JPH08314096A - Method for housing and storing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To obtain high precision in reading a magnetic record without degrading the image of the photosensitive material in the method of housing it in a cartridge and storing it by incorporating a specified compound in a rinsing water and/or a stabilizing solution. CONSTITUTION: The silver halide photographic sensitive material having a transparent support is developed, desilvered, rinsed and/or stabilized, and after drying treatment, housed and stored in the cartridge, and the rinsing water and/or the stabilizing solution contains at least one of the compounds represented by the formal in which R<10> is an alkyl, alkenyl, aryl, or alkyl- carbonyl group; each of (p) and (q) is an integer of 0-100, but (p)+(q)>=3; (r) is an integer of 0-50; and V is an H atom or sulfonic acid or phosphoric acid, when (r) is 0, and when (r) is >=1, it is a hydroxy or sulfonate or phosphate group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of storing and storing a silver halide photographic light-sensitive material (hereinafter abbreviated as a light-sensitive material) having a transparent support in a cartridge, which has a yellow fading property even after long-term storage. It is an object of the present invention to provide an excellent storage and storage method that is excellent in magnetic field and does not deteriorate the accuracy of magnetic rereading after storage.

[0002]

2. Description of the Related Art Conventionally, in a method of processing a silver halide photographic light-sensitive material (hereinafter abbreviated as a light-sensitive material), color development, desilvering, washing with water and stabilizing treatment are generally carried out. As a system for reprinting processed photosensitive material as necessary and inputting it to a video device such as a TV / video, US Pat.
296, 887, FIG. 1-FIG. The method of storing in a plastic film cartridge described in 7 is promising. Further, as disclosed in JP-A-4-68336, JP-A-4-73737, or JP-A-5-88283, by providing a transparent material with a transparent magnetic recording layer on the entire surface, the date and time of photographing, Weather, reduction /
Shooting conditions such as magnification ratio, development, printing conditions, etc. can be input to the sensitive material, and various information can be provided even when inputting to other video equipment.

It is very inconvenient to handle a conventional long film for transmitting various information from the light-sensitive material as described above, and US Pat. Nos. 4,848,893 and 5,317,355 are used. , 5,347,334, 5,
It is considered to be a simple method to handle the treated film in a cartridge described in Japanese Patent No. 296,887 or the like. By the way, when the method of storing the processed light-sensitive material in the cartridge as described above is carried out, the light-sensitive material film surface and the back film are kept under a high humidity condition such as a humidity of 80% or more for a long time. It has been found that a problem of adhesion between the surface and the surface of the magnetic recording medium occurs and the re-reading accuracy of the magnetic recording deteriorates. Further, it was also found that the image density of cyan in the light-sensitive material was significantly reduced because it was stored for a long period under high humidity conditions. Such a phenomenon is
In the case of storing a film on a conventional film sheet, the problem does not become apparent.Therefore, it is the first problem that was discovered in the method of storing the processed photosensitive material in the cartridge, and a solution to it is needed. It was

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a method for storing and storing a photosensitive material in a cartridge,
An object of the present invention is to provide excellent magnetic recording reading accuracy without deteriorating the image on the photosensitive material.

[0005]

It has been found that the above problems can be solved by carrying out the following storing and storing method. (1) Washing and / or stabilizing in a method of developing, desilvering, washing and / or stabilizing a silver halide photographic light-sensitive material having a transparent support and then storing the light-sensitive material in a cartridge after storage. A method of storing and storing a silver halide color photographic light-sensitive material, characterized in that the solution contains at least one compound represented by the following general formula (I). General formula (I)

Embedded image In the formula, R ¹⁰ is an alkyl group, an alkenyl group, an aryl group,
It represents an alkylcarbonyl group, and p and q represent a numerical value of 0 to 100. However, p + q represents 3 or more. r is 0-5
Represents a numerical value of 0. V represents a hydrogen atom, sulfonic acid, or phosphoric acid when r is 0. Further, when r is 1 or more, it represents a hydroxy group, a sulfonate ester, or a phosphate ester. (2) The light-sensitive material has at least one red-sensitive layer, green-sensitive layer and blue-sensitive layer on one of the transparent supports,
The storage and storage method according to (1), which is a silver halide color photographic light-sensitive material having a magnetic recording layer containing magnetic particles on the other side. (3) Film p when stored in the photosensitive material cartridge
H is 3.5-6, The storage preservation method in any one of (1) and (2) characterized by the above-mentioned.

When the processed light-sensitive material is stored in a cartridge, especially under high humidity conditions of 80% or more, fading of cyan is promoted and magnetic recording is impaired. Color development, desilvering, washing with water and stabilizing treatment are generally carried out in the processing method of the light-sensitive material. Even if a conventionally known anti-fading agent or antioxidant is added to the stabilizing bath or the light-sensitive material. The above problem could not be completely solved. As a result of examining the solution to the above problem in the cartridge,
It has been found that this problem can be solved by adding the compound represented by the general formula (I) to the washing and / or stabilizing bath. Furthermore, it has been found that the above-mentioned effects can be obtained more markedly in the rapid processing in which the time for washing and stabilizing treatment is 60 seconds or less, more preferably 45 seconds or less.

The compound of formula (I) is disclosed as a surfactant in JP-A-1-154153,
In particular, it is noteworthy that the application of the method of storing the light-sensitive material in the cartridge of the present invention improved the fading of cyan and prevented the deterioration of the reading accuracy of magnetic recording over time. Further, the above effect is that the film pH of the photosensitive material is 3.5 to 6,
It has been found that the most remarkable effect is obtained preferably in the range of 4 to 6.

The details of the present invention will be described below. The details of the compound represented by formula (1) will be described. In the formula, R ¹⁰ represents an alkyl group, an alkenyl group, an aryl group, or an alkylcarbonyl group, and p and q represent a numerical value of 0-100. However,
p + q represents 3 or more. r represents a numerical value of 0 to 50. V
When r is 0, represents a hydrogen atom, sulfonic acid, or phosphoric acid. Further, when r is 1 or more, it represents a hydroxy group, a sulfonate ester, or a phosphate ester. It is particularly preferred that R ¹⁰ is an aryl group, and p + q is most preferably in the range of 5 to 30. Further, r is most preferably 0 to 10.
Preferred examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

[0009]

Embedded image

[0010]

[Chemical 4]

[0011]

Embedded image

[0012]

[Chemical 6]

[0013]

[Chemical 7]

