JPH08227129A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To improve the change in cyanide concn. and output of magnetic information before and after a silver halide color photographic sensitive material having a magnetic recording layer is run. CONSTITUTION: A silver halide photographic sensitive material having at least one red-sensitive layer, green-sensitive layer and blue-sensitive layer and further a magnetic layer on one side of a transparent substrate is color-developed, then desilvered, washed with water and/or stabilized. In this case, the color developer contains a compd. shown by HO-N(R)-L-A, the amt. of the color developer to be replenished is controlled to 130-520ml per m<2> of the sensitive material, and the opening ratio for liq. of the developer tank of an automatic developing device is controlled to 0.001-0.015cm<-1> . In the formula, L is an alkylene group capable of being substituted, A is carboxyl, sulfo group, phosphono group, hydroxyl or amino group capable of being substituted by alkyl, and R is hydrogen atom or alkyl capable of being substituted.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of processing a silver halide color photographic light-sensitive material (hereinafter abbreviated as a light-sensitive material) having a magnetic layer, and particularly to a method of processing excellent in magnetic information reading performance. It is in.

[0002]

2. Description of the Related Art Conventionally, in a silver halide photographic light-sensitive material (hereinafter abbreviated as a light-sensitive material), it is almost impossible to input or output various kinds of information at the time of photographing or printing, and it is slightly optical. It was only possible to input / output the shooting date and time. By the way, JP-A-4-68336 and JP-A-4-68336.
No. 73737, or as disclosed in Japanese Patent Laid-Open No. 5-88283, by providing a transparent magnetic recording layer on the entire surface of a light-sensitive material, shooting conditions such as date and time of shooting, weather, reduction / enlargement ratio, Number of reprints, areas you want to zoom,
It is possible to input the message, development, print conditions, etc. to the sensitive material. Also, various information can be provided even when inputting to video equipment such as TV / video.
This is a promising method for the future.

On the other hand, in such a method for processing a light-sensitive material, color development, desilvering, washing with water and stabilizing treatment are generally carried out. By the way, with the recent widespread use of in-store processing such as in a minilab, there is an increasing demand for a shorter delivery time and a smaller amount of waste liquid. Therefore, various studies have been made to shorten the processing steps and reduce replenishment. In particular, in order to shorten the color development time, high concentration of the main agent and increase in processing temperature do not impair photographic characteristics,
This is one of the most desirable methods because it can shorten the processing time. By the way, when the silver halide color photographic light-sensitive material having the magnetic layer according to the present invention is subjected to a running process under the condition that the replenishment amount to the developing solution is small, the magnetic recording performance is deteriorated (S / It became clear that satisfactory information cannot be provided and that the cyan density change before and after running is particularly remarkable in terms of the influence on photographic properties. When a conventionally known hydroxylamine is used as a preservative for a color developing solution, when the replenishment amount is small, such as 130 to 520 ml per 1 m ^{2 of the} light-sensitive material, the influence on the photographic property is particularly affected before and after running. It was found that there were problems in cyan density change and magnetic information output. On the other hand, even when the processing method using a specific hydroxylamine as described in JP-A-6-95316 is adopted, the replenishing amount of the color developing solution is 130 to 1 m ^{2 of the} light-sensitive material.
In the case of 520 ml, improvement of the output of magnetic information turned out to be urgent.

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to process a light-sensitive material having a magnetic recording layer into a silver halide color photographic light-sensitive material without deteriorating the S / N ratio of magnetically recorded information. The present invention is to provide a processing method, and further to provide a processing method having excellent image storage performance and photographic performance.

[0005]

It has been found that the above problems can be solved by carrying out the following processing method. (1) A silver halide color photograph having at least one red-sensitive layer, green-sensitive layer and blue-sensitive layer on one side of a transparent support, and a magnetic recording layer containing magnetic particles on the other side. In a processing step of desilvering a light-sensitive material after processing with a color developing solution, washing with water and / or stabilizing processing, the color developing solution contains a compound of the following general formula (I), and the color developing solution is replenished The amount is 130 to ⁵ per 1 m ^{2 of} light-sensitive material
A method for processing a silver halide color photographic light-sensitive material, which is 20 ml and has a liquid opening ratio of 0.001 to 0.015 cm ^-1 in a developer tank of an automatic developing device.

[0006]

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(In the formula, L represents an optionally substituted alkylene group, A represents a carboxy group, a sulfo group, a phosphono group,
A hydroxy group and an amino group which may be substituted with alkyl are represented, and R is a hydrogen atom and an alkyl group which may be substituted. (2) In the above color developer, bromide ion is less than 0.
014 mol / l to 0.084 mol / l and iodide ion is 0.01 mmol / l to 0.10.
The method for processing a silver halide color photographic light-sensitive material as described in the above item (1), characterized in that the silver halide color photographic light-sensitive material is contained. (3) The temperature of the treatment using the color developer is 40 ° C.
-60 ° C, The method for processing a silver halide color photographic light-sensitive material according to the above item (1) or (2).

In the processing method using a specific hydroxylamine as described in JP-A-6-95316, the output of magnetic information when the replenishment amount is as small as 130 to 520 ml per 1 m ^{2 of the} light-sensitive material. As a result of diligent examination, it was found that the liquid opening ratio in a limited range is extremely important. Further, it has been found that even better magnetic recording performance and photographic performance can be realized by adopting the bromide ion concentration and iodide ion concentration in a limited range.

The details of the present invention will be described below. First, the liquid opening ratio of the developer tank will be described. For the color developer and color replenisher, in the processing tank and the replenisher tank, the value obtained by dividing the opening area (cm ² ) of the area where the solution comes into contact with air by the liquid tank (cm ³ ) in the tank is defined as the opening ratio. To do. In the present invention,
The aperture ratio is preferably 0.001 to 0.015 cm ^-1 ,
0.001 to 0.010 cm ^-1 is more preferable. The general formula (I) will be described in more detail.

[0010]

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In the formula, L represents a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted, and preferably 1 to 5 carbon atoms. Specifically, methylene, ethylene,
Trimethylene and propylene are preferred examples. The substituent represents a carboxy group, a sulfo group, a phosphono group, a hydroxy group, or an amino group which may be alkyl-substituted, and a carboxy group, a sulfo group, and a hydroxy group are preferred examples. A represents a carboxy group, a sulfo group, a phosphono group, a hydroxy group, or an amino group which may be alkyl-substituted, and a carboxy group, a sulfo group, and a hydroxy group are preferred examples. Preferred examples of -LA include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, and a hydroxyethyl group. R represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, and has 1 carbon atom.
-5 are preferable. Examples of the substituent include a carboxy group, a sulfo group, a phosphono group, a hydroxy group, and an amino group which may be alkyl-substituted, and a carboxy group, a sulfo group, and a hydroxy group can be mentioned as preferable examples. Next, specific compounds of the present invention will be described, but the invention is not limited thereto.

[0012]

[Chemical 4]

[0013]

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[0014]

[Chemical 6]

[0015]

[Chemical 7]

[0016]

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[0017]

[Chemical 9]

[0018]

[Chemical 10]

As specific compounds, Exemplified compound (2), Exemplified compound (6) and Exemplified compound (16) can be mentioned as preferable examples. The compounds of the above general formula (I) are disclosed in JP-A-3-56456 and JP-A-3-1573.
It can be synthesized by the method described in No. 54 or a method analogous thereto. The addition amount of the compound of the general formula (I) is
Preferably 0.1 g to 50 g per liter of developer,
It is more preferably 0.2 g to 30 g.

Next, the magnetic recording layer used in the present invention will be described.
And explain. The magnetic recording layer used in the present invention is a magnetic recording layer.
Aqueous or organic solvent in which binder particles are dispersed in a binder
A medium-type coating liquid is applied on a support. In the present invention
The magnetic particles used are γFe₂O₃Ferromagnetic oxidation such as
Iron, Co deposition γFe ₂O₃ , Co-deposited magnetite, Co-containing magnet
Gnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetism
Alloys, hexagonal Ba ferrite, Sr ferrite, Pb ferrite
Lights, Ca ferrite, etc. can be used. Co deposition γFe₂O
₃Co-coated ferromagnetic iron oxides such as As for the shape
It may be needle-shaped, rice grain-shaped, spherical, cubic, plate-shaped, etc.
Yes. S in specific surface area_BETAt 20m²/ g or more is preferred, 30m²
/ g or more is particularly preferable. The saturation magnetization (σs) of a ferromagnet is
Preferably 3.0 x 10^Four ~ 3.0 x 10^FiveA / m and especially preferred
4.0 x 10^Four~ 2.5 x 10^FiveA / m. Ferromagnetic particles
With silica and / or alumina or organic materials
Surface treatment may be applied. Further, magnetic particles are disclosed in JP-A-6-
Silane coupling on its surface as described in 161032.
It may be treated with an agent or a titanium coupling agent. Special
Inorganic and organic on the surface described in Kaihei 4-259911 and 5-81652
Magnetic particles coated with a substance can also be used.

