JPH10254113A - Stabilizing solution for processing silver halide color photographic sensitive material, processing method for silver halide color photographic sensitive material using same and solid stabilizer for processing silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent residual color stain and the formation of a precipitate in a stabilizing soln. for processing a silver halide color photographic sensitive material even when high sensitivity sensitive materials are processed in a high ratio by adding a specified compd. into the stabilizing soln. SOLUTION: This stabilizing soln. for processing a silver halide color photographic sensitive material contains a compd. represented by the formula but does not practically contain formaldehyde. In the formula, Q1 is a group of atoms required to form an N-contg. hetero ring which may be condensed with a 5 to 6-membered unsatd. ring and R1 is H, an alkali metallic atom, alkyl, etc., where Q' is a synonym of Q. When this stabilizing soln. is used, the amt. of a photographic processing soln. can be reduced and rapid processing is attained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilizer for processing a silver halide color photographic light-sensitive material, a method for processing a silver halide color photographic light-sensitive material using the stabilizer and a solid stabilizer for processing a silver halide color photographic light-sensitive material. About.

[0002]

2. Description of the Related Art In recent years, there has been a growing worldwide movement of regulations on wastes due to an increase in interest in the global environment. The London Treaty has been concluded in the photography industry.
Since January 1, 1996, the disposal of photographic processing wastewater into the ocean has been restricted.

On the other hand, speeds have been required for everything in recent social changes, and the demand for speeding up development processing has been increasing with the rapid increase in minilab shops. For this reason, photograph manufacturers have been examining waste liquid treatment for reducing waste liquid, reducing the amount of replenishment, and further speeding up processing.

[0004] In recent years, in the color negative film market, the use rate of high-sensitivity color negative films has been increasing. Such a high-sensitivity light-sensitive material has a large amount of silver halide and a large amount of sensitizing dye in the emulsion, and a large proportion of silver iodide in the emulsion. If the rate of processing high-sensitivity photosensitive materials is high, simply reducing the replenishment amount of the stabilizer to reduce the amount of waste liquid will increase the amount of sensitizing dye eluted in the stabilizer in the stabilizer. As a result, re-dyeing of the photosensitive material or elution of the sensitizing dye from the photosensitive material is suppressed, and the residual dye on the processed photosensitive material causes so-called residual color stain, causing color unevenness and color balance during color printing. The problem of deviation occurs. In addition, components (eg, thiosulfate, silver ions, iodide ions, etc., halides) in the fixing solution, which is a pre-bath, adhere to the photosensitive material to be processed and are brought into the stabilizing solution and accumulated in a large amount. This not only suppresses the elution of the sensitizing dye, but also precipitates in the stabilizing solution to adversely affect the processability and causes a problem of contamination of the photosensitive material. Further, when the photosensitive material is stored for a long period of time, the image quality is reduced.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a method for processing a high-sensitivity light-sensitive material even if the processing rate of the material is large. Liquid for processing a silver halide color photographic light-sensitive material capable of reducing the amount of photographic processing waste liquid and enabling rapid processing without causing generation of photographic processing liquid, a method for processing a silver halide color photographic light-sensitive material using the stable liquid, and a silver halide An object of the present invention is to provide a solid stabilizer for processing a color photographic light-sensitive material.

[0006]

An object of the present invention is to provide a stabilizing solution for processing a silver halide color photographic light-sensitive material containing a compound represented by the general formula (1), which is substantially free of formaldehyde. And the general formula (F-
1) containing at least one compound selected from compounds represented by (F-3), and having a surface tension at 20 ° C. of 1
5 to 60 dyne / cm; a solid stabilizer for processing a silver halide color photographic light-sensitive material containing the compound represented by the general formula (1); (F-3) a method for processing a silver halide color photographic light-sensitive material, which comprises a step of using a stabilizer of the following formula: This can be achieved by direct introduction into the tank, that the amount of silver applied to the light-sensitive material to be processed is 3 g / m ² or more, and that the light-sensitive material to be processed has a layer containing ferromagnetic particles.

[0007] Japanese Patent Application Laid-Open Nos. 1-261640 and 8-1
Nos. 90178, 8-201997, 8-2720
Nos. 61 and 9-212820 disclose a technique for promoting fixation by adding a heterocyclic compound having a mercapto group to a fixing solution. There is no description about improving the color stain, and these techniques cannot sufficiently solve the problem of the present invention.

Further, Japanese Patent Application Laid-Open Nos. 64-15734 and
Nos. -230043 and 2-103037 describe a technique for improving the residual color by adding a heterocyclic compound to a processing solution for a black-and-white silver halide photographic light-sensitive material. There is no disclosure of improvement, and there are also various residual color differences between black and white and color, such as sensitizing dyes contained in the light-sensitive material and processing conditions. Even if the above method is applied to a color light-sensitive material, a sufficient effect cannot be obtained and the method cannot be put to practical use.

Hereinafter, the present invention will be described in detail.

Specific examples of the compound represented by the general formula (1) to be contained in the stabilizer or solid stabilizer of the present invention are shown below, but are not limited thereto.

[0011]

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[0012]

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[0013]

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[0014]

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Among the above compounds, the compounds preferably used for the purpose of the present invention include (1-9) and (1-1)
0), (1-13), (1-31), and (1-32), and particularly preferably (1-32).

The incorporation of the compound represented by the general formula (1) into the stabilizing solution promotes the elution of the sensitizing dye remaining in the light-sensitive material, so that the replenishing amount is small and the sensitizing dye in the stabilizing solution is reduced. The generation of residual color stain can be prevented even when the amount of accumulated color is large or when the stable processing time is short.

Since these compounds are liable to interact with silver ions, these compounds are usually contained in a stabilizing solution to prevent the formation of insolubles composed of silver ions and thiosulfate decomposition products. Then, the generation of insolubles in the stabilization tank can be suppressed.

In the present invention, the compound represented by the general formula (1) is preferably contained in the stabilizer at a concentration of 0.01 to 1.0 g / l, more preferably 0.1 to 0.5 g / l. Is preferred.

When the compound represented by the general formula (1) is contained in the solid stabilizing agent, the content thereof is in the range of 2 to 50% by weight based on the total weight of the solid stabilizing agent. And more preferably 5 to 35% by weight.

It is preferable that the stabilizer of the present invention does not contain formaldehyde. Formaldehyde is stable for the purpose of blocking the reactive sites of unreacted magenta coupler contained in the photosensitive material to be processed, preventing color stain (stain) during long-term storage, and improving the fading of dye images. The solution may be contained in the solution, in which case formaldehyde reacts with the sulfite brought in together with the thiosulfate from the fixer to form precipitates or promote sulfuration.

Since the effect of the present invention and that the unreacted magenta coupler is blocked, at least one compound selected from the compounds represented by formulas (F-1) to (F-3) is added to the stabilizer of the present invention. Preferably, the seed is included.

The salt of the compound represented by the general formula (F-1) includes inorganic salts such as hydrochloride, sulfate and nitrate, organic acid salts such as phenol salt, double or complex salts with metal salts, Examples include hydrated salts and internal salts.

The compound represented by the general formula (F-1) is specifically described in Beilsteins: Handbuch der.
Organischen Hemy (Beilsteins H
andbuch der Organishen Ch
emie), Volume II, Vol. 26, pp. 200-212. Among them, those soluble in water are preferred in the present invention. The following are representative examples.

[0024]

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[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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The addition amount of the compound represented by the formula (F-1) is preferably 0.1 to 20 g per liter of the processing solution.

