JP3026132B2 - Solid stabilizing agent for silver halide photographic light-sensitive material and processing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid stabilizing agent for a silver halide photographic light-sensitive material, and more particularly, to a halogenated material having improved social environment suitability, work environment suitability, and practical use due to simple operation. The present invention relates to a solid processing agent for a silver photographic light-sensitive material.

[0002]

BACKGROUND OF THE INVENTION Silver halide photographic materials are usually black-and-white developers, fixers, color developers, bleachers, bleach-fixers,
Development processing is performed using a processing liquid such as a stabilizing liquid, and an image-wise image is obtained. Each processing solution used here is put in a plastic bottle in the form of one or a plurality of concentrated liquid parts for ease of use, and is supplied to the user as a processing agent kit. Users dissolve these treating agent kits in water to prepare and use working solutions (starting solutions or replenishing solutions).

[0003] In recent years, in the photographic processing industry, the number of small-scale developing laboratories using a small automatic developing machine called a minilab has been rapidly increasing, and with the progress of minilabs, the amount of plastic bottles for processing agents has been increasing year by year. It is increasing rapidly.

[0004] Because of its light and strong properties, this plastic has been widely used in addition to photographic processing agent bottles. The worldwide production of plastics is steadily increasing year by year, to over 100 million tons per year in 1988. On the other hand, the amount of plastic that is discarded is enormous, and even in Japan, about 40% of the production is discarded every year. When such waste plastic is dumped into the ocean, it causes deterioration of the habitat of marine organisms. In Europe, the waste plastic is burned in incinerators with inadequate exhaust gas treatment facilities. The problem has been caused, and it has become a big problem.

[0005] For this reason, urgent countermeasures are urgently required. In Europe and the United States, legislative movements such as prohibition of plastic recycling and use or mandatory use of degradable plastics are becoming active. It is a fact.

[0006] Under such circumstances, it is extremely undesirable to use a large amount of plastic bottles as a processing agent for photographic use, albeit partially.

In recent years, the need for rapid processing has been increasing, and photographic processing has been changed from minilabs to microlabs (small minilabs).
Is shifting to. Along with this, in the conventional lab, workers handling the processing solution etc. had knowledge of the processing agent, but when brought into a convenience store or drug store, for example, ordinary people, part-time workers etc. will work . Therefore, when preparing the treatment liquid, the liquid may splatter during preparation, get into the eyes, adhere to the face, and immediately wash with water. Or erroneous dissolution at the time of liquid preparation may cause the photographic light-sensitive material to become useless.

[0008] In the case of a photographic light-sensitive material, redo can be performed with paper, but redo cannot be performed with negative, which is a very serious problem.

As a countermeasure for such a problem, it is conceivable to make a concentrated solution of a photographic processing agent into a powder, but in this case, there is a high possibility that the fine powder will soar during melting and be inhaled by an operator, thereby increasing the health. There is a problem that the influence of the above is a concern, or the sowing of the processing agent component is mixed into another photographic processing solution, thereby causing a problem of contamination and trouble. For this reason, a technique of granulating a photographic processing agent to form a granular mixture is disclosed in, for example, JP-A-2-109042.
No. 2-09043, U.S. Pat.No. 2,843,484 and JP-A-3-3
It is proposed in 9735 and others.

By granulating the photographic processing agent and supplying it as a granular mixture, not only the generation of dust is prevented and the safety of workers is ensured, but also the processing liquid in the replenishment tank is oxidized and precipitated. Therefore, a good replenisher can always be supplied.

As a preferred form of the treatment agent that takes advantage of the dry state, tableting is proposed in JP-A-51-61837 and the like, but there is no disclosure of a stabilizer.

One of the reasons why a solid processing agent for a stabilizer cannot be realized is that the nonionic surfactant used in the stabilizer is a material (low melting point and liquid in shape) that is difficult to apply as granules and tablets. It is in the point. The required performance is incompatible with granule and tablet suitability. Nevertheless, considering the image storability of photographic light-sensitive materials, backside staining, uneven processing, etc., it is essential to use a surfactant in the stabilizing solution. The development of a surfactant with a certain property was desired.

[0013] By solidifying the stabilizing solution (surfactant), all processing agents are solidified, and complete bottle-free and maintenance-free are established from environmental suitability, storage stability and safety.

Conventionally, a nonionic surfactant has been used as the surfactant in the stabilizing solution. This is because, in terms of performance, the balance between hydrophilicity and hydrophobicity and the liquid preservability are good. However, most of these surfactants are liquid, and solid compounds have a low melting point, and thus have the disadvantage that the required performance is deteriorated. For these reasons, there has been an urgent need to develop a material that is solid for granules and tablets and that reduces the interfacial tension sufficient for performance.

[0015]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a solid stabilizer for a silver halide photographic material having the following features.

The use of packaging materials (especially plastic bottles) is reduced, and it is suitable for social environments.

Since the processing agent is solidified, the weight is reduced, the transportation cost is reduced, and the storage space in a developing station or the like can be reduced.

The storage stability is improved, and there is no generation of stain during development and no scratching of the photosensitive material after processing.

There is no scattering of the fine powder of the photographic processing agent, and the work environment is suitable.

The solubility of the solid stabilizing agent is improved.

[0021]

The above objects of the present invention are attained by a solid stabilizing agent for a silver halide photographic light-sensitive material, characterized by containing at least one anionic surfactant, and a processing method using the stabilizing agent. Is done.

The following items are preferred as embodiments of the present invention.

The anionic surfactant is selected from the group represented by the general formulas (1) to (4). The solid stabilizing agent contains a chelating agent. The solid stabilizing agent is a granule. The particle size of the processing agent is 100 to 800 μm, and the particle size distribution is that at least 60% of the granulated particles are ± 100 to 150 μm. The solid stabilizing agent is a tablet. 2.1 g / cm ³ Tablet-type solid stabilizing agent is a stabilizer Hereinafter, the present invention will be specifically described.

First, the compounds represented by the general formulas (Chemical Formulas 1 to 4) will be described.

[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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Of the compounds represented by the above general formulas, particularly preferred compounds are (1-2), (1-7), (1-9),
Among the compounds represented by (1-10), (1-12) and (1-16), the most preferred compounds are sodium lauroyl sarcosinate, sodium lauryl sulfate, sodium lauroylmethyltaurine, α-olefin sulfonic acid Sodium. The above compounds can be purchased from Kao Corporation, Kawaken Fine Chemicals Co., Ltd., Asahi Denka Kogyo Co., Ltd., Nippon Oil & Fats Co., Ltd., and Nikko Chemicals Co., Ltd.

The chelating agent according to the present invention is not particularly limited, but preferably has a chelating stability constant of at least 6.0 with respect to Ca ²⁺ and is formed by bonding an anionic surfactant and calcium. In order to prevent the occurrence of precipitation, there are other synergistic effects such as generation of stain and scratching of the photosensitive material. Specifically, ethylenediaminetetraacetic acid and salts, diethylenetriaminepentaacetic acid and salts thereof, cyclohexanediamine Tetraacetic acid and its salts, glycol ether diamine tetraacetic acid and its salts, nitrotriacetic acid and its salts, diaminopropane and its salts,
Triethylenetetramine hexaacetic acid and its salts, ethylenediaminetetramethylenephosphonic acid and its salts, 1-hydroxyethylidene-1,1-diphosphonic acid and its salts, and the like.

Next, the formalin substitute compound contained in the solid stabilizing agent used in the present invention will be described. Specifically, it is a compound represented by the following general formula [F].

[0035]

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In the formula, Z represents an atom group necessary for forming a carbocyclic or heterocyclic ring, X represents an aldehyde group,

[0037]

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(R ₁ and R ₂ each represent a lower alkyl group), and n represents an integer of 1-4.

In the general formula [F], Z represents a group of atoms necessary to form a substituted or unsubstituted carbocycle or a substituted or unsubstituted heterocyclic ring. May be a condensed ring, and preferably Z is an aromatic carbocyclic or heterocyclic ring having a substituent. When the substituent of Z is an aldehyde group, a hydroxyl group, an alkyl group (eg, methyl, ethyl, methoxyethyl, benzyl, carboxymethyl, sulfopropyl, etc.), an aralkyl group, an alkoxy group (eg, methoxy, ethoxy, methoxyethoxy, etc.) , A halogen atom, a nitro group, a sulfo group, a carboxy group, an amino group (eg, N, N-dimethylamino, N-ethylamino, N-phenylamino, etc.), a hydroxyalkyl group, an aryl group (eg, phenyl, p- Methoxyphenyl, etc.), cyano group, aryloxy group (eg, phenoxy, p-carboxyphenyl, etc.), acyloxy group, acylamino group, sulfonamide group, sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dimethyl) A carbamoyl group (eg, sulfamoyl)
It is preferably a carbamoyl, N-methylcarbamoyl, N, N-tetramethylenecarbamoyl or the like or a sulfonyl group (for example, methanesulfonyl, ethanesulfonyl, benzenesulfonyl, p-toluenesulfonyl, etc.).