Next, the binder used for the magnetic particles is
The thermoplastic resin, thermosetting resin, radiation-curable resin, reactive resin, acid, alkali or biodegradable polymer described in JP-A-4-219569, natural polymer (cellulose derivative,
Sugar derivatives, etc.) and mixtures thereof can be used. The Tg of the above resin is -40 ° C to 300 ° C, and the weight average molecular weight is 20,000 to 1,000,000. For example, vinyl-based copolymer,
Cellulose diacetate, cellulose triacetate,
Examples thereof include cellulose derivatives such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins, polyvinyl acetal resins, and gelatin is also preferable. Cellulose di (tri) acetate is particularly preferable. The binder can be hardened by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of the isocyanate-based cross-linking agent include isocyanates such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate, and reaction products of these isocyanates and polyalcohols (for example, tolylene diisocyanate). 3 mol of isocyanate and 1 m of trimethylolpropane
ol reaction product), and polyisocyanates produced by condensation of these isocyanates,
For example, it is described in JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic material in the binder, a kneader, a pin type mill, an annular type mill or the like is preferable and a combination thereof is also preferable, as in the method described in JP-A-6-35092. The dispersant described in JP-A-5-088283 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm
m, more preferably 0.3 μm to 3 μm. The weight ratio of the magnetic particles and the binder is preferably 0.5: 100 to 60: 100.
And more preferably 1: 100 to 30: 100. The coating amount of magnetic particles is 0.005 to 3 g / m ² , preferably 0.01 to 2
g / m ² , more preferably 0.02 to 0.5 g / m ² . The transmission yellow density of the magnetic recording layer is preferably 0.01 to 0.50,
03 to 0.20 is more preferable, and 0.04 to 0.15 is particularly preferable.
The magnetic recording layer can be provided on the entire back surface of the photographic support by coating or printing, or in the form of a stripe. As a method of applying the magnetic recording layer, an air doctor, a blade, an air knife, a squeeze, an impregnation, a reverse roll,
Transfer roll, gravure, kiss, cast, spray, dip, bar, extrusion and the like can be used, and the coating liquid described in JP-A-5-341436 is preferable.

The magnetic recording layer has improved lubricity, curl adjustment,
It may have functions such as antistatic, anti-adhesion and head polishing, or may be provided with another functional layer to impart these functions, and at least one kind of particles has a Mohs hardness of 5 or more. The above-mentioned non-spherical inorganic particle abrasives are preferable. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide, and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. The surface of these abrasives may be treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and preferably the same binder as that of the magnetic recording layer is used. US Pat. No. 5,336,589, US Pat. No. 5,250,404, US Pat.
5,229,259, 5,215,874 and EP 466,130.

Next, the polyester support used in the present invention will be described. For details, including the light-sensitive material, processing, cartridges and examples described later, open technical report, official technique number 94-6023 (Invention Society; 1994.3). .15.).
The polyester used in the present invention is formed by using a diol and an aromatic dicarboxylic acid as essential components, and the aromatic dicarboxylic acid is 2,6-, 1,5-, 1,4-, and 2,7.
-Naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, diethylene glycol as diol,
Examples include triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol.
Examples of the polymerized polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene 2,6-naphthalate is particularly preferable. Average molecular weight ranges from about 5,000 to
It is 200,000. The polyester of the present invention has a Tg of 50 ° C or higher, preferably 90 ° C or higher.

Next, the polyester support is subjected to a heat treatment at a heat treatment temperature of 40 ° C. or higher and lower than Tg, more preferably Tg−20 ° C. or higher and lower than Tg in order to prevent the curling tendency. The heat treatment may be performed at a constant temperature within this temperature range, or the heat treatment may be performed while cooling. The heat treatment time is 0.1 hour or more and 1500 hours or less, and more preferably 0.5 hour or more and 200 hours or less. The heat treatment of the support may be carried out in the form of a roll or may be carried out while being conveyed in the form of a web.
Irregularity may be imparted to the surface (for example, conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ may be applied) to improve the surface state. Further, it is desirable to devise a technique such as giving a knurl to the end and slightly raising only the end to prevent the cut end of the winding core from being exposed. These heat treatments are after the support film formation, the surface treatment,
It may be carried out at any stage after coating the back layer (antistatic agent, slip agent, etc.) and after coating the undercoat layer. Preferred is after the antistatic agent is applied. An ultraviolet absorber may be kneaded into this polyester. Also, to prevent light piping,
The purpose can be achieved by kneading a commercially available dye or pigment for polyester such as Diaresin manufactured by Mitsubishi Kasei or Kayaset manufactured by Nippon Kayaku.

Next, in the present invention, it is preferable to carry out a surface treatment in order to bond the support and the photosensitive material constituting layer. Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Surface activation treatments such as laser treatment, mixed acid treatment and ozone oxidation treatment can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment and glow treatment are preferable. Next, the undercoating method may be a single layer or two or more layers. As the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid,
Starting with copolymers starting from monomers selected from acrylic acid, itaconic acid, maleic anhydride and the like, polyethyleneimine, epoxy resins, grafted gelatin, nitrocellulose and gelatin are listed. Compounds that swell the support include resorcin and p-chlorophenol. As a gelatin hardening agent for the undercoat layer, chromium salts (chrome alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-) are used.
(Hydroxy-S-triazine, etc.), epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethylmethacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

In the present invention, an antistatic agent is preferred.
Used well. As those antistatic agents,
Polymers containing acid and carboxylate, sulfonate,
Examples include thione polymers and ionic surfactant compounds.
You can The most preferred antistatic agent is Z
nO, TiO₂, SnO₂, Al₂O₃, In₂O₃, SiO₂, MgO, BaO,
MoO₃, V₂O_FiveVolume resistivity of at least one selected from
Is 10 ⁷Ω · cm or less, more preferably 10^FiveΩ · cm or less
Particle size 0.001 to 1.0 μm Crystalline metal oxide
Or a small amount of these complex oxides (Sb, P, B, In, S, Si, C, etc.)
Particles, sol-like metal oxides, or composites of these
Fine particles of oxide. The content in the sensitive material is 5 to
500 mg / m²Is particularly preferable and 10 to 350 mg / m is particularly preferable.²And
It Conductive crystalline oxide or composite oxide thereof and vine
The ratio of the amount of the duster is preferably 1/300 to 100/1, more preferably
It is 1/100 to 100/5.

The sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. The preferred sliding property is a dynamic friction coefficient of 0.
25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball with a diameter of 5 mm is transported at 60 cm / min (25
℃, 60% RH). In this evaluation, even if the photosensitive material surface is replaced as the mating material, the values are almost the same. Examples of slip agents that can be used in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, and esters of higher fatty acids and higher alcohols. Polyorganosiloxanes include polydimethylsiloxane, polydiethylsiloxane, and polydiethylsiloxane. Styrylmethyl siloxane, polymethylphenyl siloxane, etc. can be used. The addition layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane and ester having a long chain alkyl group are preferable.

The photosensitive material of the present invention preferably contains a matting agent. The matting agent may be either on the emulsion side or the back side, but it is particularly preferable to add it to the outermost layer on the emulsion side.
The matting agent may be soluble in the treatment liquid or insoluble in the treatment liquid, and preferably both are used in combination. For example, polymethylmethacrylate, poly (methylmethacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is preferably narrow, and the average particle size is 0.9 to 1.
It is preferable that 90% or more of the total number of particles be contained in one time. It is also preferable to add fine particles of 0.8 μm or less at the same time in order to enhance the matting property. For example, polymethylmethacrylate (0.2 μm), poly (methylmethacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm)), polystyrene Particles (0.25 μm), colloidal silica (0.03 μm)
Is mentioned.

Next, the film cartridge used in the present invention will be described. The main material of the cartridge used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the cartridge of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonions, anions, cations and betaine-based surfactants or polymers can be preferably used. These antistatic patrones are described in JP-A 1-312537 and 1-312538. Particularly, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured by using a plastic in which carbon black, a pigment and the like are kneaded in order to impart a light shielding property. The size of the Patrone can be left at 135 at the moment, or to make the camera smaller,
It is also effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less. The volume of the case of the cartridge is 30 cm ³ or less, preferably 25 cm ³ or less. The weight of the plastic used in the cartridge and cartridge case is preferably 5 to 15 g.

Further, the cartridge used in the present invention may be one that rotates the spool to feed the film. Further, the structure may be such that the leading end of the film is housed in the cartridge body and the leading end of the film is fed to the outside from the port portion of the cartridge by rotating the spool shaft in the feeding direction of the film. These are disclosed in US 4,834,306 and 5,226,613. The photographic film used in the present invention may be a so-called raw film before development, or may be a photographic film subjected to development processing. The raw film and the developed photographic film may be stored in the same new cartridge,
Different patrones may be used.