In the general formula (F-2), Z represents a group of atoms necessary for forming a substituted or unsubstituted carbocyclic ring or a substituted or unsubstituted heterocyclic ring. Or 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, each group such as methyl, ethyl, methoxyethyl, benzyl, carboxymethyl, sulfopropyl), an aralkyl group, an alkoxy group (eg, methoxy, ethoxy, methoxy) Each group such as ethoxy), a halogen atom, a nitro group, a sulfo group, a carboxy group, an amino group (N, N-dimethylamino group, N-ethylamino group, N
-Phenylamino group, etc.), hydroxyalkyl group, aryl group (phenyl group, p-methoxyphenyl group, etc.), cyano group, aryloxy group (phenoxy group, p-carboxyphenyl group, etc.), acyloxy group, acylamino group, sulfone Amide group, sulfamoyl group (N-ethylsulfamoyl group, N, N-dimethylsulfamoyl group, etc.), carbamoyl group (carbamoyl group, N-methylcarbamoyl group, N, N-tetramethylenecarbamoyl group, etc.) or sulfonyl Group (methanesulfonyl group, ethanesulfonyl group, benzenesulfonyl group, p-toluenesulfonyl group, etc.).

The carbocyclic ring represented by Z is preferably a benzene ring, and the heterocyclic ring represented by Z is preferably a 5- or 6-membered heterocyclic ring. For example, as a 5-membered ring, a thiophene ring, a pyrrole ring, Furan ring, thiazole ring, imidazole ring, pyrazole ring, succinimide ring, triazole ring, tetrazole ring and the like;
Examples of the member ring include a pyridine ring, a pyrimidine ring, a triazine ring, and a thiadiazine ring.

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

Preferred examples of the compound represented by formula (F-2) are shown below.

[0036]

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The exemplified compounds (F-2-1) to (F-2-5)
2) is obtained by inserting various substituents into 1 to 6 in the above formula as shown in the following table.

[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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Among the specific examples of the compound represented by the formula (F-2), a more preferred compound is (F-2)
-2), (F-2-3), (F-2-4), (F-2-
6), (F-2-23), (F-2-24), (F-2
-52), and most preferably (F-2-
3).

The compound represented by formula (F-2) can be easily obtained as a commercial product.

The amount of the compound represented by the formula (F-2) 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.

In the general formula (F-3), at least one of Z ₁ and Z ₂ is a nitrogen atom in the general formula (F-3), X ₁
And X ₂ or a nitrogen atom, X ₃ and X ₄ are preferably non-metallic atoms necessary to form a ring capable of formally forming an aromatic ring as an aromatic ring or a tautomer. Z ₁ is a group of non-metallic atoms necessary for forming a nitrogen atom, X ₁ and X ₂ together with a nitrogen atom in the general formula (F-3) and a ring capable of forming an aromatic ring in the form of an aromatic ring or a tautomer. And Z ₂ is more preferably a non-metallic atomic group necessary for forming a non-aromatic ring together with a nitrogen atom, X ₃ and X ₄ . As the aromatic ring formed by Z ₁ or a ring in which an aromatic ring can be formally formed as a tautomer, a 5-membered ring is preferable, and a pyrazole ring and a triazole ring (1,2,4-triazole ring and 1,1) are more preferable. 2,3-triazole ring) and urazole ring. As the non-aromatic ring formed by Z ₂ , a pyrrolidine ring, a piperidine ring, a morpholine ring and a piperazine ring are preferable.

Specific examples of the compound represented by formula (F-3) are shown below.

[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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The stabilizer of the present invention has a surface tension of 15 to 60 d.
yne / cm, more preferably 15 to 45
dyne / cm. The surface tension referred to here is a general one described in "Analysis and Test Method of Surfactant" (co-authored by Fumio Kitahara, Shigeo Hayano and Ichiro Hara, published March 1, 1982, published by Kodansha Co., Ltd.). In the present invention, the value is determined by a general measurement method at 20 ° C.

The means for adjusting the surface tension of the stabilizing solution is not particularly limited, but preferably contains a water-soluble surfactant. Such a water-soluble surfactant may be represented by the following general formula (S1), (S2) or At least one compound selected from the compounds represented by (S3) and water-soluble organic siloxane compounds is particularly preferred.

[0056]

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In the formula, R ¹ represents a hydrogen atom, an aliphatic group or an acyl group, and R ² represents a hydrogen atom or an aliphatic group. E ¹ represents ethylene oxide, E ² represents propylene oxide, E ³ represents ethylene oxide, X represents an oxygen atom or a —R ³ N— group, and R ³ represents a hydrogen atom, an aliphatic group or

[0058]

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And R ⁴ represents a hydrogen atom or an aliphatic group. l ₁ , l ₂ , m ₁ , m ₂ , n ₁ and n ₂ are each from 0 to 300
Represents the value of

[0060]

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In the formula, A ² represents a monovalent organic group, for example, an alkyl group having 4 to 50 carbon atoms and optionally containing a fluorine atom, and preferably an alkyl group having 4 to 35 carbon atoms and containing a fluorine atom. An alkyl group (hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group or dodecyl group), an alkyl group having 3 to 35 carbon atoms or an alkenyl group having 2 to 35 carbon atoms. It is a substituted aryl group.

As a preferable group substituted on the aryl group, an alkyl group having 1 to 18 carbon atoms (for example, unsubstituted such as methyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl) Alkyl groups), substituted alkyl groups such as benzyl and phenethyl, and alkenyl groups having 2 to 20 carbon atoms (eg, unsubstituted alkenyl groups such as oleyl, cetyl, allyl, and substituted alkenyl groups such as styryl). Examples of the aryl group include phenyl, biphenyl, naphthyl and the like, and a phenyl group is preferable. The position to be substituted with the aryl group may be any of the ortho, meta and para positions, and a plurality of groups can be substituted.

B and C are each ethylene oxide, propylene oxide or

[0064]

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Represents the following. (Here, n ₁ , m ₁ and l ₁ each represent 0, 1, 2 or 3.) m and n are 0 to 10
Represents an integer of 0. X ¹ represents a hydrogen atom or an alkyl group, an aralkyl group or an aryl group, and examples thereof include the groups described for A ² .

Specific examples of the compounds represented by formulas (S1) and (S2) are shown below, but the invention is not limited thereto.

[0067]

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[0068]

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[0069]

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The amount of the surfactant added was 1 liter of the stabilizing solution.
0.1 to 40 g is preferable, more preferably 0.1 to 40 g.
3 to 20 g.

[0071]

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In the formula, Rf represents a saturated or unsaturated alkyl group containing at least one fluorine atom, and X ² represents a sulfonamide,

[0073]

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Wherein 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. Moreover A is _{-SO 3 M, -OSO 3 M,} -COOM, -OPO
₃ (M ₁ ) (M ₂ ), —PO ₃ (M ₁ ) (M ₂ ), etc., wherein M, M ₁ and M ₂ are each H, Li, K, Na or N
H ₄ is represented, m represents 0 or 1, n represents 0 or an integer of 1 to 10.

In the general formula (S3), Rf represents an alkyl group, an alkenyl group or an alkynyl group containing at least one fluorine atom, and preferably has 4 to 1 carbon atoms.
2, more preferably an alkyl group having 6 to 9 carbon atoms.
A is preferably -SO ₃ M, M, M ₁ and M ₂ are preferably Li, K or Na, and most preferably Li. Further, m = 0 and n = 0 are preferable.

Specific examples of the compound represented by the formula (S3) are shown below, but it should not be construed that the invention is limited thereto.

[0077]

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Of these, particularly preferred is (S
3-1), (S3-2) and (S3-3).

Examples of the water-soluble organic siloxane compound include:
A compound represented by the following general formula (SU-1) is preferable.

[0080]

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In the formula, R ₉ is a hydrogen atom, a hydroxy group, a lower alkyl group, an alkoxy group,

[0082]

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Wherein R ₁₀ , R ₁₁ and R ₁₂ each represent a hydrogen atom or a lower alkyl group. l _{1 to} l ₃ each represent 0 or an integer of 1 to 30, and p, q ₁ and q ₂ each represent 0
Or, represents an integer of 1 to 30. X ₁ and X ₂ are each

[0084]

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Represents the following.