The carbon ring represented by Z is preferably a benzene ring, and the heterocyclic ring represented by Z is preferably 5
Or a 6-membered heterocyclic ring. Examples of the 5-membered ring include thiophene, pyrrole, furan, thiazole, imidazole, pyrazole, succinimide, triazole, and tetrazole.
Pyrimidine, triazine, thiadiazine and the like are each mentioned.

Examples of the condensed ring include naphthalene, benzofuran, indole, thionaphthalene, benzimidazole, benzotriazole, quinoline and the like.

Preferred examples of the compound represented by the formula [F] are shown below.

[0043]

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The exemplified compounds (F-1) to (F-52) are obtained by inserting various substituents into 1 to 6 in the above formula as shown in the following table.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

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[0049]

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Other specific examples of the compound include the compound (76) described on pages 13 to 14 of Japanese Patent Application No. 3-89686.
To (90).

Among the specific examples of the compound represented by the general formula [F], more preferable compounds are (F-2)
(F-3), (F-4), (F-6), (F-23), (F-24),
(F-52) and (F-61), and most preferably.
(F-3).

The compound represented by the general formula [F] can be easily obtained as a commercial product.

The compound represented by the formula [F] is contained in a stabilizer for a silver halide color photographic light-sensitive material. Note that, within a range that does not impair the effects of the present invention, a processing solution used in a pre-bath of a processing bath having bleaching ability together with a stabilizing solution,
It can be contained in a processing solution having a bleaching ability, a processing solution having a fixing ability, and the like.

The addition amount of the compound represented by the formula [F] is preferably 0.05 to 20 g, more preferably 0.1 to 15 g, particularly preferably 0.5 to 10 g per liter of the stabilizing solution.

The compound represented by the general formula [F] is characterized in that it has better image storability, especially under low humidity conditions, than known formaldehyde substitute compounds.

The replenishment amount of the stabilizing solution is 6 per m ² of the photosensitive material.
It is 70 ml or less, preferably 100 ml or more and 500 ml or less, and particularly preferably 160 ml to 460 ml. When the replenishment amount of the stabilizing solution exceeds 670 ml, the amount of waste liquid increases,
It is not preferable in terms of social environment and economy, and the effect of the present invention is not remarkable. The effect of the present invention becomes more remarkable as the amount of replenishment is reduced up to 100 ml / m ² .

In the present invention, the replenishment amount means a substantial replenishment amount, and when regenerating, the replenishment amount of the regenerant is the replenishment amount.

In the present invention, the pH of the stabilizing solution is 6.0 or more, preferably 7.0 or more, more preferably 7.5 to 9.0. The pH adjusting agent that can be contained in the stabilizing solution may be any of commonly known alkali agents and acid agents.

In the present invention, the stabilizing solution preferably contains a chelating agent having a chelate stability constant for iron ions of 8 or more. Here, the chelate stability constant is
"Stability Constants" by LGSillen and AEMartell
of Metal-ion Complexes ”, The Chemical Sociery, Lo
ndon (1964), by S. Chaberek.AEMartell, "OrganicSeq
uestering Agents ", a constant generally known by Willey (1959) and the like.

The chelate stability constant for iron ions is 8
Examples of the chelating agent include an organic carboxylic acid chelating agent, an organic phosphoric acid chelating agent, an inorganic phosphoric acid chelating agent,
And polyhydroxy compounds. Here, the above iron ion means ferric ion (Fe ³⁺ ).

The chelate stability constant with ferric ion is 8
Specific examples of the chelating agent described above include the following compounds, but are not limited thereto. That is, ethylenediamine diorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, Diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid , 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,
5-diphosphonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, sodium hexametaphosphate, and particularly preferably diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and the like. Yes, especially 1
-Hydroxyethylidene-1,1-diphosphonic acid is most preferably used.

The amount of the chelating agent used is per 1 liter of the stabilizing solution.
Good results are obtained in the range of preferably 0.01 to 50 g, more preferably 0.05 to 20 g.

Preferred compounds to be added to the stabilizing solution include ammonium compounds. These are supplied by ammonium salts of various inorganic compounds,
Specific examples include ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, and ammonium phosphate. These may be used alone or in combination of two or more.
The amount of the ammonium compound added is 0.001 per liter of the stabilizing solution.
The range is preferably from 1.0 to 1.0 mol, more preferably from 0.002 to 2.
It is in the range of 0 mol.

Further, it is preferable that the stabilizing solution contains a sulfite. The sulfite may be any organic or inorganic substance as long as it releases sulfite ions, but is preferably an inorganic salt. Preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite,
Potassium metabisulfite, ammonium metabisulfite and hydrosulfite.

The above sulfite is contained in the stabilizing solution at least 1 ×.
It is preferable to add an amount so as to be 10 ⁻³ mol / l, more preferably an amount such that it becomes 5 × 10 ⁻³ to 10 ⁻¹ mol / l. It has a preventive effect. As an addition method, it may be directly added to the stabilizing solution, but is preferably added to the stable replenishing solution.

The stabilizer preferably contains a metal salt in combination with the chelating agent. Such metal salts include B
a, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb, Sn, Zn, T
There are metal salts of i, Zr, Mg, Al or Sr, halides,
It can be supplied as an inorganic salt such as a hydroxide, a sulfate, a carbonate, a phosphate, an acetate or a water-soluble chelating agent. The amount used is preferably in the range of 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably in the range of 4 × 10 ^-4 to 2 × 10 ^-2 mol per liter of the stabilizing solution.

Stabilizing solutions include organic acid salts (citrate, acetate, succinate, oxalate, benzoate, etc.), pH adjusters (phosphate, borate, hydrochloric acid, sulfate, etc.). ) Etc. can be added. The amount of these compounds added depends on the pH of the stabilizing bath.
Any amount may be used in any combination which is necessary to maintain color stability and does not adversely affect the storage stability of the color photographic image and the occurrence of precipitation.

In the present invention, a known fungicide such as 5-chloro-2-methylisothiazolin-3-one or benzisothiazoline may be used in combination with the stabilizer of the present invention as long as the effects of the present invention are not impaired. Is preferred.

In the treatment of the present invention, silver may be recovered from the stabilizing solution. Further, the stabilizer is subjected to ion exchange treatment, electrodialysis treatment (see JP-A-61-28949) and reverse osmosis treatment (see JP-A-60-28949).
-241053, 62-254151 and JP-A-2-132440) are also preferable embodiments for carrying out the present invention. It is also preferable to use water which has been previously deionized from water used for the stabilizing solution. That is, the antifungal property of the stabilizer, the stability of the stabilizer, and the image storability are improved.

As a means for the deionization treatment, any means can be used as long as the Ca and Mg ions of the washing water after the treatment are reduced to 5 ppm or less. For example, the treatment with an ion exchange resin or a reverse osmosis membrane can be used alone or separately. It is preferable to use them in combination. Ion exchange resins and reverse osmosis membranes are described in detail in Published Technical Report No. 87-1984.

The salt concentration in the stabilizing solution is preferably 1000 ppm or less, more preferably 800 ppm or less, for achieving the effects of the present invention.

The presence of a soluble iron salt in the stabilizing solution is preferred for achieving the effects of the present invention.

The soluble iron salt should be at least 5 × 10 ^{-3 in the} stabilizing solution.
It is preferably used at a concentration of mol / l, more preferably in the range of 8 × 10 ^{−3 to} 150 × 10 ⁻³ mol / l, still more preferably 12 × 10 ^{−3 to} 100 × 10 ⁻³ mol / l. 1 range.

The treatment temperature for the stabilization treatment is 15 to 70 ° C.
And more preferably in the range of 20 to 55 ° C. The processing time is preferably 150 seconds or less, more preferably 3 to 120 seconds, and most preferably 6 to 90 seconds.

The stabilization tank is preferably composed of a plurality of tanks, preferably two to six tanks, particularly preferably two to three tanks, more preferably two tanks, and a counter current system ( It is preferable to supply to the post-bath and overflow from the pre-bath).

In the present invention, even if the opening area of the stabilization tank is widened, there is an effect that sulfuration hardly occurs. That is,
It was thought that if the opening area of the stabilizing tank was widened, sulfidation was likely to occur. However, according to the treatment of the present invention, even if the opening area was widened, sulfidation was hard to occur.

Although no water washing treatment is required after the stabilization treatment, rinsing the surface of the rinse with a small amount of water washing in an extremely short time can be optionally carried out as required.

