EP0853256A2

EP0853256A2 - Stabilizing solution for processing silver halide color photographic light-sensitive material and method for processing silver halide color photographic light-sensitive material using the same

Info

Publication number: EP0853256A2
Application number: EP98300119A
Authority: EP
Inventors: Atsuro Yanata; Manabu Nakahanada; Hiroaki Kobayashi
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 1997-01-10
Filing date: 1998-01-08
Publication date: 1998-07-15
Also published as: EP0853256A3

Abstract

A stabilizing solution for processing a silver halide color photographic material and a method for processing a silver halide color photographic light material suing the stabilizing solution are disclosed. The stabilizing solution contains a compound represented by the following Formula 1;

wherein Q₁ is a group of atoms necessary to form a nitrogen-containing heterocyclic ring, R₁ is a hydrogen atom, an alkali metal atom, a

group or an alkyl group, Q' is a synonym with Q₁.

Description

FIELD OF THE INVENTION

The present invention relates to a stabilizing solution for processing a silver halide color photographic light-sensitive material and a method for processing a silver halide color photographic light-sensitive material using the above-mentioned stabilizing solution.

BACKGROUND OF THE INVENTION

Recently, regulation on waste disposal has been strengthen worldwide accompanied with increasing interest in the earth environment. In the field of photographic industry, it has been restricted to dump waste liquid of photographic processing solution into the sea according to the London Agreement.

Besides, speed is required in everything according to changing in the general public trends, and a demand on the rapidity of processing is strongly raised in the field of photographic industry accompanied with rapid increase of mini-lab shops.

Accordingly, a variety of investigation for the waste liquid treatment and reducing the replenishing amount have been carried out by many manufacturers of photographic products to reduce the waste liquid.

Recently, a share of high speed color negative film is increased in the market of color negative film. In such the high speed light-sensitive material, the amount of silver halide and sensitizing dyes in the emulsion are larger and the content of silver iodide in the emulsion is higher compared with those in a low speed light-sensitive material.

Accordingly, when the ratio of high speed light-sensitive material in the light-sensitive material to be processed is incresed, simple decrease of the amount of replenishing of stabilizing solution causes increase of amount of the sensitizing dye dissolved from the light-sensitive material accumulated in the stabilizing solution. The sensitizing dye accumulated in the stabilizing solution causes re-dyeing the light-sensitive material and inhibits dissolving out the sensitizing dye from the light-sensitive material so as to remain the dye in the light-sensitive material. The remained sensitizing dye causes a stain, so-called remained-color stain, which raises problems of color patches or divergence of color balance in the print. Furthermore, components of the fixing solution arranged just before the sensitizing bath, such as thiosulfate, silver ion and a halogen ion such as iodide ion, stuck on the light-sensitive material are brought and largely accumulated in the stabilizing solution. These components accumulated in the stabilizing solution inhibit dissolution of sensitizing dye, give bad influence on the processing ability of the stabilizing solution by forming precipitation therein, and form the stain on the light-sensitive material. Moreover, such the components accumulated in the stabilizing solution cause lowering the stability of the image during a prolonged storage. A technique for accelerating a fixing process by addition of a heterocyclic compound having a mercapto group to a fixing solution is described in Japanese Patent Publication Open to Public Inspection (JP O.P.I.) Nos. 1-261640, 8-190178, 8-201997, 8-272061 and 9-211820. However, these publications describe nothing relating to addition of the heterocyclic compound to a stabilizing solution and improving the remained-color stain. Accordingly, the problems to be solved by the present invention cannot be sufficiently solved by such the technique described in these publications.

Furthermore, a technique for improving the remained-color stain by adding a heterocyclic compound in a black-and-white photographic light-sensitive material is described in JP O.P.I. Nos. 64-15734, 1-230043 and 2-103037. However, these publications describe nothing relating to the improvement of the storage ability of dye image. Regarding the remained-color stain, various conditions such as the kind of sensitizing dye and the procssing conditions, in the black-and-white light-sensitive material are consideraably different from those in the color light-sensitive material. Accordingly, sufficient effcts cannot be obtained if the technique described in these publications is applied to the color light-sensitive materail, particularly under a recent processing in which the replenishing amount of processing solution is reduced.

SUMMARY OF THE INVENTION

The object of the invention is to provide a stabilizing solution for processing a silver halide color photographic light-sensitive material and a method for processing a silver halide color photographic light-sensitive material using the stabilizing solution, by which a decrease of the amount of waste liquids and a rapid processing can be realized without causing the remained-color stain and formation of precipitation in the stabilizing solution even when the high speed light-sensitive material is processed in a high ratio.

The above-mentioned object of the invention can be attained by a stabilizing solution for processing a silver halide color photographic light-sensitive material, which contains a composition represented by the following Formula 1;

in the formula, Q₁ represents a group of atoms necessary to form a nitrogen-containing heterocyclic ring (5- or 6-member ring including one condensed with an unsaturated ring), R₁ represents a hydrogen atom, an alkali metal atom, a

group or an alkyl group, Q' is a synonym with Q₁.

And a method for processing a silver halide color photographic light-sensitive material comprising the steps of

developeing the light-sensitive material with a color developing solution,

fixing the light-sensitive material with a fixing solution or a bleach-fixing solution, and

stabilizing the light-sensitive material with a stabilizing solution which contains a compound represented by the above-mentioned Formula 1.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 shows a position on an automatic processor, at which a solid processing composition suplying device.

Fig. 2 shows a constitution of an example of a solid processing composition supplying device.

DETAILED DESCRIPTION OF THE INVENTION

Concrete examples of the compound represented by Formula (1) to be contained in the stabilizing solution of the invention are shown below. However, the compound usable in the invention is not limited thereto.

Among the above-mentioned compounds, preferably usable compounds are (1-9), (1-10), (1-13), (1-31) and (1-32), particularly preferably (1-32), from the view point of the object of the invention.

Dissolution of sensitizing dye remained in the light-sensitive material is accelerated by the compound of Formula 1 contained in the stabilizing solution and the formation remained-color stain can be prevented even when the amount of sensitizing dye accumulated in the stabilizing solution is increased by reducing the replenishing amount of fixing solution, or the time for the stabilizing treatment is reduced.

Furthermore, the formation of insoluble substance, which is usually composed of silver ions and the decomposition product of thiosulfate, can be inhibited by adding such the compound in the stabilizing solution since the compound tend to interact with silver ions.

In the invention, it is preferred that the compound of Formula 1 is contained in the stabilizing solution in am amount of 0.01 to 1.0 g/l, more preferably 0.1 to 0.5 g/l.

The stabilizing solution according to the invention preferably contains no formaldehyde. Formaldehyde is frequently contained in a stabilizing solution for preventing the formation of color stains during prolonged storage and improving the stability of discoloration of color image by blocking the reactive portion of the unreacted coupler remained in the processed light-sensitive material. In such the case, formaldehyde reacts with sulfite which is brought from the fixing bath together with thiosulfate, and tends to form precipitates or to accelerate sulfidation of the stabilizing solution.

It is preferred that at a compound represented by Formula F-11, F-12 or F-14 is contained in the stabilizing solution according to the invention from the view point of the effect of the invention and blocking the unreacted coupler.

wherein, A₁ through A₄ are each a hydrogen atom, an alkyl group, an alkenyl group or a pyridyl group, and ℓ is 0 or 1.

As a salt of the compound represented by Formula F-11, an inorganic acid salt such as hydrochloric acid salt, sulfate and nitrate, an organic acid salt such as phenol salt, a double salt of a complex salt with a metal salt, an aqueous salt and an intramolecular salt are cited.

Concrete examples of the compound represented by Formula F-11 are described in Beilsteins Handbuch der Organishen Chemie, edition II, 26, p.p. 200 to 212. Among the compounds, water-soluble ones are preferred in the invention. Typical examples thereof are shown below.

The adding amount of the compound represented by Formula F-11 is preferably 0.1 to 20 g per liter of the stabilizing solution.

wherein, Z₄ is a group of atoms necessary for forming a hydrocarbon ring or a heterocyclic ring, X represents an aldehyde group, a

in which R₄₁ and R₄₂ are each a lower alkyl group, and n is an integer of 1 to 4.