Specific examples of the compound represented by formula (SU-1) are shown below.

[0087]

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[0088]

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The details of these compounds are described in JP-A-47-1
No. 8333, No. 49-62128, Japanese Patent Publication No. 51-37
Nos. 583 and 55-51172 and U.S. Pat.
No. 45,970, etc., and are commercially available from Union Carbide, Shin-Etsu Chemical Co., Ltd., and the like. The addition amount is preferably about 0.01 to 20 g per liter of the stabilizing solution.

The stabilizer of the present invention comprises a chelating agent (ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1-
Hydroxyethylidene-1,1-diphosphonic acid, etc.), buffers (potassium carbonate, borate, acetate, phosphate, etc.),
Fungicides (Diaside 702 (Dearborn, USA), p-chloro-m-cresol, benzoisothiazolin-3-one, etc.), optical brighteners (triazinylstilbene compounds, etc.), antioxidants ( Components normally contained in a stable liquid, such as sulfites, ascorbates, etc., and water-soluble metal salts (zinc salts, magnesium salts, etc.) can be appropriately used.

In the present invention, the replenishment amount of the stabilizing solution is preferably 1200 ml or less, more preferably 100 to 900 ml, and even more preferably 200 ml / m ^{2 of the} light-sensitive material to be processed.
By performing a process with a reduced replenishment amount such as ６650 ml, the effects of the present invention can be fully demonstrated.

The stabilization tank may be one tank, but the number of tanks can be increased up to about 2 to 10 tanks, and the replenishment amount of the stabilizing solution can be reduced by increasing the number of tanks. Considering the compact size, it is preferable to use about 2 to 6 tanks.
The replenisher may be replenished in several places, but may be replenished to the tank on the downstream side in the transport direction of the photosensitive material, and the overflow liquid (when the tanks are connected by a pipe located below the liquid level, (Including the case where the solution passes through the tube) into the front tank of the tank.
It is preferable to use a so-called counter current system (multi-stage countercurrent system), and a cascade flow system is also included as one of them. More preferably, the replenisher is replenished to the last tank with two or more stabilizing tanks, and the overflow liquid is sequentially poured into the previous tank.

Further, in the present invention, the effect of the object of the present invention can be further improved by introducing the processing solution pumped out of the stabilizing tank into the fixing solution in the fixing process or the bleach-fixing solution in the bleach-fixing process. This leads to a decrease in the amount of replenishment, which is preferable.

In the present invention, the stabilization temperature and time are 1
It is preferably 10 to 80 seconds at 0 to 50 ° C, more preferably 15 to 70 seconds at 20 to 40 ° C. The pH of the stabilizer is 3
Is preferably 10 to 10, and more preferably 6 to 9.

The processing processes employing the present invention include: (1) color development → bleaching → fixing → stable (2) color development → bleaching → fixing → first stability → second stability (3) color development → bleaching → bleaching Fixing → Fixing → Stable (4) Color development → Bleaching → Bleaching and fixing → Fixing → First stable → Second stable (5) Color developing → Bleaching and fixing → Stability.

In order to exhibit the effects of the present invention more effectively, the processing solution is preferably replenished with a solid processing agent such as powder, granules or tablets, and more preferably with a granular processing agent or tablet. , Most preferably tablets.

The term "powder" used herein refers to an aggregate of fine crystals, and the term "granules" refers to granules having a particle size of 50 to 5000 μm, and is preferably formed by granulating powder. Tablets are formed by compressing powder or granules into a certain shape.
As a tablet forming method, a method of forming a powder or a granule by tableting after granulation is preferable because more stable processing performance can be maintained.

Granulation methods for tablet formation include rolling granulation, extrusion granulation, compression granulation, pulverization granulation, stirring granulation,
Known methods such as fluidized bed granulation and spray drying granulation can be employed.
For tablet formation, the average particle size of the obtained granules is 100 to 2000 μm in that, when the granules are mixed and compressed under pressure, non-uniformity of components, that is, so-called segregation hardly occurs.
It is preferred to use
〜1500 μm. Further, the particle size distribution is preferably such that 50% or more of the granulated distribution particles have a deviation of ± 200 to 250 μm. The obtained granules can be used as they are as granules. Then, when the obtained granules are compressed under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine, and a briquetting machine can be used. Alternatively, the granules may be prepared by the above-described granulation method, and the granules and commercially available raw crystals may be mixed and tableted.

The solid processing agent obtained by pressurizing and compression can take any shape. However, from the viewpoint of productivity and handling, or from the problem of dust when used on the user side, the solid processing agent has a cylindrical shape. So-called tablets are preferred.

The silver halide of the silver halide photographic light-sensitive material to be processed is silver chloride, silver chlorobromide, silver bromide, silver iodobromide, iodobromide, provided that the silver halide is spectrally sensitized by a sensitizing dye. Any material such as silver halide may be used. However, the silver iodide content of the photographic material is relatively high, such as 5 mol% or more of silver halide, and the coated silver amount is 3 to 20 g / m ² . More preferably, the effects of the present invention can be fully exhibited in processing a color negative film of 6 to ²⁰ g / m ² .

The silver halide emulsion can be used, for example, in Research Disclosure (Research Disclosure).
e; hereinafter referred to as RD) No. 17643,22-23
Page (December 1978) I. Emulsion manufacturing (Emulsio
n preparation and types) and the same No. 18716, 648, Physics and Chemistry of Photography by Grafkides, published by Paul Montell (P. Glafk)
ides, Chemie et Physique P
photographique, Paul Motel,
1967), Duffin, "Photographic Emulsion Chemistry", published by Focal Press (GF Duffin, Photograph).
phy Emulsion Chemistry, F
ocpress, 1966), "Manufacture and Coating of Photographic Emulsions", by Zerikman et al., Focal Press (V, L. Zelikman et al, Making).
and Coating Photographic
Emulsion, Focal Press, 196
It can be prepared using the method described in 4). U.S. Pat. Nos. 3,574,628 and 3,663;
Monodisperse emulsions described in US Pat. No. 5,394 and British Patent No. 1,413,748 are also preferable. The average diameter of the particles is not limited, but is preferably 0.1 to 5 μm. Two or more types of silver halide emulsions formed separately may be used as a mixture.

Various photographic additives can be used in the silver halide emulsion before and after physical ripening or chemical ripening. Such compounds include, for example, the aforementioned RDN
o. No. 17643, ibid. 18716 and the same No. 30
Various compounds described in 8119 can be used.

In order to prevent the deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add a compound capable of reacting with formaldehyde described in JP-A Nos. 1,987 and 4,435,503 to the light-sensitive material. Further, various couplers can be used, and specific examples thereof are also described in RDNo. 17
643 and no. 308119. Further additives used are RDNo. 308119, XIV.

The present invention can be preferably used also when the silver halide photographic light-sensitive material to be processed has a layer containing magnetic particles (magnetic layer).

The magnetic layer may be in the light-sensitive material, and may or may not be adjacent to the support. It may be on the same side as the emulsion layer or on the opposite side. Magnetic particles used are ferromagnetic iron oxide such as _{γFe 2 O 3 (FeOx, 4} /
3 <x ≦ 3/2) Co-coated ferromagnetic iron oxide (FeOx, 4/3 <x ≦ 3/2), such as Co-coated γFe ₂ O ₃ , Co-coated magnetite, and other Co-containing ferromagnetic oxides Iron, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, and other ferrites such as hexagonal Ba ferrite, Sr ferrite, Pb ferrite, C
a Ferrite or a solid solution or ion-substituted material thereof can be used. Co-coated ferromagnetic iron oxide such as Co-coated γFe ₂ O ₃ having a Fe ²⁺ / Fe ³⁺ ratio of 0 to 10% is used. It is preferable in terms of transmission density.