Preferred processing steps in the processing method using the processing solution of the present invention include color development → bleach-fix → stable color development → bleach → fix → stable color development → bleach → bleach-fix → stable color development → bleach-fix → Fixing → stable color development → bleach-fix → bleach-fix → stable Color development → bleach → bleach-fix → fix → stable, but these steps are preferably and especially steps. That is, in the present invention, when a processing solution having a fixing ability is used, a bleach-fixing solution, a bleaching solution and a fixing solution, a bleaching solution and a bleach-fixing solution, a bleach-fixing solution and a fixing solution, a bleach-fixing solution, And various processing solutions such as a bleach-fixing solution or a combination thereof. In the present invention, a processing solution having a fixing ability is preferably a fixing solution.

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

[0080]

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The compound represented by formula (A) will be described below in detail.

A _{1 to} A ₄ may be the same or different and each represents —CH ₂ OH, —COOM or —PO ₃ M ₁ M ₂ ;
₁ and M ₂ each represent a hydrogen atom, an alkali metal atom (for example, a sodium atom or a potassium atom) or an ammonium group. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms (eg, trimethylene, tetramethylene, pentamethylene, etc.). Examples of the substituent of the alkylene group include a hydroxyl group and an alkyl group having 1 to 3 carbon atoms.

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

[0084]

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Other specific exemplified compounds include (A-2), (A-2) described on pages 89 to 90 of Japanese Patent Application No. 2-274026.
(A-3), (A-5) to (A-8), (A-10) to (A
-12).

As the ferric complex salts of the compounds (A-1) to (A-12), sodium, potassium or ammonium salts of these ferric complex salts can be arbitrarily used. From the viewpoint of the effect and solubility of the object of the present invention,
Ammonium salts of these ferric complex salts are preferably used.

Among the above compound examples, one particularly preferably used in the present invention is (A-1).

In another preferred embodiment of the present invention, the bleaching agent has a sufficiently high oxidizing power and the bleaching fog easily occurs in the case of an ammonium salt. Can be used in an amount of 20 mol% or less, particularly preferably 10 mol% or less.

The ferric organic acid complex salt is preferably added in an amount of 0.1 to 2.0 mol per liter of the bleaching solution, more preferably 0.15 to 1.5 mol / l.

The second kind of the organic acid represented by the general formula [A]
When using an iron complex salt and two or more ferric complex salts of other organic acids such as ethylenediaminetetraacetic acid,
The ferric complex salt of the compound represented by the general formula [A] preferably accounts for 70% or more (in terms of mol) or more, more preferably 80% or more, from the viewpoint that the effects of the present invention are more favorably exhibited. Preferably it is at least 90%, most preferably at least 95%.

The organic acid iron (III) complex salt may be used in the form of a complex salt or an iron (III) salt such as ferric sulfate, ferric chloride, ferric acetate, ammonium ferric sulfate, Phosphoric acid second
An iron (III) ion complex salt may be formed in a solution using iron or the like and an aminopolycarboxylic acid or a salt thereof. When used in the form of a complex salt, one kind of complex salt may be used, or two or more kinds of complex salts may be used. Second
When a complex salt is formed in a solution using an iron salt and an aminopolycarboxylic acid, one or more of ferric iron may be used. Furthermore, one or more aminopolycarboxylic acids may be used.

In any case, the aminopolycarboxylic acid may be used in an excess amount to form an iron (III) ion complex salt.

The bleaching solution or the bleach-fixing solution is described in Japanese Patent Application No. 63-489.
No. 31 describes imidazole and derivatives thereof or the compounds represented by the general formulas (I) to (IX) described therein and at least one of these exemplified compounds, thereby having an effect on rapidity. Can play.

In addition to the above bleaching accelerators, Japanese Patent Application No. 60-263568
Compounds described on pages 51 to 115 of the specification and JP-A-63-17445, JP-A-53-95630, and 53. Compounds described in JP-28426-A can be used in the same manner.

These bleaching accelerators may be used alone or in combination of two or more. The addition amount is generally preferably in the range of 0.01 to 100 g per liter of the bleaching solution, more preferably.
It is 0.05 to 50 g, particularly preferably 0.05 to 15 g.

When the bleaching accelerator is added, it may be added and dissolved as it is, but it is generally dissolved in water, an alkali, an organic acid or the like in advance and added. If necessary, methanol or ethanol may be added. And an organic solvent such as acetone.

The temperature of the bleaching solution or bleach-fixing solution is preferably from 20 to 50 ° C., preferably from 25 to 45 ° C.

The pH of the bleaching solution is preferably 6.0 or less, more preferably 1.0 or more and 5.5 or less.

The pH of the bleaching solution is the pH of the processing tank during the processing of the silver halide photographic light-sensitive material.
H can be clearly distinguished.

To the bleaching solution or bleach-fixing solution, a halide such as ammonium bromide, potassium bromide or sodium bromide is usually added and used. Further, various fluorescent whitening agents, antifoaming agents or surfactants can be contained.

A preferable replenishing amount of the bleaching solution is 500 ml or less, preferably 20 ml to 400 ml, and most preferably 40 ml to 3 ml / m ^{2 of the} silver halide color photographic light-sensitive material.
50 ml, and the lower the replenishment amount, the more remarkable the effect of the present invention.

In the present invention, air or oxygen may be blown in the processing bath and in the processing replenisher storage tank, if desired, in order to increase the activity of the bleaching solution or bleach-fixing solution. Agents such as hydrogen peroxide, bromate, persulfate and the like may be added as appropriate.

A member having high oxygen permeability, for example, silicone rubber or the like can be used as a pipe of an automatic developing machine.

Next, the fixing solution or the bleach-fixing solution in the fixing step employed after the bleaching step preferably contains at least a thiocyanate as a fixing agent. Is also good. The thiocyanate is preferably at least 0.3 mol / l,
3.0 mol / l is more preferred.

[0105] The replenishment rate of the fixing solution or bleach-fixing solution according to the present invention is preferably not more than the light-sensitive material 1 m ² per 900 ml, more preferably photosensitive material 1 m ² per 20～750Ml, particularly preferably 50～620Ml.

The p of the fixing solution or the bleaching solution according to the present invention.
H is preferably in the range of 4 to 8.

The fixing solution or the bleach-fixing solution is described in Japanese Patent Application No. 63-48931.
May be added the compound represented by the general formula [FA] described on page 56 of this specification and the exemplified compound, and furthermore, international publication
Compounds represented by general formula (1) or (2) described in WO 91/08517, pages 5 to 10, may be used, and a small amount of a light-sensitive material is processed over a long period of time using a bleach-fixing solution or a fixing solution. Another effect is obtained in that the amount of sludge generated during the process is extremely small.

[0108] The addition amount of the compound represented by the general formula [FA] and the compound represented by the general formula (1) or (2) is effective in a range of 0.1 to 200 g per liter of the treatment liquid.

The fixing solution or the bleach-fixing solution may contain a sulfite and a compound releasing sulfurous acid. Specific examples of these compounds include potassium sulfite, sodium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, potassium metabisulfite, sodium metabisulfite, and ammonium metabisulfite. Furthermore, Japanese Patent Application No. 63-48931, specification No. 60
The compound represented by the general formula [B-1] or [B-2] described on the page is also included.

The sulfite and the sulfite-releasing compound are used in an amount of at least 0.05 as a sulfite ion per liter of the fixing solution.
Although a mole is required, a range of 0.08 to 0.65 mol / l is preferable, and a range of 0.10 to 0.50 mol / l is particularly preferable. Particularly preferred is a range of 0.12 to 0.40 mol / l.

The processing time with the processing solution having a fixing ability according to the present invention is arbitrary, but is preferably 3 minutes 30 seconds or less, more preferably 10 seconds to 3 minutes 15 seconds, and particularly preferably 20 seconds. It is in the range of ~ 3 minutes.

In the present invention, it is preferable as an embodiment of the present invention to apply forcible liquid stirring to the stabilizing solution, the processing solution having a fixing ability, and the bleaching solution. The reason for this is not only that the effects of the object of the present invention can be achieved more favorably, but also from the viewpoint of rapid processing suitability. Here, the forced liquid stirring means that the liquid is not normally diffused and moved, but is forcibly stirred by adding a stirring means. As the forced stirring means, JP-A-64
-222259 and JP-A-1-206343 can be employed.

In the present invention, the crossover time between each tank such as a fixing tank to a stabilizing tank is within 10 seconds, preferably within 7 seconds. In addition, a method of installing a duck hill valve or the like to reduce the amount of processing liquid brought in by the photosensitive material is also a preferable embodiment for carrying out the present invention.

The silver halide color photographic light-sensitive material to which the processing method of the present invention is applied (hereinafter referred to as “light-sensitive material” if necessary)
The silver halide grains used in the present invention may be any of silver chloride, silver chlorobromide, silver bromoiodide, and silver chloroiodobromide. Is preferably used.

The average silver iodide content of all silver halide emulsions in the light-sensitive material is preferably 0.1 to 15 mol%, more preferably 0.5 to 12 mol%, and particularly preferably 1 to 10 mol%.
It is.

The average grain size of all silver halide emulsions in the photographic material is preferably 2.0 μm or less, more preferably 0.1 to 1.0 μm.
m.