In Formula F-12, Z₄ is a group of atoms necessary to form a substituted or unsubstituted carbon ring or a substituted or unsubstituted heterocyclic ring, and the carbon ring and the heterocyclic ring each may be a single ring or condensed ring. Z₄ is preferably an aromatic carbon ring having a substituent or a heterocyclic ring. The substituent of Z₄ is preferably selected from the following groups; an aldehyde group, a hydroxyl group, an alkyl group such as methyl group, ethyl group, methoxyethyl group, benzyl group, carboxymethyl group and sulfopropyl group, an aralkyl group, an alkoxy group such as methoxy group, ethoxy group and methoxyethoxy group, a halogen atom, a nitro group, a sulfo group, a carboxyl group, an amino group such as N,N-dimethylamino group, N-ethylamino group and N-phenylamino group, a hydroxyalkyl group, an aryl group such as phenyl group and p-methoxyphenyl group, a cyano group, an aryloxy group such as phenoxy group and p-carboxyphenyl group, an acyloxy group, an acylamino group, a sulfonamido group, a sulfamoyl group such as N-ethylsulfamoyl group and N,N-dimethylsulfamoyl group, a carbamoyl group such as carbamoyl group, N-methylcarbamoyl group and N-tetramethylenecarbamoyl group, and a sulfonyl group such as methanesulfonyl group, ethanesulfonyl group, benzenesulfonyl group and p-toluenesulfonyl group.

The carbon ring represented by Z₄ is preferably a benzene ring, and the heterocyclic ring represented by Z₄ is preferably a 5- or 6-member heterocyclic ring, for example, the 5-member ring includes a thiophene ring, a pyrrole ring, a furan ring, a thiazole ring, an imidazole ring, a pyrazole ring, a succinimide ring, a triazole ring, and tetrazole ring, and the 6-member ring includes a pyridine ring, a pyrimidine ring, a triazine ring and a thiazine ring.

As the condensed ring, a naphthalene ring, a benzofuran ring, an indole ring, a thionaphthalene ring, a benzimidazole ring, a benzotriazole ring and a quinoline ring may be cited.

Examples of preferred compound represented by Formula F-12 are shown below.

Exemplified compounds F-12-1 to F-12-52 are shown by inserting substituents at the positions 1 to 6 in the above-mentioned formula as shown in the following tables.

Among the exemplified compounds represented by Formula F-12, More preferable compounds are F-12-2, F-12-3, F-12-4, F-12-6, F-12-23, F-12-24, F-12-52, and the most preferable compound is F-12-3.

The compounds represented by F-12 are usually available on the market.

The adding amount of the compound represented by F-12 is preferably 0.05 to 20 g, more preferably 0.1 to 15 g, particularly preferably 0.5 to 10 g, per liter of the stabilizing solution.

The compound represented by Formula F-14 is described below.

wherein the formula, X₂, X₃, X₄ and X₅ are each -NR₆₀, =N-, -O-, -S-, -CR₆₁R₆₂-, =CR₆₃-, -CO- or -C(=NR₆₄)-, in which R₆₀, R₆₁, R₆₂, R₆₃ and R₆₄ are each a hydrogen atom or a substituent, and Z₅ and Z₆ are each a group of atoms necessary to form a 4- to 8-member ring.

In Formula F-14, it is preferable that at least one of Z₅ and Z₆ is a group of non-metal atoms necessary to form an aromatic ring or a ring, an isomeric chemical structure of which can be an aromatic ring, together with the nitrogen atom, X₂ and X₃, or the nitrogen atom, X₄ and X₅ in Formula F-14. It is more preferable that Z₅ is a group of non-metal atoms necessary to form an aromatic ring or a ring, an isomeric structure of which can be an aromatic ring, together with the nitrogen atom, X₂ and X₃ in Formula F-14 and Z₆ is a group of non-metal atom necessary to form a non-aromatic ring together with the nitrogen atom, X₄ and X₅. As the aromatic ring or the ring, the isomeric structure of which can be an aromatic ring, a 5-member ring is preferable, and a pyrazole ring, a triazole ring such as a 1,2,4-triazole ring and a 1,2,3-triazole ring and an urazole ring are more preferable. As the non-aromatic ring formed by Z₆, a pyrrolidine ring, a piperidine ring, a morpholine ring and a piperazine ring are preferable.

Examples of the compound represented by Formula F-14 are shown below.

It is preferred that the stabilizing solution according to the invention has a surface tension of 15 to 60 dyne/cm, more preferably 15 to 45 dyne/cm. The surface tension is a value determined by an usual method described in, for example, H. Kitahara, S. Hayano & I. Hara, "Analysis and Test Method of Surfactant" March 1, 1082, Kodansha. In the invention, the surface tension is a value measured by by the usual method at 20° C.

Although any means for controlling the surface tension of the stabilizing solution can be applied without any limitation, it is particularly preferred that the stabilizing solution contains a water-soluble surfactant. As the surfactant, a compound represented by the following Formula SI, SII or SIII, or a water-soluble organic siloxane compound.is particularly preferred.

wherein R¹ is a hydrogen atom, an aliphatic group or an acyl group, R² is a hydrogen atom or an aliphatic group, E¹ is an ethylene oxide group, E² is a propylene oxide group, E³ is an ethylene oxide, X is an oxygen atom or a -R³N- group, in which R³ is an aliphatic group, a hydrogen atom or an

R⁴ is a hydrogena tom or an aliphatic group, and l₁, l₂, m₁, m₂, n₁ and n₂ are each 0 or an integer of 1 to 300.

wherein A₁ is a mono-valent organic group, for example, an alkyl group having 4 to 50, preferably 4 to 35, carbon atoms such as a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group or a dodecyl group, which may be substituted by a fluorine atom, or an aryl group which is substituted by an alkyl group having 3 to 35 carbon atoms or an alkenyl group having 2 to 35 carbon atoms.

The preferable substituent of the aryl group includes the following group: an alkyl group having 1 to 18 carbon atoms, for example, an unsubstituted alkyl group such as a methyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group and a dodecyl group, a substituted alkyl group such as a benzyl group and a phenetyl group, an alkenyl group having 2 to 20 carbon atoms, for example, an unsubstituted alkenyl group such as an oleyl group, and an allyl group, and a substituted alkenyl group such as styryl group. As the aryl group, a phenyl group, a biphenyl group and a naphthyl group, preferably a phenyl group, are cited. The position of the aryl group at which the substituent is bonded may be any of orto-, metha- and para-position and a plurailty of the substituent may be bonded.

B and C are each a group, and C is a group selected from an ethylene oxide group, a propylene oxide group and a

oprovided that the group represented by B and the group represented by C is different from each other, n₁, m₁ and l₁ are each 0, 1, 2 or 3, m and n are each an integer of 0 to 100, X₁ a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, for example, a group the same as that represented by A₂.

Examples of the compound represented by Formula SI or SII are shwon below.

Compounds represented by Formula SI

Compounds represented by Formula SII

The adding amount of the water-soluble surfactant is preferably 0.1 to 40 g, more preferably 0.3 to 20 g per liter of the stabilizing solution.

Formula SIII is described below. Formula SIII Rf-(x)_m-(Y)_n-A

In Formula SIII, Rf is a saturated or unsaturated hydrocarbon group each having a fluorine atoms, X is a sulfonamido group, a

Y is an alkylene oxide group or an alkylene group, Rf' is a saturated or unsaturated hydrocarbon group each having a fluorine atoms, A is a hydrophilic group such as an -SO₃M group, an -OSO₃M group, a -COOM group, an -OPO₃(M₁) (M₂) group or a -PO₃(M₁) (M₂) group, M, M₁ and M₂ are each a hydrogen atom, a lithium atom, a potassium atom, a sodium atom or an ammonium group, m is 0 or 1, and n is 0 or an integer of 1 to 10.

In Formula SIII, Rf is a saturated or unsaturated hydrocarbon group such as an alkyl group, an alkenyl group or an alkinyl group each ahving a fluorine atom, and is preferably an alkyl group having 4 to 12 carbon atoms, more preferably 6 to 9 carbon atoms, which has a fluorine atom. A is preferably an -SO₃M group, M, M₁ and M₂ are preferably a lithium atom, a potassium atom or a sodium atom, more preferably a lithium atom. m is 0 or 1, n is 0 or an integer of 1 to 10, and preferably both of m and n are 0.

Examples of the compound represented by Formula SIII are shown below. SIII-1 C₈F₁₇SO₃K SIII-2 C₈F₁₇SO₃Li SIII-3 C₈F₁₇COOK

SIII-1, SIII-2 and SIII-3 are particularly preferred among the above examples.

A compound represented by the following Formula SU-I is preferable as the water-soluble organic siloxane compound.

In the above formul, R₉ is a hydrogen atom, a hydroxyl group, a lower alkyl group, an alkoxy group, an

or an

R₁₀, R₁₁ and R₁₂ are each a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, the groups each represented by R₁₀, R₁₁ and R₁₂ may be the same or different. l₁, l₂ and l₃ are each 0 or an integer of 1 to 30 and p, q₁ and q₂ are each 0 or an integer of 1 to 30.