The production methods of these ferromagnetic powders are known.
The ferromagnetic material used in the present invention can also be manufactured according to a known method. The shape of the ferromagnetic material may be any of a needle shape, a rice grain shape, a spherical shape, a cubic shape, a plate shape, and the like, but a needle shape is preferable in terms of electromagnetic conversion characteristics. The particle size is
In the case of a needle shape, the major axis is preferably 0.01 to 0.8 μm, the major axis / minor axis ratio is preferably 2 to 100, and the major axis is preferably 0.05 to 0.1 μm.
3 μm, and the ratio of long axis / short axis is preferably 4 to 15. Preferably 20 m ² / g or more S _BET is the specific surface area, 30 m ² / g
The above is particularly preferred.

The larger the saturation magnetization (σs) of the ferromagnetic material, the better, but it is preferably 50 emu / g or more, more preferably 70 emu / g or more.
emu / g or more, and practically 100 emu / g or less. The squareness ratio (σr / σs) of the ferromagnetic material is 40
% Or more, more preferably 45% or more. Coercive force (Hc)
If the value is too small, it will be easily erased, and if it is too large, it will not be possible to write depending on the system, so an appropriate value is preferable,
About 200-3000 Oersted, preferably 500
~ 2000 Oersted, more preferably 650-95
0 Oersted.

When a silver halide photographic light-sensitive material having a magnetic layer containing a ferromagnetic fine powder is processed with a stabilizing solution, various problems relating to the present invention become particularly apparent. It has been known that when reading magnetic information recorded in a layer, problems such as clogging of a read head and deterioration of magnetic properties occur. By applying the stabilizing solution or the processing method of the present invention, these problems are solved. Was found to be resolved.

The magnetic layer is described in JP-A-8-952.
The various additives, binders, supports, production methods, and the like described in JP-A No. 18 [0009] to [0051] can be applied.

[0110]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 A Konica Color Negative Film LV400 (manufactured by Konica Corp.), which was actually exposed by a camera, was exposed to a color negative processor (CL-KP) in the following processing steps.
-50QA), using a processing solution and a replenisher having a prescription described later in the section, a 135-24 size film is formed at a rate of 60 films per day at 8 times.
A weekly running process was performed.

(Processing step) (Processing time) (Processing temperature) (Replenishment amount) Color development 3 minutes 15 seconds 38 ° C. 520 ml / m ² Bleaching 45 seconds 38 ° C. 100 ml / m ² Fixing-1 45 seconds 38 ° C. Fixing-2 45 seconds 38 ° C. 510 ml / m ² Stable-1 20 seconds 38 ° C. Stable-2 20 seconds 38 ° C. Stable-3 20 seconds 38 ° C. 860 ml / m ² Drying 80 seconds 55 ° C. Refill is 3 → 2 → 1
Is a countercurrent method.

(Color development start solution) Water 600 ml Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.2 g Potassium iodide 0.6 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4 -Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.6 g Diethylenetriaminepentaacetic acid sodium salt 3.0 g Potassium hydroxide 1.2 g Water was added to make 1 liter, and potassium hydroxide or Adjust to pH = 10.0 with 20% sulfuric acid.

(Color developing replenisher) Water 600 ml Potassium carbonate 40 g Sodium bicarbonate 3 g Potassium sulfite 7 g Sodium bromide 0.5 g Hydroxylamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β -Hydroxyethyl) Aniline sulfate 6.5 g Diethylenetriamine pentaacetate sodium salt 3.0 g Potassium hydroxide 2 g Add water to make 1 liter, and adjust to pH = 10.2 using potassium hydroxide or 20% sulfuric acid.

(Bleaching start liquid) Water 500 ml 1,3-Propylenediaminetetraacetic acid ferric ammonium 133 g 1,3-propylenediaminetetraacetic acid 10 g Ammonium bromide 100 g Succinic acid 30 g Maleic acid 70 g Water was added to make 1 liter, and ammonia was added. PH = 4 using water.
Adjust to 4.

(Bleaching replenisher) Water 500 ml 1,3-Propylenediaminetetraacetic acid ferric ammonium 175 g 1,3-propylenediaminetetraacetic acid 2 g Ammonium bromide 120 g Succinic acid 40 g Maleic acid 80 g Water was added to make 1 liter, and ammonia was added. PH = 3 using water.
Adjust to 4.

(Fixing Solution, Fixing Replenisher) Water 500 ml Sodium thiosulfate 25 g Ammonium thiosulfate 225 g Sodium sulfite 18 g Potassium carbonate 2 g Ethylenediaminetetraacetic acid disodium 2 g Water is added to make up to 1 liter.

(Stabilizing Solution, Stabilizing Replenishing Solution) Water 700 ml m-hydroxybenzaldehyde 1.5 g (Exemplified compound F-2-3) Sodium lauryl sulfate 0.2 g Ethylenediaminetetraacetic acid disodium 0.6 g Lithium hydroxide monohydrate 0 0.7 g Compound described in Table 1 0.2 g Make up to 1 liter by adding water.

After the completion of the running process, the unexposed light-sensitive material was processed. X-r
It is measured by an item densitometer (manufactured by Nippon Lithographic Equipment Co., Ltd.), and is defined as D _min (R). Further, in order to completely remove the sensitizing dye remaining in the light-sensitive material, the light-sensitive material was washed with pure water at 40 ° C. for 10 minutes or more with sufficient stirring, dried, and the red density was measured again. This is D ' _min (R)
And From D _min (R) minus the D _'min (R), which is the degree ΔD _min (R) of Zanshoku stain.

If the degree of residual color is 0.05 or less, it can be said that there is no problem in practical use, and it is more preferable to be close to 0.

Then, the photosensitive material which has been subjected to the usual wedge exposure is processed, and the maximum density portion of the processed photosensitive material is reduced to 4%.
The transmission density at 40 nm was measured. Further, the processed photographic material is subjected to 7000 under an environment of 40 ° C. and 30% RH.
The cells were stored in a bright room at 0 Lux / h for 10 days. After saving,
The transmission density was measured again, and the density change rate (yellow discoloration rate) due to storage was calculated.

Further, the state of the first stabilization tank after the running processing was completed was observed and evaluated as follows.

○: No sedimentation was observed in the first tank. Δ: Slight sedimentation was observed in the first tank, but at a level that was not problematic for practical use. X: A large amount of sediment was observed in the first tank. This is a practically problematic level.

Table 1 shows the degree of residual color, the state of the first stabilization tank, and the results of the yellow fading rate.

[0125]

[Table 1]

Thus, by adding the compound represented by the general formula (1) of the present invention to the stabilizing solution, not only the residual color is improved, but also the stability of the dye image after long-term storage is improved. It can also be seen that the state of the first stabilization tank is also kept good for a long period of time.

Example 2 In Example 1, the compositions of the stabilizing solution and the replenishing solution were changed as follows.

Water 700 ml m-Hydroxybenzaldehyde 1.5 g Disodium ethylenediaminetetraacetate 0.6 g Lithium hydroxide monohydrate 0.7 g Compound (1-32) 0.2 g Compound (S3-2) * Add water Finish to 1 liter.

* The compound (S3-2) was added in an appropriate amount so that the surface tension of the stabilizer became the value shown in Table 2.

The same running treatment as in Example 1 was performed using the above-mentioned stabilizing solution. After the running, the unexposed photosensitive material was processed, the condition of the stain on the back surface was observed, and the evaluation was made according to the following criteria.

：: No stain is seen on the back surface. Δ: Slight stain is found on the back surface. ×: Stain is found on the back surface, which is a practically problematic level.

Further, as in Example 1, the state of the first stabilization tank was observed.

Table 2 shows the results.