When the silver halide emulsion is (grain size / grain thickness)
In the case where particles having an average value of less than 5 are contained, the particle size distribution is preferably monodisperse from the viewpoint of desilvering.

A monodisperse silver halide emulsion is one in which the weight of silver halide contained within a grain size range of ± 20% around the average grain size is 60% or more of the total weight of silver halide grains. , Preferably 70% or more, more preferably 80% or more.

[0119] The average particle size here is the product ni × ri ³ of frequency ni and ri ³ particles having a particle size ri is defined as the particle size ri when the maximum (three significant figures, the least significant digit Round off to the nearest 4).

The particle size referred to here is the diameter of spherical silver halide grains, or the diameter of a projected image converted to a circular image of the same area for grains having a shape other than spherical. It is.

The particle diameter can be obtained, for example, by photographing the particle with an electron microscope at a magnification of 10,000 to 50,000 times and measuring the particle diameter or the area at the time of projection on the print (measurement). The number of particles shall be 1000 or more indiscriminately).

Particularly preferred highly monodispersed emulsions are those having a distribution width of not more than 20% defined by (standard deviation / average particle size) × 100 = width of distribution (%),
It is more preferably at most 15%.

The crystal of the silver halide grains may be a normal crystal, a twin crystal or any other crystal, and any ratio of [1.0.0] plane to [1.1.1] plane can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may be a layered structure (core-shell type) in which the inside and the outside are different. Further, these silver halides are of a type in which a latent image is mainly formed on the surface,
It may be of a type formed inside the particles. Further, tabular silver halide grains (see JP-A-58-113934 and JP-A-59-170070) can also be used.

The silver halide grains may be obtained by any preparation method such as an acid method, a neutral method or an ammonia method.

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

The preparation of silver halide grains is preferably carried out as described above. The composition containing the silver halide grains is referred to herein as a silver halide emulsion.

Further, in the silver halide color photographic light-sensitive material of the present invention, the silver halide emulsion may be selected from a research emulsion.
Disclosure 308119 (hereinafter abbreviated as RD308119) can be used. The places to be described are shown below.

[Item] [Page of RD308119] Iodine composition 993 IA Section Manufacturing method 993 IA and 994 E Crystal habit Normal crystal 993 IA section Twin 〃 Epitaxial ハ ロ ゲ ン Halogen composition uniform 993 I- Item B Non-uniform 〃 Halogen Conversion 994 IC Item 置換 Substitution 〃 Metal Containing 994 ID Monodisperse 995 Item IF Addition of Solvent 潜 Latent Image Forming Position Surface 995 IG Inside 〃 Applicable Sensitive Material Negative 995 Item IH Positive (including internal fog grains) 用 い る Use mixed emulsion. 995 IJ Desalination 995 II-A In the present invention, the silver halide emulsion is subjected to physical ripening, chemical ripening and spectral sensitization. Use what you did. Additives used in such a process are described in Research Disclosure Nos. 17643, 18716 and 308119 (hereinafter abbreviated as RD17643, RD18716 and RD308119, respectively).

The following shows the places to be described.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A 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 Known photographs that can be used in the present invention Additives for use are also described in the above-mentioned Research Disclosure. The relevant sections are described below.

[Item] [Page of RD308119] [RD17643] [RD18716] Anti-turbidity agent 1002 Section VII-I 25 650 Dye image stabilizer 1001 Section VII-J 25 Brightener 998 V 24 UV absorber 1003 VIII C , XIII C 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 XVI Developer (contained in photosensitive material) 1011 XX-B Various photosensitive materials used in the present invention Couplers can be used, examples of which are described in Research Disclosure, supra. The relevant sections are described below.

[Items] [Page of RD308119] [RD17643] [RD18716] Yellow coupler 1001 VII-D VII CG-G Magenta coupler 1001 VII-D VII C-G cyan coupler 1001 VII-D VIIC ~ G DIR coupler 1001 VII-F VIIF BAR coupler 1002 VII-F Other useful residue releasing coupler 1001 VII-F Alkali-soluble coupler 1001 VII-E The additive used in the present invention is: It can be added by a dispersion method described in XIV of RD308119 and the like.

In the present invention, RD17643, page 28, RD
The supports described on pages 18716 647-8 and RD308119 XIX can be used.

The light-sensitive material can be provided with an auxiliary layer such as a filter layer or an intermediate layer described in RD308119, section VII-K. The photosensitive material is VII-K of RD308119 described above.
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in the section can be adopted.

Furthermore, in the present invention, the silver halide color photographic light-sensitive material preferably contains at least one of the compounds represented by the following formulas [B-1] to [B-3].

[0136]

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In the formula, R ¹ represents an alkyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxycarbonyl group, an amino group, a carboxylic acid group (including its salt) or a sulfonic acid group (including its salt). R ² and R ³ are each a hydrogen atom, a halogen atom, an amino group, a nitro group, a hydroxyl group, an alkoxycarbonyl group, a carboxylic acid group (including a salt thereof)
Or a sulfonic acid group (including a salt thereof). M represents a hydrogen atom, an alkali metal atom or an ammonium group.

[0138]

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[0139]

Embedded image

In the formula, R ⁴ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a halogenated alkyl group, —R ¹²
—OR ¹³ , —CONHR ¹⁴ (where R ¹² represents an alkylene group, R ¹³ and R ¹⁴ each represent a hydrogen atom, an alkyl group or an arylalkyl group) or an arylalkyl group, and R ⁵ and R ⁶ represent each a hydrogen atom, a halogen atom, a halogenated alkyl group or an alkyl group, R ⁷
Represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group,
Halogenated alkyl group, arylalkyl group, -R ¹⁵ -O
R ¹⁶ or —CONHR ¹⁷ (where R ¹⁵ is an alkylene group,
R ¹⁶ and R ¹⁷ both represent a hydrogen atom as an alkyl group. ), R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an amino group or a nitro group.

Specific examples of the compound represented by the formula [B-1] include the following exemplified compounds.

[0142]

Embedded image

Other specific examples include Japanese Patent Application No. 2-2740.
No. 26, pages 130 to 132 (B-1-4) to (B-
1-15) and (B-1-17).

Some of the compounds represented by the above formula [B-1] are known as preservatives such as citrus and some are commercially available, and can be easily obtained by those skilled in the art.

Preferred compounds among the above exemplified compounds are
(B-1-1), (B-1-2), (B-1-3), (B-1
-4) and (B-1-5).

The compound of the formula [B-1] used in the solid stabilizing agent of the present invention is preferably used in an amount of 0.03 to 50 g per liter of the stabilizing solution of the present invention, more preferably.
It is 0.12 to 10 g, particularly preferably 0.15 to 5 g.

Specific examples of the compound represented by the formula [B-2] or [B-3] are described below.
It is not limited to these.

(B-2-1) 2-methyl-4-isothiazolin-3-one (B-2-2) 5-chloro-2-methyl-4-isothiazoline
-3-one (B-2-3) 2-methyl-5-phenyl-4-isothiazolin-3-one (B-2-4) 4-bromo-5-chloro-2-methyl-4-isothiazoline-3 -One (B-2-5) 2-hydroxymethyl-4-isothiazolin-3-one (B-2-6) 2- (2-ethoxyethyl) -4-isothiazolin-3-one (B-2-7) 2- (N-methyl-carbamoyl) -4-isothiazolin-3-one (B-2-8) 5-bromomethyl-2- (N-dichlorophenyl-carbamoyl) -4-isothiazolin-3-one (B-2 -9) 5-chloro-2- (2-phenylethyl) -4-isothiazolin-3-one (B-2-10) 4-methyl-2- (3,4-dichlorophenyl)-
4-isothiazolin-3-one (B-3-1) 1,2-benzisothiazolin-3-one (B-3-2) 2- (2-bromoethyl) -1,2-benzisothiazolin-3-one ( B-3-3) 2-Methyl-1,2-benzisothiazoline-
3-one (B-3-4) 2-ethyl-5-nitro-1,2-benzisothiazolin-3-one (B-3-5) 2-benzyl-1,2-benzisothiazolin-3-one ( B-3-6) 5-Chloro-1,2-benzisothiazoline-
3-one These exemplified compounds are described in U.S. Pat.No. 2,767,172, U.S. Pat.No. Describes synthesis methods and examples of application to other fields. Some are commercially available, and Topside 300 (Permachem Asia)
Co., Ltd.), Topside 600 (Permachem Asia Co., Ltd.),
Fine Side J-700 (Tokyo Fine Chemical Co., Ltd.), P
It can be obtained under the trade name of roxel GXL (ICI Corporation).

The compounds represented by the general formulas [B-1] to [B-3] are used in an amount of 0.1 to 500 mg, preferably 0.5 to 100 mg per 1 m ² of the light-sensitive material.

The compounds represented by [B-1] to [B-3] may be used in combination of two or more.

