JP3215996B2 - Solid stabilizing agent for silver halide photographic light-sensitive material, stabilizing composition, and method for processing silver halide photographic light-sensitive material using the solid processing agent - 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 stabilizer and a composition for a silver halide photographic material.

[0002]

2. Description of the Related Art 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 plastics are dumped in the ocean, they cause serious environmental problems such as deterioration of habitat of marine organisms.

[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 who handle the processing solution etc. had knowledge of the processing agent, but for example, when the above lab is brought to a convenience store or drug store, ordinary people who do not have knowledge of the processing agent , Part-time job, etc. will work. Therefore, when preparing the treatment liquid, the liquid may splatter during preparation, enter the eyes, adhere to the face, and immediately wash with water. Or erroneous dissolution at the time of preparation may cause the photographic material to become useless.In the case of photographic material, paper can be redone, but negative cannot be redone. Is a big problem.

For this reason, techniques for solidifying a photographic processing agent and using the same have been proposed in, for example, JP-A-2-09042, JP-A-2-09043, US Pat. No. 2,843,484 and JP-A-3-39735. Japanese Patent Laid-Open No. 5-119454 discloses a technique of solidifying a photographic processing agent and directly charging the photographic processing agent into an automatic developing machine in accordance with the processing amount of the photosensitive material.
And the like. According to this technique, the use of a plastic bottle is avoided, and the operator is not directly in contact with the photographic processing agent, thereby improving the safety and the convenience of replenishment.

[0009]

However, the stable liquid includes:
Usually, a hydrocarbon-based nonionic surfactant is commonly used for the purpose of improving the wettability of a photosensitive material and preventing unevenness of water droplets and stains on the back surface. These are U.S. Pat.No. 3,404,004,
It is known in JP-A-57-197540 and JP-A-55-36560.
However, these hydrocarbon-based nonionic surfactants have a low melting point, and liquid ones are commonly used, and when used as a solid processing agent, the shape of the solid processing agent changes during storage and is a material that is completely unsuitable for practical use. .

Further investigations by the present inventors have revealed that, even when a solid or pasty hydrocarbon nonionic surfactant or other hydrocarbon surfactant is used, storage of the granules and tablets in a solid state can be carried out at a high temperature. The agent expands with time to increase the porosity, and the contained processing agent component is decomposed and reduced, or, in the case of powder or granules, causes blocking and cannot be constantly supplied to the processing tank. In the case of tablets, it has also been found that there is a new problem that the strength is reduced and the tablet is broken to cause poor feeding.

Therefore, there has been a demand for the development of a solid stabilizing agent which is free from unevenness of water droplets and stains on the back surface and which has excellent storage stability.

Not only the problem of the solid processing agent but also the problem of the performance of the stabilizing solution, those containing these hydrocarbon-based nonionic surfactants have a large temperature dependency and can be continuously used in an environment having a temperature change. It has been found that oily suspended matter may be generated when the treatment is carried out, and even a small amount of this oil promotes the generation of tar and causes abrasion of the photosensitive material by the suspended matter. Further, it was also found that if the treatment is further continued, a large amount of oily suspended matter degrades the wettability of the stabilizing solution, and the water droplet unevenness and the back surface stain increase.

Accordingly, it is an object of the present invention to provide a silver halide which is effective in preventing unevenness of water droplets, stains on the back surface, scratches and floating substances in a stabilizing solution of a light-sensitive material and having excellent storage stability when used as a solid stabilizing agent. An object of the present invention is to provide a stabilizing composition for a photographic light-sensitive material and a solid stabilizing agent whose performance is guaranteed.

[0014]

An object of the present invention is to provide a solid stabilizing agent for a silver halide photographic light-sensitive material containing a fluorine-based anionic surfactant and a fluorine-based anionic surfactant represented by the general formula (I) That the solid stabilizing agent is in the form of granules or tablets weighed in advance, and that the tablet or bulk density of the bulk density is 1.0 to 2.5 g / cm ^3.
0.4 to 1.7 g / cm ³ granules, water content of 0.1
A method of processing a silver halide photographic light-sensitive material, wherein the solid stabilizing agent for the silver halide photographic light-sensitive material is substantially directly replenished to a stabilization processing tank of an automatic processor; A stabilizing composition for a silver halide photographic light-sensitive material containing a compound represented by the above general formula [I],
Is achieved by

That is, as a result of various studies by the present inventors, among the anionic surfactants, those substituted with fluorine have a stable performance even during continuous processing, and the same results with the solid processing agent. The present invention has been found to be a stabilizer having good storage stability without causing blocking or swelling, and the present invention has been accomplished.

Hereinafter, the present invention will be described specifically.

First, in the general formula [I], Rf represents a saturated or unsaturated alkyl group containing at least one fluorine atom (for example, an alkyl group, an alkenyl group, an alkynyl group), and preferably has 4 to 12 carbon atoms. And more preferably an alkyl group having 6 to 9 carbon atoms. A is preferably —SO ₃ M, and M, M ₁ and M ₂ are preferably Li,
K and Na are most preferably Li. m is 0 or 1, n is 0
Or an integer of 1 to 10, preferably m = 0, n = 0
It is.

The representative compounds represented by the general formula [I] are shown below, but are not limited thereto.

[0019]

Embedded image

[0020]

Embedded image

Among the above compounds, particularly preferred compounds are
(I-1), (I-2) and (I-4).

The amount of the compound represented by the general formula [I] is preferably in the range of 0.01 to 0.5 g, more preferably in the range of 0.03 to 0.1 g per liter of the stabilizing solution. When the solid stabilizing agent is used, the content of the compound represented by the general formula [I] is
It is 0.1 to 100% by weight, preferably 0.1 to 90% by weight, more preferably 1 to 30% by weight.

