 3] The stabilizer is replenished in the second tank, and the overflow solution is sequentially flown into the tank and the fixing layer in a cascade system.

The processing liquid for the automatic processing machine was prepared by the following method. Color developing tank solution (23.0 l) 18 l of 35 ° C. warm water was placed in the developing machine color developing tank, and 314 prepared color developing replenishing tablets for color paper were added and dissolved. Next, 23 starters of the following formulation, which were separately tabletted as starter components, were added, and after dissolution, warm water was added up to the tank mark to complete the tank solution.

Color developing starter for color paper Potassium chloride 4.0 g Potassium hydrogen carbonate 4.8 g Potassium carbonate 2.1 g

Bleaching solution (15.0 liters) 10.0 liters of warm water at 35 ° C. was placed in a bleaching tank for an automatic developing machine, and 700 bleaching replenishing tablets for color negative film prepared in Example 4 were charged and dissolved. Next, 20 tablets of the bleaching starter prepared in Example 4 were added and completely dissolved,
Hot water was added up to the tank mark to complete the tank solution.

Fixing Solution (15.0 L) 10.0 L of warm water at 35 ° C. was placed in a fixing tank of a developing machine, and 120 fixing replenishing tablets for color negative film prepared in Example 4 were charged and dissolved. Next, warm water was added up to the tank mark to complete the tank solution.

Stabilizer (1.5 liters for both 1st and 2nd tanks) 1st tank of automatic processing machine 1st tank
Each 2.0 liters were put in, and 60 tablets for stable replenishment for color paper were put and dissolved in each. Next, warm water was added up to the marked line to complete the tank solution.

Next, each of the replenishing tablets was set in the replenishing tablet feeding device provided on the automatic developing machine, 20 pieces each. This replenishing tablet is added one by one when color paper is processed for 3200 cm ² , and at the same time, replenishing hot water from the hot water supply device is 40 ml in the color developing tank, 10 ml in the bleaching tank, and 40 ml in the fixing tank in the stabilizing tank. It was set so that 80 ml was supplied.

The color paper prepared by the method described in the Japanese Patent Application No. 3-47516, was subjected to wedge exposure according to a conventional method and then subjected to running treatment according to the above-mentioned treatment steps. However, the running treatment was continuously carried out until the double amount of the bleaching tank layer was replenished (2R).

About each photographic light-sensitive material after processing Example 4
The residual silver amount, color recoloring property, and bleaching fog were evaluated by the same method as described in (1). The results are shown in Table 7.

[0183]

[Table 7] From Table 7, it can be seen that the processing method using the bleaching agent of the present invention shows less bleaching fog and exhibits good bleaching performance.

[0184]

According to the present invention, the first object is to provide a solid bleaching agent having excellent solubility and storability, and secondly.
To provide a solid bleaching agent having excellent bleaching performance. Third is the provision of processing technology suitable for global environment conservation. Fourthly, it is possible to provide processing technology suitable for occupational safety and health.

[Brief description of drawings]

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

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

[Explanation of symbols]

 1 Color developing tank 2 Bleaching tank 3 Fixing tank 4 Washing tank 5 Stabilizing tank 5 Drying section 7 Drying area 7 Photosensitive material area detection sensor 8 Solid photoprocessing agent replenishing device 9 Liquid level detection sensor 10 Replenishing water tank 11 Control section 12 Replenishing water supply apparatus 13 Photosensitive Material insertion part 14 Washing warm water 15 Water supply pipe 16 Processing tank 17 Processing liquid 18 Circulation pump 19 Temperature control heater 20 Sub-tank 21 Filtration filter 22 Cam 23 Solid photo processing agent pushing claw 24 Solid replenishing agent 25 Cartridge 26 Solid replenishing agent pushing spring 28 Overflow mouth

Claims (6)

[Claims] 1. The following general formulas [AI], [A-II],
[A-III], [A-IV], [AV] or [A
-VI] containing at least one ferric complex salt of the compound represented by the formula [VI] and at least one compound represented by the following general formula (II) or (III). Solid bleaching agent for photographic light-sensitive materials. ## STR00001 ## General formula [A-I] [In the formula, A _{1 to} A ₄ may be the same or different and each represents a hydrogen atom, a hydroxy group, —COOM, —PO
_{3 represents} (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 , or —CH ₂ CO.
OM ₂ . M, M ₁ and M ₂ each represent a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. Embedded image General formula [A-II] _Wherein, A 11 _{to A 14} may each be the same or _different, -CH 2 _OH, -COOM ₃ or _-PO 3 _(M 4)
Represents ₂ . M ₃ and M ₄ each represent a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. X
Is an alkylene group having 2 to 6 carbon atoms or-(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. ## STR00003 ## General Formula [A-III] [In the formula, A _{21 to} A ₂₄ may be the same or different and each is —CH ₂ OH, —COOM ₅ or —PO ₃ (M ₆ ).
Represents ₂ . 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 represents an integer of 1 to 8, and B ₁₁ and B ₁₂ may be the same or different,
It 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. ] [Formula 4] General formula [A-IV] [In the formula, R ₁ and R ₂ each represent a hydrogen atom, or an optionally substituted alkyl group or aryl group. L is , 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. ] General formula [A-V] [In the formula, each of R _{1 to} R ₃ represents a hydrogen atom, an optionally substituted alkyl group or an aryl group. L is a general formula [A
-IV] is synonymous with L. W represents a divalent linking group. ] [Formula 7] General formula [A-VI] [Wherein, 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,
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, or an alkyl group which may be substituted. Alternatively, it represents 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 are 0 or 1 respectively
Represents 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. ] 2. The solid bleaching agent for silver halide color photographic light-sensitive materials according to claim 1, wherein the solid bleaching agent is a tablet consisting of one part. 3. The solid bleaching treatment for a silver halide color photographic light-sensitive material according to claim 1 or 2, wherein the ratio of ammonium ions to all cations in the solid bleaching agent is 50 mol% or less. Agent. 4. A solid bleaching agent for a silver halide color photographic light-sensitive material according to claim 3, wherein the ratio of ammonium ions to all cations in said solid bleaching agent is 20 mol% or less. . 5. The solid bleaching agent for silver halide color photographic light-sensitive materials according to claim 1, 2, 3 or 4, wherein the solid bleaching agent contains a carbonate. 6. A silver halide color characterized by using the solid bleaching agent according to any one of claims 1 to 5 in bleaching after color development of a silver halide color photographic light-sensitive material.
Processing method for photographic light-sensitive material.