The present invention is directed to color photographic light-sensitive materials such as color paper, color negative film, color reversal film, color reversal paper, direct positive color paper, color film for movies, and color film for television used for general or movie use. Can be applied to

Next, the solid (photographic) processing agent of the present invention will be described.

In the present invention, the solid processing agent is
Any treatment agent having an external appearance in a solid state may be used, and specific examples thereof include the following.

Tablets, granules (granules), powders, or other simple substances or aggregates thereof The above-mentioned simple substances, aggregates, or treatment solutions containing the compounds of the present invention are encapsulated in a water-soluble, acid-soluble or alkali-soluble resin. The above-mentioned simple substance or aggregate is wrapped in a water-soluble, acid-soluble or alkali-soluble resin film, and a treatment agent having an external shape made of a non-flowable solid substance, such as a paste-like treatment. Agents and the like.

To solidify the photographic processing agent, a concentrated solution, a fine powder or a granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binder is sprayed on the surface of the temporarily formed photographic processing agent. By doing so, any means such as forming a coating layer can be adopted (Japanese Patent Application No. 2-135887,
2-223165, 2-203166, 2-203167, 2-2031
Nos. 68 and 2-300409).

Among the above-mentioned solid processing agents, tablets are the most preferable for practicing the present invention, and it is also a preferable embodiment that the above-mentioned processing agents are packaged or bound / coated with a water-soluble film or binder.

A method for producing a tablet processing agent is described in, for example,
51-61837, 54-155038, 52-88025, UK Patent 1
213808 can be produced by a general method described in the specification, further granule treatment agent, for example, JP-A-2-09042,
It can be produced by a general method described in the specification of JP-A-2-109043, JP-A-3-39735 and JP-A-3-39739. Furthermore, powder processing agents are described, for example, in JP-A-54-133332, British Patent 72589.
No. 2,729862 and German Patent No. 3738661 can be produced by a general method.

Solid processing agents can be damaged during storage, transport, and handling by atmospheric humidity, such as high humidity, rain, and fog, and by splashing or wet hands causing sudden contact with water. To prevent from, it is preferable to be packaged in a moisture-proof packaging material, as the moisture-proof packaging material, a film having a film thickness of 10 to 150 μm is preferable, the moisture-proof packaging material is polyethylene terephthalate, polyethylene, a polyolefin film such as polypropylene, Select from kraft paper, wax paper, moisture resistant cellophane, glassine, polyester, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide, polycarbonate, acrylonitrile and metal foils such as aluminum and metallized polymer films that can have moisture resistance effect with polyethylene. Preferably, at least one of It may be a composite material using.

However, in the present invention, the moisture-proof packaging material is preferably a degradable plastic, particularly a biodegradable or photodegradable plastic.

Examples of the biodegradable plastic include those composed of natural polymers, polymers produced from microorganisms, synthetic polymers having good biodegradability, and the incorporation of biodegradable natural polymers into plastics. Specifically, the following are mentioned.

Examples of the natural polymer include polysaccharides, cellulose, polylactic acid, chitin, chitosan, polyamino acids, and microbial-produced polymers such as PHB-PHV (3-
“Polypol” (copolymer of hydroxybutyrate and 3-hydroxyvalerate) as a component, “Biopol” (manufactured by ICI), and biodegradable synthetic polymers such as cellulose produced by microorganisms include polyvinyl alcohol and polycaprolactone. Alternatively, natural polymers having good biodegradability used for blending a biodegradable natural polymer into a plastic of a copolymer or a mixture thereof include starch and cellulose. Examples of the degradable plastic include those in which a group which is excited by ultraviolet rays and is linked to cleavage is present in the main chain.
Specifically, there is introduction of a carbonyl group for photodisintegration and the like, and an ultraviolet absorber may be further added for accelerating disintegration.

Further, in addition to the polymers listed above, those having both functions of photodegradability and biodegradability at the same time are preferably used.

For such degradable plastics,
"Science and Industry" Vol. 64, No. 10, pp. 478-484 (1990),
“Functional materials”, generally described in July 1990, pp. 23-34, can be used. In addition, Biopol (manufactured by ICI), Eco (manufactured by Union Carbide), Ecolite (manufactured by Eco Plastic), Ec
Commercially available degradable plastics such as ostar (Ecostar) (St. Lawrence Starch) and Knuckle P (Nippon Unicar) can be used.

The moisture-proof packaging material preferably has a moisture permeability coefficient of 10 g · mm / m ² 24 hr or less, more preferably 5 g · mm / m ² 24 hr or less.

The bulk density of the solid photographic processing agent of the present invention is from the viewpoint of its solubility and the purpose of achieving the object of the present invention.
Those having 5 to 6.0 g / cm ³ are preferable, and those having 1.0 to 5.0 g / cm ³ are particularly preferably used.

The granules in the present invention are those having an average particle size of 100 to 2,000 μm obtained by granulating a powder, preferably 100 to 800 μm, more preferably 200 to 700 μm.
It is. In addition, the particle size distribution is more than ± 100%
Those with a deviation of 150150 μm are preferred.

Specific methods for dissolving the solid processing agent include a method in which the solid processing agent is dissolved in water once stored in a replenishing tank and then replenishing the processing tank, and a method in which the solid processing agent is directly poured into the processing tank together with the replenishing water and dissolved. No. In the former case, a replenishment tank is required separately from the processing tank, so that a space is required. The latter is more preferable because it does not take up space.

In the present invention, in order to supply the solid photographic processing agent to the automatic processing machine, the area of the processed photosensitive material is integrated by a detecting device attached to the photosensitive material insertion opening of the automatic processing machine, and reaches a certain unit. Then, a predetermined amount of the replenishing processing agent is directly replenished to the processing tank portion of the automatic processing machine one by one or several when solidified.

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

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

When a solidified solid photographic processing agent is used, the size and shape of the solid photographic processing agent can be freely changed according to the unit to be replenished. From the upper part of the tank, the processing liquid circulation system, the temperature control tank, the processing liquid filtration filter section, etc., through the replenishment mechanism, receive the signal transmitted from the area detection device of the photosensitive material to be processed by a predetermined amount, and for each unit Preferably, it is replenished.

Further, the solid photographic processing agent replenishment section is devised so that the scattered processing liquid due to the processing tank section of the automatic processing machine, the temperature of the outside air, and the photosensitive material to be processed does not come into contact with the solid photographic processing agent before replenishment. More preferably, it is performed.

(Processing Method of the Present Invention) Next, the solid (photographic) processing agent of the present invention will be described.

In the present invention, the solid processing agent refers to
Any treatment agent having an external appearance in a solid state may be used, and specific examples thereof include the following.

Tablets, granules (granules), powders or other simple substances or aggregates thereof The above-mentioned simple substances or aggregates or the treatment liquid containing the compound of the present invention are encapsulated in a water-soluble, acid-soluble or alkali-soluble resin. The above-mentioned simple substance or aggregate is wrapped in a water-soluble, acid-soluble or alkali-soluble resin film, and a treatment agent having an external shape made of a non-flowable solid substance, such as a paste-like treatment. Agents and the like.

To solidify the photographic processing agent, a concentrated solution, a fine powder or a granular photographic processing agent and a water-soluble binder are kneaded and molded, or a water-soluble binder is sprayed on the surface of the temporarily formed photographic processing agent. By doing so, any means such as forming a coating layer can be adopted (Japanese Patent Application No. 2-135887,
2-223165, 2-203166, 2-203167, 2-2031
Nos. 68 and 2-300409).

Among the above-mentioned solid processing agents, tablets are the most preferable for practicing the present invention, and it is also a preferable embodiment that the above-mentioned processing agents are wrapped or bound / covered with a water-soluble film or binder.

A method for producing a tablet processing agent is described in, for example,
51-61837, 54-155038, 52-88025, UK Patent 1
213808 can be produced by a general method described in the specification, further granule treatment agent, for example, JP-A-2-09042,
It can be produced by a general method described in the specification of JP-A-2-109043, JP-A-3-39735 and JP-A-3-39739. Furthermore, powder processing agents are described, for example, in JP-A-54-133332, British Patent 72589.
No. 2,729862 and German Patent No. 3738661 can be produced by a general method.

The solid processing agents may be damaged during storage, transport, and handling by atmospheric humidity, such as high humidity, rain, and fog, and from sudden splashing or contact with water by splashing or wet hands. To prevent from, it is preferable to be packaged in a moisture-proof packaging material, as the moisture-proof packaging material, a film having a film thickness of 10 to 150 μm is preferable, the moisture-proof packaging material is polyethylene terephthalate, polyethylene, a polyolefin film such as polypropylene, Select from kraft paper, wax paper, moisture resistant cellophane, glassine, polyester, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide, polycarbonate, acrylonitrile and metal foils such as aluminum and metallized polymer films that can have moisture resistance effect with polyethylene. Preferably, at least one of It may be a composite material using.