These compounds can be synthesized by a usual method, and are also available as commercial products.

Next, the solid stabilizing agent and the composition of the present invention preferably contain a formalin substitute compound, which is becoming the mainstream stabilizer instead of formalin in recent years. The formalin replacement compound is usually a powder in many cases, and is desirably made into granules or tablets. However, even if it is attempted to granulate and tablet alone, it is difficult to granulate due to its weak bonding force, and even if it is compressed, the tablet becomes brittle. Therefore, when granulating with the surfactant of the present invention (general formula [I]),
A granulated product having an average particle size (200 to 750 μm) can be obtained, and it is compressed into a tablet to obtain a tablet having a hardness of 60 kg or more and a good formability. In addition, the present inventors have found a new effect of preventing sticking when compressing a powder.

Specifically, formalin substitute compounds are represented by the following general formulas [F], [G], [K-1], [K-2] and [K-3]
And a hexamethylenetetramine-based compound.

[0026]

Embedded image

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

[0028]

Embedded image

(R ₁ and R ₂ each represent an alkyl group having 1 to 5 carbon atoms), and n represents an integer of 1 to 4.

In the general formula [F], Z represents a group of atoms necessary for forming 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.

[0034]

Embedded image

[0035]

Embedded image

Other specific examples of the compounds include compounds (1) described on pages 9 to 14 of JP-A-4-299340.
To (90).

Among the specific examples of the compound represented by the general formula [F], the most preferred compound is F-2.

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

The amount of the compound represented by the general 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.

Next, the compound represented by the general formula [G] used in the present invention will be described.

[0041]

Embedded image

Wherein R ₃ and R ₄ are a hydrogen atom, a substituent, or
R ₃ and R ₄ represent a ring fused together to form a ring containing 1 or 2 nitrogen atoms. Further, R ₃ and R ₄ may be the same or different.

In the general formula [G], the substituents represented by R ₃ and R ₄ are not particularly limited, but are typically alkyl (having 1 to 10 carbon atoms, and may be linear or branched. ), Aryl (preferably phenyl), anilino, acylamino (alkylcarbonylamino group, arylcarbonylamino group, etc.), sulfonamide (alkylsulfonylamino group, arylsulfonylamino group, etc.), alkylthio, arylthio, alkenyl (preferably Is a group having 2 to 11 carbon atoms, which may be straight-chain or branched), and cycloalkyl (preferably having 3 to 10 carbon atoms, particularly 5 to 7 carbon atoms). And cycloalkenyl (preferably having 3 carbon atoms)
~ 12, especially 5 ~ 7), alkynyl, heterocyclic (5 ~ 7
Preferred is a 7-membered one. Specifically, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, etc., sulfonyl (alkylsulfonyl, arylsulfonyl, etc.), sulfinyl (alkylsulfinyl, etc.) , Arylsulfinyl group, etc.), phosphonyl (alkylphosphonyl group, alkoxyphosphonyl group, aryloxyphosphonyl group, arylphosphonyl group, etc.), acyl (alkylcarbonyl group, arylcarbonyl group, etc.),
Carbamoyl (alkylcarbamoyl group, arylcarbamoyl group, etc.), sulfamoyl (alkylsulfamoyl group, arylsulfamoyl group, etc.), cyano, alkoxy, aryloxy, heterocyclic oxy (one having a 5- to 7-membered heterocyclic ring) Preferably, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5-
Oxy group, etc., siloxy (trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.), acyloxy (alkylcarbonyloxy group, arylcarbonyloxy group, etc.), carbamoyloxy (alkylcarbamoyloxy group, arylcarbamoyloxy group, etc.) , Amino, alkylamino, imide (succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarimide group, etc.), ureide (alkylureido group, arylureido group, etc.), sulfamoylamino (alkylsulfur Famoylamino groups, arylsulfamoylamino groups, etc.), alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio (5 to 7-membered heterocyclic thio groups are preferred). Properly, for example, 2-pyridylthio group,
2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5-
Such as triazole-6-thio group), spiro compound residue (spiro [3.3] heptan-1-yl etc.), bridged hydrocarbon compound residue (bicyclo [2.2.1] heptan-1-yl) , Tricyclo [3.3.1.1] decan-1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl, etc.).

Each of the groups represented by R ₃ and R ₄ includes those further having a substituent. Preferred specific substituents are a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group,
Examples include an amino group, an acid group, and an alkoxy group.

Examples of the compounds represented by the general formula [G] are shown below.

[0046]

Embedded image

Specific illustrative compounds including these include compounds described in JP-A-4-359249, pp. 10-20 (A-
1) to (A-76), Compounds (X-1) to (X-76) described in 4-362943, pp. 14 to 23, and compounds described in 6-83008, pp. 18 to 19 Examples (F-1) to (F-17) are mentioned.

Among the specific examples of the compounds represented by the general formula [G], the most preferred compounds are G-3, G-5 and G-6.
Is mentioned.

The compound represented by the general formula [G] is preferably used in combination with a nitrogen-containing heteroaromatic compound. As the nitrogen-containing heteroaromatic ring compound, specifically, 1,2,4-
Examples thereof include triazole and imidazole, and examples thereof include exemplified compounds (I-1) to (I-48) described on page 4 to page 7 of JP-A-4-359249.

The amount of the compound represented by the general formula [G] is preferably 0.05 to 20 g, more preferably 0.1 to 15 g, and particularly preferably 0.5 to 15 g per liter of the stabilizing solution.
It is in the range of 10 g.

The general formulas [K-1] to [K-3] will be described.