X₁ and X₂ are each a -CH₂CH₂- group, a -CH₂CH₂CH₂-group, a

or a

Examples of the compound represented by Formula SU-I are shown below.

The adding amount of the water-soluble organic siloxane compound having a polysiloxane group is preferable 0.01 to 20 g per liter of the stabilizing solution.

In the invention, the water-soluble organic siloxane compound includes usual organic compounds such as ones described in, for example, JP O.P.I. Nos. 47-19333 and 49-62128, Japanese Patent Nos. 55-51172 and 51-37538, and U.S. Patent 3,545,970.

These water-soluble organic siloxane compounds are available from Union Carbide Co., Ltd. or Shin'etsu Kagaku Kogyo Co., Ltd.

Components usually used in a stabilizing solution, for example, a chelating agent such as ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid and 1-hydroxyethylidene-l,l-disulfonic acid, a buffering agnet such as potassium carbonate, a borate, an acetate and a phosphate, an anti-mold agent such as Diacide 702(trade name), p-chloro-m-cresole and benzo-iso-thiazoline-3-one, a fluorescent whitening agent such as a triazinylstylbene compound, an antioxidant such as a sulfite and an ascorbic acid, and a metal salt such as a zinc salt and a magnesium salt, may be optionally added in the stabilizing solution according to the invention.

In the invention, the effect of the invention is enhanced when the processing is carried out by applying a reduced replenishing amount of the stabilizing solution, the replenishing amount is preferably not more than 1200 ml, more preferably 100 to 900 ml, further preferably 200 to 650 ml, per 1 m² of the light-sensitive material to be processed.

Although the number of the stabilizing tank may be one, the number of the tank may be increased by 2 to 10. The number of the stabilizing tank is preferably 2 to 6 from the viewpoint of compactness of the processor. Although the replenishing solution may be supplied to the stabilizing tank separately from several portions, it is preferred that the replenishing solution is supplied by a method so-called counter-current method. By such the method, the replenishing solution is supplied to the tank arranged at a lower course of the conveying direction of light-sensitive material and the overflow from the tank is introduced into the tank arranged before the tank to which the replenishing solution is supplied. This method includes a case in which these tanks are connected by a pipe and the overflow is flow through the pipe. A cascade-flow method is also included in this method. It is further preferred that two or more tanks are provided and the replenishing solution is supplied to the tank arranged at the last step and the overflow is successively flowed to the tank arranged at the upper course.

In the invention, it is further preferable that the processing solution take out from the stabilizing tank is introduced into a fixing solution in the fixing process or a bleach-fixing solution in the bleach-fixing process which are the processes positioned just before the stabilizing process. Such the procedure is preferable since the procedure enhances the effect of the invention and results reducing the amount of the replenishing solution.

In the invention, the temperature and time of the stabilizing treatment are preferably 10 to 50° C and 10 to 80 seconds, more preferably 20° C and 70 seconds, further preferably 20 to 40° C and 15 to 70 seconds, respectively. The pH value of the stabilizing solution is preferable 3 to 10. more preferably 6 to 9.

The treating process to which the present invention is applied includes the followings;

(1) Color developing → Bleaching → Fixing → Stabilizing

(2) Color developing → Bleaching → Fixing → First stabilizing → Second stabilizing

(3) Color developing → Bleaching → Bleach-fixing → Fixing → Stabilizing

(4) Color developing → Bleaching → Bleach-fixing → Fixing → First stabilizing → Second stabilizing Fixing

(5) Color developing → Bleach-fixing → Stabilizing.

It is preferable for enhancing the effect of the invention that a solid processing composition in a form of powder, granule or tablet is used for replenishing the processing solution. Among them, the granuled processing composition and tableted processing composition are more preferable and the tableted composition is most preferable.

The powder is a mass of fine crystals, and the granule is a grain-shape matter having a diameter of 50 to 5000 µm, which is preferably prepared by granulation of the powder. The tablet is a product prepared by compressing the powder or the granule to a certain form. It is preferable that the tablet is prepared by the method by which powder or granules are granuled and then the granuled matter is tableted since the processing ability of the composition can be stably maintained.

As the method of granulation for preparation of the tablet, a known method such as a tumbling granulation, an extruding granulation, a compressing granulation, a crushing granulation, agitation granulation, fluidized-bed granulation or spray-drying granulation, can be applied. The average diameter of the granuled matter is preferably 100 to 2,000 µm. more preferably 200 to 1,500 µm, for tableting since unevenness of the composition, so-called segregation, is hardly occurred at the time of compressing the granuled matter. It is preferable that the sizes of the grains accounting for 50 % of the whale granules are within a deviation range of ±200 to 250 µm. Thus obtained granuled matter may be directly used as the granuled processing composition. A known compressing machine such as an oil-pressure compressing machine, a single tableting machine, a rotary tableting machine or a briquetting machine can be used for compressing the granuled matter. It is allowed that the granuled matter prepared by the above-mentioned method and a crystalline material available on the market are mixed and tableted.

Although the solid processing composition prepared by compressing may be formed in any shape, the cylindrical shape, so-called tablet, is preferred from the viewpoint of the production efficiency, handling facility and formation of powder dust in the practical use.

Silver halide used in the silver halide photographic light-sensitive material to be processed may be any one such as silver chloride, silver chlorobromide, silver bromide, silver iodobromide and silver iodide as far as the silver halide is spectrally sensitized by a sensitizing dye. The effect of the invention is enhanced in the processing of a light-sensitive material for photographing by a camera which includes a silver halide having relatively high silver iodide content such as 5 mol-% or more, and has a coating amount of silver is 3 to 20 g/m², preferably 6 to 20 g/m².

The silver halide emulsion can be prepared according to the methods described in, for example, Research Disclosure, hereinafter referred to RD, No. 17643, p.p. 22-23, I. Emulsion preparation and types, December 1978, RD No. 18716, p. 648, P. Glafkides, Chimie et Phisique Photographique, Paul Montel, 1967, G. F. Duffin, Photographic Emulsion Chemistry, Focal Press, 1966, V. L. Zelikman et al. Making and Coating Photographic Emulsion, Focal Press, 1964. Monodisperse emulsions described in U. S. Patent Nos. 3,574,628 and 3,665,394, and British Patent No. 1,413,748 are also preferred. Although the average grain diameter is without any limitation, 0.1 to 5 µm is preferable. Two or more kinds of separately prepared emulsions may be mixed for used.

Various kinds of photographic additives may be used to the emulsion in the course of physical ripening or chemical ripening process. Various compounds described in RD Nos. 17643, 18716 and 308119 can be used as the additives.

A compound described in U. S. Patent Nos. 4,411,987 and 4,435,503, which is capable of reacting with formaldehyde and fixing it, is preferably added to the light-sensitive material to prevent degradation of the photographic properties caused by formaldehyde gas. Various kinds of coupler can be used, concrete examples thereof are described in RD Nos. 17643 and 308119. The additives can be added by the dispersing method described in RD No. 308119, XIV.

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

The magnetic layer may be provided at any portion in the light-sensitive material, for example, the magnetic layer may be not adjoined to the support. The magnetic layer may be arranged on the emulsion side or the opposite side of the support. As the ferromagnetic particles, ferromagnetic iron oxide such as γ-Fe₂O₃ (FeO_x, 4/3 < x ≤ 3/2), Cobalt-adhered ferromagnetic iron oxide such as Co-adhered γ-Fe₂O₃ (FeO_x, 4/3 < x ≤ 3/2), Co-adhered magnetite, another Cobalt-containing ferromagnetic iron oxide, Co-containing magnetite, ferromagnetic chromium dioxide, a ferromagnetic metal, a ferromagnetic alloy, another ferrite such as hexagonal Baferrite, Sr-ferrite, Pb-ferrite, Ca-ferrite, a solid solution of them or a ion substituted substance of them, are usable, and a Cobalt-adhered ferromagnetic iron oxide such as Co-adhered Fe₂O₃ having a Fe²⁺/Fe³⁺ ratio of 0 to 10%, is preferable from the viewpoint of transparent density.

The preparation method of these ferromagnetic particles has be known, and the ferromagnetic particle usable in the light-sensitive material of the invention can be also prepared by the known method. Although the shape of the ferromagnetic particle may be any of a needle-like, rice grain-like, spherical, cubic and tabular, the needle-like particle is preferable from the viewpoint of electromagnetic conversion property. In the case of the needle-like particle, the particle size in the major axis length of 0.01 to 0.8 µm and the ratio of major axis/minor axis is 2 to 100, are preferable, and the major axis length of 0.05 to 0.3 µm and the major axis/minor axis ratio of 4 to 15 are more preferable. The specific surface area S_BET of the ferromagnetic particles is preferably not less than 20 m²/g, more preferably 30 m²/g.