However, in the present invention, the moisture-proof packaging material is more preferably a degradable plastic, particularly a biodegradable or photodegradable plastic.

Examples of the biodegradable plastic include those made of natural polymers, microorganism-produced polymers, synthetic polymers having good biodegradability, and the incorporation of biodegradable natural polymers into plastics. Specifically, the following are mentioned.

Examples of natural polymers include polysaccharides, cellulose, polylactic acid, chitin, chitosan, polyamino acids, and microbial-produced polymers such as PHB-PHV (3-
“Polypol” (copolymer of hydroxybutyrate and 3-hydroxyvalerate) as a component, “Biopol” (manufactured by ICI), and biodegradable synthetic polymers such as cellulose produced by microorganisms include polyvinyl alcohol and polycaprolactone. Alternatively, natural polymers having good biodegradability used for blending a biodegradable natural polymer into a plastic of a copolymer or a mixture thereof include starch and cellulose. Examples of the degradable plastic include those in which a group which is excited by ultraviolet rays and is linked to cleavage is present in the main chain.
Specifically, there is introduction of a carbonyl group for photodisintegration and the like, and an ultraviolet absorber may be further added for accelerating disintegration.

Further, in addition to the polymers listed above, those having both functions of photodegradability and biodegradability at the same time are preferably used.

With respect to such degradable plastics,
"Science and Industry" Vol. 64, No. 10, pp. 478-484 (1990),
“Functional materials”, generally described in July 1990, pp. 23-34, can be used. In addition, Biopol (manufactured by ICI), Eco (manufactured by Union Carbide), Ecolite (manufactured by Eco Plastic), Ec
Commercially available degradable plastics such as ostar (Ecostar) (St. Lawrence Starch) and Knuckle P (Nippon Unicar) can be used.

The moisture-proof packaging material preferably has a moisture permeability coefficient of 10 g · mm / m ² 24 hr or less, more preferably 5 g · mm / m ² 24 hr or less.

The bulk density of the solid photographic processing agent of the present invention is from the viewpoint of its solubility and the achievement of the object of the present invention.
Those having 5 to 6.0 g / cm ³ are preferable, and those having 1.0 to 5.0 g / cm ³ are particularly preferably used.

The granules in the present invention are those having an average particle diameter of 100 to 2,000 μm obtained by granulating a powder, preferably 100 to 800 μm, more preferably 200 to 700 μm.
It is. In addition, the particle size distribution is more than ± 100%
Those with a deviation of 150150 μm are preferred.

Specific methods for dissolving the solid processing agent include a method in which the solid processing agent is dissolved in water once stored in a replenishing tank and then replenishing the processing tank, and a method in which the solid processing agent is directly poured into the processing tank together with the replenishing water and dissolved. No. In the former case, a replenishment tank is required separately from the processing tank, so that a space is required. The latter is more preferable because it does not take up space.

In the present invention, in order to supply the solid photographic processing agent to the automatic processing machine, the area of the processed photosensitive material is integrated by a detecting device attached to the photosensitive material insertion opening of the automatic processing machine, and reaches a certain unit. Then, a predetermined amount of the replenishing processing agent is directly replenished to the processing tank portion of the automatic processing machine one by one or several when solidified.

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

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

When a solidified solid photographic processing agent is used, the size and shape of the solid photographic processing agent can be freely changed according to the unit to be replenished. From the upper part of the tank, the processing liquid circulation system, the temperature control tank, the processing liquid filtration filter section, etc., through the replenishment mechanism, receive the signal transmitted from the area detection device of the photosensitive material to be processed by a predetermined amount, and for each unit Preferably, it is replenished.

Further, the solid photographic processing agent replenishing section is devised so that the scattered processing solution due to the processing tank section of the automatic processing machine, the temperature of the outside air, and the photosensitive material to be processed does not contact the solid photographic processing agent before replenishment. More preferably, it is performed.

(Processing Method of the Present Invention) Next, a preferred embodiment of the present invention will be described.

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

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

When the temperature of the automatic processing machine is controlled for several hours, the processing liquid 17 in each of the processing tanks 1 to 3 evaporates. When the processing liquid 17 falls below a certain liquid level, the liquid level detection sensor 9 operates and the control unit 11 operates. In response to this signal, the replenishment water replenishing device 10 and the solenoid valve 12 are operated, and the replenishment water for evaporation correction is replenished until the upper limit detection mechanism of the liquid level detection sensor 9 operates. In addition, it is preferable that the temperature of the washing hot water 14, which is the replenishing water supplied by the replenishing water replenishing pipe 15, is adjusted for both the replenishing water for adjusting liquid and the replenishing water for evaporating correction. Each of the processing tanks 1 to 3 is a color developing tank, 1 is a bleach-fixing tank, and 3 is a stabilizing tank. 4 is a drying section.

FIG. 2 is a schematic explanatory view of the tablet-type processing agent supply device 8.

Photosensitive material area detection sensor 7 (see FIG. 1)
When the control unit 11 shown in FIG. 1 operates and the tablet-type processing agent supply stepping motor 95 is operated, the driving unit engages with the rack 94A of the tablet-type processing agent supply push-out plunger 94 directly. The pinion 96 is one step,
The plunger 94 having the rack 94A is raised by the pitch thickness P of the thickness of the processing agent, so that the uppermost tablet-type processing agent 24A in the supply tray main body 91 of the processing agent 24 waits at the loading drop position. The tablet-type treating agent 24 stored in the tray body 91 is treated with a treating agent replenishing tank (hereinafter, referred to as a treating agent dissolving unit).
The preparation for putting one into the filtering device 21 in the sub tank 20 is completed.

As described above, the tablet-type treating agent 24A waiting at the uppermost portion moves the guide plate 20A above the sub-tank 20 and the ceiling by the forward movement of the plunger 99 reciprocating horizontally on the piston slide 92. The inside of the tunnel formed by the cover 20B is slid laterally and falls on the liquid surface of the filtering device 21 of the sub tank 20. The plunger 99 has a rack 99A provided in a part thereof meshed with a pinion 98 directly connected to the stepping motor 97, and the stepping motor 97 is started by a command signal, whereby reciprocating operation is performed. When the tablet type processing agent 24A has been charged into the sub tank 20 in the forward movement, the stepping motor 97 rotates in the reverse direction, the plunger 99 returns to the original position, and waits until the next command signal comes. . In some cases, the command signal instructs the supply of a plurality of tablet-type processing agents. In this case, the above operation is repeated a predetermined number of times.

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

If the circulating pump 18 is configured so that all or most of the circulating flow of the processing liquid 17 circulating between the main processing tank 16 and the sub-tank 20 passes directly through the filtration device 21 in the sub-tank 20, the tablet The solubility of the mold treating agent 24 is further enhanced.

In the figure, 19 is a temperature control heater, 27 is a communication pipe 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 body 91 of the tablet-type processing agent supply device 8 is surrounded by four vertical walls, and the plunger is
94 is designed to reciprocate up and down. As described above, the tablet-type processing agent 24 is protected in the supply tray in a substantially sealed state, and the uppermost tablet-type processing agent 24A is also substantially sealed in the tunnel to the sub-tank 20 as described above. Since they are extruded in a state, they are not contaminated by the effects of the rebound and evaporation of each processing solution.

Also, the forward movement speed of the plunger 99 is set to an appropriate value, and the direction of injection of the tablet-type processing agent is the direction shown in FIG. 2 so that the flat surface is vertical. Decrease.

In response to the signal from the photosensitive material area detection sensor 7, the control section 11 operates to operate the stepping motors 95 and 97 for refilling the tablet type processing agent and the pinion 96 driven by the stepping motors 95 and 97.
A plunger 94 having a rack 94A and a plunger 99 having a rack 99A which operate linearly thereby actuate the plunger 99 to replenish the tablet-type treatment agent 24 and at the same time replenish the water.
The solenoid valve 10 and the solenoid valve 12 operate, and the replenishing water for liquid preparation is supplied. The replenishing amount of the replenishing water for preparing the solution may be at least the amount required to dissolve the tablet-type treating agent 24, and the operation time of the solenoid valve 12 and the replenishing water replenishing device 10 may be input to the control unit 11 in advance. Solvable.

If the liquid level of the processing liquid 17 in the processing tank drops due to evaporation while the temperature of the processing machine is being controlled or stopped, the liquid level detecting sensor 9 detects the lowered liquid level and controls the signal. Part 11
The solenoid valve 12 and the replenishment water replenishing device 10 are operated to replenish the evaporation correction replenishment water to the normal liquid level. When the liquid level 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 solenoid valve 12 and the replenishing water supply device 10.

[0208]

EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

Example 1 The solid stabilizing agent (replenisher) of the present invention was prepared according to the following procedure.
100 liters).

Operation (1) m-hydroxybenzaldehyde 200 g, Emulgen 913
(Polyoxyethylene nonyl phenyl ether): 10
g and 45 g of potassium carbonate were pulverized in an air jet pulverizer until the average particle size became 10 μm.