The amount of these compounds added to washing water or a stabilizing bath is about 0.01 g to 2.0 g / liter, preferably about 0.05 g to 0.5 g / liter. These compounds are easily available as commercial products. Details of the washing and stabilizing bath of the present invention will be described later. The silver halide photographic material carrying magnetic recording preferably used in the present invention is disclosed in JP-A-6-35118 and JP-A-6-1752.
8. Pre-heat treated polyester thin layer support as described in detail in JIII Journal of Technical Disclosure 94-6023, for example:
Polyethylene aromatic dicarboxylate type polyester support, 50 μm to 300 μm, preferably 50 μm
˜200 μm, more preferably 80 to 115 μm, and particularly preferably 85 to 105 μm is heat-treated (annealed) at a temperature of 40 ° C. or higher and a glass transition temperature or lower for 1 to 1500 hours to obtain JP-B-43-2603 and JP-B-43-260.
4, UV irradiation described in Japanese Patent Publication No. 45-3828, Japanese Patent Publication No. 4
8-5043, corona discharge described in JP-A-51-131576, JP-B-35-7578, JP-B-46-434.
80, surface treatment such as glow discharge, USP 5,32
6, 689 undercoat and if necessary USP2,
The undercoat layer described in Japanese Patent No.
9-23505, JP-A-4-195726, JP-A-6-
The ferromagnetic particles described in 59357 may be applied. The magnetic layer described above may have the stripe shape described in JP-A-4-124642 and JP-A-4-124645.
Further, if necessary, an antistatic treatment described in JP-A-4-62543 is carried out, and finally a silver halide emulsion is coated to be used. The silver halide emulsion used here is disclosed in JP-A-4-166.
932, JP-A-3-41436, and JP-A-3-41437.
To use. It is preferable that the light-sensitive material thus produced is manufactured by the manufacturing control method described in Japanese Patent Publication No. 4-86817, and the manufacturing data is recorded by the method described in Japanese Patent Publication No. 6-87146. afterwards,
Or before that, according to the method described in Japanese Patent Laid-Open No. 4-125560, the film is cut into a film narrower than the conventional 135 size, and the perforation is made on one side per small format screen so as to match the small format screen smaller than the conventional one. Drill 2 holes. The film thus produced is the cartridge package of JP-A-4-157459, the cartridge shown in FIG. 9 of the embodiment of JP-A-5-210202, or the film cartridge of USP 4, 221, 479 or USP 4,834,306, US4,834,3.
66, USP 5,226, 613, USP 4,846,
It is used by putting it in a cartridge described in 418. The film cartridge or film cartridge used here is USP 4,848,693, USP 5,317,35.
A type capable of accommodating a tongue, such as No. 5, is preferable from the viewpoint of light shielding properties. In addition, cartridges with a locking mechanism such as USP5, 296, 886 and USP5, 347, 3
A cartridge in which the usage status described in 34 is displayed,
A cartridge having a double exposure preventing function is preferable. Further, as described in JP-A-6-85128, a cartridge in which the film is easily attached by simply inserting the film into the cartridge may be used.

The film cartridge thus produced can be used for the purpose of photographing, developing, and enjoying various photographs by using a camera, a developing machine, and a laboratory device described below.
For example, a simple loading type camera described in JP-A-6-8886 or 6-99908, an automatic winding type camera described in JP-A-6-57398 or 6-101135, or a shooting process described in JP-A-6-205690. A camera in which the type of film can be taken out and exchanged with JP-A-5-29313
8. A camera capable of magnetically recording information on photographing, for example, panoramic photographing, high-definition photographing, and normal photographing (magnetic recording capable of selecting print aspect ratio) described in JP-A-5-283382 or JP-A-6-101194.
And a camera having a double exposure prevention function described in
If a camera or the like having a function of displaying the use state of the film described in 150577 is used, the function of the film cartridge (patrone) can be sufficiently exhibited. Films photographed in this manner are disclosed in JP-A-6-222514 and JP-A-6-222514.
The processing is performed by the automatic processor described in 222522, or before, during, or after the processing.
The method of using magnetic recording on a film described in 123054 may be used, or the aspect ratio selection function described in JP-A-5-19364 may be used. In the case of cine type development, splicing is performed by the method described in JP-A-5-119461. Also, during or after the development process, the attach and detach processes described in JP-A-6-148805 are performed. After processing in this way, Japanese Patent Laid-Open No. 2-1848
35, JP-A-4-186335, and JP-A-6-79968.
The film information may be converted into a print through the back print and the front print on the color paper by the method described in (1). Furthermore, JP-A-5-11353 and JP-A-5-11353
It may be returned to the customer together with the index print and return cartridge described in 232594.

Cartridges used in the present invention include US Pat. Nos. 4, 848, 893 and 5, 316, US Pat.
No. 355, No. 5, 347, 334, No. 5, 296, 8
Nos. 86 and 6-85128 are preferable. Particularly, in the thrust type in which the tongue is not exposed, the effect of the present invention becomes closer to the closed chamber state in the cartridge, and the effect of the present invention becomes more remarkable.

A preferred embodiment of a camera for photographing the light-sensitive material of the present invention will be described. JP-A-6-888 for simple loading
No. 6, No. 6-99908, No. 6-57398, No. 6-101135 as automatic winding, No. 6-205690 as taking out during photographing, and No. 5-293138 as print aspect ratio selective recording function.
No. 5,283,382, JP-A No. 6-101194 as a double exposure prevention function, and JP-A No. 5-150577 as a use state display function are preferable. The preferred embodiments of the laboratory processing and equipment used in the present invention will be described. Regarding the use of magnetic recording, JP-A-6-95265 and 4-
No. 123054, US Pat. Nos. 5,034,838 and 5,041,933, JP-A-5-19364 as a print aspect ratio selectable mechanism, and JP-A-2-184835 as an information printing function. -18
No. 6335, No. 6-79968, and Japanese Patent Laid-Open Nos. 5-11353 and 5-2325 as index print functions.
No. 94, Japanese Patent Laid-Open No. 6-14 as an attach / detach function.
No. 8805, Japanese Patent Laid-Open No. 5-1194 as a splice function
No. 61, Japanese Patent Laid-Open No. 4-3 as a cartridge magazine function
The aspect of 46346 and 5-19439 is preferable.