[0134]

[Table 2]

As can be seen from the table, the surface tension of the stabilizer was 60%.
When it is not more than 45 dyne / cm, the condition of stain on the back surface is particularly good, and when it is not more than 45 dyne / cm, the state of the first stabilization tank is particularly well maintained, which is particularly preferable as an embodiment of the present invention.

Example 3 The same experiment as in Example 1 was carried out except that the concentrations of the compound of the present invention in the stabilizing solution and the stabilizing replenishing solution were changed as shown in Table 3. Table 3 shows the results.

[0137]

[Table 3]

Thus, when the amount of the compound of the present invention is 0.01 to 1.0 g / l, the residual color stain can be sufficiently reduced and the state in the stabilization tank can be maintained well. I understand. It can also be seen that 0.1 to 0.5 g / l is better.

Example 4 The same experiment as in Example 1 was carried out except that the compositions of the stabilizing solution and the stabilizing replenishing solution were changed as follows.

Water 700 ml formalin Compound (1-32) shown in Table 3 Sodium lauryl sulfate 0.2 g shown in Table 3 Disodium ethylenediaminetetraacetate 0.6 g Lithium hydroxide monohydrate 0.7 g Water is added to make up to 1 liter. .

The formalin referred to here is an approximately 37% aqueous solution of formaldehyde.

Here, as in Example 2, the condition of the back surface of the photosensitive material after the completion of the running process was evaluated, and the condition of the second stabilization tank was observed. Further, the red density of the unexposed portion of the photosensitive material was measured, and the degree of the residual color was calculated.

(Evaluation of the condition of the second stabilization tank) ：: No abnormality is observed at all Δ: Slight dirt is observed X: Clear sulfurization is recognized, which is a level that poses a practical problem.

Table 4 shows the results.

[0145]

[Table 4]

As a result, the effect of reducing the residual color stain by containing the compound of the present invention is greater when formaldehyde is not used, which is usually used in the stabilizing solution. It can be seen that this is more preferable.

Example 5 The same experiment as in Example 1 was performed, except that the compositions of the stabilizer and the replenisher were changed as follows.

Water 700 ml Compounds represented by formulas (F-1) to (F-3) Compounds of the present invention shown in Table 5 (1-32) Sodium lauryl sulfate shown in Table 5 0.2 g Ethylenediaminetetraacetic acid 2 Sodium 0.6g Lithium hydroxide monohydrate 0.7g Water is added to make up to 1 liter.

In addition to calculating the degree of residual color stain from the measurement of red density, the processed photographic material was heated at 75 ° C. and 10% R
The sample was stored in a dark place under the condition of H for 10 days, and the difference in yellow transmission density (yellow stain density) before and after storage was measured.
Table 5 shows the results.

[0150]

[Table 5]

Thus, the above general formulas (F-1) to (F-1)
It can be seen that the generation of yellow stain is improved by incorporating the compound represented by -3) into the stabilizer in combination.

Example 6 The experiment No. 1 of Example 1 was performed by changing the replenishing amount of the stabilizing solution. 1
An experiment similar to -1 was performed. Table 6 shows the results.

[0153]

[Table 6]

Example 1 was repeated by changing the replenishing amount of the stabilizing solution.
Experiment No. The same experiment as in 1-6 was performed. Table 7 shows the results
Shown in

[0155]

[Table 7]

From the comparison of the results in Tables 6 and 7, it can be seen that the effect of the present invention becomes remarkable when the replenishment rate of the stabilizing solution is 1000 ml / m ² or less.

Example 7 Color negative film processor CL- manufactured by Konica Corporation
KP-50QA refilling unit was modified as shown in FIG.
Replenishment was performed using the solid processing agent supply (feeding) device of FIG. Imagewise exposed Konica Color LV40 manufactured by Konica Corporation
For the 0 film, a column-shaped container containing tablets was set in the solid processing agent charging section, and a running treatment was performed for 60 weeks a day for 8 weeks.

FIG. 1 shows a solid processing agent replenishing apparatus 2A, 2B, 2
C, 2D indicate positions where KP-50QA (hereinafter also referred to as an automatic developing machine) is attached, and 2A, 2B, 2C,
D is attached to the upper part of the color developing tank 1A, the bleaching tank 1B, the fixing tank 1C, and the stabilizing tank 1D as indicated by oblique lines.

FIG. 2 is a block diagram showing an example of a solid processing agent replenishing apparatus. A dissolution chamber 106 for charging a solid processing agent 111 is provided beside each tank of the automatic developing machine. The solid processing agent (tablet in the figure) 111 is housed in a container (cartridge) 101 divided into a plurality of rooms, and is sealed by a slide-type cap 102. When this cartridge is set on a cartridge support table 103 of an automatic solid processing agent supply device installed above a processing tank of an automatic developing machine, a cap 102 is opened, and tablets are obliquely fixed from a cartridge fixed at an angle to a rotating cylinder 104. Slit 105
Rolls down. Notch 10 of this rotating cylinder 104
5 is alternately cut so that a plurality of tablets stored in different rooms of the cartridge do not roll down at the same time.

The processing steps are described below.

(Processing Step) (Processing Time) (Processing Temperature) (Replenishing Water Amount) Color Developing 3 min 15 sec 38 ° C. 450 ml / m ² Bleaching 45 sec 38 ° C. 100 ml / m ² Fixing-1 45 sec 38 ° C. Fixing-2 45 seconds 38 ° C. 400 ml / m ² Stable-1 20 seconds 38 ° C. Stable-2 20 seconds 38 ° C. Stable-3 20 seconds 38 ° C. 750 ml / m ² Drying 80 seconds 50-70 ° C. Fixing 2 → 1, stable 3 → 2 → 1 countercurrent method,
The replenishment of the second fixing tank was performed by pouring the tank liquid of the first stable tank into a pump. In addition, color development, bleaching,
Fixing-1, Fixing-2, Stable-1, Stable-2, Stable-3 in each tank, 10ml, 6.5ml, 7m per hour, respectively
Evaporation correction was performed by a program for supplying 1, 7 ml, 8.6 ml, 8.6 ml, and 9.3 ml of water for evaporation correction. When not in operation, the non-operation time is accumulated, and color development, bleaching, fixing-1, fixing-2, stable-1, stable-2, stable-
7.5 ml, 5 ml, 6
ml, 6 ml, 5 ml, 5 ml, and 5 ml were collectively rehydrated at the start of operation. The tank liquid at the start was Konica Color Negative Film Processing Agent CN manufactured by Konica Corporation.
It was prepared using a K-4-52 replenisher and a starter.

On the other hand, the following color negative treating agents were prepared.

1) Tablet for replenishing color development for color negative film Operation (1) CD-4 (4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate) as a developing agent
60 g are ground in a commercial hammer mill until the average particle size is 10 μm. After granulating this fine powder in a commercially available stirring granulator at room temperature for about 7 minutes by adding 10 ml of water, the granulated product is dried at 40 ° C. for 2 hours in a fluidized bed drier. The water was almost completely removed to prepare granules (1) for replenishing color development for color negative films.

Operation (2) 69.4 g of hydroxylamine sulfate and 4 g of pine flow (manufactured by Matsutani Chemical) were ground in the same manner as in operation (1), and then mixed and granulated. The amount of water added was 3.5 ml, and after granulation
The granules were dried at 0 ° C. for 30 minutes to almost completely remove the water content of the granules, thereby preparing color development replenishing granules (2) for color negative films.

Operation (3) 15 g of disodium 1-hydroxyethane-1,1-diphosphonate, 72.8 g of potassium sulfite, 350 g of potassium carbonate, 3 g of sodium hydrogen carbonate, 3.7 g of sodium bromide and 22 g of mannitol, polyethylene glycol 5.0 g of # 6000 was pulverized and mixed in the same manner as in the operation (1), and the amount of water added was 40 ml to perform granulation. After the granulation, the granulated product was dried at 70 ° C. for 60 minutes to remove the water almost completely, thereby producing a color development replenishing granule (3) for a color negative film.