Further, the mixture was uniformly mixed for 10 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH or less.
I got

Operation (2) The above crushed mixture A was granulated by spraying 3.0 ml of water at room temperature for about 7 minutes at room temperature in a commercially available fluidized bed spray granulator, and then at 30 ° C. in vacuum. After drying for 8 hours, the granulated product B
Was sticky and could not be formed into granules or tablets.

Operation (3) Here, Emulgen 913 was changed to Emulgen 985, and pulverization and granulation were performed in the same manner as in Operations (1) and (2), whereby a pulverized mixture C and a granulated product D were obtained.

Operation (4) Further, the above granulated material D was compressed and compressed into tablets using a tableting machine obtained by modifying a Tough Press Collect 1527HU manufactured by Kikusui Seisakusho to make the filling amount per tablet 1.0 g. A tablet E for stable replenishment was prepared.

Operation (5) Next, emulgen 985 was changed to sodium lauryl sulfate, and pulverization, granulation and tableting were carried out in the same manner as in operations (1), (2) and (4). , Granulated material G, tablet H
I got

The samples A to H obtained by the above operation were subjected to
A storage test was carried out for one week, followed by storage at a temperature of 50 ° C. and a humidity of 60% RH for one week and further at −1 ° C. for one month. Thereafter, 2.0 g of each of the granules and the pulverized product or 2 tablets were dissolved in 1000 ml, and the solubility was observed. Further, 20 g of the granules and pulverized product or 10 tablets were placed in a polyethylene bag, shaken gently, and observed for their scattering properties. Table 4 shows the results of observation of the state of the solid processing agent after the test.

(Evaluation method) Solubility: 溶解 dissolves quickly ○ dissolves ○ dissolves over time × does not dissolve easily Dispersibility: し な い does not scatter 飛 slightly scatters △ scatters when there is a wind current × considerably scatters Preservability: ◎ No change in shape and moisture absorption ○ Slight moisture absorption but no change in shape △ Hygroscopic and change in shape × Absorbs moisture and dissolves

[0218]

[Table 4]

However, * became sticky during granulation or storage and was excluded from the evaluation.

From the results shown in Table 4 above, it can be seen that the solid processing agent of the present invention is excellent in all of the solubility, the scattering property, and the storage stability.

Example 2 Next, a solid stabilizing agent for a color negative film was prepared according to the following procedure.

Operation (6) 200 g of m-hydroxybenzaldehyde, 10 g of sodium lauryl sulfate and 45 g of potassium carbonate were pulverized, mixed and granulated, and the operations (1) to (1) were carried out so that the average particle diameter became the value shown in Table 2. 3) was repeated to prepare Samples 1 to 11.

Operation (7) 200 g of the granulated product obtained in the above operation was placed in a polyethylene bag, sealed, stored at 65 ° C. for 2 months, and the state of caking was observed.

Next, 2.0 g of the obtained granules were dissolved in 1000 ml of water, and the solubility was observed. Table 5 shows the results.

(Evaluation method) Solubility ：: dissolves promptly ：: dissolves ：: dissolves with time ×: does not dissolve readily 有無: has fluidity ：: has fluidity ：: caking is observed in some places △ ： Cakes as a whole but breaks down with hands × ： Completely blocked

[0226]

[Table 5]

From the results shown in Table 5, the solid processing agent of the present invention is excellent in both solubility and caking, but particularly preferably has an average particle size of 100 to 800 μm.

Example 3 The deviation of the particle diameter in each granulation operation of Example 2 was measured as shown in Table 6.
The same operation experiment as in Example 2 was performed except that the values were adjusted to the described values, and samples 12 to 21 were prepared. Table 6 shows the results.

[0229]

[Table 6]

According to Table 6, the particle size distribution of the granulated product was ± 100 to 1
It can be seen that by setting the particle size to 50 μm or less and 60% or more, there is no sticking of fine powder to the punches of the tableting machine, and the trouble during continuous tableting is extremely small.

Example 4 Operation (8) 200 g of m-hydroxybenzaldehyde, 10 g of sodium lauryl sulfate and 45 g of potassium carbonate were ground and mixed according to the operations (1) to (3), and the average particle size was 100 to 800 μm, and the particle size distribution was ± 1
A granulated product was prepared with a size of 00 μm and 70%.

Operation (9) The granules were tableted according to the operation (4). Accordingly, the filling amount of the granules was set to 2.0 g, the tableting pressure was adjusted, and the solid stable tablet for color negative 22 was adjusted so that the bulk density became the value shown in Table 7.
Each of ~ 33 was made 10 pieces.

Operation (10) After the above tablets were stored under the same conditions as in operation (7), one of them was taken out, dissolved in 1000 ml of water, the dissolution rate was measured, and The shape when dropped from a height of 1 m was also observed.

(Evaluation method) Dissolution rate With sample 22 as a reference 100, the smaller the relative value is, the higher the solubility is. Tablet strength Indicates the shape change when a tablet is dropped from a height of 1 m. : No change in shape △: Edge of tablet is broken ×: Disintegration

[0235]

[Table 7]

* However, the tablet strength of sample 22 was not evaluated because it was not tableted. From the results shown in Table 7 above, the solid processing agent of the present invention was excellent in both solubility and tablet strength. Density 1.1 ~
2.1 g / cm ³ .

Example 5 A processed tablet for a color negative film was prepared according to the following procedure.

1) Tablet for replenishing color development for color negative Operation (11) CD-4 [4-amino-3-methyl-N-ethyl-β-
(Hydroxy) ethylaniline sulfate] in an air jet pulverizer until the average particle diameter becomes 10 μm. This fine powder is granulated by spraying 5.0 ml of water for about 7 minutes at room temperature in a commercially available fluidized bed spray granulator, and the granulated product is dried at 63 ° C. for 8 minutes. Next, the granules are dried at 40 ° C. for 2 hours in a vacuum to remove the moisture of the granules almost completely.

Operation (12) Pulverize and granulate 64 g of hydroxylamine sulfate in the same manner as in the operation (11). Spraying amount of water is 2.6ml, after granulation, 60 ℃
And dry for 7 minutes. Next, the granules are dried at 40 ° C. for 2 hours in a vacuum to remove the moisture of the granules almost completely.

Operation (13) Disodium 1-hydroxyethane-1,1-diphosphonate 60
g, 80 g of sodium sulfite, 700 g of potassium carbonate, 60 g of sodium bicarbonate, 8 g of sodium bromide and 60 g of diethylenetriaminepentaacetic acid are ground in the same manner as in (11), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in (11), granulation is performed with the spray amount of water set to 200 ml. After granulation, the granulated material is 70 ℃
And then dry the granules in vacuo at 40 ° C. for 2 hours to remove almost completely the moisture of the granules.

Operation (14) The granulated product prepared in the above operations (11) to (13) was subjected to a 40%
Mix evenly for 10 minutes using a mixer in a room humidified below RH. Next, the mixture was subjected to compression tableting using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho, with the filling amount per tablet being 5.8 g, to produce 160 color developing color replenishing tablets for color negative.

2) Tablet for bleach replenishment for color negative Operation (15) Ferric ammonium monohydrate 1,3-propanediaminetetraacetate
175 g, 60 g of succinic acid, 73 g of maleic acid, and 2 g of 1,3-propanediaminetetraacetic acid are pulverized and granulated in the same manner as in the operation (11).
The spray amount of water is 5.0 ml, and after granulation, it is dried at 60 ° C. for 7 minutes. Next, the granules are dried at 40 ° C. for 2 hours in a vacuum to remove the moisture of the granules almost completely.

Operation (16) 80 g of potassium nitrate, 200 g of ammonium bromide and 60 g of potassium carbonate are ground and granulated in the same manner as in the operation (11). The spray amount of water is 1.0 ml, and after granulation, it is dried at 70 ° C. for 3 minutes. Next, the granules are dried at 40 ° C. for 2 hours in a vacuum to remove the moisture of the granules almost completely.

Operation (17) The granulated product prepared in the above operations (15) and (16) was subjected to 40%
Mix evenly for 10 minutes using a mixer in a room humidified below RH. Next, the mixture was subjected to compression tableting using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho, with the filling amount per tablet being 6.5 g, and 80 bleaching replenishing tablets for color negative were prepared.

3) Tablet for fixing replenishment for color negative Operation (18) 2500 g of ammonium thiosulfate, 150 g of sodium sulfite,
150 g of potassium carbonate and 20 g of disodium ethylenediaminetetraacetic acid are pulverized and granulated in the same manner as in the operation (11). The spray amount of water is 30 ml, and after granulation, it is dried at 60 ° C. for 60 minutes. Next, the granules are dried at 40 ° C. for 8 hours in a vacuum to remove the moisture of the granules almost completely.