As the cartridge used in the present invention, US Pat. Nos. 4,848,893 and 5,317,
355, 5,347,334, 5,296,8
Nos. 86 and 6-85128 are preferable. A preferred embodiment as a camera for photographing the light-sensitive material of the present invention will be described. JP-A-6-8886 and 6-9 for simple loading
No. 9908, Japanese Patent Laid-Open No. 6-57398 as automatic winding.
No. 6-101135, No. 6-205690 for taking out during shooting, and No. 5-293138, 5-283 for print aspect ratio selection recording function.
No. 382, JP-A-6-1011 as a double exposure preventing function.
No. 94, Japanese Laid-Open Patent Publication No. 5-15057 as a use status display function.
The seventh aspect is preferred. Lab processing used in the present invention,
Preferred embodiments of the device will be described. Regarding the use of magnetic recording, JP-A-6-95265 and JP-A-4-123054,
US Pat. Nos. 5,034,838 and 5,041,933
No. 5, as a mechanism capable of selecting a print aspect ratio
No. 19364, and Japanese Patent Laid-Open Nos. 2-184835, 4-186335, and 6-
No. 79968, Japanese Patent Laid-Open Nos. 5-11353 and 5-232594 as an index print function, attach,
JP-A-6-148805 as a detach function, JP-A-5-119461 as a splice function, and JP-A-4-346346 and JP-A-4-346346 as a cartridge magazine function.
The embodiment of No. -19439 is preferable.

The photosensitive material used in the present invention may have at least one photosensitive layer provided on a support.
As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. Is. The photosensitive layer is a unit photosensitive layer having a color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material,
In general, the unit photosensitive layers are arranged in order from the support side in the order of red color sensitive layer, green color sensitive layer, and blue color sensitive layer. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor, etc. described later. A plurality of silver halide emulsion layers constituting each unit photosensitive layer is DE 1,121,470 or GB 923,045.
It is preferable to arrange the two layers of the high-sensitivity emulsion layer and the low-sensitivity emulsion layer so that the sensitivities are lowered toward the support as described above. In addition, JP-A-57-112751, 62-
As described in 200350, 62-206541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support, low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / RH It can be installed in the order of. In addition, as described in JP-B-55-34932, the blue-sensitive layer / GH /
It can also be arranged in the order of RH / GL / RL. Also, JP-A-56
-25738 and 62-63936, it is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is a silver halide emulsion layer having a higher sensitivity than the middle layer. An example is an arrangement in which low silver halide emulsion layers are arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of such three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitivity emulsion layer / high-sensitivity layer is separated from the side distant from the support. You may arrange in order of a speed emulsion layer / a low speed emulsion layer. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in the case of four or more layers, the arrangement may be changed as described above. In order to improve color reproducibility, US 4,663,271, US 4,705,744, US 4,707,4
36, JP-A-62-160448 and JP-A-63-89850, a donor layer (CL) having a multi-layer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL and RL is adjacent to the main photosensitive layer. Alternatively, it is preferable to arrange them in close proximity.

The preferred silver halide used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, which contains about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about 0.2 μm or less
It may be large-sized grains up to 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), 22-23.
Page, "I. Emulsion preparation and type
s) ”and ibid. No. 18716 (November 1979), p. 648, ibid N.
o.307105 (November 1989), pages 863-865, and Graphide, Physics and Chemistry of Photography, published by Paul Montel (P.Gl).
afkides, Chemie et Phisique Photographique, Paul M
ontel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion C
hemistry, Focal Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VL Ze
likman, et al., Making and Coating Photographic Em
ulsion, Focal Press, 1964) and the like.

US 3,574,628, US 3,655,394 and GB 1,4
The monodisperse emulsions described in 13,748 are also preferred. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutof, Photographic Science and Engineering (Gutof
f, Photographic Science and Engineering), Volume 14
248-257 (1970); US 4,434,226, US 4,414,310,
It can be easily prepared by the method described in 4,433,048, 4,439,520 and GB 2,112,157. The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, and may be joined with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion is a surface latent image type that forms a latent image mainly on the surface,
Either an internal latent image type formed inside the grain or a type having a latent image both on the surface and inside may be used, but it is necessary that the emulsion is a negative type. Of the internal latent image types, JP-A-6
The core / shell type internal latent image type emulsion described in 3-264740 may be used, and its preparation method is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such processes are RD No.17643 and RD No.187.
16 and No. 307105, and the relevant parts are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used. US Pat. No. 4,082,553, the surface of which is covered with silver halide grains, US Pat. No. 4,626,498, and JP-A-59-21.
4852, a silver halide grain in which the inside of the grain is fogged,
It is preferred to apply colloidal silver to the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. , Its preparation method is described in US 4,626,498 and JP-A-59-214852. The silver halide forming the inner core of a core / shell type silver halide grain having a fogged inside may have a different halogen composition.
As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm,
It is particularly preferably 0.05 to 0.6 μm. The grain shape may be regular grains or polydisperse emulsions, but monodisperse grains (weight of silver halide grains or grain number of at least 95
% Having a particle size within ± 40% of the average particle size).

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide, if necessary. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. The surface of the silver halide grain does not need to be optically sensitized nor spectrally sensitized. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be contained in the fine silver halide grain-containing layer. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

The photographic additives that can be used in the present invention are also described in RD, and the relevant portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 page right column page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to 868, supersensitizer, page 649, right column 4. Whitening agent, page 24, 647, right column, page 868, 5 Light absorber, pages 25 to 26, page 649, right column, page 873, filter, page 650, left column, dye, ultraviolet absorber 6. Binder, page 26, page 651, left column 873 to 874, page 7. Plasticizer, page 27, page 650, right Column 876 Lubricants 8. Coating aids, 26-27 Pages 650 Right column 875-876 Pages Surfactants 9. Static 27 pages 650 Page right columns 876-877 Inhibitors 10. Matting agents 878-879

Although various dye-forming couplers can be used in the light-sensitive material of the present invention, the following couplers are particularly preferable. Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (particularly Y-28 on page 18); EP 568,037A Claim 1
A coupler represented by formula (I) in US Pat. No. 5,066,576, column 1, lines 45 to 55; a coupler represented by formula (I) in paragraph 0008 of JP-A-4-274425; Couplers according to claim 1 of page 4 of EP 498,381A1 (especially D-35 on page 18); couplers of formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17), Y- 54 (p. 41)); US
Couplers represented by formulas (II) to (IV) at 4,476,219, column 7, lines 36 to 58 (especially II-17,19 (column 17), II-24 (column 19)). Magenta coupler; JP-A-3-39737 (L-57 (page 11, lower right), L-
68 (bottom right of page 12), L-77 (bottom right of page 13); EP 456,257, A-4 -6
3 (134 pages), A-4 -73, -75 (139 pages); EP 486,965 M-4, -6
(Page 26), M-7 (page 27); M-45 of EP 571,959A (page 19);
5-204106 (M-1) (page 6); JP-A-4-362631, paragraph 0237, M-
twenty two. Cyan coupler: CX-1,3,4,5,11,12,1 of JP-A-4-204843
4,15 (pages 14 to 16); C-7,10 (page 35) of JP-A-4-43345, 3
4,35 (page 37), (I-1), (I-17) (pages 42 to 43); JP-A-6-67385
A coupler represented by the general formula (Ia) or (Ib) according to claim 1. Polymer coupler: JP-A-2-44345, P-1, P-5 (page 11).

Examples of couplers in which the coloring dye has a suitable diffusibility include US 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. The coupler for correcting the unwanted absorption of the color forming dye is a yellow-colored cyan coupler represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), the EP
Yellow colored magenta coupler ExM-7 (202
Page), EX-1 (page 249), EX-7 (page 251), US 4,833,069
Magenta colored cyan coupler CC-9 (column
8), CC-13 (column 10), US 4,837,136 (2) (column 8),
The colorless masking couplers represented by formula (A) in claim 1 of WO92 / 11575 (in particular, the exemplified compounds on pages 36 to 45) are preferred. Examples of the compound (including a coupler) which reacts with an oxidized product of a developing agent to release a photographically useful compound residue include the following. Development inhibitor releasing compound: EP 37
Compounds represented by formulas (I), (II), (III) and (IV) described on page 11 of 8,236A1 (particularly T-101 (page 30), T-104 (page 31), T-113 ( 36
Page), T-131 (page 45), T-144 (page 51), T-158 (page 58)), EP436, 93
Compounds represented by formula (I) on page 7 of 8A2 (especially D-4
9 (page 51)), compounds represented by formula (1) of EP 568,037A (particularly (23) (page 11)), formulas (I), (II), and EP 440,195A2 on pages 5 to 6, Compounds represented by (III) (especially I- on page 29)
(1)); Bleach accelerator releasing compounds: compounds represented by formulas (I) and (I ′) on page 5 of EP 310,125A2 (particularly (60) and (6 on page 61)
1)) and a compound represented by the formula (I) of claim 1 of JP-A-6-59411 (particularly (7) (page 7); Ligand releasing compound: US
Compound represented by LIG-X described in claim 1 of 4,555,478 (especially compound on lines 21 to 41 of column 12); Leuco dye-releasing compound: compound 1 of columns 3 to 8 of US 4,749,641
~ 6; Fluorescent dye-releasing compound: C in claim 1 of US 4,774,181
Compounds represented by OUP-DYE (particularly compounds 1 to 11 in columns 7 to 10); development accelerator or fogging agent releasing compound: US
Compounds represented by formulas (1), (2), and (3) in 4,656,123, column 3 (particularly (I-22) in column 25) and EP 450,637A2
ExZK-2, lines 75-36, page 75; Compounds that release dye groups only upon elimination: Formula (I) of claim 1 of US 4,857,447
Compounds represented by (especially Y-1 to Y-19 in columns 25 to 36)
.