The granules (1) to (3) were mixed, and 2 g of sodium N-myristoylalanine was added.
Using a mixer in a room conditioned to 40% RH or less
Mix evenly for minutes. Next, the mixture was compression-compressed to a filling amount of 10 g using a modified tableting machine of Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd.
A tablet for color development replenishment for a color negative film having a thickness of 10 mm was prepared.

2) Preparation of tablet for replenishing bleaching for color negative film Operation (4) Ferric ammonium 1,3-propanediaminetetraacetate 1
175 g of water salt, 2 g of 1,3-propanediaminetetraacetic acid,
17 g of pine flow (manufactured by Matsutani Chemical Co., Ltd.) is ground and mixed in the same manner as in the operation (1), and the amount of water added is 8 ml to perform granulation. After the granulation, the granules are dried at 60 ° C. for 30 minutes to almost completely remove the moisture of the granules.

Operation (5) 133 g of succinic acid, 200 g of ammonium bromide and 10.2 g of pine flow are pulverized, mixed and granulated in the same manner as in the operation (1). The amount of water added was 17 ml, and after granulation,
After drying for 0 minutes, the water content of the granules is almost completely removed.

Operation (6) 66.7 g of potassium sulfate, 60 g of potassium hydrogen carbonate and 8 g of mannite are ground, mixed and granulated in the same manner as in the operation (1). The added amount of water was 13 ml, and after granulation,
After drying for a minute, the water content of the granules is almost completely removed.

The granules prepared in operations (4) to (6) were
Mix uniformly for 10 minutes using a mixer in a room conditioned at 5 ° C. and 40% RH or less. Next, 6 g of N-lauroyl sarcosine sodium is added to the mixture and mixed for 3 minutes. Next, Kikusui Seisakusho's Tough Press Collect 1
527HU was subjected to compression tableting using a modified tableting machine with a filling amount of 10 g to prepare tablets for replenishing bleaching for color negative films having a diameter of 30 mm and a thickness of 10 mm.

3) Preparation of Fixing Replenishment Processing Agent for Color Negative Film Operation (7) Sodium thiosulfate / ammonium thiosulfate = 1700
g / 80 g, sodium sulfite 180 g, potassium carbonate 20 g, ethylenediaminetetraacetic acid disodium salt 20 g
70 g of Pine Flow (Matsuya Chemical Co., Ltd.) is pulverized in a commercially available bandam mill to an average particle size of 30 μm, and the powder is granulated in a stirring granulator at room temperature for about 10 minutes by adding 50 ml of water. After granulation, the granulated product is subjected to 60
After drying at 120 ° C. for 120 minutes, the water of the granules is almost completely removed. Next, the dried granules were classified so that the average particle size was 80 μm and 50% or more of the particles were within the deviation of ± (200 to 250) μm.

Operation (8) 30 g of N-lauroyl sarcosine sodium is added to the granules prepared in operation (7), and the mixture is mixed in a room conditioned at 25 ° C. and 40% RH or less using a mixer for 5 minutes. Next, the mixture was subjected to tough press collect 152 manufactured by Kikusui Seisakusho Co., Ltd.
7HU was subjected to compression tableting with a modified tableting machine at a filling amount of 10 g to prepare a fixation replenishment tablet for a color negative film having a diameter of 30 mm and a thickness of 10 mm.

4) Preparation of tablets for stable replenishment for color negative films Operation (9) 150 g of m-hydroxybenzaldehyde, 20 g of sodium lauryl sulfate, 60 g of disodium ethylenediaminetetraacetate, 65 g of lithium hydroxide monohydrate, 65 g of compound (1)
-32) Pulverize, mix and granulate 20 g and 10 g of pine flow (described above) in the same manner as in the operation (1). The amount of water added is 1
After the granulation, the granulated product is dried at 50 ° C. for 2 hours to remove the moisture of the granulated product almost completely.

The granulated product prepared by the above operation was heated at 25.degree.
In a room conditioned at% RH or less, a tableting machine modified from Tough Press Collect 1572HU manufactured by Kikusui Seisakusho Co., Ltd. was used to prepare a stable refill tablet for color negative film with a filling amount of 10 g, a diameter of 30 mm and a thickness of 10 mm.

A tablet was prepared in the same manner as in the operation (9), without adding the compound (1-32).

The replenishing tablets were charged into the processing tank at the following intervals.

Replenishment tablet feeding interval Color development replenishment tablet Color negative (24EX) 8.3 tablets One bleach replenishment tablet Color negative (24EX) 5.2 tablets One fixation replenishment tablet Color negative (24EX) 2 .1 tablet per 4 tablets for stable replenishment 1 tablet per 131 color negative (24EX) tablets The replenishment form using the above tablets is Form 2, the replenishment form using replenisher is Form 1, and the composition of the stabilizer is shown in Table 1. 8 and evaluated in the same manner as in Example 1.

[0178]

[Table 8]

Further, an experiment was carried out in the same manner using a stable replenisher and a tablet for stable replenishment stored at 55 ° C. for 6 weeks and evaluated. Table 9 shows the results.

[0180]

[Table 9]

Thus, the replenishment form using the tablet containing the compound of the present invention can further improve the residual color, and can maintain good processing performance even when the processing agent after long-term storage is used. I understand.

When the tablet after storage was observed, the tablet prepared by the operation (9) showed no particular change in appearance from that before storage, but the compound (1-32) was not added. The prepared tablet had a part of green chipped and fine powder was generated.

Example 8 In Example 1, 255 ml per 1 m ^{2 of} photosensitive material was supplied from the tank closest to the fixing tank to the immediately preceding fixing processing tank by a bellows pump from among the three stabilizing processing tanks. The replenishing solution was doubled and 255 ml of the replenished fixing replenisher per m ² of the photosensitive material was replenished in the ^second fixing tank, and the running process was performed in the same manner as in Example 1 to evaluate. The degree of the color was 0, and the effect of the residual color improvement was further improved. Further, the total amount of photographic waste liquid generated during this treatment was reduced by about 21%.

Further, the fixing solution in the second fixing tank after the completion of the running was placed in a container having an opening area ratio of 10 cm ² / l,
The solution was stored at a temperature of 1 ° C. for one week, and the storage stability of the fixing solution was evaluated according to the following criteria.

：: No precipitation or turbidity of the liquid was observed. ：: Turbidity occurred in the liquid, and some suspended matter was confirmed on the surface. X: Precipitation occurred and was fixed to the wall of the container.

The results are shown in Table 10.

[0187]

[Table 10]

By supplying a part or all of the stabilizing solution of the present invention to the fixing tank, not only the effect of the present invention can be obtained well, but also the storage stability of the fixing solution is improved.
It can be seen that the amount of photographic waste liquid can be reduced.

Example 9 Preparation of Magnetic Recording Medium << Preparation of Support >> 0.1 part by weight of calcium acetate hydrate as a transesterification catalyst was added to 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate and 60 parts by weight of ethylene glycol. After the addition, a transesterification reaction was carried out according to a conventional method.
To the obtained product, 0.05 parts by weight of antimony trioxide,
0.03 parts by weight of trimethyl phosphate was added.
Then, gradually raise the temperature and reduce the pressure, 290 ° C, 0.05 mm
Polymerization was performed under the conditions of Hg to obtain polyethylene-2,6-naphthalate having an intrinsic viscosity of 0.60.

This was vacuum-dried at 150 ° C. for 8 hours, melt-extruded in a layer form from a T-die at 300 ° C., brought into close contact with a 50 ° C. cooling drum while applying static electricity, cooled and solidified, and an unstretched sheet was obtained. Obtained. This unstretched sheet was stretched 3.3 times in the machine direction at 135 ° C. using a roll-type longitudinal stretching machine.