Next, the magnetic recording layer used in the present invention will be described. The magnetic recording layer used in the present invention is one in which an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder is coated on a support. Magnetic particles used in the present invention include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co coated magnetite, Co containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy Hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite, etc. can be used. Co deposition γFe2O3
Co-coated ferromagnetic iron oxides such as The shape may be needle-like, rice grain-like, spherical, cubic, plate-like or the like.
The specific surface area of SBET is preferably 20 m ² / g or more, and more preferably 30 m ² / g or more. The saturation magnetization (σs) of the ferromagnetic material is preferably 3.0 × 10 4 to 3.0 × 10 5 A / m, particularly preferably 4.0 × 10 4 to 2.5 × 10 5 A / m. Ferromagnetic particles,
Surface treatment with silica and / or alumina or an organic material may be performed. Further, magnetic particles are disclosed in JP-A-6-1610.
The surface may be treated with a silane coupling agent or a titanium coupling agent as described in 32. In addition,
The magnetic particles described in 4-259911 and 5-81652 whose surface is coated with an inorganic or organic 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 of dispersing the above-mentioned magnetic material in the binder, a kneader, a pin type mill, an annular type mill, etc. are 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 film support used in the present invention will be described. In the present invention, any film support can be used, but in the sense that the effect of the present invention is more exerted, a polyester support (PEN) is used.
Is preferred. Details of the polyester support will be described, but details such as a photosensitive material, a treatment, a cartridge and an example described later are described in Public Technical Report No. 94-6023 (Invention Society; 1994.3.15.). There is. The polyester used in the present invention is formed by using a diol and an aromatic dicarboxylic acid as essential components.
6-, 1,5-, 1,4-, and 2,7-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid,
Examples of the diol include diethylene glycol, 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. The average molecular weight range is about 5,000 to 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 preferably 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 (APEN) in order to prevent curling habit. The heat treatment may be performed at a constant temperature within this temperature range, or the heat treatment may be performed while cooling. This heat treatment time is 0.1 hours or more and 1500 hours or less, more preferably 0.5 hours 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 may be carried out at any stage after the film formation on the support, after the surface treatment, after the coating of the back layer (antistatic agent, lubricant, etc.), and after the coating of the undercoat. Preferred is after the antistatic agent is applied. An ultraviolet absorber may be kneaded into this polyester. Further, in order to prevent light piping, it is possible to achieve the object by kneading a commercially available dye or pigment for polyester such as Diaresin manufactured by Mitsubishi Kasei and 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. Examples of the binder for the undercoat layer include vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, and a copolymer having a monomer selected from among maleic anhydride as a starting material. Examples thereof include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose and gelatin.
Compounds that swell the support include resorcin and p-chlorophenol. In the undercoat layer, as a gelatin hardening agent, 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. SiO2, TiO2, 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 preferably used. Examples of these antistatic agents include carboxylic acids and carboxylates, polymers containing sulfonates, cationic polymers, and ionic surfactant compounds. The most preferred antistatic agent is Z
nO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO,
At least one kind selected from MoO ₃ and V ₂ O ₅ has a volume resistivity of 107 Ω · cm or less, more preferably 105 Ω · cm or less, and a particle size 0.001 to 1.0 μm crystalline metal oxide. Alternatively, they are fine particles of these complex oxides (Sb, P, B, In, S, Si, C, etc.), and further are sol-like metal oxides or fine particles of these complex oxides. The content in the sensitive material is 5 to
500 mg / m ² are preferred and particularly preferably 10 to 350 mg / m ^2. The ratio of the conductive crystalline oxide or its composite oxide to the binder is preferably 1/300 to 100/1, more preferably 1/100 to 100/5.

The photosensitive 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 processing method of the present invention will be described in detail. The color developing solution (color developing solution) used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component.
As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino.
-N, N diethylaniline, 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, 4-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-
Examples include 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-toluenesulfonates or sulfates are preferred. 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 preferably 0.0002 mol to 0.2 mol, and more preferably 0.001 mol to 1 mol, per liter of the color developing solution.
It is 0.1 mol. Color developing solutions include hydroxylamine and diethylhydroxylamine, as well as JP-A-3-144.
Hydroxylamines represented by the general formula (I) of No. 446, sulfites, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acid, Organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, 1-phenyl-3
-Auxiliary developing agents such as pyrazolidone, tackifiers, various chelating agents represented by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids, 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-
Representative examples are N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

Among the above, substituted hydroxylamine is most preferable as the preservative, and among them, diethylhydroxylamine, monomethylhydroxylamine or an alkyl group substituted with a water-soluble group such as a sulfo group, a carboxy group or a hydroxyl group is used as a substituent. Those having are preferred. The most preferable example is N, N-bis (2-sulfoethyl).
Hydroxylamine, monomethylhydroxylamine,
Examples include diethylhydroxylamine.

Any antifoggant can be added to the color developing solution used in the present invention, if necessary. 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 has a preferable pH range of about 9.5 to 10.5. If the developing activity can be maintained, it is preferable that the pH of the developing tank liquid is low also in the sense of preventing the generation of ammonia gas from the waste liquid. The most preferable pH of the tank liquid is 9.9 to 1
It is about 0.4. In order to maintain the above pH, it is preferable to use various buffers. As the buffer, carbonate,
Phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, amino Butyrate,
2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. The use of carbonate is particularly preferable. The amount of the buffer added to the developer is
It is preferably 0.1 mol / liter or more, and particularly
It is particularly preferably from 0.1 mol / liter to 0.4 mol / liter. Further, a compound having biodegradability is preferable as the chelating agent. An example of this is Japanese Patent Laid-Open No. 63-
146998, JP-A-63-199295, JP-A-63-267750, JP-A-63-267751,
JP-A-2-229146, JP-A-3-186841
Examples thereof include chelating agents described in German Patent No. 3739610, European Patent No. 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 developer in the present invention is 3
The temperature is 0 to 55 ° C, preferably 35 to 55 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 for the photographic light-sensitive material.
Second to 3 minutes and 20 seconds. The replenishment amount is 30 to 800 ml, preferably 50 to 500, per 1 square meter of the light-sensitive material.
It is about 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-fix (Step 2) Bleach-bleach-fix (Step 3) Bleach-bleach-fix-fix (Step 4) Fix-bleach-fix (Step 5) Bleach-fix

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 a ferric complex salt in a liquid having a 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, α-methyl-nitrilotriacetic acid, 1,4-diaminobutanetetraacetic acid, glycol ether diaminetetraacetic acid, N- (2-carboxyphenyl) iminodiacetic acid, Ethylenediamine
N- (2-carboxyphenyl) -N, N ', N'-triacetic acid, ethylenediamine-N, N'-disuccinic acid, 1,
Examples thereof include 3-diaminopropane-N, N'-disuccinic acid, ethylenediamine-N, N'-dimalonic acid, and 1,3-diaminopropane-N, N'-dimalonic acid, but are particularly limited to these. is not.

The concentration of the ferric complex salt in the bleaching treatment solution 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.