Operation (19) The granulated product prepared in the above operation (18) is uniformly mixed for 10 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH or less. Next, the mixture was added to Kikusui Seisakusho's Tough Press Collect 15
A tableting machine modified from 27HU reduces the filling amount per tablet to 9.
The tablet was compressed to 3 g and compression tableting was performed to prepare 200 fixing replenishment tablets for color negative.

4) Tablet for stable replenishment for color negative Operation (20) 200 g of m-hydroxybenzaldehyde, surfactant (Table 9)
10g and 45g of potassium carbonate are ground and granulated in the same manner as in the operation (11). The spray amount of water is 3.0 ml, and after granulation, the granules are dried in vacuum at 30 ° C. for 8 hours to almost completely remove water from the granules.

Operation (21) The granules prepared in the above operation (20) are uniformly mixed for 10 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH or less. Next, the mixture was added to Kikusui Seisakusho's Tough Press Collect 15
The filling amount per tablet was reduced to 0.
The tablet was compressed to 2 g and compression tableting was performed to prepare 1060 color replenishing fixation tablets for color negative.

[Color Negative Processing Step] Next, a method for processing a photographic material using the self-developing machine of the present invention will be described below. Konica Color Negative Film Processor CL-KP
A tablet supply function, a liquid level detection function, and a hot water supply function were provided by modification to -500QA, and the following processing experiments were performed. Table 8 shows the standard processing conditions of the automatic processing machine.

[0250]

[Table 8]

The stabilizer is replenished to the third tank, and the second tank, the
It is a cascade system in which overflow liquid flows into the tank.

Preparation of the processing liquid for the automatic processing machine was performed by the following method.

Color developing tank solution (21.0 liters) Fill the color developing tank of an automatic developing machine with 15 liters of warm water at 35 ° C., and add 399 tablets of color developing and replenishing color developing film prepared in the same manner as in steps (11) to (14). The pieces were charged and dissolved. Next, 21 starters of the following formulation, which were separately tableted, were added as starter components, and after dissolution, warm water was added to the tank mark line to complete a tank liquid.

Color Negative Color Developing Starter Sodium Bromide 0.8g Sodium Iodide 2.0mg Sodium Bicarbonate 3.0g Potassium Carbonate 0.5g Bleaching Solution (5.0l) Put 3.0l of warm water at 35 ° C into the bleaching tank of the automatic developing machine, and operate ( 1
5) 350 bleach replenishing tablets for color negative film prepared in the same manner as in (17) were charged and dissolved. Next, 10 starters of the following formulation, which were separately tableted, were added as starter components, and after dissolution, warm water was added up to the tank mark line to complete a tank liquid.

Color Negative Bleaching Starter Potassium Bromide 10.0 g Sodium Bicarbonate 1.5 g Potassium Carbonate 3.5 g Fixing Solution (4.5 L for the first tank, 4.5 L for the second tank) ℃ hot water 3.
0 l, and 112 fixing refill tablets for color negative film prepared in the same manner as in steps (18) and (19),
Dissolved. Next, hot water was added up to the tank mark to complete the tank liquid.

Stabilizing solution (3.2 liters for each of the first to third tanks) 3.0 liters of 35 ° C. warm water was added to the first, second, and third tanks of the stabilizing tank of the automatic processing machine, respectively. 40 tablets for stable replenishment for a color negative film prepared in the same manner as described above were charged and dissolved at a time. Next, hot water was added up to the tank mark to complete the tank liquid.

Next, during the temperature control of the automatic developing machine, 20 refilling tablets prepared in the operations (11) to (21) were set in a refilling tablet supply device provided to the automatic developing machine. This replenishing tablet is supplied one by one when two 135-size film-taken films are processed, and at the same time, replenished hot water is supplied from a hot water supply device to the color developing tank 40 ml, the bleaching tank 10 ml, and the fixing tank 40 ml. In the stabilization tank
Set to supply 80ml.

The running process is carried out until a stable replenisher of twice the capacity of the stabilization tank of the Konica Color Negative Film DD-100 (manufactured by Konica) is replenished (0.07R per day (R = total replenisher) After the completion of the running process, the film subjected to imagewise exposure was processed, and the state of precipitation of sulfide in the stabilization tank, the state of tar generation, the state of generation of fixed matter on the tank wall, and the running were further performed. After the processing, the processed film sample was observed for dirt, scratches, and foreign matter adhesion, and the highest density magenta density of the processed film sample was measured, and then measured at 70 ° C. and 70% relative humidity. After storage, the maximum density of magenta after storage was measured, and the fading rate of the dye was determined, and the results are shown in Tables 9 and 10.

The evaluation criteria were set as follows. (Same as in Example 6) [Evaluation criteria] Presence or absence of precipitation of sulfides ○ No at all △ No precipitation on liquid surface, but can be confirmed as suspended matter and may have practical problems × suspended matter and precipitated ×× The number of suspended solids and precipitates, which are fixed to the liquid interface of the rack, increases, indicating that the amount of precipitates is large.

Generation of tar ○ Not at all △ Slightly present and may have a problem in practical use × Many Presence or absence of sticking ○ No at all △ There is a slight but no problem as a product × Unable to produce a product ×× At all Not possible Dirt after treatment ○ Not at all △ Slightly present but no problem as product × Not possible as product × Scratch or foreign matter adhered after treatment ○ Not at all △ Slight but not problematic as product × Not possible as product ×× Not at all product Can't

[0261]

[Table 9]

[0262]

[Table 10]

From Tables 9 and 10 above, it can be seen that the objective effects of the present invention are excellent when treated with a supplementary tablet for solid stabilization using the surfactant of the present invention (compound represented by the general formula [I]). I understand.

Example 6 The supplementary tablets for solid stabilization of the present invention used in Example 5 were added with a chelating agent having a stability constant of 6.0 or more against Ca ²⁺ , sodium ethylenediaminetetraacetate, 1-hydroxyethylidene-1, A running experiment was performed in the same manner as in Example 5 except that sodium 1-diphosphonate was added.

As a result, the discoloration rate of magenta was almost the same, but the precipitation of sulfide, stains after treatment, scratches, and adhesion of foreign matter were further improved, and the effect of the present invention was further enhanced.

[0266]

Thus, according to the present invention, suitability for social environment, suitability for working environment, laminating at tableting (lateral cracking), storage stability (staining at development, generation of scratches on photographic material after processing), In addition to improving solubility, solution stability, etc., while suppressing color fading, precipitation of sulfides in the stabilizing bath, generation of flocculent suspended matter and tar, and adhesion of adhered substances to the stabilization tank wall surface Thus, it is possible to provide a method for processing a silver halide color photographic light-sensitive material capable of reliably preventing the occurrence of tar, scratches, and foreign matter on the light-sensitive material after drying.

[Brief description of the drawings]

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

FIG. 2 is a schematic explanatory view showing one embodiment of a tablet type processing agent supply device.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Color developing tank 2 Bleaching and fixing tank 3 Stabilizing tank 4 Drying section 7 Photosensitive material area detection sensor 8 Refillable tablet type processing agent replenishment device 9 Liquid level detection sensor 10 Replenishment water replenishment device 11 Control section 12 Solenoid valve 13 Photosensitive material insertion section 14 Rinse hot water 15 Refill water supply pipe 16 Main processing tank 17 Processing liquid 18 Circulation pump 19 Temperature control heater 20 Sub tank 21 Filtration device 24 Refill tablet processing agent 24A Top refill tablet processing agent 25 Supply tray 26 Push spring 39 Filtration filter 91 Supply tray body 94, 99 Plunger 94A, 99A Rack 95, 97 Stepper motor 96, 98 Pinion

Claims (8)

(57) [Claims] 1. A solid stabilizer for a silver halide photographic light-sensitive material, comprising at least one anionic surfactant. 2. The solid stabilizer for a silver halide photographic material according to claim 1, wherein said anionic surfactant is selected from the group represented by the following general formula. Embedded image Embedded image Embedded image Embedded image 3. The solid stabilizer for a silver halide photographic light-sensitive material according to claim 1, wherein the solid stabilizer comprises a chelating agent. 4. The solid stabilizing agent for a silver halide photographic light-sensitive material according to claim 1, wherein said solid stabilizing agent is granules. 5. The granule solid stabilizing agent has a particle size of 100-8.
00 μm, particle size distribution: 60% or more of granulated particles ± 100 to 150
The solid stabilizing agent for a silver halide photographic light-sensitive material according to any one of claims 1 to 4, wherein the solid stabilizing agent is a silver halide photographic material. 6. The solid stabilizer for a silver halide photographic light-sensitive material according to claim 1, wherein the solid stabilizer is a tablet. 7. The tablet-type solid stabilizing agent has a bulk density of 1.
7. The solid stabilizing agent for a silver halide photographic light-sensitive material according to claim 1, wherein the amount is 1 to 2.1 g / cm < ³ >. 8. A method for processing a silver halide photographic light-sensitive material, comprising using the solid stabilizing agent according to claim 1.