As the additives other than the coupler, the following are preferable. Dispersion medium of oil-soluble organic compound: P-3,5 of JP-A-62-215272
16,19,25,30,42,49,54,55,66,81,85,86,93 (140〜144
Page); Latex for impregnation of oil-soluble organic compounds: US 4,199,
Latex described in 363; Oxidized developer scavenger: a compound represented by the formula (I) in column 2, lines 54 to 62 of US Pat. ) (Column 4-
5), US Pat. No. 4,923,787, column 2, lines 5-10 (especially compound 1 (column 3); stain inhibitor: EP 298321A, 4).
Formulas (I)-(III) on pages 30-33, especially I-47, 72, III-1, 27 (24
~ Page 48); Anti-fading agent: A-6,7,20,21,23,2 of EP 298321A
4,25,26,30,37,40,42,48,63,90,92,94,164 (69〜118
Pp.), US 5,122,444, columns 25-38, II-1 to III-23, especially
III-10, EP 471347A, pages 8-12, I-1 to III-4, especially II-
2, US 5,139,931 columns 32-40 A-1 to 48, especially A-39,
42; Materials that reduce the use of color-enhancing agents or color-mixing inhibitors: I-1 to II-15 on pages 5 to 24 of EP 411324A, especially I-4
6; Formalin scavenger: EP 477932A, pages 24 to 29, SCV-1 to 28, especially SCV-8; Hardener: JP-A 1-214845
Formulas in columns 13-23 of H-1,4,6,8,14, US 4,618,573 on page 17
Compounds (H-1 to 54) represented by (VII) to (XII), JP-A-2-
214852, page 8, lower right, compound represented by formula (6) (H-1 to 7
6), especially the compound described in claim 1 of H-14, US 3,325,287; Development inhibitor precursor: P-2 of JP-A-62-168139
4,37,39 (pages 6-7); compounds as claimed in claim 1 of US 5,019,492, in particular column 7, 28,29; preservatives, fungicides: US
4,923,790 columns 3 to 15 I-1 to III-43, especially II-1,
9,10,18, III-25; Stabilizers, antifoggants: US 4,923,79
I-1 to (14) in columns 6 to 16 of 3, especially I-1,60, (2), (13), U
S 4,952,483 columns 25-32 compounds 1-65, especially 36:
Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: 15-18 of JP-A-3-156450
A-1 to b-20, especially a-1,12,18,27,35,36, b-5,27 to 29
Pages V-1 to 23, especially V-1, EP 445627A pages 33 to 55 FI-
1 to F-II-43, especially FI-11, F-II-8, EP 457153A 17 to 28
Pages III-1 to 36, especially III-1,3, WO 88/04794 8-26
Microcrystalline dispersion of Dye-1 to 124, compounds 1 to 22 of EP 319999A, pages 6 to 11, especially compound 1, compounds D-1 to 87 (3) represented by formulas (1) to (3) of EP 519306A. ~ Page 28), US 4,26
Compounds 1-22 represented by formula (I) of 8,622 (columns 3-1
0), a compound (1) represented by the formula (I) of US 4,923,788 ~
(31) (Columns 2 to 9); UV absorber: Formula of JP-A-46-3335
Compounds (18b) to (18r), 101 to 427 (6 to
(Page 9), compounds (3) to (6 represented by formula (I) of EP 520938A.
6) (pages 10 to 44) and the compound HBT-1 represented by the formula (III).
~ 10 (page 14), compounds represented by formula (1) of EP 521823A
(1) to (31) (columns 2 to 9).

In the light-sensitive material used in the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less.
18 μm or less is more preferable, and 16 μm or less is particularly preferable. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is a color developer at 30 ° C, 3
When 90% of the maximum swollen film thickness reached after processing for 15 minutes is the saturated film thickness, it is defined as the time until the film thickness reaches 1/2. The film thickness is 25 ° C and 55% relative humidity (2
Meaning the film thickness measured in days), T _1/2 is A. Green et al.'S Photographic Science and Engineering (Photogr.Sci.Eng.), 19 squares,
It can be measured by using a swellometer of the type described on pages 2,124 to 129. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. Swelling rate, from the maximum swollen film thickness under the conditions described above,
It can be calculated by the formula: (maximum swollen film thickness-film thickness) / film thickness. The photographic material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surface active agent. The swelling ratio of this back layer is preferably 150 to 500%.

Next, the processing method of the present invention will be described in detail. The color developing solution (color developing solution) used in the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N diethylaniline and 3-methyl. -4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-Methanesulfonamidoethylaniline, 3-methyl-4-
Amino-N-ethyl-β-methoxyethylaniline, 4-amino-3-methyl-N-methyl-N- (3-hydroxypropyl)
Aniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (2-hydroxypropyl) aniline, 4-amino- 3-
Ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline, 4-amino-3-propyl-N-methyl
-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-methyl-N- (4-hydroxybutyl) aniline, 4-
Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl)
Aniline, 4-amino-3-methyl-N-propyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxy-2-methylpropyl) aniline, Four-
Amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-methyl-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-methyl-N- (5-Hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-
Amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethoxy-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N
-(4-hydroxybutyl) aniline, and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, especially 3-methyl-4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 4-amino-3
-Methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, and their hydrochlorides, p-toluenesulfonic acid Salts or sulfates are preferable in that the deterioration of magnetic recording is small. Two or more of these compounds can be used in combination depending on the purpose.

The amount of the aromatic primary amine developing agent used is 0.02 mol to 0.1 mol, and more preferably 0.025 mol to 0.08 mol, per liter of the color developing solution.

Color developing solutions include various preservatives such as sulfite, triethanolamine and catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol,
Quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkyls Phosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1 -Diphosphonic acid, Nitrilo-N, N, N-
Trimethylenephosphonic acid, ethylenediamine-N, N, N, N-
Tetramethylenephosphonic acid, ethylenediamine-di (o
-Hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples.

If desired, any antifoggant can be added to the color developer used in the present invention. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of the organic antifoggants include benzotriazole, 6-nitrobenzimidazole,
5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-
Representative examples thereof include nitrogen-containing heterocyclic compounds such as benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

The color developing solution used in the present invention preferably has a pH range of about 9.0 to 11.0. The most preferable pH of the tank liquid is about 9.8 to 10.5. the above
In order to maintain the pH, it is preferable to use various buffers. As the buffering agent, carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N
-Dimethylglycine salt, leucine salt, norleucine salt,
Guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt, etc. Can be used. The use of carbonate is particularly preferable. The amount of the buffer added to the developer is preferably 0.1 mol / liter or more, and particularly 0.1 mol / liter to 0.4 mol / liter.
It is particularly preferable that it is mol / liter. Further, a compound having biodegradability is preferable as the chelating agent. Examples of this are Japanese Patent Laid-Open Nos. 63-146998 and 6-1988.
3-199295, JP-A-63-267750, JP-A-63-267751, and JP-A-2-229146.
No. 3, JP-A-3-186841, German Patent 373961
0, and chelating agents described in European Patent 468325 and the like. It is preferable that the processing solution in the color developing solution replenishing tank or the processing tank is shielded with a liquid agent such as a high-boiling point organic solvent to reduce the contact area with air. Liquid paraffin is most preferable as the liquid shield agent. It is particularly preferable to use it as a replenisher. The processing temperature of the color developing solution in the present invention is preferably a high temperature, preferably 40 to 60 ° C., and preferably 42 to 55 ° C., for the purpose of speeding up.
The processing time is 20 seconds to 2 minutes, preferably 30 seconds to 1 minute 30 seconds in the light-sensitive material for photographing. In addition, the replenishment amount is 1
30-800 ml per square meter, preferably 50
~ 500 ml.

When reversal processing is carried out, black and white development is usually carried out before color development. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. Any development accelerator can be added to the developer used in the present invention, if necessary. As a development accelerator, Japanese Patent Publication No. 37-16088, No. 37-5987, No. 38-7826
No. 44-12380, No. 45-9019 and U.S. Pat.
Thioether compounds represented by JP-A No. 247, etc.
-49829 and 50-15554, p-phenylenediamine compounds, JP-A-50-137726, JP-B-44-300
74, quaternary ammonium salts represented by JP-A-56-156826 and JP-A-52-43429, U.S. Pat. No. 2,494,903,
No. 3,128,182, No. 4,230,796, No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Patent No. 2,482,546, No. 2,596,92
6 and 3,582,346, etc., amine compounds, JP-B-37-16088, JP-B-42-25201, U.S. Pat.
No. 4, Japanese Patent Publication Nos. 41-11431 and 42-23883, and U.S. Pat.
Polyalkylene oxides represented by 532,501 and the like,
In addition, 1-phenyl-3-pyrazolidones, imidazoles, etc. can be added as necessary. next,
The desilvering process of the present invention will be described in detail. The desilvering process generally has a bleaching process, a bleach-fixing process, and a fixing process, and there are various processes. Specific steps are shown below, but the invention is not limited thereto.

(Step 1) Bleach-fixing (step 2) Bleach-bleach-fixing (step 3) Bleach-bleach-fixing-fixing (step 4) Fixing-bleach-fixing (step 5) Bleach-fixing In the present invention, washing or stabilizing Especially when the pre-bath of the bleaching step is the bleach-fixing step, a remarkable effect is exhibited.