A larger saturation magnetization (σs) value is preferred, and a saturate magnetization of not less that 50 emu/g is preferable and that not less than 70 emu/g is more preferable, the value is practically not more than 100 emu. The square ratio (σr/σs) of the ferromagnetic substance is preferably not less than 40%, more preferably not less than 45%. A proper coercive force (Hc) is preferred. When the coercive force is too small, recorded signals is too easily erased and when the coercive force is too large, signals are hardly written. The coercive force is usually 200 to 3,000 Oe, preferably 500 to 2,000, more preferably 650 to 950 Oe.

It has been found that various problems relating to the invention are raised when the light-sensitive material having the magnetic layer containing the ferromagnetic particles is treated by a stabilizing solution. Furthermore, it has been found that problems such as block of a reading head and degradation in the magnetic property are raised when information recorded in the magnetic layer of the light-sensitive material is read. Such the problems can be solved by applying the stabilizing solution or the processing method according to the invention.

Various kinds of additives, binders, supports and producing methods described in JP O.P.I. 8-95218, [0009]-[0051] can be applied to the magnetic layer.

EXAMPLES Example 1

Konica Color Negative Film LV400, manufactured by Konica Corporation, was imagewise exposed by a camera and processed by a color negative film processor CL-KP-50QA using processing solutions and replenishing solutions prepared by the following receipts. The processing was run for 8 weeks. In the course of the running of the processing, 60 roles of 135-24 size film were processed per day.

(Processing steps)
	Time	Temperature	Replenishing amount
Color developing	3min. 15 sec.	38° C	520 ml/m²
Bleaching	45 sec.	38° C	100 ml/m²
Fixing-1	45 sec.	38° C
Fixing-2	45 sec.	38° C	510 ml/m²
Stabilizing-1	20 sec.	38° C
Stabilizing-2	20 sec.	38° C
Stabilizing-3	20 sec.	38° C	860 ml/m²
Drying	80 sec.	55° C

The replenishments in the fixing process and the stabilizing process were each carried out by counter flow systems in the order of Fixing-2 → Fixing-1, and stabilizing-3 → stabilizing-2→ stabilizing-1, respectively.

Color developer initial 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
Pentasodium diethylenetriaminepentaacetate	3.0 g
Potassium hydroxide	1.2 g
Water to make	1 l
Adjust pH to 10.0 using potassium hydroxide or 20% sulfuric acid.

Replenishing solution for color developing solution
Water	600 ml
Potassium carbonate	40 g
Sodium hydrogen carbonate	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
Pentasodium diethylenetriaminepentaacetate	3.0 g
Potassium hydroxide	2 g
Water to make	1 l
Adjust pH to 10.2 using potassium hydroxide or 20% sulfuric acid.

Bleaching solution
Water	500 ml
Ferric ammonium 1,3-propylenediaminetetraacetate	133 g
1,3-propylenediaminetetraacetic acid	10 g
Ammonium bromide	100 g
Succinic acid	30 g
Maleic acid	70 g
Water to make	1 l
Adjust pH to 4.4 using ammonia water

Replenishing solution for bleaching solution
Water	500 ml
Ferric ammonium 1,3-propylenediaminetetraacetate	175 g
1,3-propylenediaminetetraacetic acid	2 g
Ammonium bromide	120 g
Succinic acid	40 g
Maleic acid	80 g
Water to make	1 l
Adjust pH to 3.4 using ammonia water

Fixing solution and replenishing solution for fixing solution
Water	500 ml
Sodium thiosulfate	25 g
Ammonium thiosulfate	225 g
Sodium sulfite	18 g
Potassium carbonate	2 g
Disodium ethylenediaminetetraacetate	2 g
Water to make	1 l

Stabilizing solution and replenishing solution for stabilizing solution
Water	700 ml
m-hydroxybenzaldehyde	1.5 g
Exemplified compound F-12-3
Sodium laurylsulfate	0.2 g
Disodium ethylenediaminetetraacetate	0.6 g
Lithium hydroxide monohydrate	0.7 g
Compound described in Table 1	0.2 g
Water to make	1 l

After finish of the runningof the processing, an unexposed specimen of the light-sensitive material was processed and the red density of the processed specimen, D_min(R), was measure by X-rite densitometer, Manufactured by Nihon Heihankizai Co., Ltd. The specimen was washed in pure water at 40° C for 10 minutes or more with sufficiently stirring to completely remove the sensitizing dye remained in the light-sensitive material. The red density of the washed specimen, D'_min(R), was measured after drying. Degree of the remained-color stain ΔD_min(R) was defined by the different of D_min(R) and D'_min(R) .

The degree of the remained-color stain of 0.05 or less is a level of the stain acceptable for practical use, and a value nearer to 0 is preferred.

Besides, a specimen of the light-sensitive material exposed through an optical wedge was processed. The transparent density at 440 nm of the maximum density portion of the processed specimen was measured. Then the specimen was stood in a lighted room for 10 days inder conditions of a temperature of 40° C, a relative humidity of 30% and a lightness of 70,000 Lux/h. After standing, the specimen was subjected to densitometry and a ratio of the difference of the density caused by the standing, a discoloration ratio of yellow color, was determined.

An appearance of the first stabilizing tank was visually observed after Finnish of the running of the processing, and evaluated according to the followings.

A: No precipitation was observed in the first stabilizing tank

B Precipitation was slightly observed in the first tank, but the degree of the precipitation was acceptable for practical use.

C: Large amount of precipitation was observed, the degree of the precipitation was not acceptable for practical use.

Degree of the remained-color stain and the appearance of the first stabilizing tank are shown in Table 1.

Experiment No.	Compound of Formula (1)	Degree of remained-color stain	Appearance of first stabilizing tank	Discoloration ratio of yellow color (%)	Remarks
101	-	0.16	C	34	Comparative
102	1-9 (0.2 g/l)	0.05	A	16	Inventive
103	1-10 (0.2 g/l)	0.03	A	15	Inventive
104	1-13 (0.2 g/l)	0.04	A	19	Inventive
105	1-31 (0.2 g/l)	0.03	A	12	Inventive
106	1-32 (0.2 g/l)	0.02	A	8	Inventive

It is understood by the above-mentioned results that the remained-color stain is reduced, the stability of the dye image during a prolonged period is raised, and the appearance of the first stabilizing tank is appropriately maintained for a prolonged period by the addition of the compound represented by Formula 1.

Example 2

Experiments were carried out in the same manner as in Example 1 except that the composition of the stabilizing solution and the reoplenishing solution for the stabilizing solution was changed as follows.

Water	700 ml
m-hydroxybenzaldehyde	1.5 g
Disodium ethylenediamineteraacetate	0.6 g
Lithium hydroxide monohydrate	0.7 g
Compound 1-32	0.2 g
Compound SIII-2	See below

The processing was run in the same manneras in Example 1 using the above-mentioned stabilizing solution. An unexposed specimen of the light-sensitive material was processed and the stain on the back surface of the specimen was observed and ranked as follows.

Evaluation of stains on the back surface

A: No stain was observed on the back surface of the specimen.

B: A little stain was obseved on the back surface of the specimen.

C: A stain was apparently observed on the back sruface of the specimen. The degree of the stain was unacceptable for practical use.

The appearance of the first stabilizing tank was observed in the same amnner as in Example 1.

Results of the experiments are shown in Table 2.

Experiment No.	Surface tension of stabilizing solution (dyne/cm)	Stain on back surface	Appearance in first stabilizing tank
2-1	65	B	B
2-2	58	B-A	B-A
2-3	43	A	A
2-4	35	A	A
2-5	23	A	A

As is understood from the results shown in Table 2, the condition of the stain on the back surface of the specimen is particularly excellent when the surface tension of the stabilizing solution is 60 dyne/cm or less, and the appearance of the first stabilizing tank is particularly maintained clear when the surface tension is 45 dyne/cm or less. Accordingly, such the condition is particularly preferred as the embodiment of the invention.

Example 3

Experiments were carried out in the same manner as in Example 1 except that the concentration of the compound of the invention in the stabilizing solution an the replenishing solution for stabilizing solution was changed as shown in Table 3. Furthermore, the descoloration ratio of yellow color was determined in the sam manner as in Example 2. Results of the experiments are listed in Table 3.