[0052]

Embedded image

In the formula, R represents a hydrogen atom or an aliphatic hydrocarbon group, V represents a group which leaves by hydrolysis, M and Y each represent a hydrogen atom or a group which leaves by hydrolysis, n Represents an integer of 1 to 10, Z represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a group capable of leaving by hydrolysis, and R ₅ represents an aliphatic hydrocarbon group or an aryl group. Z may combine with R ₅ to form a ring.

The aliphatic hydrocarbon groups represented by R, R ₅ and Z include saturated alkyl groups (for example, unsubstituted alkyl groups such as methyl, ethyl and butyl, and carboxymethyl, methoxymethyl, methoxyethyl and hydroxy). And substituted alkyl groups such as ethyl and benzyl), unsaturated alkyl groups (eg, allyl and 2-butenyl), and cyclic alkyl groups (eg, cyclopentyl and cyclohexyl). The aryl group represented by R ₅ and Z may be substituted, and examples of the substituent include an alkyl group (methyl, ethyl, methoxyethyl, benzyl, carboxymethyl, sulfopropyl, etc.) and an aryl group (phenyl, p-
Methoxyphenyl etc.), hydroxy group, alkoxy group (methoxy, ethoxy, methoxyethoxy etc.), aryloxy group (phenoxy, p-carboxyphenyl etc.),
Carboxy group, sulfo group, alkoxycarbonyl group (methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl group (phenoxycarbonyl, etc.), amino group (N, N-dimethylamino, N-ethylamino, N-phenylamino, etc.), Acylamide groups (acetamido, benzamide, etc.), carbamoyl groups (carbamoyl, N-methylcarbamoyl, N, N-tetramethylenecarbamoyl, etc.),
Sulfonamide group (methanesulfonamide, benzenesulfonamide, etc.), sulfamoyl group (N-ethylsulfamoyl, N, N-diethylsulfamoyl, etc.), alkylsulfonyl group (methanesulfonyl, ethanesulfonyl, etc.), arylsulfonyl group (Benzenesulfonyl, p-
Groups such as toluenesulfonyl) and an acyl group (acetyl, benzoyl, etc.).

Examples of the leaving group by hydrolysis represented by V, W, Y and Z include, for example, an acyl group (acetyl, benzoyl, trifluoroacetyl, monochloroacetyl, etc.), a trialkylsilyl group (trimethylsilyl, etc.) and the like. No.

The ring formed by combining R ₅ with Z is 5-8
And a membered saturated or fused ring in which a part of the bonding carbon chain is substituted by another hetero atom. Specifically, rings such as 1,2-dioxacyclopentane, m-dioxane, trioxane, tetraoxane, benzodioxolan, and the like can be mentioned.

Examples of the cation represented by M include a hydrogen ion, an alkali metal ion (an ion such as lithium, sodium and potassium), an alkaline earth metal ion (an ion such as magnesium and calcium), an ammonium ion,
Examples thereof include organic ammonium ions (ammonium ions such as triethylammonium, tripropylammonium, and tetramethylammonium), and pyridinium ions.

The aliphatic hydrocarbon group represented by R is preferably a lower alkyl group having 1 or 2 carbon atoms, and more preferably a hydrogen atom.

Specific examples of the compounds are shown below, but the invention is not limited thereto.

[0060]

Embedded image

[0061]

Embedded image

Of these, preferred is (K-1-
1), (K-1-2), (K-1-3), (K-2-4), (K-3-4),
(K-3-4), (K-3-6) and (K-3-7).
Also, the amount of these compounds to be added is 0.01 to 1 liter of the stabilizing solution.
An amount of 20 g is preferable, more preferably 0.03 to 15 g,
Particularly preferred is 0.05 to 10 g.

The above general formulas [F], [G], [K-1], [K
-2] and a compound represented by [K-3], a hexamethylenetetramine-based compound can also be used. Specific compound examples are shown below.

[0064]

Embedded image

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

Preferred among these compounds are A-1 to A-1.
A-7, and particularly preferably A-1.

The hexamethylenetetramine compound is preferably used in an amount of 0.01 to 20 g per liter of the stabilizing solution.

The above general formulas [F], [G], [K-1], [K
-2], when the compound represented by [K-3] and the hexamethylenetetramine-based compound are contained in the solid treating agent, the content is 10 to 90% by weight, preferably 50 to 80% by weight.

In the present invention, the solid stabilizing agent preferably contains a chelating agent having a chelate stability constant of 8 or more with respect to iron ions. Here, the chelate stability constant is defined as “Stability Co.” by LGSillen / AEMartell.
nstants of Metal-ion Complexes ”, The Chemical Soc
iery, London (1964), by S. Chaberek. AEMartell, "Or
ganic Sequestering Agents ", 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 above chelating agent is used in an amount of 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 agent include ammonium compounds. These are supplied by ammonium salts of various inorganic compounds, specifically, ammonium bromide, ammonium carbonate,
Ammonium chloride, ammonium phosphate and the like. These may be used alone or in combination of two or more. The amount of the ammonium compound added is preferably in the range of 0.001 to 1.0 mol, more preferably in the range of 0.002 to 2.0 mol, per liter of the stabilizing solution.

Further, the stabilizing agent preferably 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,
Examples include ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite.

The above-mentioned sulfite is used as a stabilizing agent in at least one form.
It is preferable to add an amount such that the amount becomes × 10 ⁻³ mol / l, more preferably an amount such that the amount becomes 5 × 10 ⁻³ to 10 ⁻¹ mol / l. Has a preventive effect.

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

The stabilizing solution includes organic acid salts (citrate, acetate, succinate, oxalate, benzoate, etc.), pH adjusters (phosphate, borate, hydrochloric acid, sulfate, etc.). ) Etc. can be added. The addition amount of these compounds is p
Any combination of amounts necessary to maintain H and not adversely affect the storage stability and precipitation of color photographic images can be used.