As the bleaching agent used in the processing solution having bleaching ability, aminopolycarboxylic acid iron (III) complex, persulfate, bromate, hydrogen peroxide, red blood salt and the like can be used. The polycarboxylic acid (III) complex can be most preferably used. The ferric iron complex salt used in the present invention may be added and dissolved as a complexed iron complex salt in advance, and the complex forming compound and the ferric iron salt (for example, ferric sulfate, ferric chloride) may be added. Iron, ferric bromide, iron (III) nitrate, iron (III) ammonium sulfate, etc.) may coexist to form a complex salt in a liquid having a bleaching ability. The complex-forming compound may be slightly in excess of the amount required for complex formation with ferric ion, and when it is added in an excess amount, it is usually 0.01 to 1
It is preferable to make it excessive in the range of 0%.

In the present invention, as the compound forming the ferric complex salt in the liquid having bleaching ability, ethylenediaminetetraacetic acid (EDTA), 1,3-propanediaminetetraacetic acid (1,3-PDTA), Diethylenetriaminepentaacetic acid, 1,2-cyclohexanediaminetetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, N- (2-acetamido) iminodiacetic acid, nitrilotriacetic acid, N- (2-carboxyethyl) iminodiacetic acid, N- (2-Carboxymethyl) iminodipropionic acid, β-alanine diacetic acid, 1,
4-diaminobutane tetraacetic acid, glycol ether diamine tetraacetic acid, N- (2-carboxyphenyl) iminodiacetic acid, ethylenediamine-N- (2-carboxyphenyl) -N, N ', N'-triacetic acid, ethylenediamine-
N, N'-disuccinic acid, 1,3-diaminopropane-
N, N'-disuccinic acid, ethylenediamine-N, N'-
Examples thereof include dimaleonic acid and 1,3-diaminopropane-N, N′-dimalonic acid, but are not particularly limited thereto.

The concentration of the ferric complex salt in the treatment solution having a bleaching ability of the present invention is appropriately in the range of 0.005 to 1.0 mol / liter, and 0.01 to 0.50 mol / liter.
It is preferably in the range of liter, more preferably 0.02.
The range is from 0.30 mol / liter. The concentration of the ferric complex salt in the replenisher for the processing solution having bleaching ability is
The amount is preferably 0.005 to 2 mol / liter, more preferably 0.01 to 1.0 mol / liter.

Various compounds can be used as a bleaching accelerator in a bath having a bleaching ability or a prebath thereof. For example, compounds having a mercapto group or a disulfide bond described in U.S. Pat. No. 3,893,858, German Patent 1,290,812, JP-A-53-95630 and Research Disclosure No. 17129 (July 1978). And Japanese Patent Publication No. 45-8506, Japanese Patent Laid-Open Nos. 52-20832, 53-3
2735, U.S. Pat. No. 3,706,561 and the like, and thiourea compounds or halides such as iodine and bromine ions are preferable because of their excellent bleaching power.

Other bleaching baths applicable to the present invention include bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride). Alternatively, a rehalogenating agent such as iodide (eg, ammonium iodide) can be included. PH of borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, malonic acid, succinic acid, glutaric acid, etc. It is possible to add one or more kinds of inorganic acids and organic acids having a buffering capacity and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine. Further, the bath having a bleaching ability may contain various other fluorescent whitening agents, antifoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol.

The fixing agent component in the bleach-fixing solution or the fixing solution is
Known fixing agents, ie, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; sodium thiocyanate,
Thiocyanates such as ammonium thiocyanate; ethylenebisthioglycolic acid, 3,6-dithia-1,8-
It is a water-soluble silver halide solubilizer such as thioether compounds such as octanediol, mesoionic compounds and thioureas, and these can be used alone or in admixture of two or more. Further, a special bleach-fixing solution containing a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, it is preferable to use thiosulfates, particularly ammonium thiosulfate and sodium thiosulfate. The amount of fixer per liter is 0.3
Is preferably 2 to 2 mol, more preferably 0.5 to 1.0 mol.

The bleach-fixing solution and the fixing solution of the present invention preferably contain a sulfite (or bisulfite or metabisulfite) as a preservative, but especially from 0.08 to
0.4 mol / liter, more preferably 0.1 to 0.3
It is preferable that the content is mol / liter. By using this concentration range and further using the final bath of the present invention, not only the magnetic recording performance was remarkably improved, but also desirable results were shown in terms of image storability. The bleach-fixing solution or fixing solution of the present invention is a sulfite (for example, sodium sulfite, potassium sulfite, ammonium sulfite) or bisulfite (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite) described above as a preservative. In addition to containing sulfite ion-releasing compounds such as metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite), aldehydes (benzaldexide, acetaldehyde, etc.), ketones (acetone, etc.) , Ascorbic acid, hydroxylamines and the like can be added as necessary. Further, a bleaching solution, a bleach-fixing solution and a fixing solution may be added with a buffering agent, a fluorescent whitening agent, a chelating agent, a defoaming agent, an antifungal agent and the like, if necessary.

As a preservative for the bleach-fixing solution and the fixing solution,
Although sulfite is generally added, ascorbic acid, carbonyl bisulfite adduct, carbonyl compound, or the like may be added, and benzenesulfinic acids are also effective. Furthermore, a buffer for the bleach-fixing solution and the fixing solution,
A fluorescent whitening agent, a chelating agent, a defoaming agent, an antifungal agent and the like may be added as necessary.

In the bleaching solution and the bleach-fixing solution used in the present invention, the pH range used is 3 to 6, and most preferably 4 to 5.5. Here, when the pH is lower than 3, or conversely higher than 6, the effect of improving the N / S ratio of the magnetic information becomes small. Further, in the fixing solution, the pH is 3 to
9 is preferable. The bleaching solution, the bleach-fixing bath, and the replenishing amount to the fixing bath are 20 to 300 ml per 1 m ² of the light-sensitive material. Particularly preferred is 25 to 200 ml,
More preferably, it is 30 to 150 ml. The processing temperature of each of the bleaching solution, the bleach-fixing solution and the fixing solution applicable to the present invention is 20 to 50 ° C., preferably 30 to 4 ° C.
5 ° C. The processing time of the desilvering step is preferably 20 seconds to 2 minutes.

The processing liquid having a bleaching ability of the present invention is particularly preferably subjected to aeration during processing because the photographic performance can be kept extremely stable. Means known in the art can be used for the aeration, and blowing of air into the processing liquid having a bleaching ability or absorption of air using an ejector can be performed. At the time of blowing air, it is preferable to discharge the air into the liquid through an air diffusing tube having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Z-121, Eusing Process C-41, No. 3, issued by Eastman Kodak Company.
The matters described in the edition (1982), pages BL-1 to BL-2 can be used. In the processing using the processing solution having the bleaching ability of the present invention, it is preferable that the stirring is strengthened, and the implementation thereof is described in JP-A-3-33847, No. 8
The contents of the page, upper right column, line 6 to lower left column, line 2
It can be used as is.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. Specific examples of the method for strengthening stirring include a method in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, and JP-A-62-1834.
A method of increasing the stirring effect using the rotating means of No. 61, and further moving the light-sensitive material while bringing the emulsion surface into contact with the wiper blade provided in the liquid to make the emulsion surface turbulent, thereby further improving the stirring effect. Examples thereof include a method for improving the method and a method for increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator.

The automatic processor used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257, JP-A-60-191258 and JP-A-60-1912.
It is preferable to have a photosensitive material conveying means described in No. 59. As described in the above-mentioned JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The processing solution having bleaching ability of the present invention is
The overflow solution after use in the treatment can be recovered, the components can be added to modify the composition, and then the overflow solution can be reused. Such usage is usually called regeneration, but the present invention can also favor such regeneration. For details of the reproduction, see Fuji Film Processing Manual issued by Fuji Photo Film Co., Ltd., Fuji Color Negative Film, CN-16 processing (revised August 1990), pp. 39-.
The matters described on page 40 can be applied. The kit for adjusting the processing solution having a bleaching ability of the present invention may be a liquid or a powder, but when ammonium salts are excluded, most of the raw materials are supplied as a powder, and since the hygroscopicity is also small,
Makes powder easier. From the viewpoint of reducing the amount of waste liquid, the regenerating kit is preferably a powder because it can be added directly without using excess water.

Regarding the regeneration of the processing solution having the bleaching ability,
In addition to the aeration mentioned above, "Basics of photographic engineering-silver salt photography-" (edited by the Photographic Society of Japan, published by Corona Publishing Co., 1979)
Year)) etc. can be used. Specifically, in addition to electric field regeneration, there is a method for regenerating bleaching solution with bromic acid, zincic acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using catalyst, bromic acid, ozone, etc. Can be mentioned.
In the electrolytic regeneration, the cathode and the anode are put in the same bleaching bath, or the diaphragm and the anode tank and the cathode bath are separated into different baths, and the bleaching solution and the developer and / or the diaphragm are also used. Alternatively, the fixing solution can be regenerated at the same time. The fixing solution and the bleach-fixing solution are regenerated by electrolytically reducing accumulated silver ions. Other,
It is also preferable to remove accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance.