The obtained uniaxially stretched film was stretched by a tenter type transverse stretching machine in a first stretching zone at 145 ° C. by 50% of the total transverse stretching ratio, and further in a second stretching zone at 155 ° C. by a total transverse stretching ratio of 3. The film was stretched three times. Then 10
Heat treated at 0 ° C for 2 seconds, and further heat-fixed zone 200 ° C
For 5 seconds and a second heat setting zone at 240 ° C. for 15 seconds. Next, the film was gradually cooled to room temperature over 30 seconds while performing a 5% relaxation treatment in the lateral direction to obtain a polyethylene naphthalate film having a thickness of 85 μm.

This is wound around a stainless steel core, and
A heat treatment (annealing treatment) was performed at 10 ° C. for 48 hours to form a support.

On both sides of this support, 12 W / m ² / min
Of the undercoating coating solution B-1
Is applied to a dry film thickness of 0.4 μm, and 1
A 2 W / m ² / min corona discharge treatment was applied, and the undercoat coating solution B-2 was applied so as to have a dry film thickness of 0.06 μm.

On the other surface subjected to the corona discharge treatment at 12 W / m ² / min, the undercoating coating solution B-3 was dried to a dry film thickness of 0.1 W / m ² / min.
2 μm, and 12 W / m ² / m
An in-corona discharge treatment was performed, and a coating solution B-4 was applied so as to have a dry film thickness of 0.2 μm.

Each of the layers was dried at 90 ° C. for 10 seconds after the application, and after the application of the four layers, a heat treatment was performed at 110 ° C. for 2 minutes, followed by a cooling treatment at 50 ° C. for 30 seconds.

<Undercoat Coating Solution B-1> A copolymer latex liquid of 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene and 25% by weight of 2-hydroxyethyl acrylate (solid content: 30% 125 g Compound (UL-1) 0.4 g Hexamethylene-1,6-bis (ethylene urea) 0.05 g Finish with water 1000 ml <Subbing coating solution B-2> Hydroxidation of styrene-maleic anhydride copolymer Sodium aqueous solution (solid content 6%) 50 g Compound (UL-1) 0.6 g Compound (UL-2) 0.09 g Silica particles (average particle size 3 μm) 0.2 g Finish with water 1000 ml <Coating solution B-3> Butyl 30% by weight of acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene and 2-hydroxyacrylate 2 5% by weight copolymer latex liquid (solid content 30%) 50g Compound (UL-1) 0.3g Hexamethylene-1,6-bis (ethylene urea) 1.1g Finish with water 1000ml

[0197]

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<Coating Solution B-4> 60 mol% of dimethyl terephthalate, 30 mol% of dimethyl isophthalate, 10 mol% of a sodium salt of dimethyl 5-sulfoisophthalate, 50 mol% of ethylene glycol as a glycol component, 50 mol% of diethylene glycol was copolymerized by a conventional method. The copolymer was stirred in hot water at 95 ° C. for 3 hours to obtain a 15% by weight aqueous dispersion A.

Aqueous dispersion of tin oxide-antimony oxide composite fine particles (average particle size: 0.2 μm) (solid content: 40% by weight) 109 g Aqueous dispersion A 67 g Finished with water 1000 ml << Coating of magnetic recording layer >> Sublayer U- for processing support
4 On the layer coated with the coating solution, a magnetic recording layer coating solution having the following composition was dried with a precision extrusion coater to a dry film thickness of 0.
The coating was applied so as to have a thickness of 8 μm, and at the same time as drying, the magnetic substance was oriented in the application direction in an orientation magnetic field while the coating film was not dried, thereby achieving high output during magnetic recording and reproduction.

[Composition and Preparation of Magnetic Recording Layer Coating Solution M-1] Cobalt-containing gamma iron oxide (average major axis length 0.12 μm, minor axis length 0.015 μm, Fe ²⁺ / Fe ³⁺ = 0.2, Specific surface area 40 m ² / g, Hc = 750 Oersted 10 parts by weight Alumina (α-Al ₂ O ₃ , average particle size 0.2 μm) 3 parts by weight Diacetyl cellulose (manufactured by Teijin Limited) 150 parts by weight Polyurethane (N3132, Nippon Polyurethane Co., Ltd.) 15 parts by weight Stearic acid 2 parts by weight Cyclohexanone 920 parts by weight Acetone 920 parts by weight After thoroughly mixing and dispersing the above, and then dispersing with a sand mill, coronate-3041 of polyisocyanate (manufactured by Nippon Polyurethane Co., Ltd.) (50% by weight of solid content), and then sufficiently stirred and mixed to obtain a magnetic coating material M-1.

<< Coating of Lubricating Layer >> A lubricant coating solution (wax liquid described below) was prepared by dispersing a carnauba wax in a water / methanol mixed solution so as to contain 0.1% of the carnauba wax on the magnetic recording layer. Was applied so that the coating weight of was 15 mg / m ² . The raw material after the wax application was passed through a heat treatment zone at 100 ° C. for 5 minutes to dry, and then left in an oven at 40 ° C. for 5 days to sufficiently perform a crosslinking reaction of isocyanate.

(Preparation of Wax Liquid) Polyoxyethylene lauryl ether 4 was added to 100 parts by weight of water heated to 90 ° C.
Parts by weight, and 40 parts by weight of carnauba wax separately melted at 90 ° C. were added thereto, followed by sufficiently stirring using a high-speed stirring homogenizer to prepare a dispersion of carnauba wax (WAX1). .

Next, 995 parts by weight of water, 900 parts by weight of methanol and 10 parts by weight of propylene glycol monomethyl ether 10
0 parts by weight, and 5 parts by weight of WAX1 was added thereto.
By stirring, a wax liquid was prepared.

After providing the undercoating layer with the undercoating coating liquids B-1 and B-2 under the same conditions on the side of the magnetic recording medium opposite to the magnetic recording layer side, A sample 101 was provided with a photographic component layer. The addition amount is expressed in grams per 1 m ^2. However, silver halide and colloidal silver were converted to the amount of silver, and the increasing dye (indicated by SD) was shown in moles per mole of silver.