Expeiment No.	Additive	Adding amount (g/l)	Degree of remained-color stain	Appearance of first stabilizing tank	Discoloration ratio of yellow (%)	Remarks
3-1	None	-	0.16	C	34	Comparative
3-2	1-32	0.01	0.05	A	21	Inventive
3-3	1-32	0.05	0.04	A	12	Inventive
3-4	1-32	0.1	0.02	A	10	Inventive
3-5	1-32	0.2	0.02	A	8	Inventive
3-6	1-32	0.3	0.02	A	6	Inventive
3-7	1-32	0.5	0.02	A	7	Inventive
3-8	1-32	0.8	0.02	B	12	Inventive
3-9	1-32	1.0	0.02	B	17	Inventive
3-10	1-32	1.2	0.04	B	15	Inventive
3-11	1-32	1.5	0.05	B	11	Inventive

It is understood by the above-mentioned results that the remained-color stain is sufficiently reduced and the appearance in the first stabilizing tank is appropriately maintained when the adding amount of the compound of the invention is within the range of from 0.01 to 1.0 g/l, and the results are better when the amount is 0.1 g to 0.5 g/l.

Example 4

Experiments were carried out in the same manner as in Example 1 except that the compositions of the stabilizing solution and the replenishing solution for stabilizing solution were changed as follows.

Water	700 ml
Formalin	See Table 3
Compound 1-32	See Table 3
Sodium laurylsulfate	0.2 g
Disodium ethylenediaminetetraacetate	0.6 g
Lithium hydroxide monohydrate	0.7 g
Water to make	1 l

In the above-mentioned, formalin is an about 37% aqueous solution of formaldehyde.

In this example, the stain on the back surface of the light-sensitive material and the appearance of the second stabilizing tank were observed after running of the processing. Furthermore, the red color density of the unexposed portion of the processed light-sensitive material was measured and the degree of remained color was calculated. The stain on the back surface was eavaluated in the same manner as in Example 2 and the appearance in the second stabilizing thank was ranked accoeding to the followings.

Appearance in the second stabilizing tank

A: No change was observed

B: Some degree of muddiness was observed.

C: Obvious sulfidation was observed, the level of it was unacceptable for practical use.

Results are shown in Table 4.

Experiment No.	Formalin	Additive	Degree of remained color	Stain on back surface	Appearance in second stabilizing tank	Remarks
4-1	2 ml/l	-	0.30	C	C	Comp.
4-2	2 ml/l	1-32 (0.2 g/l)	0.05	B	B	Inv.
4-3	0	1-32 (0.2 g/l)	0.03	A	A	Inv.

The stain decreasing effect of the compound of the invention is enhanced and the back surface stain and the appearance in the second stabilizing tank are also improved when the stabilizing solution contains no formaldehyde which is usually used in an ordinary stabilizing solution.

Example 5

Experiments were carried out in the same manner as in Example 1 except that the compositions of the stabilizing solution and the replenishing solution were changed as follows.

Water	700 ml
Compound of Formula F-11, F-12 or F-14
	See Table 4
Compound of the invention 1-32	See Table 4
Sodium laurylsulfate	0.2 g
Disodium ethylenediaminetetraacetate	0.6 g
Lithium hydroxide monohydrate	0.7 g
Water to make	1 l

Further to the determination of the remained-color stain by measuring the red density, the processed sample is stored for 10 days at a temperature of 75° C and a relative humidity of 10%, and the difference of the yellow densities before and after storage of the sample, yellow stain, was determined. Results are shown in Table 5.

Experiment No.	Additive of Formula (F-1) to (F-4)	Additive of Formula (1)	Degree of remained -color stain	Appearance of the first stabilizing tank	Yellow stain density	Remarks
5-1	-	-	0.18	C	0.08	Comparative
5-2	F-12-3 (2 g/l)	-	0.16	C	0.04	Comparative
5-3	-	1-32 (0.2 g/l)	0.04	A	0.06	Inventive
5-4	F-11-1 (2 g/l)	1-32 (0.2 g/l)	0.03	A	0.03	Inventive
5-5	F-12-3 (2 g/l)	1-32 (0.2 g/l)	0.02	A	0.02	Inventive
5-6	F-14-18 (2 g/l)	1-32 (0.2 g/l)	0.03	A	0.03	Inventive

It is understood according to the results that the formation of the yellow stain can be improved by the addition of the compound represented by Formula F-11, F-12 or F-14 to the stabilizing solution.

Example 6

Examples were carried out in the same manner as in Experiment No. 1-1 in Example 1 except that the replenishing amount for the stabilizing solution was changed. The stabilizing solution and the replenishing solution therefor used in the experiments contain no compound represented by Formula 1. Results are shown in Table 6.

Experiment No.	Replenishing amount (ml/m²)	Degree of remained-color stain	Appearance in the first stabilizing tank
6-1-1	1,500	0.02	A
6-1-2	1,200	0.04	B
6-1-3	1,000	0.10	C
6-1-4	900	0.16	C
6-1-5	800	0.20	C
6-1-6	650	0.24	C
6-1-7	400	0.26	C
6-1-8	200	0.28	C
6-1-9	100	0.30	C

Besides, examples were carried out in the same manner as in Experiment No. 1-6 in Example 1 except that the replenishing amount for the stabilizing solution was changed. The stabilizing solution and the replenishing solution therefor contains 02 g/l of compound 1-32 represented by Formula 1 of the invention. Results are shown in Table 7.

Experiment No.	Replenishing amount (ml/m²)	Degree of remained-color stain	Appearance in the first stabilizing tank
6-2-1	1,500	0.01	A
6-2-2	1,200	0.01	A
6-2-3	1,000	0.02	A
6-2-4	900	0.02	A
6-2-5	800	0.02	A
6-2-6	650	0.03	A
6-2-7	400	0.04	A
6-2-8	200	0.04	A
6-2-9	100	0.05	B

It is understood from comparing of the results in Table 6 and Table 7 that the effect of the invention is enhanced when the replenishing amount for the stabilizing solution is 1,000 ml/l or less.

Example 7

Color negative film processor CL-KP-50QA, manufactured by Konica Corporation) was used, the replenishing device of which was modified as shown in Fig. 1. The replenishment was carried out by the use of a solid processing composition supplying device shown in Fig. 2. A pillar-shaped container including tablets was set on the solid processing composition supplying device, and imagewise exposed Konica Color LV400 Film, manufactured by Konica Corporation, was processed in a rate of 60 rolls per day. The processing was run for 8 weeks.

Fig. 1 shows the constitution of KP-50QA (hereinafter referred to automatic processor), in which 1A is a developing tank and 1B is a bleaching tank, 1C₁ to 1C₂ were each a first and second fixing tank, and 1D₁ to 1D₃ are each first, second and third stabilizing tank, respectively, and F is a drying zone. Solid processing

composition supplying devices

2A, 2B, 2C and 2D, each shown by hatching, were each attached the upper portion of color developing tank 1A, bleaching tank 1B, second fixing tank 1C₂ and third stabilizing tank 1D₃, respectively. The fixing process-1 and -2 were carried out in the fixing tanks C₁ and C₂, and the stabilizing process-1, -2 and -3 were carried out in the stabilizing

tanks

1D₁, 1D₂, and 1D₃, respectively.

Fig. 2 shows the constitution of the solid processing composition supplying device. A dissolving chamber 106, in which a solid processing composition 111 is supplied, is provided at a side of each of the processing tanks. The solid processing composition (a tablet in the drawing) 111 is packed in a container (cartridge) 101 and sealed by a slidable cap 102. When the cartridge is set on a cartridge holder 103 of the solid processing composition supplying device attached at the upper portion of each the processing tank, the slidable cap 102 is open and the tablet is rolled down into a pocket 105 of the rotating cylinder 104. A plurarity of pocket 105 was made on the rotating cylinder 104 at staggered positions so that two or more tablets contained in the container was hardly rolled down in the same time.

The processing procedure is shown below.

Process	Time	Temperature	Replenished water amount
Color developing	3 min. 15 sec.	38° C	450 ml/m²
Bleaching	45 sec.	38 C	100 ml/m²
Fixing-1	45 sec.	38° C
Fixing-2	45 sec.	38° C	400 ml/m²
Stabilizing-1	20 sec.	38° C
Stabilizing-2	20 sec.	38° C
Stabilizing-3	20 sec.	38° C	750 ml/m²
Drying	80 sec.	50 - 70° C

The fixing process and the stabilizing process were each carried out by counter flow systems in the order of fixing-2 → fixing-1 and stabilizing-3 → stabilizing 2 → stabilizing-1, respectively. For compensating the evaporation, 10 ml, 6.5 ml, 7 ml, 7 ml, 8.6 ml, 8.6 ml and 9.3 ml per hour of water was replenished to each the tank of color developing, bleaching, fixing-1, fixing-2, stabilizing-1, stabilizing-2 and stabilizng-3, respectively, while the temperature was controlled. For compensating the evaporation between the rest of the processor, 7.5 ml, 5 ml, 6 ml, 6 ml, 5 ml, 5 ml and 5 ml per hour of water was replenished to each the tank of color developing, bleaching, fixing-1, fixing-2, stabilizing-1, stabilizing-2 and stabilizng-3 at the time of restart the processing based on the integration of the rest time. The tank solutions at the start of running of the processing were prepared by using the starter and the replenisher of Processing composition CNK-4-52 for Konica Color Negative Film, manufactured by Konica Corporation.

