JPH07333764A - Silver halide photographic material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic material which maintains its transparency, has good flaw resistance and has a magnetic recording layer. CONSTITUTION:This silver halide photographic material has one or more silver halide emulsion layers on at least one side of a carrier and has at least one antistatic layer and at least one transparent magnetic recording layer on the other side; at least one of the layers located on the side where the transparent magnetic recording layer is provided contains ceramic fine particles by 0.01-15wt.% of binder, the average diameter of the ceramic fine particles being 0.01-1.0mum.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material having an optically transparent magnetic recording layer.

[0002]

2. Description of the Related Art For silver halide photographic light-sensitive materials, for example,
Type of photographic light-sensitive material, serial number, manufacturer name, emulsion No.
Various information related to photographic light-sensitive materials, such as shooting date / time, aperture, exposure time, lighting conditions, filter used, weather, size of shooting frame, model of camera, use of anamorphic lens, etc. Various information when shooting with the camera,
For example, various information necessary for printing such as the number of prints, filter selection, customer color preference, trimming frame size, etc., for example, number of prints, filter selection, customer color preference, trimming frame size. It has been desired to input various kinds of information obtained at the time of printing such as the above and other customer information in terms of management, improvement of print quality, and efficiency of printing work.

Therefore, since the magnetic recording method is easy to record / reproduce, it has been studied to use the magnetic recording method for inputting the above various information to the photographic light-sensitive material.
Various technologies have been proposed. For example, on the back surface of a photographic light-sensitive material, it is necessary to provide a transparent magnetic recording layer having the required transparency by selecting the amount and size of magnetizable particles. US Pat. Nos. 3,782,947 and 4,279,945 Id., 4,302,
No. 523, etc.

By providing these magnetic recording layers, it becomes possible to record the above-mentioned various kinds of information in the photographic light-sensitive material, which has been difficult in the past, and it is possible to record voices and image signals. is doing.

[0005]

However, since a silver halide photographic light-sensitive material having a transparent magnetic recording layer is rubbed by a magnetic head, it is required to have a strong scratch resistance, which has not been found in conventional silver halide photographic light-sensitive materials. It Further, since it may be printed or projected through the transparent magnetic recording layer that is rubbed by a magnetic head, it is required to have higher scratch resistance than that required for a conventional magnetic recording medium. However,
The conventional transparent magnetic layer has a problem that the scratch resistance is weak.

An object of the present invention is to provide a photographic light-sensitive material having a magnetic recording layer which is excellent in scratch resistance while maintaining the transparency required for the photographic light-sensitive material.

[0007]

The above object of the present invention can be achieved by the following constitutions.

1) At least one silver halide emulsion layer is provided on one side of a support, and at least one antistatic layer (hereinafter also referred to as ANS layer) and at least one transparent magnetic layer are provided on the other side. In a silver halide photographic light-sensitive material having a recording layer (hereinafter also referred to as MG layer), at least one layer on the side having the transparent magnetic recording layer has an average grain size of 0.01 to 1.0.
0.01 to 15w of μm ceramic particles to binder
A silver halide photographic light-sensitive material characterized by containing t.%.

2) Ceramic fine particles are ZrO ₂ , Al ₂ O ₃ and TiO
Of the _two , one of the main components is Al ₂ O ₃ , TiO ₂ ,
1. The silver halide photographic light-sensitive material described in 1 above, which contains one or several kinds selected from SiO ₂ , Fe ₂ O ₃ and K ₂ O.

3) A silver halide having at least one silver halide emulsion layer on at least one side on a support, and at least one antistatic layer and at least one transparent magnetic recording layer on the other side. In the photographic light-sensitive material, at least one layer on the side having the transparent magnetic recording layer has an average particle size of 0.01 to
0.01 to 15w of 2.0μm glass particles to binder
A silver halide photographic light-sensitive material characterized by containing t.%.

4) The fine glass particles contain SiO ₂ as a main component,
4. The silver halide photographic light-sensitive material according to the above 3, which contains one or several kinds selected from CaO, Al ₂ O ₃ , Na ₂ O, B ₂ O ₃ , MgO and K ₂ O. material.

5) The silver halide photographic light-sensitive material described in any one of 1 to 4 above, wherein the shape of the fine ceramic particles and / or fine glass particles is an irregular shape such as a needle shape or a polygonal cross section.

6) A silver halide photograph according to claim 1, wherein the layer containing the ceramic fine particles and / or the glass fine particles is a protective layer on the side having the transparent magnetic recording layer. Photosensitive material.

7) The silver halide photographic light-sensitive material described in any one of 1 to 6 above, wherein the layer containing ceramic fine particles and / or glass fine particles is a transparent magnetic layer.

8) A silver halide photograph as described in any one of 1 to 6 above, wherein the layer containing fine ceramic particles and / or fine glass particles is an antistatic layer on the side having a transparent magnetic recording layer. Photosensitive material.

The present invention will be described in detail below.

The transparent magnetic recording layer in the present invention specifically means a magnetic recording layer having a maximum optical density of 1.5 or less. The optical density in the present invention is an optical densitometer PDA-65 (manufactured by Konica Corp.)
It means the optical densities Db, Dg, and Dr measured through G and R. The maximum value among them is Dmax. The maximum optical density Dmax of the magnetic recording layer of the present invention may be 1.5 or less, but it is preferably small in consideration of the influence on photographic images, preferably 0.8 or less, and particularly preferably 0.3 or less.