In the processing apparatus of the present invention, after desilvering processing,
It is common to go through a washing and / or stabilizing step. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions It can be set in a wide range. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in Journal.
of the Society of Motion Picture and Television En
It can be determined by the method described in gineers, Volume 64, P. 248 to 253 (May 1955 issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention,
As a solution to this problem, the method of reducing calcium and magnesium ions described in JP-A-62-288,838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antibacterial and fungicide" (1986) Sankyo Publishing, Sanitary Technology Society, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society for Antibacterial and Antifungal, "Encyclopedia of Antibacterial and Antifungal Agents" (1986
Year) can also be used.

Rinsing water in processing the light-sensitive material of the present invention
The pH is 4-9, preferably 5-8. The washing water temperature and the washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but in general, it is 20 seconds to 10 minutes at 15 to 45 ° C., preferably
A range of 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used.

In the stabilizing solution, compounds that stabilize the dye image, for example, benzaldehydes such as formalin and m-hydroxybenzaldehyde, formaldehyde bisulfite adduct, hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, N-methylol compounds such as dimethylol urea and N-methylol pyrazole, organic acids and pH buffering agents are included. The addition amount of these compounds is preferably 0.001 to 0.02 mol per liter of the stabilizing solution, but the lower the free formaldehyde concentration in the stabilizing solution is, the less the formaldehyde gas is scattered, which is preferable. From this point of view, examples of the dye image stabilizer include m-hydroxybenzaldehyde, hexamethylenetetramine, N-methylolpyrazole, N-methylolazoles described in JP-A-4-270344, N, N'-bis (1 , 2,4-Triazol-1-ylmethyl) piperazine etc.
Azolylmethylamines described in 13753 are preferred. Particularly, azoles such as 1,2,4-triazole described in JP-A-4-359249 (corresponding to European Patent Publication No. 519190A2) and 1,4-bis (1,2,4)
The combined use of azolylmethylamine and its derivatives such as -triazol-1-ylmethyl) piperazine is preferable because of high image stability and low formaldehyde vapor pressure. In addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners, hardeners, US Pat.
It is also preferable to contain an alkanolamine described in JP-A-86,583 or a preservative that can be contained in the fixing solution or the bleach-fixing solution, for example, a sulfinic acid compound described in JP-A-1-231510. .

The washing water and / or the stabilizing solution may contain various surfactants in order to prevent unevenness of water droplets during drying of the processed light-sensitive material. Among these, it is preferable to use a nonionic surfactant, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

Various chelating agents are preferably contained in the wash water and / or the stabilizing solution. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N '.
-Trimethylenephosphonic acid, diethylenetriamine-
Organic phosphonic acids such as N, N, N ', N'-tetramethylenephosphonic acid, or European Patent 345,172A
Examples thereof include the hydrolyzate of the maleic anhydride polymer described in No. 1 and the like.

The overflow solution that accompanies the washing with water and / or the supplement of the stabilizing solution can be reused in other steps such as the desilvering step. Regarding the processor of the present invention, the parts other than the drive will be described. In the present invention, in order to perform the processing rapidly, the shorter the air time when the photosensitive material moves between the processing solutions, that is, the shorter the crossover time, the better, preferably 20 seconds or less, more preferably 10 seconds or less, More preferably, it is 5 seconds or less. In order to achieve the above-mentioned short-time crossover, it is preferable to use a cine type automatic developing machine in the present invention, and a leader conveyance system or a roller conveyance system is particularly preferable. Such a system is used for the automatic developing machine FP-560B manufactured by Fuji Photo Film Co., Ltd. or the same PP1820V.
It is used for The linear velocity of conveyance is preferably high, but is generally 30 cm to 30 m / min, preferably 50 cm to 10 m. As a reader and a conveying means for the photosensitive material, there are disclosed in JP-A-60-191257 and 60-
The belt conveying methods described in JP-A-191258 and JP-A-60-191259 are preferable, and particularly, as the conveying mechanism, Japanese Patent Application Nos. 1-265794, 1-266915 and 1-
It is preferable to adopt each method described in No. 266916. Further, in order to shorten the crossover time and prevent the processing liquid from being mixed, the structure of the crossover rack preferably has a mixing prevention plate described in Japanese Patent Application No. 1-265795.

It is preferable to perform so-called evaporation correction by supplying water corresponding to the evaporation of the processing liquid to each processing liquid in the present invention. Particularly, it is preferable in a color developing solution, a bleaching solution or a bleach-fixing solution. The specific method for replenishing such water is not particularly limited, but among them, a monitor water tank different from the bleaching tank described in JP-A-1-254959 and 1-254960 is installed. The method of calculating the amount of evaporation of water inside, calculating the amount of evaporation of water in the bleaching tank from this evaporation amount, and replenishing the bleaching tank with water in proportion to this evaporation amount, and Japanese Patent Application No. 2-46743, 2-4
No. 7777, No. 2-47778, No. 2-47779
The evaporation correction method using a liquid level sensor and an overflow sensor described in JP-A No. 2-117792 / 1990 is preferable. The most preferable evaporation correction method is to predict and add water corresponding to the amount of evaporation.
As described in No. 3, the amount of water added is calculated by a coefficient previously obtained based on the information on the operating time, stop time and temperature control time of the automatic processor.

Further, it is necessary to devise a method for reducing the amount of evaporation, and it is required to reduce the opening area and adjust the air volume of the exhaust fan. For example, the preferable opening ratio of the color developing solution is as described above, but it is preferable to reduce the opening area of other processing solutions as well. The exhaust fan is attached to prevent condensation during temperature control,
Preferred emissions, per minute 0.1 m ³ to 1 m ^3,
Particularly preferred engine displacement, a 0.2m ³ ~0.4m ^3. Further, the drying condition of the photosensitive material also affects the evaporation of the processing liquid. The drying method is preferably a ceramic hot air heater is preferably min 4m ³ to 20 m ³ as feed air volume, particularly 6 m ³ through 10m ³ preferred. The heating prevention thermostat of the ceramic warm air heater is preferably operated by heat transfer, and the mounting position is preferably attached to the leeward or upwind side through the heat radiation fins or the heat transfer portion. The drying temperature is preferably adjusted according to the water content of the light-sensitive material to be processed, 45-55 ° C for 35 mm wide film, 55-65 ° C for Brownie film,
For printing materials, 60 to 90 ° C is optimal. A replenishing pump is used for replenishing the processing liquid, but a bellows type replenishing pump is preferable. Further, as a method of improving the replenishment accuracy, it is effective to reduce the diameter of the liquid supply tube to the replenishment nozzle in order to prevent backflow when the pump is stopped. A preferable inner diameter is 1 to 8 mm, and a particularly preferable inner diameter is 2 to 5 mm.

The supply form of the treating agent used in the present invention is as follows:
It may be in any form such as a concentrated or concentrated liquid preparation, a granule, a powder, a tablet, a paste or an emulsion. As an example of such a treating agent, JP-A-63-1
7453 is a liquid agent stored in a container with low oxygen permeability,
19655 and 4-230748 are vacuum packed powders or granules, and 4-21951 are granules containing a water-soluble polymer,
JP-A-51-61837 and JP-A-6-102628 have tablets and special tables
00485 discloses a paste-like treatment agent, and any of them can be preferably used, but from the viewpoint of ease of use,
It is preferable to use a liquid which has been prepared in advance in a concentration at the state of use. Polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon and the like are used alone or as a composite material in a container for containing these treatment agents. These are selected according to the level of oxygen permeability required. For a liquid such as a color developing solution which is easily oxidized, a material having low oxygen permeability is preferable, and specifically, polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. These materials have a thickness of 500 to 1500 μm, are used for a container, and preferably have an oxygen permeability of 20 ml / m ² · 24 hrs · atm or less.

[0073]

EXAMPLES The present invention will be described in more detail with reference to specific examples, but the invention is not limited to the examples as long as the gist of the invention is not exceeded. (Example 1) 1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 100
After drying 3 parts by weight and 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy Co., Ltd.) as an ultraviolet absorber, 300 ° C.
After melting at T, it is extruded from a T-die, longitudinally stretched 3.3 times at 140 ° C, then transversely stretched 3.3 times at 130 ° C, and heat-set at 250 ° C for 6 seconds to form a PEN with a thickness of 90μm.
I got a film. This PEN film contains blue dye, magenta dye, and yellow dye (I-1, I-4, I-6, I-24, I-26, I- in Public Technical Report No. 94-6023). 27, II-5)
Was added in an appropriate amount. Furthermore, it was wound on a stainless steel core having a diameter of 20 cm and subjected to a heat history of 110 ° C. for 48 hours to obtain a support with less curling tendency.