In the present invention, known fungicides such as 5-chloro-2-methylisothiazolin-3-one and benzisothiazoline are preferably used in combination as long as the effects of the present invention are not impaired.

Preferred processing steps in the processing method using the stabilizing agent 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 → fixation → stable color development → bleach-fix → bleach-fix → stable color development → bleach → bleach-fix → fix → stable. 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.

To solidify the photographic processing agent, a concentrated liquid or a fine or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binder is added to the surface of the temporarily formed photographic processing agent. Any means can be adopted such as forming a coating layer by spraying (Japanese Patent Laid-Open Nos. 4-29136, 4-85533,
4-85534, 4-85535, 4-85536, 4-172
No. 341).

The solid processing agent referred to in the present invention may be in the form of powder, granules, pills or tablets, but is preferably in the form of granules and tablets.

A preferred tablet production method is a method in which a powdery solid processing agent is granulated and then subjected to a tableting step to form the tablet. There is an advantage that the solubility and storage stability are improved as compared to a solid processing agent formed by simply mixing a solid processing agent component and a tableting step, and as a result, photographic performance is also stabilized.

As a granulation method for tablet formation, known methods such as tumbling granulation, extrusion granulation, compression granulation, pulverization granulation, stirring granulation, fluidized bed granulation, and spray drying granulation are used. Can be.

The average particle size of the obtained granules is 100 to 800
μm, preferably 200 μm.
750750 μm. The average particle size is smaller than 100 μm,
Alternatively, when it is larger than 800 μm, when the above-mentioned granulated material is mixed and compressed under pressure, the components become non-uniform, so-called segregation, which is not preferable.

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

When the obtained granules are compressed under pressure, a known compressor, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a briquetting machine may be used. it can.

In the present invention, the water content of the solid processing agent set by adding water during granulation and drying conditions may be in the range of 0.1 to 15% by weight, preferably 0.3 to 10% by weight.
It is. Here, the moisture content is determined using a commercially available electronic moisture meter.
Heat until constant weight at 105 ° C, determine the reduced weight,
The water content is calculated as the water content.

[0092] The bulk density of the solid processing agent, and in view of its solubility, may solid processing agent is a tablet 1.0g / cm ³ ~2.5g / cm ³ from the viewpoint of the desired effect of the present invention preferably , more preferably from ^{1.5g / cm 3 ~2.0g / cm 3} . 1.0g / cm ³
It is preferable that the ratio is larger than 2.5 g / cm ^{3 in} terms of the strength of the obtained solid, from the viewpoint of the solubility of the obtained solid. When the solid processing agent is granules or powder, the bulk density is 0.4
Preferably having ~1.7g / cm ^3, more preferably 0.7 to
1.25 g / cm ³ . Here, the bulk density, in the case of granular,
10 g of the sample is gently injected into a commercially available 25 ml measuring cylinder, and the volume is measured as the weight / volume. In the case of a tablet, the weight / volume is used.

The physical strength Z of the tablet-like solid processing agent of the present invention
Is from 0.8 to 4, preferably from 1.5 to 3.5. When the strength is less than 0.8, the obtained solid processing agent is extremely brittle and cannot be put to practical use. Note that the physical strength Z here is defined by the following equation.

Z = Compressive breaking strength of tablet (kg) / Length of tablet in longitudinal direction (mm) The compressive breaking strength of tablet is the breaking strength when pressure is applied to the longitudinal direction of tablet. Monsanto type hardness tester, Stoke type hardness tester, speed checker (manufactured by Okada Seiko Co., Ltd.)
It can be measured using a commercially available instrument or the like.

The tablet of the present invention can take any shape, but a disk-shaped tablet is preferred from the viewpoint of productivity and handling. In the case of the disc-shaped tablet, the length in the longitudinal direction of the tablet refers to the diameter of the tablet, and the diameter at this time can be set to an arbitrary value according to the purpose of use. From the viewpoint of productivity, preferably 5 to 50 mm, more preferably 7 to 30 mm
It is. On the other hand, the ratio x of the length x in the longitudinal direction of the tablet to the thickness h
/ H is preferably in the range of 1.0 to 6.0, more preferably 2.5 to 5.0. When the above ratio is less than 1.0, the thickness of the obtained tablet is increased, so that the solubility is deteriorated and the productivity is deteriorated. If it exceeds 6.0, the desired strength cannot be obtained.

The tablet according to the present invention preferably has a weight per tablet of 0.1 to 30 g from the viewpoint of productivity.

The form of use of the tablet-like solid processing agent according to the present invention can be any method depending on the purpose. However, from the viewpoint of miniaturization of the automatic developing machine and reduction of the processing waste liquid, etc. A method of directly charging a replenisher into a treatment tank is preferred.

In the present invention, in order to supply the solid photographic processing agent to the automatic processing machine, the area of the processed photographic material is integrated by a detecting device attached to the photosensitive material insertion opening of the automatic processing machine to reach 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 the solidification is performed.

The area detecting device for 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 it can surely detect the photosensitive material to be processed.

Regarding the method of replenishing the solid photographic processing agent, the solid photographic processing agent is directly replenished to a processing tank portion of an automatic developing machine, for example, a processing solution tank, a processing solution circulating system or a temperature control tank and a processing solution filtration filter portion.

When a 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 circulating system, the temperature control tank, the processing liquid filtration filter section, etc., a signal is sent from the area detecting device of the photosensitive material to be processed by a predetermined amount through the replenishment mechanism, and the photosensitive material is replenished for each unit. Is preferred.

Further, the solid photographic processing agent replenishing section is devised so that the scattered processing solution due to the temperature of the processing tank of the automatic processing machine, 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.