1) Color developer substituents tablet for color negative film Procedure 1

In a hammer mill available on the market, 60 g of a color developing agent CD-4, 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate, was powdered so that the average particle size was become 10 µm. The fine powder was granuled together with 10 ml of water in a granulating machine available on the market for 7 minutes at a room temperature. the granules were dried for 2 hours at 40° C by a fluid bed drying machine to almost completely remove moisture. Thus color developer replenisher granule 1 for color negative film was prepared.

Procedure 2

In a manner similar to procedure 1, 69.4 g of hydroxylamine and 4 g of Painflow, manufactured by Matsutani Kagaku Co., Ltd., were powdered, mixed and granuled. Adding amount of water was 3.5 ml. After granulation, granules were dried for 30 minutes at 60° C to almost completely remove moisture. Thus color developer replenisher granule 2 for color negative film was prepared.

Procedure 3

In a manner similar to procedure 1, 15 g of sodium 1-hydroxyethane-l,l-disulfonate, 72.8 g of potassium sulfite, 350 g of potassium carbonate, 3 g of sodium hydrogen carbonate, 3.7 g of sodium bromide, 22 g of mannitol and 5.0 g of polyethylene glycol #6000 were powdered, mixed and granuled together with 40 ml of water. After granulation, granules were dried for 60 minutes at 70° C to almost completely remove moisture. Thus color developer replenisher granule 3 for color negative film was prepared.

The above-mentioned granules 1 to 3 were mixed, and 2 g of sodium N-myristoylalanine was added to the mixture. The mixture was uniformly mixed by a mixer installed in a room conditioned at a temperature of 25° C and a relative humidity of not more than 40%. The mixture was tableted by a tableting machine, modified Tough Press Collect 1527HU, manufactured by Kikusui Seisakusho Co., Ltd., in a rate of 10 g per tablet to prepare a color developer replenisher tablet for color negative film having a diameter of 30 mm and a thickness of 10 mm.

2) Preparation of bleaching solution replenisher tablet for color negative film Procedure 4

In a manner similar to procedure 1, 175 g of ferric ammonium 1,3-propanediaminetetraacetate monohydrate, 2 g of 1,3-propanediaminetetraacetic acid and 17 g of Painflow, manufactured by Matsutani Kagaku Co., Lid., were powdered, mixed and granuled. The amount of water was 8 ml. After granulation, granules were dried for 30 minutes at 60° C to almost completely remove moisture.

Procedure 5

In a manner similar to procedure 1, 133 g succinic acid, 200 g of ammonium bromide and 10.2 g of Painflow were powdered, mixed and granuled. The amount of water was 17 ml. After granulation, granules were dried for 60 minutes at 60° C to almost completely remove moisture.

Procedure 6

In a manner similar to procedure 1, 66.7 g of potassium sulfate, 60 g of potassium hydrogen carbonate and 8 g of mannitol were powdered, mixed and granuled. The amount of water was 13 ml. After granulation, granules were dried for 60 minutes at 60° C to almost completely remove moisture.

The granules prepared by procedures 4 to 6 were uniformly mixed for 10 minutes by a mixer installed in a room conditioned at a temperature of 25° C and a relative humidity of not more than 40%. The mixture was tableted by a tableting machine, modified Tough Press Collect 1527HU in a rate of 10 g per tablet to prepare a bleaching solution replenisher tablet for color negative film having a diameter of 30 mm and a thickness of 10 mm.

3) Preparation of fixing solution replenisher tablet for color negative film Procedure 7

In a vandal mill available on the market, a mixture of 1,700 g of sodium thiosulfate and 80 g of ammonium thiosulfate, 180 g of sodium sulfite, 20 g of potassium carbonate, 20 g of disodium ethylenediaminetetraacetate and 70 g of Painflow were powdered so that the average diameter of the particles was become 30 µm. The powder was granuled together with 50 ml of water by a stirring granulation machine for 10 minutes. The granules thus granuled were dried by a fluid bed drying machine for 120 minutes at 60° C to almost completely remove moisture.

Procedure 8

To the granules obtained by Procedure 7, 30 g of sodium salt of lauroylsarcosine was added, and the mixture was mixed for 5 minutes by a mixer installed in a room conditioned at a temperature of 25° C and a relative humidity of not more than 40%. The mixture was tableted by a tableting machine, modified Tough Press Collect 1527HU in a rate of 10 g per tablet to prepare a fixing solution replenisher tablet for color negative film having a diameter of 30 mm and a thickness of 10 mm.

4) Preparation of stabilizing solution replenisher tablet for color negative film Procedure 9

In a manner similar to procedure 1, 150 g of m-hydroxybenzaldehyde, 20 g of sodium laurylsulfonate, 60 g of disodium ethylenediaminetetraacetate, 65 g of lithium hydroxide monohydrate, 20 g of Compound 1-32 and 10 g of Painflow were powdered, mixed and granuled. The amount of water was 10 ml. After granulation, granules were dried for 2 hours at 50° C to almost completely remove moisture.

The granules prepared by the above-mentioned procedure were tableted by a tableting machine, modified Tough Press Collect 1527HU in a rate of 10 g per tablet to prepare a stabilizing solution replenisher tablet for color negative film having a diameter of 30 mm and a thickness of 10 mm.

These replenisher tables are supplied to the processing tanks at the following intervals.

Color developer replenishing tablet: one tablet pre 8.3 rolls of the color negative film (24EX)

Bleaching solution replenishing tablet: one tablet per 5.2 rolls of the color negative film (24EX)

Fixing solution replenishing tablet: one tablet per 2.4 rolls of the color negative film (24EX)

Stabilizing solution replenishing tablet: one tablet per 131 rolls of the color negative film (24EX)

The above-mentioned replenishing method using the tablets was referred to embodiment 2, and the replenishing method using replenishing solutions was referred to embodiment 1. Evaluation was carried out in the same manner as in Example 1 except that the composition of the stabilizing solution was changed as shown in Table 8.

Experiment No.	Additive	Replenishing embodiment	Degree of remained color stein	Appearance of the first stabilizing tank	Remarks
7-1-1	1-32 (0 g/l)	1	0.16	C	Comparative
7-1-2	1-32 (0.2 g/l)	1	0.02	A	Inventive
7-1-3	1-32 (0 g/l)	2	0.15	C	Comparative
7-1-4	1-32 (0.2 g/l)	2	0.01	A	Inventive

Furthermore, experiments were carried out in the same manner as in the above-mentioned except that the replenishing solution for the stabilizing solution and the replenishing tablet for stabilizing solution were used after storage for 6 weeks at 55° C. Results of the evaluation are shown in Table 9.

Experiment No.	Additive	Replenishing embodiment	Degree of remained color stein	Appearance of the first stabilizing tank	Remarks
7-2-1	1-32 (0 g/l)	1	0.20	C	Comparative
7-2-2	1-32 (0.2 g/l)	1	0.04	B	Inventive
7-2-3	1-32 (0 g/l)	2	0.16	C	Comparative
7-2-4	1-32 (0.2 g/l)	2	0.01	A	Inventive

It is understood by the foregoing experiments that the color remaining is improved and the sufficient processing properties can be maintained when the processing composition was used after storage by the use of the replenishing embodiment using the tablet in the presence of the compound of the invention.

Example 8

A processing was run in the same manner as in Example 1 except that 255 ml/m² of the light-sensitive material of the stabilizing solution was introduced to the fixing tank from the stabilizing tank nearest the fixing tank among the tree stabilizing tanks and a stabilizing solution having a concentration 2 times of that of the replenishing solution used in Example 1 is replenished to the second stabilizing tank in a rate of 255 ml/m² of the light-sensitive material. As a result, the degree of the remained-color stain at the finish of the running of processing was become 0 and the improvement effect on the color remaining was enhanced. The total amount of the exhausted waste liquid was reduced by about 21%.

Besides, after running, the fixing solution in the second fixing tank was stored for 1 week at 50° C in a container having a ratio of area opened to air to volume of the solution of 10 cm²/l, and the storage stability of the stabilizing solution was evaluated according to the following norm.

A: Precipitation or turbid was not observed in the solution.

B: The solution was turbid and some floating matters were observed on the surface of the solution.

C: Precipitation was formed and fixed on the wall of the container.

Results are shown in Table 10.