In addition, the bath having a bleaching ability applicable to the present invention includes 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 bleach-fixing solution and the fixing agent component in the fixing solution are
Preference is given to using thiosulfates. Examples of the thiosulfate include sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate and the like. Other known fixing agents, thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylenebisthioglycolic acid,
It is also possible to use thioether compounds such as 3,6-dithia-1,8-octanediol, mesoionic compounds, and water-soluble silver halide solubilizers such as thioureas. In the present invention, it is preferable to use thiosulfates, particularly ammonium thiosulfate and sodium thiosulfate. The total amount of the fixing agent per liter is preferably 0.3 to 3 mol, more preferably 0.5 to 2.0 mol. The processing liquid having fixing ability of the present invention preferably contains the compound of the following general formula (II) in the sense that deterioration of reading accuracy of magnetic recording due to aging after processing is suppressed. General formula (II)

[0041]

Embedded image

In the formula, R represents a substituent of the benzene ring, and n represents an integer of 0-6. When n is 2 or more, R
May be the same or different. Preferred substituents include
It represents an alkyl group having 1 to 3 carbon atoms, a substituted alkyl group, an alkoxy group, a hydroxyl group, a nitro group, a carboxylic acid, a sulfonic acid, a halogen atom, a phosphonic acid, or the like. As the substituent of the alkyl group, a hydroxy group, carboxylic acid, sulfonic acid and the like are preferable. M represents a hydrogen atom, an alkali metal, an alkaline earth, ammonium, or an amine. Specific examples of preferable compounds are shown below, but the invention is not limited thereto.

[0043]

[Chemical 9]

[0044]

[Chemical 10]

[0045]

[Chemical 11]

[0046]

[Chemical 12]

The amount of these compounds added is 0.01 to 2 mol, preferably 0.05 to 1 mol, per liter of the treatment liquid. As a preservative in the bleach-fixing solution and fixing solution of the present invention, sulfite (or bisulfite or metabisulfite) is used.
It is desirable to contain 0.03 to 0.5
It is preferable that the content is mol / liter, and more preferably 0.05 to 0.3 mol / liter. The bleach-fixing solution and the fixing solution of the present invention include sulfites (for example,
Sodium sulfite, potassium sulfite, ammonium sulfite), bisulfite (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite), metabisulfite (for example, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite) ) And other sulfite ion-releasing compounds, aldehydes (benzaldexide, acetaldehyde, etc.), ketones (acetone, etc.), ascorbic acids, hydroxylamines, benzenesulfinic acids, alkylsulfinic acids, etc. are added as necessary. can do.

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. In the bleaching solution and the bleach-fixing solution used in the present invention, the preferable pH range is 4-8.
And more preferably 4.5 to 6.5. The bleaching solution, the bleach-fixing solution, and the replenishing amount to the fixing solution used in the present invention are 50 to 2000 ml per 1 m ² of the light-sensitive material.
In particular, the effect of the present invention is remarkably exhibited when the replenishing amount of the bath having fixing ability is 100 to 550 ml. Also, wash water as a post-bath or overflow solution of the stabilizing bath,
You may replenish it as needed. The processing temperature of the bleaching solution, the bleach-fixing solution, and the fixing solution is 20 to 50 ° C., preferably 30.
~ 45 ° C. The processing time is 10 seconds to 4 minutes, preferably 20 seconds to 2 minutes. The shorter the desilvering time, particularly 2 minutes or less, the remarkable effect of the present invention can be obtained.

The processing solution having a bleaching ability of the present invention is particularly preferably subjected to aeration during processing because the photographic performance is 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.

After the desilvering step, washing or stabilizing treatment is generally performed. In the washing step and / or the stabilizing step, at least one compound selected from the above-mentioned general formula (I) is contained. A diamine etc. can be mentioned.

The replenishing amount in the washing and stabilizing steps can be arbitrarily selected and is about 50 ml to 5 liters per 1 m ^{2 of} the light-sensitive material. For the purpose of remarkably obtaining the effect of the present invention, the replenishment from the prebath is performed. Low replenishment of about 1 to 30 times the carry-in amount is preferable. Here, the amount brought in from the front bath is
Since it is generally about 50 ml per 1 m ^{2 of} photosensitive material,
The actual replenishment amount is about 50 ml to 1500 ml. It is more preferably about 1 to 10 times. Most preferably, it is 1 to 5 times.

The amount of rinsing water in the rinsing process or the stable liquid amount in the stabilizing process depends on the characteristics of the light-sensitive material (for example, depending on the material used such as coupler), application, liquid temperature, number of tanks (number of stages), countercurrent,
It can be set within various ranges depending on various conditions such as a replenishment method such as normal flow. Normally, the number of stages in the multi-stage countercurrent system is 2
6 is preferable, and 2 to 4 is particularly preferable.

It is also possible to perform the treatment with the stabilizing solution directly after the above washing step or without going through the washing step. A compound having an image stabilizing function is added to the stabilizer, and examples thereof include an aldehyde compound typified by formalin, a buffering agent for adjusting the membrane pH suitable for dye stabilization, and an ammonium compound. Further, various germicides and fungicides can be used in order to prevent the growth of bacteria in the liquid and to impart antifungal properties to the processed light-sensitive material.

Further, a surface active agent, an optical brightening agent and a hardener may be added. In the processing of the light-sensitive material of the present invention, when the stabilization is directly carried out without undergoing a washing step, known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 are used. , All can be used.
In addition, it is also a preferred embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound. It is also a preferred embodiment to add a fungicide / antifungal agent represented by isothiazolones and benzothiazoles.

The automatic processor used in 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.

Of the final bath in the processing of the light-sensitive material of the present invention
Although the pH can be set to any value, it is preferably 3.5 to 6, and more preferably 4 to 6 in order to exert the effect of the present invention. The above pH is preferably set so as to reflect the film pH of the processed light-sensitive material, and for that purpose, it is most preferable to contain the organic acid of the following general formula (III) in the final bath and set to the above pH. It is a mode.

[0058]

[Chemical 13]

In the formula, when n = 1, A represents an alkylene group or a phenyl group, when n = 2, A represents a single bond or a divalent linking group, and when n = 3, A is a trivalent group. Represents M
Represents a hydrogen atom, an alkali metal or an ammonium salt.

Next, the details of the compound represented by formula (III) will be described. When n = 1, the alkylene group for A preferably has 1 to 10 carbon atoms, and more preferably 2 to 2 carbon atoms.
It is 5. The alkylene group and the phenyl group may have a substituent, and examples of the substituent include a hydroxy group, a halogen atom, an amino group, a sulfo group and an acylamino group, and a hydroxy group is particularly preferable.