FIGS. 2 to 4 show an example of a solid processing agent supply device in the case where tablets are aligned and stored as a solid processing agent kit. In FIG. 2, the solid processing agent 16 is a solid processing agent storage cylinder.
23-1, 23-2, and 23-3 are stored in a predetermined amount, and the rotating disk 21 connected to the motor 14 rotates according to the processing amount of the photosensitive material, and is stored in the solid processing agent storage cylinder. 1 of solid processing agent
One of them is stored in a solid processing agent transport pocket, transported to the drop port 22, and put into a filter tank (or dissolution tank) attached to a processing tank in an automatic developing machine, one tablet at a time.

In FIG. 4, a solid processing agent (hereinafter also referred to as a tablet or tablet chemical) 111 is housed in a container (cartridge) 101 divided into a plurality of rooms, and is sealed by a slide cap 102. When this cartridge is set on a cartridge support table 103 of a solid processing agent automatic supply device installed at the upper part of the processing tank of the automatic developing machine, the cap 102 is opened, and tablets are obliquely fixed from the cartridge to the rotary cylinder. It rolls into the slit 105 of 104.
The cutouts 105 of the rotary cylinder 104 are cut differently so that a plurality of tablets stored in different rooms in the cartridge do not roll down at the same time.

In accordance with the processing amount of the photosensitive material, the rotating cylinder 104
However, the shutter is opened at the same time as the shutter 108 is opened, and tablets are supplied one by one into a filter tank (or dissolution tank) 106 provided in the processing tank.

FIG. 5 shows an example of a tablet parts feeder type feeding apparatus packaged in a package and a solid processing agent package. When the packaged package of tablet chemicals is opened and put into the hopper 133, the movable member 124 rotates according to the processing amount of the photosensitive material, and the tablet chemicals are aligned with the tablet alignment unit 129. After a certain amount of alignment, the movable member 124 stops. At this time, the sweeper 123 is very effective for the tablet to enter the pocket 122 of the movable member 124 and to be aligned with the tablet alignment section 129.

The first shutter 131 rotates according to the processing amount of the photosensitive material, and the tablet chemical falls. Next, the first shutter 131 is rotated in the reverse direction, and one tablet is released from the shutters 131 and 13.
Sandwich between two. The shutter 132 rotates, and the tablet chemical passes through the discharge section and is supplied to the input section. Next, shutter 132
Rotates in the reverse direction, and the shutter 131 closes.

[0108]

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

Example 1 A solid stabilizing agent for color negative of the present invention (corresponding to 100 l of replenisher) was prepared according to the following procedure.

Operation (1) 200 g of m-hydroxybenzaldehyde (hereinafter sometimes abbreviated as mHBA) and 21 g of lithium hydroxide monohydrate were pulverized in an air jet pulverizer until the average particle diameter 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, and the pulverized mixture A-1 was used.
I got

Operation (2) The above ground mixture A-1 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. Let dry for hours. Next, the granules are placed in a vacuum.
After drying at 40 ° C. for 2 hours, the water content of the granulated product is 0.1 to 0.3.
It was removed until the weight% was reached, and a granulated product A-2 was obtained. The particle size of the granulated product was 300 to 600 μm, and the bulk density was 0.8 g / cm ³ .

Operation (3) Further, the above granulated product A-2 was subjected to compression tableting using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho to make the filling amount per tablet 9.0 g, and compressed tablets. A color negative tablet A-3 having a diameter of 30 mm for stable replenishment was prepared. The bulk density of this tablet was 1.7 g / cm ³ .

Operation (4) Emulgen 985 (polyoxyethylene nonylphenyl ether) was added to 200 g of m-hydroxybenzaldehyde and 21 g of lithium hydroxide monohydrate, and pulverized and granulated in the same manner as in operations (1) to (3). Then, tableting was performed to obtain a crushed mixture B-1, a granulated product B-2, and a tablet B-3.

Operation (5) Next, emulgen 985 was replaced with tetramethylammonium chloride, and pulverization, granulation, and the like were performed in the same manner as in operations (1) to (3).
Tableting was performed to obtain a crushed mixture C-1, a granulated product C-2, and a tablet C-3.

Operation (6) Further, the tetramethylammonium chloride was replaced with the compound represented by the general formula [I] (described in Table 1), and the pulverized mixtures D-1 to J-1 and the granulated products D-2 to J- 2. Tablets D-3 to J-3 were obtained.

The samples A-1 to J-3 obtained by the above operation were sealed in a polyethylene bag, and were kept at -1 ° C. for 1 week,
A storage test was performed under the conditions of storage at 50 ° C. and a humidity of 60% RH for 1 week and further at −1 ° C. for 1 month, and the storage method was evaluated by the following method.

(Evaluation method) (a) Reduction rate of m-HBA The sample after storage was opened, 45 g of granules and 5 tablets were dispensed, completely dissolved in 1 liter of water, and spectrophotometer (Shimadzu The absorbance at 254 nm was measured using a UV-160A (manufactured by Seisakusho), and the reduction ratio after storage was calculated as compared with that before storage.

(A) State after storage The sample after storage was opened and observed visually.

(C) Expansion Ratio of Diameter The sample of the tablet after storage was opened, 10 pieces were taken out, the diameter was measured with a vernier caliper, and the average value was compared with the diameter before storage to calculate the expansion ratio.

(D) Presence or absence of blocking A sample of the pulverized mixture and the granules after storage was opened, 40 g of each sample was taken out, sieved with a 2 mm mesh sieve, and the remaining granules were visually checked to evaluate the blocking.