2) Coating of undercoat layer The above-mentioned support was subjected to corona discharge treatment, UV discharge treatment, and glow discharge treatment on both sides thereof, and then gelatin 0.1 g / m ² and sodium α-sulfodione on each side. -2-ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p
-Chlorophenol 0.2 g / m ² , (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂
CH ₂ 0.012 g / m ² , a polyamide-epichlorohydrin polycondensate 0.02 g / m ² undercoat liquid was applied (10 cc / m ² , using a bar coater), and an undercoat layer was provided on the high temperature surface side during stretching. Dry 1
The test was carried out at 15 ° C for 6 minutes (the temperature of the rollers and the conveying device in the drying zone are 115 ° C). 3) Coating of back layer After the undercoating, an antistatic layer having the following composition, a magnetic recording layer and a sliding layer were coated as back layers on one surface of the support.

3-1) Coating of antistatic layer A tin oxide-antimony oxide composite having an average particle size of 0.005 μm has a specific resistance of 5 Ω · cm and is a dispersion of fine particle powder (secondary agglomerated particle size of about 0.08 μm). 0.2 g / m ^2, gelatin 0.05g / m ^2, (C
H ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.02g / m ² , poly (degree of polymerization 1
0) Oxyethylene-p-nonylphenol 0.005g / m ²
And Resorcin. 3-2) Coating of magnetic recording layer 3-Poly (degree of polymerization 15) Cobalt-γ-iron oxide coated with oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ² / g, Long axis 0.14μm, uniaxial 0.03μm, saturation magnetization 89emu / g, Fe ^{+ 2} / Fe ⁺³ = 6/94, surface is treated with aluminum oxide silicon oxide at 2% by weight of iron oxide) 0.06g / m ² is diacetyl cellulose 1.2 g / m ² (iron oxide was dispersed in an open kneader and a sand mill), C ₂ H ₅ C (CH ₂ OCONH-C ₆ H ₃ (CH ₃ ) NCO) ₃ as a curing agent
0.3 g / m ² was applied with a bar coater using acetone, methyl ethyl ketone, and cyclohexanone as a solvent,
A magnetic recording layer having a thickness of 1.2 μm was obtained. As a matting agent, silica particles (0.3 μm) and abrasive aluminum oxide (0.15 μm) coated with 3-poly (polymerization degree 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) were coated, respectively.
It was added at 10 mg / m ² . Drying was carried out at 115 ° C for 6 minutes (all rollers and conveyors in the drying zone are 115
° C). The color density increase of D ^B of the magnetic recording layer by the X-light (blue filter) is about 0.1, the saturation magnetization moment of the magnetic recording layer is 4.2 emu / g, the coercive force is 7.3 × 10 ⁴ A / m, and the squareness ratio is Was 65%.

3-3) Preparation of sliding layer Diacetyl cellulose (25 mg / m ² ), C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ C
OOC ₄₀ H ₈₁ (Compound a, 6 mg / m ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H
The (compound b, 9 mg / m ² ) mixture was applied. This mixture is xylene / propylene monomethyl ether (1/1)
It was melted at 105 ° C. in water, poured into and dispersed in propylene monomethyl ether (10 times amount) at room temperature to prepare a dispersion (average particle diameter 0.01 μm) in acetone, and then added. Silica particles (0.3 μm) as a matting agent and 3-poly (polymerization degree 15) oxyethylene-propyloxytrimethoxysilane (aluminum oxide coated with 15% by weight (0.15 μm) as an abrasive were 15 mg / m ² and The amount of drying was 115
C., 6 minutes (115 ° C. for all rollers and conveyors in the drying zone). The sliding layer had an excellent dynamic friction coefficient of 0.06 (stainless steel ball of 5 mmφ, load 100 g, speed of 6 cm / min), static friction coefficient of 0.07 (clip method), and the dynamic friction coefficient of the emulsion surface, which will be described later, was 0.12. .

4) Coating of Photosensitive Layer Next, each layer having the following composition was multilayer coated on the side opposite to the back layer obtained above to prepare a color negative film.
This is designated as Sample 101.

(Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H: Gelatin hardening agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, for the sensitizing dye, the coating amount is shown in mol units with respect to 1 mol of silver halide in the same layer.

First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid Disperse Dye ExF-2 0.030 Solid Disperse Dye ExF-3 0.040 HBS-1 0.15 HBS- 2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M Silver 0.065 ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion A Silver 0.25 Silver Iodobromide Emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.70 ExS-1 3.5 × 10 ⁻⁴ ExS-2 1.6 × 10 ⁻⁵ ExS-3 5.1 × 10 ⁻⁴ ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.40 ExS-1 2.4 × 10 ⁻⁴ ExS-2 1.0 × 10 ⁻⁴ ExS-3 3.4 × 10 ⁻⁴ ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion E Silver 0.15 Silver iodobromide emulsion F Silver 0.10 Silver iodobromide emulsion G Silver 0.10 ExS-4 3.0 × 10 ⁻⁵ ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80

Ninth Layer (High-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion I Silver 1.25 ExS-4 3.7 × 10 ⁻⁵ ExS-5 8.1 × 10 ⁻⁵ ExS-6 3.2 × 10 ⁻⁴ ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60

11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

Twelfth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 1.00 ExS-7 4.0 × 10 ⁻⁴ ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

13th layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 gelatin 1.8

14th layer (second protective layer) Silver iodobromide emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ⁻² B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 70

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0094]

[Table 1]

In Table 1, (1) Emulsions J to L were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid in accordance with the examples of JP-A-2-91938. (2) Emulsions A to I were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. ing. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the example of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains using a high voltage electron microscope. (5) Emulsion L is a double-structured grain containing an internal high iodine core described in JP-A-60-143331.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% sodium p-octylphenoxyethoxyethoxyethane sulfonate and 5% aqueous solution
0.5 g of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) of the aqueous solution was put in a 700 ml pot mill, and 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added. The material was dispersed for 2 hours. A BO type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After the dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye particles is 0.44
μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the dye fine particles were 0.24 μm, 0.45 μm and 0.52 μm, respectively.
ExF-5 was dispersed by the microprecipitation dispersion method described in Example 1 of EP549,489A. The average particle size was 0.06 μm.

[0098]

[Chemical 11]

[0099]

[Chemical 12]

[0100]

[Chemical 13]

[0101]

Embedded image

[0102]

[Chemical 15]

[0103]

Embedded image

[0104]

[Chemical 17]

[0105]

Embedded image

[0106]

[Chemical 19]

[0107]

Embedded image

[0108]

[Chemical 21]

[0109]

[Chemical formula 22]

[0110]

[Chemical formula 23]

[0111]

[Chemical formula 24]

[0112]

[Chemical 25]

[0113]

[Chemical formula 26]

The light-sensitive material prepared as described above is set to 24 mm.
The width is cut into 160 cm, and two perforations of 2 mm square are provided at a distance of 5.8 mm at a position 0.7 mm from one side width direction of the photosensitive material. A device in which these two sets are provided at intervals of 32 mm is prepared, and is shown in US Pat. No. 5,296,887, FIG. 1-FIG. It was housed in the plastic film cartridge described in 7. An audio type magnetic recording head made of a permalloy material having a head gap of 5 μm, a turn number of 50, and a feed rate of 10 was applied to this sample from the coated surface side of the magnetic recording layer.
Digital saturation recording was performed at a recording wavelength of 50 μm at 0 mm / sec.

Sample 101 described above was tested for color temperature 4800
It was subjected to a gray exposure of 5 cms with K, processed with a cine type automatic processor with the following processing steps and processing solutions, and then stored again in the original plastic film cartridge.
The following treatment was carried out for 2 m ² per day for 30 days (running treatment). The treatment process and the treatment liquid composition are shown below.

(Processing step) Step Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 05 seconds 38.0 ° C See Table 2 17 liters Bleach 50 seconds 38.0 ° C 100 ml / m ² 5 liter Fixing (1) 50 seconds 38.0 ° C −5 liters Fixing (2) 50 seconds 38.0 ° C 300 ml / m ² 5 liters Water washing 30 seconds 38.0 ° C 500 ml / m ² 3.5 liters Stable (1) 20 seconds 38.0 ° C −3 liters stable (2) 20 seconds 38.0 ° C 500 ml / m ² 3 liter Dry 90 seconds 60 ° C Stabilizer and fixer are countercurrent from (2) to (1).
The overflow of washing water was introduced into the fixing bath.
Incidentally, amount carried to the bleaching step of the color developing solution, the amount of carryover of the fixing step of the bleaching solution, bring volume to the washing step of the fixer photosensitive material 35mm wide 1 m ² per each 65 ml 50 ml 50 ml, It was 50 milliliters. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developer) Tank solution (g) Replenisher solution (g) Diethylenetriaminepentaacetic acid 3.0 3.0 Catechol-3,5-disulfonate dinatrium salt 0.3 0.3 Sodium sulfite 3.9 5.3 Potassium carbonate 39.0 39.0 Disodium-N, N-bis (2-sulfonateethyl) hydroxylamine 1.5 2.0 Potassium bromide See Table 2 See Table 2 Potassium iodide See Table 2 Table 2 Preservative ( (See Table 2) 30 mM 41 mM 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.05-2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] Aniline sulfate 4.5 6.5 Add water 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18

(Bleaching Solution) Tank Solution (g) Replenishing Solution (g) 1,3-Propylenediaminetetraacetic Acid Iron (III) Ammonium Salt 113.0 170.0 Ammonium Bromide 70.0 105.0 Ammonium Nitrate 14.0 21.0 Succinic acid 34.0 51.0 Maleic acid 28.0 42.0 Add water 1000 ml 1000 ml pH (adjust with ammonia water and nitric acid) 4.6 4.0

(Fixing (1) Tank Liquid) A 5:95 (volume ratio) mixture of the above bleaching tank liquid and the following fixing tank liquid. (PH 6.8)

(Fixing Solution (2)) Tank Solution (g) Replenishing Solution (g) Ammonium Thiosulfate Aqueous Solution (750 g / L) 240.0 ml 720.0 ml Ammonium methanethiosulfonate 5.0 15.0 Ammonium methanesulfinate 10 0.0 30.0 Ethylenediaminetetraacetic acid 13.0 39.0 Imidazole 7.0 21.0 Add water 1000 ml 1000 ml pH (adjust with ammonia water and acetic acid) 7.4 7.5

(Washing Water) Common to Tank Liquid and Replenisher Tap water is H type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type strongly basic anion exchange resin (Amberlite IRA). -4
00) packed in a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, and then 20 mg of sodium diisocyanurate dichloride /
L and 150 mg / L of sodium sulfate were added. The pH of this liquid was in the range of 6.5 to 7.5.