First Layer (Antihalation Layer) Black Colloidal Silver 0.16 UV-1 0.3 CM-1 0.044 OIL-1 0.044 Gelatin 1.33 Second Layer (Intermediate Layer) AS-10 .16 OIL-1 0.20 Gelatin 1.40 Third layer (low-sensitivity red-sensitive layer) Silver iodobromide a 0.12 Silver iodobromide b 0.50 SD-1 3.0 × 10 ^-5 SD-4 1.5 × 10 ^-4 SD-3 3.0 × 10 ^-4 SD-6 3.0 × 10 ^-6 C-1 0.51 CC-1 0.047 OIL-2 0.45 AS- 2 0.005 Gelatin 1.40 4th layer (medium-speed red-sensitive layer) Silver iodobromide c 0.64 SD-1 3.0 × 10 ^-5 SD-2 1.5 × 10 ^-4 SD- ^{3 3.0 × 10 -4 C-2} 0.22 CC-1 0.028 DI-1 0.002 OIL-2 0.21 AS-3 0.006 Zera Down 0.87 Fifth Layer (high sensitivity red-sensitive layer) Silver iodobromide c 0.13 Silver iodobromide d 1.14 SD-1 3.0 × 10 -5 SD-2 1.5 × 10 ^-4 SD-3 3.0 × 10 ^-4 C-2 0.085 C-3 0.084 CC-1 0.029 DI-1 0.027 OIL-2 0.23 AS-3 0.013 Gelatin 1 .23 6th layer (intermediate layer) OIL-1 0.29 AS-1 0.23 gelatin 1.00 7th layer (low-sensitivity green color-sensitive layer) Silver iodobromide a 0.245 Silver iodobromide b 0.105 SD-6 5.0 × 10 ^-4 SD-5 5.0 × 10 ^-4 M-1 0.21 CM-2 0.039 OIL-1 0.25 AS-2 0.003 AS-4 0.063 gelatin 0.98 8th layer (intermediate layer) M-1 0.03 CM-2 0.005 OIL-1 0.16 AS-1 0.11 gelatin 0.80 9th layer (medium speed green color-sensitive layer) Silver iodobromide e 0.87 SD-7 3.0 × 10 ^-4 SD-8 6.0 × 10 ^-5 SD-9 4.0 × 10 ^-5 M-1 0.17 CM-2 0.048 CM-3 0.059 DI-2 0.012 OIL-1 0.29 AS-4 0.05 AS-2 0.005 Gelatin 1.43 10 layers (high sensitivity green color-sensitive layer) Silver iodobromide f 1.19 SD-7 4.0 × 10 ^-4 SD-8 8.0 × 10 ^-5 SD-9 5.0 × 10 ^-5 M -1 0.09 CM-3 0.020 DI-3 0.005 OIL-1 0.11 AS-4 0.026 AS-5 0.014 AS-6 0.006 Gelatin 0.78 11th layer (yellow Filter layer) Yellow colloidal silver 0.05 OIL-1 0.18 AS-7 0.16 Gelatin 1.00 12th layer (low sensitivity blue color Silver iodobromide g 0.29 Silver iodobromide h 0.19 SD-10 8.0 × 10 ^-4 SD-11 3.1 × 10 ^-4 Y-1 0.91 DI-40 022 OIL-1 0.37 AS-2 0.002 Gelatin 1.29 13th layer (high-sensitivity blue-sensitive layer) Silver iodobromide h 0.13 Silver iodobromide i 1.00 SD-10 4. 4 × 10 ^-4 SD-11 1.5 × 10 ^-4 Y-1 0.48 DI-4 0.019 OIL-1 0.21 AS-2 0.004 Gelatin 1.55 14th layer (first protection) Layer) Silver iodobromide j 0.30 UV-1 0.055 UV-2 0.110 OIL-2 0.63 Gelatin 1.32 15th layer (second protective layer) PM-1 0.15 PM-2 0.04 WAX-1 0.02 D-1 0.001 Gelatin 0.55 In addition to the above composition, coating aids SU-1 and S -
2, SU-3, dispersing aid SU-4, viscosity modifier V-1,
Stabilizers ST-1, ST-2, antifoggant AF-1, weight average molecular weight: 10,000 and weight average molecular weight: 1,
100,000 two types of polyvinylpyrrolidone (AF-
2), inhibitors AF-3, AF-4, AF-5, hardener H
-1, H-2 and the preservative Ase-1 were added.

The structure of the compound used in the above sample is shown below. Table 11 shows the used silver iodobromide.

[0207]

[Table 11]

[0208]

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[0209]

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[0210]

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[0211]

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[0212]

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[0213]

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[0214]

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[0215]

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[0216]

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The prepared sample was 35 mm wide and 100 m long.
Then, a 6 kHz square wave signal was recorded at a transport speed of 100 mm / S by a magnetic write head and wound around a reel.

The same stabilizing solution and stabilizing replenishing solution as in Example 5 were used. After performing the same continuous processing as in 1-1 and 1-6, the light-sensitive material prepared by the above-described method is processed, the residual color stain is evaluated in the same manner as in Example 1, and the processed light-sensitive material is further processed. Was evaluated according to the following criteria.

<Evaluation of clogging of magnetic head> A square wave signal was read from the processed photosensitive material with a magnetic reading head at the same conveyance speed, and a head clog was generated at a point where the output dropped by 3 dB or more from the initial value. The occurrence level of head clog was evaluated based on the length (m) from the start of the test. The smaller the numerical value, that is, the more unfavorable the occurrence of head clog at a short distance, the more unfavorable.

<Evaluation of Magnetic Characteristics> In the same manner as in the test for evaluation of clogging of the magnetic head, the magnetic head was 0.5 dB lower than the initial value.
再生, 0.5 dB or more and 1 d
Those reproduced with a decrease of less than B were marked with Δ, and those reproduced with a decrease of 1 dB or more were marked X.

The results are shown in Table 12.

[0222]

[Table 12]

Example 10 The coated silver amount of the light-sensitive material sample prepared in Example 9 was 6.85 g.
Samples were prepared by changing the amount of silver halide in each emulsion layer at the same ratio as shown in Table 13 / m ² .
The sensitizing dye amount also changes in proportion to the silver amount. The same experiment as in Example 8 was performed using each sample, and the residual color stain was evaluated. Table 13 shows the results.

[0224]

[Table 13]

From this, it can be seen that the effect of the present invention is remarkable when processing a photographic material having a coated silver amount of 3 g / l or more, more preferably 6 g / l or more.

[0226]

According to the present invention, even if the rate of processing a high-sensitivity photosensitive material is large, the generation of residual color stain and precipitation in a stable solution is not caused, and the amount of photographic processing waste liquid can be reduced. .

[Brief description of the drawings]

FIG. 1 is a diagram showing a position where a solid processing agent replenishing device is attached to an automatic developing machine.

FIG. 2 is a configuration diagram illustrating an example of a solid processing agent replenishing device.

[Explanation of symbols]

 1A to 1E Processing tank 2A to 2D Solid processing agent replenishing device 101 Cartridge 102 Sliding cap 103 Cartridge support base 104 Rotating cylinder 105 Notch 106 Melting chamber 107 Filter 108 Shutter 109 Processing tank 110 Canopy 111 Solid processing agent (tablet)

Claims (10)

[Claims] 1. A stabilizing solution for processing a silver halide color photographic light-sensitive material, comprising a compound represented by the following general formula (1). Embedded image 2. The stabilizing solution for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the stabilizer is substantially free of formaldehyde. 3. The silver halide color photographic light-sensitive material according to claim 2, comprising at least one compound selected from compounds represented by the following formulas (F-1) to (F-3). Stabilizer for material processing. Embedded image [In the formula, A _{1 to} A ₄ represent a hydrogen atom, an alkyl group, an alkenyl group, or a pyridyl group. l represents 0 or 1. [Chemical formula 3] [Wherein, Z represents a group of atoms necessary to form a hydrocarbon ring or a heterocyclic ring, X represents an aldehyde group, Wherein R ₂ and R ₃ each represent a lower alkyl group, and n represents an integer of 1 to 4. [Chemical formula 5] Wherein X ₁ , X ₂ , X ₃ and X ₄ are each —NR ₄ —,
N -, - O -, - S -, - CR 5 R 6 -, = CR 7 -, -
CO— or —C (＝ NR ₈ ) —, wherein R ₄ , R ₅ , R ₆ ,
R ₇ and R ₈ each represent a hydrogen atom or a substituent. Z ₁ and Z ₂ each represent a group of non-metallic atoms necessary to form a 4- to 8-membered ring. ] 4. A surface tension at 20 ° C. of 15 to 60 d.
4. The stable solution for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the stability liquid is yne / cm. 5. A solid stabilizer for processing a silver halide color photographic light-sensitive material, comprising a compound represented by the formula (1). 6. The silver halide color photographic photosensitive material according to claim 5, comprising at least one compound selected from the compounds represented by formulas (F-1) to (F-3). Solid stabilizer for material processing. 7. A method for processing a silver halide color photographic light-sensitive material, comprising a step of using the stabilizing solution according to claim 1. 8. The method for processing a silver halide color photographic light-sensitive material according to claim 7, wherein the stabilizing solution of the step is introduced into the processing tank of the immediately preceding step. 9. The photosensitive material to be processed has a coated silver amount of 3 g / g.
The method for processing a silver halide color photographic material as claimed in claim 7 or 8, characterized in that m ² or more. 10. The method for processing a silver halide color photographic light-sensitive material according to claim 7, wherein the light-sensitive material to be processed has a layer containing magnetic particles.