When n = 2, A is specifically a substituted or unsubstituted alkylene group, alkenyl group, phenyl group, cyclohexyl group, heterocyclic group (for example, N as a hetero atom,
A 5- to 8-membered ring compound containing at least one of O and S is preferable, and a 5- to 6-membered ring compound containing N is particularly preferable. For example, pyrrole, pyridine, pyrrolidine, piperidine, etc. can be mentioned. ) Etc. n = 3
In this case, A represents a trivalent linking group, specifically, a phenyl group, a cyclohexyl group, a heterocyclic group (for example, a 5- to 8-membered ring containing at least one hetero atom, N, O, S, etc.). Is preferable, and a 5- or 6-membered ring compound containing N is particularly preferable, and examples thereof include pyrrole, pyridine, pyrrolidine, and piperidine). The carbon number of the group represented by A in the case of n = 2 and n = 3 is preferably 10 or less. The n M's may be the same or different. Specific examples are shown below, but the present invention is not limited to these.

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[0063]

[Chemical 15]

[0064]

Embedded image

[0065]

[Chemical 17]

Among the above compounds, in the present invention, n = 2
Dicarboxylic acids of are preferred. Specifically, III-20, III-
21, III-22, III-23, III-24, III-26, III-
27, III-28, and III-29 can be mentioned. The amount of these organic acids added is 0.0 per 1 liter of the final bath.
05 to 0.5 mol, preferably 0.005 to 0.1 mol. If the pH of the membrane can be maintained, it is preferable that the added amount be small. If necessary, two or more kinds may be used in combination. The compound of the general formula (III) is known, and a commercially available product can be easily purchased.

The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but generally 20 to 45 ° C.
At 20 seconds to 5 minutes, preferably at 25 to 40 ° C. for 30 seconds to 3 minutes. 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 a stabilizing process, JP-A-57-8543 and 58-58 are used.
All known methods described in -14834 and 60-220345 can be used.

In the stabilizing solution, compounds for stabilizing the dye image, for example, benzaldehydes such as formalin and m-hydroxybenzaldehyde, formaldehyde bisulfite adduct, hexamethylenetetramine and its derivative, hexahydrotriazine and its derivative, Examples include N-methylol compounds such as dimethylol urea and N-methylol pyrazole, organic acids and pH buffering agents. 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. It is preferable to add various chelating agents to 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 and diethylenetriamine-N, N,
Examples thereof include organic phosphonic acids such as N ', N'-tetramethylenephosphonic acid, and hydrolyzates of maleic anhydride polymers described in European Patent 345,172A1.

The total treatment time of the washing and / or stabilizing step of the present invention can be set arbitrarily, but is preferably 10 seconds to 60 seconds, most preferably 15 seconds to 45 seconds. In such a short time of washing with water and / or the stabilizing step, the remarkable effect of the present invention can be obtained. The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when each processing solution described above is concentrated by evaporation, in order to correct the concentration by evaporation, it is necessary to replenish an appropriate amount of water or a correction solution or a processing replenishing solution. preferable. The specific method for replenishing water is not particularly limited, but among them, JP-A-1-254959 and 1-25.
A monitor water tank different from the bleaching tank described in Japanese Patent No. 4960 is installed, the evaporation amount of water in the monitor water tank is obtained, and the evaporation amount of water in the bleaching tank is calculated from the evaporation amount of this water. A method of proportionally replenishing a bleaching tank with water
No. 248155, No. 3-249644, No. 3-249.
The evaporation correction method using a liquid level sensor or an overflow sensor described in Japanese Patent Nos. 645 and 3-249646 is preferable. The water to correct the evaporation of each treatment liquid is
Although tap water may be used, deionized water or sterilized water which is preferably used in the above washing step is preferably used.

In the present invention, the light-sensitive material which has been washed and / or stabilized is dried in a drying step, and after reading necessary information such as print, the light-sensitive material is rolled up and stored in the above-mentioned cartridge. Drying methods include, but any method can be selected, it is preferable to use a ceramic hot air heater, every minute as the supply air volume 4m ³ to 20 m ³
It is preferred, 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 depending on the water content of the light-sensitive material to be processed, and is 45 to 80 ° C. for a 24 mm or 35 mm wide film and 55 for a Brownie film.
The optimum temperature is ~ 65 ° C, and 60 ~ 100 ° C for printing materials. The drying time is preferably 10 seconds to 2 minutes, especially 20 seconds to
50 seconds is more preferable.

Next, the light-sensitive material of the present invention will be described.
The present invention can be applied to any light-sensitive material having the above-mentioned transmission support, but is preferably applied to a color negative film and a color reversal film. The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied in the present invention, and the processing method and processing additive applied for processing the light-sensitive material are , The following patent publications, especially European patents EP 0,3
Those described in No. 55,660A2 (Japanese Patent Application No. 1-107011) are preferably used.

[0073]

[Table 1]

[0074]

[Table 2]

[0075]

[Table 3]

[0076]

[Table 4]

[0077]

[Table 5]

The silver halide emulsion used in the present invention is
Silver iodobromide, silver iodochloride, silver iodochlorobromide, silver chlorobromide, silver bromide,
Emulsions of various halogen compositions such as silver chloride can be used. In particular, the present invention preferably has a layer containing a silver iodobromide emulsion and has an iodine content of 1.0 to 10
It is preferable to use an emulsion containing about mol%. As the coating amount of silver is not particularly limited, 2g~8g / m ² approximately, and more preferably may contain about 3 to 6 g / m ^2. If the amount is less than the main coating silver amount, the image quality is deteriorated, and if it is more than the main coating silver amount, the magnetic reading accuracy is deteriorated, which is not preferable. The light-sensitive material used in the present invention may contain various couplers, but details are shown in Table 2.
As described in. Furthermore, as a cyan coupler,
In addition to the diphenylimidazole type cyan couplers described in JP-A-2-33144, 3-hydroxypyridine type cyan couplers (among others, couplers (42) listed as specific examples) described in EP 0,333,185A2 Equivalent couplers having a chlorine-releasing group to make them two equivalents, couplers (6) and (9) are particularly preferable), and cyclic active methylene cyan couplers described in JP-A-64-32260 (specifically, The use of coupler examples 3,8,34 listed as examples) is particularly preferred).

In the light-sensitive material of the present invention, a hydrophilic colloid layer can be decolorized by the treatment described in European Patent EP 0,337,490A2, pages 27 to 76 for the purpose of improving the sharpness of an image. Such dyes (among others, oxonol dyes) can be added so that the optical reflection density at 680 nm of the photosensitive material becomes 0.70 or more. In the color photographic light-sensitive material according to the present invention, it is preferable to use a color image storability-improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler.