(Evaluation Criteria) (A) State after Storage ◎: No change before and after storage ：: Some spots are observed, but almost no change △: Surface is colored black ×: Shape changes, The surface is also colored black. (D) Presence or absence of blocking ：: All of the crushed mixture and granules have passed. １〜: 1 to 2% of the whole remained, but crushed with a finger. All passed. △: 10% or more of the whole There were some that remained uncrushed by 1 to 2% even when crushed with a finger. ×: There were 20% or more that were not crushed even when crushed with a finger. Table 1 shows the results.

[0123]

[Table 1]

From the results shown in Table 1, it can be seen that the solid stabilizing agent of the present invention is very excellent in storage stability.

Example 2 Next, tablets were prepared in the same manner as in Experiment No. 1-15 of Example 1 except that m-HBA (exemplified compound F-2) was replaced with the compounds shown in Table 2. The same evaluation was performed.

Table 2 shows the results.

[0127]

[Table 2]

From the results shown in Table 2, it can be seen that the effect of the present invention is more remarkably exhibited when a formaldehyde substitute compound is used in combination.

Example 3 In Experiment No. 1-15 of Example 1, the kneading time during granulation and the amount of added water were adjusted to produce a granulated product having a bulk density shown in Table 3. Further, the tableting pressure at the time of compression was adjusted to produce tablets having a bulk density shown in Table 3. The sample thus prepared was sealed with a polyethylene bag and kept at -1 ° C for 2 weeks.
Subsequently, it was stored at 60 ° C. and 80% RH for one week and further at −1 ° C. for one month, and evaluated in the same manner as in Example 1.

Table 3 shows the results.

[0131]

[Table 3]

According to Table 3, in the present invention, when the bulk density of the granules is 0.4 to 1.7 g / cm ³ , it is further 0.7 to 1.25 g / cm ^3.
It can be seen that the effect is superior to the case of. When the tablet has a bulk density of 1.0 to 2.5 g / cm ³ ,
It can be seen that the effect is more excellent when g / cm ³ .

Example 4 In Experiment No. 1-15 of Example 1, the drying time was adjusted to produce the one having the water content shown in Table 4. The sample thus prepared was sealed with a polyethylene bag and kept at -1 ° C for 2 hours.
After storage at 60 ° C. and 80% RH for one week and then at −1 ° C. for one month, evaluation was performed in the same manner as in Example 1.

Table 4 shows the results.

[0135]

[Table 4]

Table 4 shows that in the present invention, the water content was 0.1%.
It can be seen that excellent effects are exhibited when the amount is up to 15% by weight, more preferably 0.3 to 10% by weight.

Example 5 A replenishing unit of a color negative film processor CL-KP-50QA was modified as shown in FIG. 1, and a solid processing agent replenishing unit shown in FIG. 3 was used. After imagewise exposing the Konica Color Super DD100 film, a columnar container containing the tablets was set in the tablet charging section, and processing was performed at a rate of 15 tablets per day.

FIG. 1 shows a solid processing agent replenishing apparatus 2A of the present invention.
FIG. 4 is a view showing a mounting position where 2B, 2C, and 2D are mounted on a KP-50QA (autonomous machine A);
A, 2B, 2C, and 2D are a color developing tank 1A and a bleaching tank 1 respectively.
B, fixing tank 1C, and stabilizing tank 1D are attached at the positions shown by oblique lines above. FIGS. 2, 3 and 4 are block diagrams showing one embodiment of the solid processing agent replenishing (feeding) devices 2A, 2B, 2C and 2D, in which the solid processing agent 1 is fed to the side of each tank. A room 11 is provided.

In FIG. 3, while the solid processing agent is dissolved in the dissolution chamber 11, the concentration in the processing tank is adjusted via the filter 12 provided in the processing tank. Further, the processing amount information detecting means detects the processing amount of the film processed in the self-developing machine, and the detected information is transmitted to the processing amount supply control means, which controls the start and stop of the motor 14 by the processing amount supply control means. I do.
That is, when the processing amount reaches a certain amount and the concentration of the processing liquid deteriorates, the motor 14 rotates to move the slide plate 15 with the gear 31 and the pushing plate 32, and the solid processing agent storage cylinders 2-1, 2 -2, 2-
From 3, the solid processing agent 16 is received by the transfer port 18 and supplied to the melting chamber 11. Reference numeral 30 denotes a solid processing agent storage case. In FIG. 2, three solid processing agent storage tubes 23-1, 23-2, and 23-3 are provided. In addition, 21 is a rotating disk, 22 is a drop port, and 24 is a solid processing agent.

In FIG. 3, the solid processing agent storage cylinders 2-1, 2, 3
When the supply is completed, the lid 19 is opened so that the lid 19 can be opened and replaced all at once, or can be replaced for each storage cylinder.

The processing steps are described below.

Processing time Processing time Processing temperature Color development 3 minutes 15 seconds 38.0 ° C Bleaching 45 seconds 38.0 ° C Fixing-1 45 seconds 38.0 ° C Fixing-2 45 seconds 38.0 ° C Stable-1 20 seconds 38.0 ° C Stable-2 20 seconds 38.0 ℃ Stable-3 20 seconds 38.0 ° C. Drying 80 seconds 55 ° C. Fixing is from 2 to 1 and stabilizing is from 3 to 2, 2 to 1. The bleaching tank was aerated with an air pump.

Further, the evaporation correction is performed at the time of temperature control in the color developing, bleaching, fixing-1, fixing-2, stable-1, stable-2, and stable-3 tanks for 10 hours, 6.5 ml, 7 ml, and 7 ml per hour, respectively. , 8.6ml, 8.6ml, 9.3
Evaporation correction was performed by a program for performing evaporative rehydration of ml.
When not in operation, the non-operation time is counted and color development, bleaching,
Evaporation-corrected water for fixing-1, fixing-2, stable-1, stable-2, stable-3 was 7.5 ml, 5 ml, 6 ml, 6 ml, 5 ml, and 1 hour, respectively.
5 ml and 5 ml were refilled at the start of operation. The tank liquid at the start was prepared using a replenisher of Konica Color Negative Film processing agent CNK-4-52 and a starter.