Embodiment of replenishing	Appearance of fixing solution
Stabilizing solution is not introduced to fixing solution	B
Stabilizing solution is introduced to fixing solution	A

It is understood from the above-mentioned results that the storage stability of the fixing solution is raised and the amount of the exhausted waste liquid can be reduced as well as the effect of the invention is enhanced by supplying all or a part of the stabilizing solution to the fixing tank.

Example 9 Preparation of magnetic recording medium <Preparation of support>

To a mixture of 100 parts by weight of dimetyl 2,6-naphthalenedicarboxylate and 60 parts by weight of ethylene glycol, 0.1 parts by weight of hydrated calcium acetate as an ester exchange catalyst, and an ester exchanging reaction was performed according to an ordinary method. To the product thus obtained, 0.05 parts by weight of antimony trioxide and 0.03 parts by weight of trimethyl phosphate were added. Then the mixture was gradually heated under a reduced pressure, and polymerized at a temperature of 290° C and a pressure of 0.05 mmHg. Thus a polyethylene-2,6-naphthalate was obtained which had an intrinsic viscosity of 0.60.

The polymer was dried in a vacuum for 8 hours at 150° C, and molten and extruded from a T-die in a form of layer. The extruded layer of the polymer was contacted on a cooling drum of 50° C while applying a electrostatic field to solidify to obtain a non-expanded sheet. The non-expanded sheet was longitudinally expanded 3.3 times at 135° C by a roller type expanding machine.

Thus obtained uniaxis-expanded film was laterally expanded by a tenter type lateral expanding machine by 50% of the total lateral expanding ratio at 45 ° C in the first expanding zone, and further expanded in the second expanding zone so that the total expanding ration was 3.3 times. The sheet was heated for 2 seconds at 100° C, and thermally fixed at 200° C for 5 seconds in the first thermal fixing zone and at 240° C for 15 seconds in the second thermal fixing zone. Then the sheets was gradually cooled to a room temperature spending 30 seconds while slacking laterally by 5 % to obtain a polyethylene naphthalate film having a thickness of 85 µm.

The film was wound on a core made by stainless steel and annealed at 110° C for 48 hours. Thus a support was prepared.

A corona discharge treatment of 12W/m²/min. was applied on the both sided of the support. On one of the surface of the support the following subbing liquid B-1 was coated so that the dried layer thickness of it was 0.2 µm, and a corona discharge treatment of 12W/m²/min. was applied on it. Then the following subbing liquid B-2 was coated on this surface so that the dried layer thickness was 0.2 µm.

On the other surface of the support, which had been treated by corona discharge of 12W/m²/min., the following subbing liquid B-3 was coated and corona discharge of 12W/m²/min. was further applied. Then the following subbing liquid B-4 was coated on this surface.

Each of the layers was dried after coating at 90° C for 10 seconds. The support was treated at 110° C for 2 minutes just after coating of the four layers and cooling at 50° C for 30 seconds.

Subbing liquid B-1
Latex of copolymer of 30 weight-% of t-butyl acrylate, 20 weight-% of t-butyl acrylate, 25 weight-% of styrene and 25 weight-% of 1-hydroxyethyl acrylate (solid content of 30%)	125 g
Compound (UL-1)	0.4 g
Hexamethylene-1,6-bis (ethylenurea)	0.05 g
Water to make	1,000 ml

Subbing liquid B-2
Styrene-maleic anhydride dissolved in a sodium hydroxide aqueous solution (solid content of 6%)	50 g
Compound (UL-1)	0.6 g
Compound (UL-2)	0.09 g
Silica particles (average diameter: 3 µm)	0.2 g
Water to make	1,000 ml

Subbing liquid B-3
Latex of a copolymer of 30 weight-% of butyl acrylate, 20 weight-% of t-butyl acrylate, 25 weight-% 0f styrene and 25 weight-% 0f 2-hydroxy acrylate (solid content: 30%)	50 g
Compound (UL-1)	0.3 g
Hexamethylene-1,6-bis(ethyleneurea)	1.1 g
Water to make	1,000 ml

Subbing liquid B-4

Sixty mole-% of dimethyl terephthalate, 30 mole-% dimethyl iso-phthalate and 10 mole-% of sodium salt of dimethyl 5-sulfophthalate as carboxylic acid components, and 50 mole-% of ethylene glycol and 50 mole-% of diethylene glycol as glycol components, were copolymerized by an ordinary method. The polymer was stirred in hot water of 95° C for 3 hours to obtain 15 weight-% of an aqueous dispersion A.

Aqueous dispersion of combined particles of tin oxide and antimony oxide (average diameter: 0.2 µm, solid content: 40% by weight)	109 g
Aqueous dispersion A	67 g
Water to make	1,000 ml

On the surface of the support, on which subbing liquid U-4 had been provided, a magnetic recording layer having the following composition was coated by a precision µm, and the magnetic particles in the coated layer were oriented along the coating direction in an orientation magnetic field before drying the coated layer for raising the output level of playback signal of the magnetic record.

Composition and preparation of coating liquid of magnetic recording layer M-1
Cobalt-containing γ-iron oxide (average major axis length: 0.12 µm, average minor axis length: 0.015 µm, Fe²⁺/Fe³⁺ = 0.2, specific surface area 40 m²/g, Hc = 750 Oe)	10 parts by weight
Alumina (α-Al₂O₃, average diameter: 0.2 µm)	3 parts by weight
Diacetyl cellulose (Teijin Co., Lid.)	150 parts by weight
Polyurethane (N3132, Nihon Polyurethane Co., Ltd.)	15 parts by weight
Stearic acid	2 parts by weight
Cyclohexanone	920 parts by weight
Acetone	920 parts by weight

The above-mentioned components were sufficiently mixed and dispersed. Fifty parts by weight of polyisocyanate, Colonate-3041, manufactured by Nihon Urethane Co., Ltd., solid content: 50%, was added to the above-mentioned materials after sufficiently mixed and dispersed by a sand mill. Thus magnetic layer coating liquid M-1 was prepared.

Coating of lubricating layer

A lubricant coating liquid or the later-mentioned wax liquid was prepared by dispersing carnauba wax in a water/methanol mixture solvent so that the solution contained 0.15 of carnauba wax. The lubricant liquid was coated on the above-mentioned magnetic recording layer so that the coated amount of the wax was 15 mg/m². The bulk support coated with the wax was dried for 5 minutes at 100° C by passing through a thermal treatment zone, and stored in an oven for 5 days at 40° C so that the cross-linking reaction of isocyanate was sufficiently progressed.

Preparation of wax liquid

With 100 parts by weight of water heated at 90° C, 4 parts by weight of polyoxyethylene lauryl ether was mixed. Then 40 parts by weight of carnauba wax molten at 90° C was added to the mixture and sufficiently stirred by a high-speed homogenizer to prepare a dispersion of carnauba wax.

To a mixture of 995 parts by weight of water and 900 parts by weight of methanol, 5 parts by weight of the above-mentioned carnuba wax dispersion was added and stirred to prepare a wax liquid.

On the side of the above-mentioned magnetic recording medium opposite to the magnetic recording layer coated side, a subbing layer was provided by coating the following subbing liquids B-1 and B-2 under the same condition. Photographic constituting layers having the following compositions were provided to prepare Sample 101. The adding amounts are described in grams per square meter, provided that the amounts of silver halide emulsion and that of colloidal silver are described in terms of silver and the amount of sensitizing dye, referred to SD, is described in terms of moles per mole of silver.

1st layer: Anti-halation layer
Black colloidal silver	0.16
UV-1	0.3
CM-1	0.044
OIL-1	0.044
Gelatin	1.33

2nd layer: Interlayer
AS-1	0.16
OIL-1	0.20
Gelatin	1.40

3rd layer: Low speed red-sensitive layer
Silver iodobromide a	0.12
Silver iodobromide b	0.50
SD-1	3.0 x 10^-5
SD-4	1.5 x 10^-4
SD-3	3.0 x 10^-4
SD-6	3.0 x 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 x 10^-5
SD-2	1.5 x 10^-4
SD-3	3.0 x 10^-4
C-2	0.22
CC-1	0.028
DI-1	0.002
OIL-2	0.21
AS-3	0.006
Gelatin	0.87

5th layer: High speed red-sensitive layer
Silver iodobromide c	0.13
Silver iodobromide d	1.14
SD-1	3.0 x 10^-5
SD-2	1.5 x 10^-4
SD-3	3.0 x 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: Interlayer
OIL-1	0.29
AS-1	0.23
Gelatin	1.00

7th layer: Low speed green-sensitive layer
Silver iodobromide a	0.245
Silver iodobromide b	0.105
SD-6	5.0 x 10^-4
SD-5	5.0 x 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: Interlayer
M-1	0.03
CM-2	0.005
OIL-1	0.16
AS-1	0.11
Gelatin	0.80