That is, a compound (F) and // which chemically bonds with the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound.
Alternatively, the compound (G) which chemically bonds with an oxidized product of an aromatic amine color developing agent remaining after the color developing treatment to form a chemically inactive and substantially colorless compound is used simultaneously or alone. However, it is preferable to prevent the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction of the residual color developing agent in the film or the oxidant thereof with the coupler during storage after processing. Further, to the light-sensitive material according to the present invention, a fungicide such as that described in JP-A-63-271247 is added in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. Preferably. In the present invention, it is preferable that the dry film thickness of the silver halide color photographic light-sensitive material excluding the support is 25 μm or less in order to reduce the carryover amount and increase the silver recovery rate. Particularly, it is preferably about 13 to 23 μm, more preferably about 9 to 19 μm. These film thicknesses can be reduced by reducing the gelatin amount, silver amount, oil amount, coupler amount, etc., but it is most preferable to reduce the gelatin amount. Here, the film thickness is 25 ° C. for the sample,
After being left at 60 RH% for 2 weeks, it can be measured by a conventional method. In the silver halide color photographic light-sensitive material used in the present invention, the photographic layer has a film swelling degree of from 1.5 to 4.0.
Is preferable from the viewpoint of improving stain and improving image storability. Particularly, in the range of 1.5 to 3.0, a further effect can be obtained. The swelling degree of the present invention means a value obtained by dividing the film thickness of the photographic layer after dipping the color light-sensitive material in distilled water at 33 ° C. for 2 minutes by the film thickness of the dried photographic layer.

The term "photographic layer" as used herein refers to a laminated hydrophilic colloid group layer containing at least one photosensitive silver halide emulsion layer and having a water-permeable relationship with this layer. The back layer provided on the opposite side of the support from the photographic photosensitive layer is not included. The photographic layer is usually formed of a plurality of layers involved in photographic image formation, and in addition to the silver halide emulsion layer, an intermediate layer, a filter layer, an antihalation layer, a protective layer and the like are included.

Any method may be used to adjust the degree of swelling. For example, the amount and type of gelatin used in the photographic film, the amount and type of hardener, or the drying conditions after coating the photographic layer. And can be adjusted by changing the aging condition. It is advantageous to use gelatin for the photographic layer, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. Use of various synthetic hydrophilic polymer substances such as single or copolymers of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole. You can As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used. Examples of the gelatin derivative include gelatin such as acid halide,
Those obtained by reacting various compounds such as acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides and epoxy compounds are used.

As the gelatin-graft polymer, a homopolymer or a copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile and styrene are grafted onto gelatin. What was made to use can be used. In particular, a graft polymer with a polymer having a certain degree of compatibility with gelatin, for example, a polymer such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, or hydroxyacyl methacrylate is preferable.
Examples of these are U.S. Pat. Nos. 2,763,625 and 2,8.
31, 767, 2,956, 884 and the like. Typical synthetic hydrophilic polymer substances are, for example, West German patent application (OLS) 2,312,708, US Pat.
No. 620,751, No. 3,879,205, Japanese Patent Publication No. 4
No. 3-7561.

Examples of the hardening agent include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glital aldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane. Derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinyl Sulfonyl) propionamide] etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid etc.), isoxazoles, dialdehyde starch, 2-black And 6-hydroxy-triazinyl gelatin can be used alone or in combination. Particularly preferred hardeners are aldehydes,
They are active vinyl compounds and active halogen compounds.

The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable. Further, it is preferable to use the band stop filter described in U.S. Pat. No. 4,880,726 upon exposure. As a result, light color mixture is removed, and color reproducibility is significantly improved.

[0086]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Example 1 (1) Material of Support, etc. Each support used in this example was prepared by the following method. PEN: 100 parts by weight of commercially available poly (ethylene-2,6-naphthalate) polymer and Tinuvi as an ultraviolet absorber
n 2 parts by weight of P.326 (manufactured by Geigy) was dried by a conventional method, melted at 300 ° C., and then extruded from a T-die 14
The film was longitudinally stretched 3.3 times at 0 ° C, and then 3.3 times at 130 ° C.
Double stretching was performed, and heat setting was further performed at 250 ° C. for 6 seconds. The glass transition temperature was 120 ° C.・ TAC: Methylene chloride / methanol = 82/8 wt by a normal solution casting method of triacetyl cellulose
Ratio, TAC concentration 13%, plasticizer TPP / BDP = 2/1
(Here TPP; triphenyl phosphate, BD
15% by weight of P; biphenyl diphenyl phosphate)
The band method was used. As described above, PEN (APEN) heat-treated on the support
101 using the sample, and PEN without heat treatment
Was designated as Sample 103. Also, 1 sample using TAC
02.

(2) Coating of Undercoat Layer Each of the above-mentioned supports is subjected to corona discharge treatment on both sides thereof, and then the undercoat liquid having the following composition is applied to provide the undercoat layer on the high temperature surface side during stretching. It was For the corona discharge treatment, a solid state corona treatment machine 6KVA model manufactured by Pillar Co. is used, and a 30 cm width support is treated at 20 m / min. At this time, the object to be treated was treated at 0.375 KV · A · min / m ^{2 based on} the current / voltage readings. The discharge frequency during processing is 9.6KHz,
The gap clearance between the electrode and the dielectric roll is 1.6.
It was mm.

Gelatin 3 g Distilled water 250 ml Sodium-α-sulfodi-2-ethylhexyl succinate 0.05 g Formaldehyde 0.02 g Further, the support TAC was provided with an undercoat layer having the following composition. Gelatin 0.2g Salicylic acid 0.1g Methanol 15ml Acetone 85ml Formaldehyde 0.01g

(3) Coating of Back Layer The following back layers 1 to 3 were coated on one side of the undercoated support prepared in (2). A) Back first layer Co-containing acicular γ-iron oxide fine powder (included as gelatin dispersion, average particle size 0.08 μm) 0.2 g / m ² gelatin 3 g / m ² described in the following chemical formula 18. 0.1 g / m ² Compound described in Chemical formula 19 below 0.02 g / m ² Poly (ethyl acrylate) (average diameter 0.08 μm) 1 g / m ²

[0090]

Embedded image

[0091]

[Chemical 19]

(B) Second layer of back gelatin 0.05 g / m ² conductive material [S _n O ₂ / Sb ₂ O ₃ (9: 1), particle size 0.15 μm] 0.16 mg / m ² dodecylbenzenesulfone Acid soda 0.05g / m ²

C) Third layer of back gelatin 0.5 g / m ² polymethylmethacrylate (average particle size 1.5 μm) 0.02 g / m ² cetyl stearate (sodium dodecylbenzenesulfonate dispersion) 0.01 g / m ² Sodium di (2-ethylhexyl) sulfosuccinate 0.01 g / m ² Compound described in the following chemical formula 21 0.01 g / m ²

[0094]

Embedded image

The coercive force of the obtained back layer is 960 Oe.
Met. (4) Heat Treatment of Support After the undercoat layer and the back layer were applied and dried and wound by the above method, heat treatment was performed at 110 ° C. for 48 hours. The photosensitive layer shown in (5) was coated on the two types of supports prepared by the above method to prepare a photosensitive material. The PEN support was used as sample 101, and the TAC support was used as sample 102. A sample 103 was the PEN support that had not been subjected to the heat treatment (4).