Next, the following color negative treating agents were prepared.

1) Tablet for replenishing color development for color negative film Operation (7) CD-4 [4-amino-3-methyl-N-ethyl-β- (hydroxy) ethylaniline sulfate] 60 g of developing agent In a commercially available hammer mill And pulverize until the average particle size becomes 10 μm. After granulating this fine powder by adding 10 ml of water for about 7 minutes at room temperature in a commercially available stirring granulator, the granulated material is dried with a fluid bed dryer.
After drying at 40 ° C. for 2 hours, the water content of the granulated product was almost completely removed to prepare granules (8) for replenishing color development for color negative.

Operation (8) 69.4 g of hydroxylamine sulfate and 4 g of Pine Flow (manufactured by Matsutani Chemical) are ground in the same manner as in the operation (1), and then mixed and granulated. The amount of water added was 3.5 ml, and after granulation,
After drying for 0 minutes, the water content of the granulated product was almost completely removed to prepare granules (9) for replenishing color development for color negative.

Operation (9) Disodium 1-hydroxyethane-1,1-diphosphonate 15
g, 72.8 g of potassium sulfite, 350 g of potassium carbonate, 3 g of sodium hydrogencarbonate, 3.7 g of sodium bromide and 22 g of mannitol 22 g of polyethylene glycol 6000 5.0 g were ground and mixed in the same manner as in steps (1) and (2), and water was added. Quantity 40
Perform granulation in ml. After the granulation, the granulated product was dried at 70 ° C. for 60 minutes to almost completely remove the moisture from the granulated product, thereby producing a color developing replenishing granule (10) for color negative.

The above-mentioned granules (8) to (10) for color development and replenishment for color negative were mixed, and 2 g of sodium N-myristoylalanine was added to the granules thus prepared. Mix for 10 minutes in a humidified room using a mixer. Next, the mixture was added to Kikusui Seisakusho Co., Ltd.
Using a tableting machine modified from Tough Press Collect 1527HU, a tableting machine was compressed and tableted with a filling amount of 10 g per tablet to prepare a color developing replenishing tablet for color negative having a diameter of 30 mm.

2) Tablet for bleach replenishment for color negative Operation (10) 1,3-propanediaminetetraacetic acid potassium ferric monohydrate 237
g, 70 g of succinic acid and 10 g of 1,3-propanediaminetetraacetic acid
Is crushed and granulated in the same manner as in the operations (1) and (2). The amount of water spray is adjusted to 5.0 ml, and after granulation, the granules are dried at 60 ° C. for 7 minutes. Next, the granules are dried at 40 ° C. for 2 hours in vacuum to remove water almost completely.

Operation (11) 90 g of potassium bromide, 104 g of potassium carbonate, 100 g of succinic acid
Is crushed and granulated in the same manner as in the operations (1) and (2). The amount of water spray was adjusted to 1.0 ml, and after granulation, the granulated product was dried at 70 ° C. for 3 minutes. Next, the granulated material is dried in vacuum at 40 ° C. for 120 minutes to remove water almost completely.

Operation (12) The granulated product prepared in the above operations (11) and (12) is
Mix evenly for 10 minutes using a mixer in a room humidified below RH. Next, the mixture was filled into tablets using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho.
The tablet was compressed to 10.0 g and compression tableting was performed to prepare 80 tablets for replenishing bleaching for color negative.

3) Tablet for fixation replenishment for color negative Operation (13) 950 g of potassium thiosulfate, sodium thiocyanate 2020
g, 120 g of sodium sulfite, 150 g of potassium carbonate, and 10 g of disodium ethylenediaminetetraacetate (1).
Pulverization and granulation are performed as in (2). The spray amount of water is 30.0 ml, and after granulation, it is dried at 65 ° C. for 60 minutes. Next, the granulated material is dried at 40 ° C. for 480 minutes in a vacuum to remove water almost completely.

Operation (14) The granules prepared in the above operation (14) 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
A tableting machine modified from 27HU with a filling amount of 10.0 g per tablet
Then, compression tableting was carried out to prepare 200 fixing refill tablets for color negative.

4) Tablet for stable replenishment for color negative The tablets described in Table 5 are used.

By repeating the above operation, the required number of tablets for processing were prepared for the following running experiments.

Each of the refill tablets prepared by the above-described operation during the temperature control of the automatic developing machine is individually supplied to the refill tablet supplying device provided to the automatic developing machine.
I set 20 pieces. For color development replenishment tablets, 7.1 135-size 24 film films, 3.6 for bleach replenishment tablets, 1.2 for fixation replenishment tablets, and 125 for stable replenishment tablets, one for each filter tank. Is done.

When two 135-size 24 film films are processed, replenished hot water is supplied from the hot water supply device to the color developing tank.
40ml, 10ml for bleaching tank, 40ml for fixing tank, 80ml for stabilizing tank
Set as supplied.

Color negative film DD-100 (Konica Corporation)
Was used as a test photosensitive material.

After the photosensitive material sample was imagewise exposed according to a conventional method,
A running process was performed according to the above process steps. However, the running process was continuously performed (2R) until twice the capacity of the bleach tank layer was replenished.

After the running process, the film subjected to the imagewise exposure was processed, and the sulfide was precipitated in the stabilizing tank, tar was generated, and the adhered matter was formed on the tank wall. The processed film after the running was completed. The sample was observed for dirt, scratches, and foreign matter adhesion. The highest density part magenta density and the lowest density part yellow density of the processed film sample were measured, and then measured at 70 ° C. and 25% relative humidity.
After storage for a day, the maximum density of magenta and the maximum density of yellow after storage were measured, and the fading rate and the rate of density increase of the dye were determined. Table 5 shows the results.