(Stabilizer) Tank solution and replenisher common 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 g 1,2,4-triazole 1.3 g polyoxyethylene-p -Monononyl phenyl ether 0.2 g (average degree of polymerization 10) Disodium salt of ethylenediaminetetraacetic acid 0.05 g Sodium p-toluenesulfinate 0.03 g 1,2-Benzisothiazolin-3-one. Sodium 0.10 g Gentamicin 0.01 g Water was added to 1 liter pH (adjusted with ammonia water and nitric acid) 8.5

It was confirmed that the bromide ion and iodide ion concentrations of the color developing solution were substantially constant before and after running. With respect to the light-sensitive material treated by the above method, the change in cyan density before and after running and the output of magnetic recording were evaluated by the following method. -Cyan density change before and after running The density of the light-sensitive material was measured. The difference (ΔD) between the cyan density at the beginning of the running and the cyan density after the running was determined for the exposure amount giving a cyan density of 1.5 in the characteristic curve at the beginning of the running. (ΔD) = (cyan density at the beginning of running) − (cyan density after running) -Measurement of output of magnetic recording The processed photosensitive material was treated with a head gap of 2.5 μm,
The output signal level of the isolated reproduction wave was measured using a magnetic reproduction head of 2000 turns and made of a permalloy material. From the above results, the average output level of the first photosensitive material was 10
The average output of the 100th light-sensitive material was expressed as% and shown in Table 2.

[0124]

[Table 2]

If 85% or more of the output of the magnetic recording information is not secured, a read error will occur. When the cyan density change is 0.05 or more, it is a practically problematic level. From the results of Table 2, the following can be understood. From Experiments 1, 2, 8 and 9, the replenishment amount of the color developing solution was 60.
Even if hydroxylamine and the compound of the present invention are used as preservatives at 0 mL, the change in cyan density before and after running in photographic properties and the output of magnetic information are both OK levels. However, from Experiments 3 to 7, the supplement amount was 520 mL.
In the following cases, when the preservative is hydroxylamine, the change in cyan concentration before and after running and the output of magnetic information are both NG level, which is a problem. On the other hand, Experiments 11-
From 18, it is surprising that when the replenishment amount is in the range of 130 to 520 mL, the use of a specific preservative and the aperture ratio of 0.001 to 0.015 result in photographic properties and magnetic information reading performance. It turns out that Unexpectedly, the bromide ion concentration was 0.014.
Mol / l to 0.084 mol / l, and the iodide ion concentration is 0.01 mmol / l to 0.
The range of 10 mmol / l has been found to be more preferred.

As a preservative for the color developing solution, the exemplified compounds
(1), exemplified compound (8), exemplified compound (10), exemplified compound (1
2), exemplary compound (16), exemplary compound (23), exemplary compound (2
4), using the exemplified compound (28), a comparative test was conducted under the conditions of Experiments 17 and 18 to evaluate, and similar favorable results to the exemplified compound (6) and the exemplified compound (2) were obtained.

Example 2 Using the sample 101 of Example 1, continuous processing was carried out by changing to the following processing steps. The cyan density change before and after running and the output of magnetic information were evaluated. The results are shown in Table 3. (Treatment process) Treatment process Temperature Time Replenishment amount Color development See Table 3 See Table 3 See Table 3 Bleach and fix 40 ℃ 70 sec 260ml / m ² Stability (1) 40 ℃ 13 sec-Stability (2) 40 ℃ 13 Second--Stability (3) 40 ° C 13 seconds 390ml / m ² Dry 75 ° C 30 seconds-(Stability was set to 3 tank countercurrent method from (3) to (1).)

The composition of each processing liquid is as follows. (Color developer) (Unit: g) Tank solution Replenisher Diethylenetriaminepentaacetic acid 4.0 4.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.0 Sodium sulfite 4.0 6.7 Potassium carbonate 39.0 39.0 Potassium bromide See Table 3 See Table 3 Iodide Potassium See Table 3 See Table 3 Preservatives (See Table 3) 40 mM 55 mM 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 10.0 13.3 Add water 1.0 liter 1.0 Liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.35

(Bleach-fixing solution) (Unit: g) Tank solution Replenishing solution Ethylenediamine- (2-carboxyphenyl) -N, N ', N'-triacetic acid 0.18 mol 0.20 mol Ferric chloride 0.16 mol 0.18 mol Ammonium thiosulfate aqueous solution (700 g / liter) 300 ml 330 ml Ammonium iodide 1.0 ---- Ammonium sulfite 20.0 45.0 Sodium p-toluenesulfinate 20.0 25 Succinic acid 12.0 12.0 Add water 1.0 liter 1.0 liter pH (in nitric acid and ammonia water) Adjustment) 6.0 5.5

(Stabilizing Solution) The tank solution and the replenishing solution have the same formulation (unit: g) sodium p-toluenesulfinate 0.03 1,2-benzisothiazolin-3-one 0.05 polyoxyethylene-p-monononylphenyl ether (average polymerization 10) 0.2 ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazol 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 1000 ml pH (NaOH / glyco -In acid) 6.5

In the same manner as in Example 1, changes in cyan density before and after running and output of magnetic information were evaluated.

[0132]

[Table 3]

From the results of Table 3, the following can be understood. In the high temperature rapid processing system, when the replenishing amount is 600 mL, there is no problem in the cyan concentration change and the output of magnetic information with hydroxylamine as the preservative and the compound of the present invention. However, when hydroxylamine is used as a preservative, the supplement amount is 1
In the case of 30 to 520 mL, both the cyan density change and the output of magnetic information are at unacceptable levels.
On the other hand, the compound of the present invention is used as a preservative even under the condition that the replenishing amount is 130 to 520 mL in the high temperature rapid processing system,
Moreover, it was found that when the aperture ratio was 0.001 to 0.015, both the photographic property and the output of magnetic information were at an acceptable level.

[Procedure amendment]

[Submission date] July 12, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0117

[Correction method] Change

[Correction content]

The composition of the processing liquid is shown below. (Color developer) Tank solution (g) Replenisher solution (g) Diethylenetriaminepentaacetic acid 3.0 3.0 Catechol-3,5-disulfonate dinatrium salt 0.3 0.3 Sodium sulfite 3.9 5.3 Potassium carbonate 39.0 39.0 Potassium bromide See Table 2 See Table 2 Potassium iodide See Table 2 See Table 2 Preservative (See Table 2) 30 mM 41 mM 4-hydroxy-6-methyl-1,3,3a, 7- Tetrazaindene 0.05-2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulphate 4.5 6.5 Water added 1.0 liter 1.0 liter pH (Adjust with potassium hydroxide and sulfuric acid) 10.05 10.18

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location G03C 7/413 G03C 7/413 7/44 7/44 G03D 3/00 G03D 3/00 C

Claims (3)

[Claims] 1. A silver halide color photograph having at least one red-sensitive layer, green-sensitive layer and blue-sensitive layer on one side of a transparent support, and a magnetic recording layer containing magnetic particles on the other side. In the processing step of desilvering a light-sensitive material after processing with a color developing solution, washing with water and / or stabilizing processing, the color developing solution contains a compound of the following general formula (I), and the color developing solution is replenished. The amount is 13 per 1 m ^{2 of} light-sensitive material
A method for processing a silver halide color photographic light-sensitive material, characterized in that it is 0 to 520 ml and the liquid opening ratio of a developer tank of an automatic developing device is 0.001 to 0.015 cm ^-1 . General formula (I) (In the formula, L represents an optionally substituted alkylene group, and A
Represents a carboxy group, a sulfo group, a phosphono group, a hydroxy group, an amino group which may be substituted with alkyl, and R represents a hydrogen atom and an alkyl group which may be substituted. ) 2. A bromide ion of 0.014 mol / liter to 0.084 mol / liter and an iodide ion of 0.01 mmol / liter to about in the color developing solution.
2. The method for processing a silver halide color photographic light-sensitive material according to claim 1, which contains 0.10 mmol / liter. 3. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the temperature of the processing using the color developing solution is 40 ° C. to 60 ° C.