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

Eleventh 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

12th 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 0.70

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.

[0112]

[Table 6]

In Table 6, (1) Emulsions J to L were prepared in accordance with the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to I were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains by using a high voltage electron microscope. (5) Emulsion L is a double structure 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 an aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) 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 contents were 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 is a microprecipitation described in Example 1 of European Patent Application Publication (EP) 549,489A.
It was dispersed by the dispersion method. The average particle size was 0.06 μm.

[0116]

[Chemical 21]

[0117]

[Chemical formula 22]

[0118]

[Chemical formula 23]

[0119]

[Chemical formula 24]

[0120]

[Chemical 25]

[0121]

[Chemical formula 26]

[0122]

[Chemical 27]

[0123]

[Chemical 28]

[0124]

[Chemical 29]

[0125]

Embedded image

[0126]

[Chemical 31]

[0127]

Embedded image

[0128]

[Chemical 33]

[0129]

Embedded image

[0130]

Embedded image

[0131]

Embedded image

The photosensitive material prepared as described above is used for 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 FM signal was recorded on this sample at a feed rate of 100 mm / s during the above-mentioned perforation of the photosensitive material by using a head gap of 5 μm from the coated surface side of the magnetic recording layer and a turnable number of 2000. FM
After recording the signal, the emulsion surface was exposed uniformly for 1000 cms and each processing was performed by the methods described below, and then the emulsion was stored again in the original plastic film cartridge. When stored, 40 ° C / 85% RH, 4
Stored for a week. Next, pull out the stored film,
The signal was read at the same speed as when the signal was recorded by the above head, and it was examined whether the signal was output correctly. Table 7 shows the ratio of the number of error bits to the number of input bits.
It was shown to. If this error rate is 0.01% or less, there is no practical problem, but if it is 0.1% or more, it is NG. At the same time, the adhesive state of the film after aging was evaluated by the following method. (Evaluation of Adhesion Level) After adhesion of the film pulled out from the cartridge, it is visually evaluated. ⊚: There is nothing after adhesion. ◯: Adhesion marks are slightly visible, but when printed, they do not appear on the print. Δ: Adhesion marks are visually visible, and when printed, they are slightly visible on the print. X: A level where the adhesion mark can be visually confirmed and, when printed, can be sufficiently confirmed on the print. With respect to the processed light-sensitive material, the fading rate of cyan was evaluated by the following method.

(Measurement of Cyan Fading Rate) The point of yellow density 2.0 of the light-sensitive material immediately after the processing was recorded, and after the above storage with time, the reduction rate of the same density was measured by a Macbeth densitometer.

Next, the details of the processing executed will be described. The samples described above were subjected to gray exposure through a wedge wedge at a color temperature of 4800K at 20 cms, and then processed by the cine type automatic processor with the following processing steps and processing solutions. still,
As shown in Table 7, the stabilizing solution was prepared by changing the compound of the general formula (I) and changing the pH, and sequentially treated each of them.

(Processing step) Processing step Temperature Time Color development 40 ° C 90 seconds Bleach fixing 40 ° C 90 seconds Stability (1) 40 ° C 10 seconds Stability (2) 40 ° C 10 seconds Stability (3) 40 ° C 10 seconds Dry 75 ℃ 60 seconds (Stabilization was done by 3 tank counter-current method from (3) to (1).)

The composition of each processing liquid is as follows. (Color developer) (Unit: g) Tank solution Diethylenetriaminepentaacetic acid 4.0 4,5-Dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 Sodium sulfite 4.0 Potassium carbonate 38.0 Potassium bromide 1.4 Potassium iodide 1.0m N, N -(Disulfonate ethyl) hydroxylamine 5.0 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 13.0 Water was added to 1.0 liter pH (with potassium hydroxide and sulfuric acid. Adjustment) 10.10

(Bleaching Fixing Solution) (Unit: g) Tank Solution Ethylenediamine- (2-carboxy 0.15 mol 4-methylphenyl) -N, N ′, N′-triacetic acid Ethylenediaminetetraacetic acid 0.02 mol Ferric chloride 0.15 mol Thio Aqueous ammonium sulfate solution (700 g / liter) (ATS) 1.5 mol Ammonium iodide 0.010 mol Ammonium sulfite 25.0 Succinic acid 20.0 Water is added to 1.0 liter pH (adjusted with nitric acid and aqueous ammonia) 6.0

(Stabilizer) (Unit: g) Sodium chlorinated isocyanurate 0.02 Deionized water (conductivity 5 μs / cm or less) Compound of general formula (I) See Table 7 Compound III-21 0.02 mol 1000 ml pH No. See Table 2. The pH of the stabilizing solution was changed by the amount of sodium hydroxide added, and each of them was treated. Table 7 shows the results of the ease of adhesion, the magnetic reading accuracy, and the cyan fading.

[0139]

[Table 7]

As is clear from the results of Table 7, in the present invention, the fading rate of the cyan dye in the treated film is improved, and the magnetic reading accuracy and adhesiveness after aging are not deteriorated and are excellent. The results were shown. Especially the membrane pH is 3.5
In the state of ~ 6, the most excellent result was shown.

Example 2 No. 1 in Table 7 of Example 1 Table 8 shows the results obtained by treating Samples 102 and 103 of Example 1 in the same manner with the stabilizers 1 to 4 and 13 to 18 and similarly treating the error rate and the adhesiveness.

[0142]

[Table 8]

From the results shown in Table 8, it can be seen that the sample 101 using the heat-treated PEN support shows the most excellent result. Example 3 No. 1 of Example 1. In the stabilizing solution of 19, instead of III-21, equimolar amounts of III-22, III-23, III-26, III-34 and II
Treatment with each of them using I-35 gave equally good results.