The evaluation criteria were set as follows.

(Evaluation Criteria) Presence or absence of sulfide precipitates ◎ Not at all ○ No precipitate on liquid surface, but can be confirmed as suspended matter and may have practical problems △ Suspended matter, sedimentation × Suspended matter, sedimentation And generation of tar adhered to the liquid interface of the rack. ○ Not at all △ There is a slight amount, and there may be a problem in practical use. × Many presence or absence of adhered substances ◎ Not at all ○ Slight, but there is no problem as a product △ Can not be made into a product × Can not be made into a product at all Stain on the back surface after processing ○ No

[0163]

[Table 5]

From the results shown in Table 5, it can be seen that when the solid stabilizing agent of the present invention is used for the treatment, the desired effects of the present invention are favorably exhibited. That is, the solid stabilizing agent for processing a silver halide photographic light-sensitive material of the present invention is a solid processing agent that enables the use of a solid chemical without complicated operation by a user,
In addition, the generation of precipitates and suspended solids in the stabilizing solution is prevented, and the storage stability of the stabilizing solution is improved.
It can be seen that the occurrence of the back surface stain and yellow stain is improved, and a solid processing agent having good image stability can be provided.

Example 6 Tablets for stable replenishment used in Example 5 (listed in Table 5)
Dissolve 10 of them in 50 l of water to make a stable replenisher,
80ml each time 2 pieces of 5mm size 24 film are processed
A pump was provided so as to be supplied, and continuous processing (2R) was performed in the same manner as in Example 5 to evaluate the results. The same results as in Example 5 were obtained.

[0166]

According to the present invention, a solid stabilizing agent for a silver halide photographic material having the following features can be provided.

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

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

There is no generation of floating matter during processing and no unevenness of water droplets, stains on the back surface, and scratches on the processed photosensitive material.

The storage stability of the solid stabilizing agent is improved.

[Brief description of the drawings]

FIG. 1 is a configuration diagram showing a mounting position of a solid processing agent replenishing device on an automatic processing machine.

FIG. 2 is a mechanism diagram of a solid processing agent charging device.

FIG. 3 is a configuration diagram of another solid processing agent introducing device.

FIG. 4 is a configuration diagram of an example of a solid processing agent supply device, an explanatory diagram of a rotary cylinder, and a perspective view of a slide-type cap and a cartridge (discharge unit).

FIG. 5 is a cross-sectional view of an example of a parts feeder type supply device and a perspective view of a solid processing agent package.

[Explanation of symbols]

 １ Solid processing agent 1A ～ 1D processing tank 2-1、2-2、2-3 Solid processing agent storage cylinder 2A 、 2B 、 2C 、 2D Solid processing agent replenishing device 11 Melting chamber 12 Filter 13 Storage unit 14 Motor 15 Slide plate 16 Solid processing agent 18 Transfer port 19 Lid 20 Solid processing agent transport pocket 21 Turntable 22 Drop outlet 23-1, 2, 3 Solid processing agent storage cylinder 25 Motor 30 Storage case (solid processing agent) 31 Gear 32 Extruder F Drying Part 101 Cartridge 102 Slide cap 103 Cartridge support 104 Rotating cylinder 105 Cutout 106 Filter tank 107 Filter 108 Shutter 109 Processing tank 110 Canopy 111 Solid processing agent (tablet) 122 Pocket 123 Shielding plate 124 Moving member 125 Motor 128 Solid processing agent (tablet) 129 Tablet alignment section 130 Motor 131 Shutter 132 Shutter 133 Hopper

Claims (8)

(57) [Claims] 1. A solid stabilizer for a silver halide photographic light-sensitive material, comprising a fluorine-based anionic surfactant. 2. The solid stabilizer for a silver halide photographic light-sensitive material according to claim 1, wherein said fluorine-based anionic surfactant is represented by the following general formula [I]. Embedded image [In the formula, Rf represents a saturated or unsaturated alkyl group containing at least one fluorine atom, X represents a sulfonamide, And Y represents an alkylene oxide group or an alkylene group, and Rf ′ represents a saturated or unsaturated hydrocarbon group containing at least one fluorine atom. A is -SO
₃ M, -OSO ₃ M, -COOM, -OPO ₃ (M ₁ ) (M ₂ ), -PO ₃ (M ₁ ) (M ₂ )
And M, M ₁ and M ₂ are H, Li, K, Na or
NH ₄ is represented, m is 0 or 1, n is 0 or an integer of 1 to 10. ] 3. The solid stabilizer for a silver halide photographic light-sensitive material according to claim 1, wherein the solid stabilizing agent for a silver halide photographic light-sensitive material is in the form of granules or tablets weighed in advance. Processing agent. 4. The solid stabilizing agent for silver halide photographic light-sensitive materials according to claim 3, which is in the form of a tablet having a bulk density of 1.0 to 2.5 g / cm ³ . 5. The solid stabilizing agent for a silver halide photographic light-sensitive material according to claim 3, which is in the form of granules having a bulk density of 0.4 to 1.7 g / cm ³ . 6. The solid stabilizing agent for a silver halide photographic light-sensitive material according to claim 1, wherein the water content is in the range of 0.1 to 15% by weight. 7. A silver halide photographic light-sensitive material wherein the solid stabilizing agent for a silver halide photographic light-sensitive material according to claim 1 is substantially directly replenished to a stable processing tank of an automatic developing machine. Material treatment method. 8. A stabilizing composition for a silver halide photographic light-sensitive material, comprising a compound represented by the above general formula [I].