9th layer: Medium speed green-sensitive layer
Silver iodobromide e	0.87
SD-7	3.0 x 10^-4
SD-8	6.0 x 10^-5
SD-9	4.0 x 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

10th layer: High speed green-sensitive layer
Silver iodobromide f	1.19
SD-7	4.0 x 10^-4
SD-8	8.0 x 10^-5
SD-9	5.0 x 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
SD-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 speed blue-sensitive layer
Silver iodobromide g	0.29
Silver iodobromide h	0.19
SD-10	8.0 x 10^-4
SD-11	3.1 x 10^-4
Y-1	0.91
DI-4	0.022
OIL-1	0.37
AS-2	0.002
Gelatin	1.29

13th layer: High speed green-sensitive layer
Silver iodobromide h	0.13
Silver iodobromide i	1.00
SD-10	4.4 x 10^-4
SD-ll	1.5 x 10^-4
Y-1	0.48
DI-4	0.019
OIL-1	0.21
AS-2	0.004
Gelatin	1.55

14th layer: First protective 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

Moreover, coating aids SU-1, SU-2 and SU-3, a dispersion aid SU-4, a viscosity controlling agent V-1, stabilizing agents ST-1 and ST-2, an anti-foggant AF-1, two kinds of polyvinylpyrrolidone AF-2 each having weight average molecular weights of 1,100,000 and 10,000, stabilizing agents AF-3, AF-4 and AF-5, Gardeners H-1 and H-2 and an antiseptic agent Ase-1 were added other than the above-mentioned components.

The chemical structures of the compounds used in the foregoing sample are shown below, and the kinds of silver iodobromide are listed in Table 11.

Emulsion No.	Average diameter (µm)	Average AgI content (mole-%)	Diameter/ thickness
Silver iodobromide a	0.30	2.0	1.0
Silver iodobromide b	0.40	8.0	1.4
Silver iodobromide c	0.60	7.0	3.1
Silver iodobromide d	0.75	7.0	5.0
Silver iodobromide e	0.60	7.0	4.1
Silver iodobromide f	0.65	9.0	6.5
Silver iodobromide g	0.40	2.0	4.0
Silver iodobromide h	0.65	8.0	1.4
Silver iodobromide i	1.00	8.0	2.0
Silver iodobromide j	0.05	2.0	1.0

Ase-1 (mixture of the following three components)

Thus prepared sample was slit in a size of a width of 35 mm and a length of 100 m, and a 6 kHz square wave signal was recorded on the sample at a speed of 100 m/s by a recording magnetic head. The samples was wound on a reel.

The light-sensitive material prepared as above was processed by using the stabilizing solution and the replenishing solution for stabilizing solution the same as in Example 5. The processing was run in the same manner as in Experiment No. 1-1 or 1-6. The remained-color stain was evaluated in the same manner as in Example 1 and the magnetic record of the magnetic recording layer of the processed light-sensitive material was evaluated according to the following norms.

Evaluation of the clogging of the magnetic head

The square wave signal recorded on the processed light-sensitive material was read by a reading head at an uniform conveying speed and a point at which the output was lowered by 3 dB was defined as the head clogging point. The level of head clog was evaluated according to the length in meter of the light-sensitive material for the starting point to the head cloggin point. A lower value, namely the head was clogged after passing a shorter length, means an undesirable property.

Evaluation of magnetic property

The test was carried out in the same manner as in the evaluation of the clogging of the magnetic head, and the samples by each of which the lowering of the playback signal level from the initial level was less than 0.5 dB, not less than 0.5 dB and less than 1 dB, and 1 dB or more were classified as A, B and C, respectively.

Results are shown in Table 12.

	Additive in stabilizing solution
Experiment No.	Compound of Formula 1	Compound of F-11, F-12 or F-14	Degree of remained color	Head clogging	Magnetic property	Remarks
9-1	-	-	0.16	430	C	Comparative
9-2	1-32 (0.2 g/l)	-	0.03	512	B	Inventive
9-3	1-32 (0.2 g/l)	F-12-3 (2 g/l)	0.02	553	A	Inventive

Example 10

Samples of light-sensitive material were prepared in the same manner in Example 9 except that the coating amount of silver of 6.85 g/m² was changed as to be the amount shown in Table 13 by changing the amount of silver halide in each of the emulsion layers in the same proportion. The amount of each of the sensitizing dyes was also changed in proportion of the amount of silver. The samples were each subjected to experiment the same as in example 9 for evaluating the remained-color stain in the samples. Results are shown in table 13.

Experiment No.	Coating amount of silver (g/m²)	Additive in stabilizing solution	Degree of color remaining	Remarks
10-1	3.00	None	0.01	Comparative
10-2	3.00	1-32 (0.2 g/l)	0	Inventive
10-3	4.00	None	0.01	Comparative
10-4	4.00	1-32 (0.2 g/l)	0	Inventive
10-5	5.00	None	0.03	Comparative
10-6	5.00	1-32 (0.2 g/l)	0.01	Inventive
10-7	5.50	None	0.05	Comparative
10-8	5.50	1-32 (0.2 g/l)	0.01	Inventive
10-9	6.00	None	0.10	Comparative
10-10	6.00	1-32 (0.2 g/l)	0.02	Inventive
10-11	6.50	None	0.16	Comparative
10-12	6.50	1-32 (0.2 g/l)	0.02	Inventive
10-13	7.50	None	0.20	Comparative
10-14	7.50	1-32 (0.2 g/l)	0.02	Inventive

It is understood from the above-mentioned results that the effect of the invention is enhanced when the light-sensitive material having a silver coating amount of not less than 3 g/l, particularly not less than 6 g/l, is processed.

The N-containing heterocyclic ring completed by Q₁ (or by Q') may be a 5- to 10- membered, preferably 5- or 6-membered, heterocyclic ring optionally containing one or more further heteroatoms chosen from e.g. O, N or S. The heterocyclic ring may be optionally substituted.

The alkali metal atom represented by R₁ may be a sodium, potassium or caesium atom. The alkyl group represented by R₁ may be substituted and is preferably C_1-6, more preferably C_1-4.

The alkyl or alkenyl groups represented by A₁ to A₄ may be optionally substituted, and are preferably C_1-6, more preferably C_1-4.

The substituents R_60-64 are preferably those which may be included on ring Z₄.

Claims

A stabilizing solution for processing a silver halide color photographic light-sensitive material, which contains a compound represented by the following Formula 1;
wherein Q₁ is a group of atoms necessary to form a nitrogen-containing heterocyclic ring, R₁ is a hydrogen atom, an alkali metal atom, a
or an alkyl group, Q' is a synonym with Q₁.
The stabilizing solution of claim 1, wherein said stabilizing solution contains substantially no formaldehyde.
The stabilizing solution of claim 1, wherein said stabilizing solution contains a compound represented by Formula F-11, F-12 or F-14;
wherein A₁ to A₄ are each a hydrogen atom, an alkyl group, an alkenyl group or a pyridyl group, and ℓ is 0 or 1,
wherein Z₄ is a group of atoms necessary for forming a hydrocarbon ring or a heterocyclic ring, X is an aldehyde group, a
group or a
group, in which R₄₁ and R₄₂ each represents an alkyl group having 1 to 9 carbon atoms, and n is an integer of 1 to 4,
wherein X₂, X₃, X₄ and X₅ each represents -NR₆₀, =N-, -O-, - S-, -CR₆₁R₆₂-, =CR₆₃-, -CO- or -C(=NR₆₄)-, in which R₆₀, R₆₁, R₆₂, R₆₃ and R₆₄ are each a hydrogen atom or a substituent, and Z₅ and z₆ are each a group of atoms necessary to form a 4- to 8-member ring.
The stabilizing solution of claim 1, wherein said stabilizing solution has a surface tension of 15 to 60 dyne/cm at 20° C.
A method for processing a silver halide color photographic light-sensitive material comprising the steps of

developing the light-sensitive material with a color developing solution,

Fixing the light-sensitive material with a fixing solution, and

stabilizing the light-sensitive material with a stabilizing solution containing a compound represented by Formula 1;
wherein Q₁ is a group of atoms necessary to form a nitrogen-containing heterocyclic ring, R₁ is a hydrogen atom, an alkali metal atom, a
group or an alkyl group, Q' is a synonym with Q₁.
The method of claim 5, wherein said stabilizing solution is introduced to a tank of processing just before the stabilizing process.
The method of claim 5, wherein the light-sensitive material to be processed by said stabilizing solution has a coating amount of silver of not less than 3 g per square meter.
The method of claim 5, wherein the light-sensitive material to be processed by said stabilizing solution has a layer containing ferromagnetic particles.