Example 4 Using the sample 101 of Example 1, the following treatment was carried out. (Treatment process) Treatment process Temperature Time Replenishment amount Color development 45 ° C 90 seconds 260ml / m ² Bleach-fixing 45 ° C 90 seconds 260ml / m ² Stability (1) 45 ° C 12 seconds --Stability (2) 45 ° C 12 seconds --Stable (3) 45 ℃ 12 seconds 780ml / m ² Dry 75 ℃ 40 seconds-(Stability is 3 tank counter current system 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 2.4 --- Potassium iodide 0.0013 --- Disodium-N, N-bis (2-sulfonateethyl) hydroxylamine 15.0 20.0 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 10.0 15.3 Water In addition 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.35

(Bleaching Fixing Solution) (Unit: g) Tank Solution Replenishing Solution Ethylenediamine- (2-carboxyphenyl) -N, N ', N'-triacetic acid 0.20 mol 0.25 mol Ferric chloride 0.18 mol 0.23 mol Ammonium thiosulfate aqueous solution (700 g / l) 300 ml 350 ml Ammonium iodide 1.0 ---- Ammonium sulfite 20.0 45.0 General formula (II) compound 0.15 mol 0.20 mol Water added 1.0 liter 1.0 liter pH (adjusted with nitric acid and ammonia water) 5.4 5.0

(Stabilizing Solution) The tank solution and the replenishing solution have the same formulation (unit: g) ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazol 1.3 1,4-bis (1,2,4-triazo-) Ru-1-ylmethyl) piperazine 0.75 compound of general formula (I) 0.20 1000 ml pH (with NaOH / glycolic acid) 5.5

After imagewise exposure of the above samples, as shown in Table 9, the composition of the bleach-fixing solution and the composition of the stabilizing solution were changed, and each of them was subjected to a running treatment of 5 m ² per day for 2 days. went. The last one photosensitive material was stored in the same manner as in Example 1 to evaluate the adhesiveness and the fading rate of the magenta dye. The results are shown in Table 4.

[0149]

[Table 9]

From Table 9, in the present invention, the adhesiveness is improved and the fading of the cyan dye is improved. Above all, the case where the compound of the general formula (II) was contained in the bleach-fixing solution showed the most preferable results.

Example. 4 Using the sample 101 of Example 1, continuous processing was performed by changing to the following processing steps. (Processing step) Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 05 seconds 38.0 ℃ 260 ml / m ² 17 liters Bleach 40 seconds 38.0 ℃ 100 ml / m ² 5 liter Fixing (1) 40 seconds 38.0 ℃ − 5 liter Fixing (2) 40 seconds 38.0 ° C 300 ml / m ² 5 liters Stable (1) 30 seconds 38.0 ° C-3.5 liters Stable (2) 20 seconds 38.0 ° C-3 liters Stable (3) 20 seconds 38.0 ° C 900 ml / m ² 3 liter Dry 90 seconds 60 ° C. Stabilizer and fixer are countercurrent system from (3) to (1), and the overflow of stabilizer is all introduced into the fixing bath. The amount of the color developing solution brought into the bleaching process, the amount of the bleaching solution brought into the fixing process, and the amount of the fixing solution brought into the stabilizing process were 65 ml, 50 ml, and 50 ml per 1 m ^{2 of the} light-sensitive material of 35 mm width, respectively. Fifty
It was 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-sulfonate ethyl) hydroxylamine 6.0 10.0 Potassium bromide 1.40-Potassium iodide 1.3 mg-4-hydroxy-6-methyl- 1,3,3a, 7-Tetrazaindene 0.05-2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 7.5 Add water 1 0.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.10 10.20

(Bleaching Solution) Tank Solution (g) Replenishing Solution (g) 1,3-Diaminopropanetetraacetic Acid Iron (III) Ammonium Salt 100.0 150.0 Ammonium Bromide 40.0 65.0 Ammonium Nitrate 14.0 21.0 Succinic acid 20.0 31.0 Maleic acid 10.0 22.0 Add water 1000 ml 1000 ml pH (adjust with ammonia water and nitric acid) 5.1 4.5

(Fixing (1) Tank Liquid) A 5:95 (volume ratio) mixture of the above bleaching tank liquid and the following fixing tank liquid. (P
H6.8)

(Fixing solution (2)) Tank solution (g) Replenishing solution (g) Ammonium thiosulfate aqueous solution (750 g / liter) 180.0 ml 360.0 ml Ammonium methanethiosulfonate 5.0 15.0 Ammonium methanesulfinate 10 0.0 30.0 Ethylenediaminetetraacetic acid 13.0 39.0 Water was added to 1000 ml 1000 ml pH (adjusted with ammonia water and acetic acid) 7.4 7.5

(Rinsing water) Tank liquid and replenisher common 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.

(Stabilizing Solution) Tank Solution and Replenishing Solution Common 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 g 1,2,4-triazole 1.3 g Ethylenediaminetetraacetic acid disodium salt Salt 0.05 g Sodium p-toluenesulfinate 0.03 g III-21 5.0 g Compound of general formula (I) 0.02 g Water added 1 liter pH (adjusted with ammonia water and nitric acid) See Table 10.

[0158] In the above treatment step, the formulation of stable liquid and pH
Was changed as shown in Table 10, and for each of them,
The running treatment was carried out for 2 m ² per day for 10 days. The same evaluation as in Example 1 was performed on the last one photosensitive material. The results are shown in Table 10.

[0159]

[Table 10]

From Table 10, in the present invention, excellent performance was exhibited with little cyan fading and no decrease in adhesiveness. Especially, the best results were shown in the pH range of 4 to 6.

Claims (3)

[Claims] 1. A method of storing a silver halide photographic light-sensitive material having a transparent support after development, desilvering, washing with water and / or stabilization and drying, and then storing the light-sensitive material in a cartridge for washing and / or stabilization. A method of storing and storing a silver halide color photographic light-sensitive material, characterized in that the solution contains at least one compound represented by the following general formula (I). General formula (I) In the formula, R ¹⁰ is an alkyl group, an alkenyl group, an aryl group,
It represents an alkylcarbonyl group, and p and q represent a numerical value of 0 to 100. However, p + q represents 3 or more. r is 0-5
Represents a numerical value of 0. V represents a hydrogen atom, sulfonic acid, or phosphoric acid when r is 0. Further, when r is 1 or more, it represents a hydroxy group, a sulfonate ester, or a phosphate ester. 2. A magnetic recording layer, wherein the light-sensitive material has at least one red-sensitive layer, green-sensitive layer and blue-sensitive layer on one side of a transparent support, and magnetic particles on the other side. 2. The storage and storage method according to claim 1, which is a silver halide color photographic light-sensitive material having the same. 3. The film pH of the photosensitive material stored in the cartridge is 3.5 to 6.
And the storage and storage method according to claim 2.