In the present invention, various supports can be used. Examples of supports that can be used include polyester films such as polyethylene terephthalate and polyethylene naphthalate, cellulose triacetate films, cellulose diacetate films, polycarbonate films, polystyrene films, and polyolefin films.

When the support is a polyester film, the polyester constituting the polyester film is not particularly limited, but is a polyester having a dicarboxylic acid component and a diol component as main components and having film-forming properties. Is preferred.

The main constituent dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2-6 naphthalene dicarboxylic acid, 2-7 naphthalene dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl ether diphenyl acid, diphenyl ethane dicarboxylic acid. , Cyclohexanedicarboxylic acid, diphenyldicarboxylic acid, diphenylthioetherdicarboxylic acid, diphenylketone dicarboxylic acid, phenylindanedicarboxylic acid and the like. Further, as the diol component, ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-
(Hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bisphenol full orange hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol, etc. . Among the polyesters containing these as the main constituents, terephthalic acid and / or 2-6 naphthalenedicarboxylic acid as the dicarboxylic acid component and ethylene glycol and diol as the diol component from the viewpoints of transparency, mechanical strength, dimensional stability, etc. And / or a polyester containing 1-4 cyclohexanedimethanol as a main component is preferred. Among them, polyethylene terephthalate, polyethylene 2-6 naphthalate, terephthalic acid and 2
-6 A polyester composed of naphthalene dicarboxylic acid and ethylene glycol, and a polyester having a mixture of two or more of these polyesters as main constituents are preferable. 70% ethylene terephthalate units and / or 2-6 ethylene naphthalate units for polyester
When it is contained in an amount of not less than wt%, a film having excellent transparency, mechanical strength, dimensional stability and the like can be obtained.

The polyester constituting the polyester film may be copolymerized with another copolymerization component, or may be mixed with another polyester, as long as the effect of the present invention is not impaired. Examples of these include the above-mentioned dicarboxylic acid component, diol component, and polyester.

The polyester constituting the polyester film is obtained by copolymerizing at least one compound having at least one hydrophilic group to obtain appropriate water absorption,
At the time of the heat treatment described below, it is easy to allow the film to contain an appropriate amount of water, which is preferable.

The hydrophilic group of the compound having at least one hydrophilic group is sulfonic acid, sulfinic acid, phosphonic acid, carboxylic acid or a salt thereof, polyoxyalkylene group, sulfamoyl group, carbamoyl group, acylamino group, sulfonamide. Group, disulfonamide group, ureido group, urethane group, alkylsulfonyl group, alkoxysulfonyl group, and the like, among them, sulfonic acid, sulfinic acid, phosphonic acid, carboxylic acid or a salt thereof, a polyoxyalkylene group, A disulfonamide group is preferred.

Examples of the compound having a hydrophilic group include an aromatic dicarboxylic acid having a sulfonate group or an ester-forming derivative thereof, a dicarboxylic acid having a polyoxyalkylene group or an ester-forming derivative thereof, and a diol having a polyoxyalkylene group. Is mentioned. Above all, in terms of polymerization reactivity of polyester and transparency of the film,
5-sodium sulfoisophthalic acid, 2-sodium sulphoterephthalic acid, 4-sodium sulfophthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid and their sodium to other metals (eg potassium, lithium, etc.) A compound substituted with an ammonium salt, a phosphonium salt, or the like, or an ester-forming derivative thereof, polyethylene glycol, polytetramethylene glycol, a polyethylene glycol-polypropylene glycol copolymer, or a hydroxy group at both ends thereof is oxidized to a carboxyl group. Compounds and the like are preferable.

These compounds having a hydrophilic group may be used alone or in combination of two or more. In particular, it is preferable that both the aromatic dicarboxylic acid component having a sulfonate group and the compound component having a polyoxyalkylene group are copolymerized with the polyester because the water absorption of the film is further improved.

The copolymerization ratio of the aromatic dicarboxylic acid component having a sulfonate group is preferably 0.5 to 10 mol% based on the difunctional dicarboxylic acid constituting the polyester.

The number average molecular weight of the compound component having a polyoxyalkylene group is preferably 300 to 20,000, and further 600
It is preferably in the range of up to 10,000, especially in the range of 1000 to 5000. The copolymerization ratio is preferably 0.5 to 15% by weight based on the polyester of the reaction product.

When the copolymerization ratio of the aromatic dicarboxylic acid component having a sulfonate group, the number average molecular weight of the compound component having a polyoxyalkylene group, and the copolymerization ratio are within these ranges, the transparency and mechanical strength of the film will be impaired. It is possible to improve the water absorption.

For the purpose of improving the heat resistance of the film, a bisphenol compound, a compound having a naphthalene ring or a cyclohexane ring can be copolymerized. The copolymerization ratio of these is 3 to 20 mol% based on the difunctional dicarboxylic acid constituting the polyester.
Is preferred.

The polyester used in the present invention may contain an antioxidant. In particular, the effect becomes remarkable when the polyester contains a compound having a polyoxyalkylene group. The antioxidant to be contained is not particularly limited as to its type, and various antioxidants can be used, for example, hindered phenol compounds,
Antioxidants such as phosphite compounds and thioether compounds can be mentioned. Among them, antioxidants of hindered phenolic compounds are preferable in terms of transparency.

The content of the antioxidant is usually 0.01 to 2% by weight, preferably 0.1 to 1.5% by weight, based on the polyester.
Is. When the content of the antioxidant is small, a so-called fog phenomenon in which the density of the unexposed portion of the photographic light-sensitive material becomes high is likely to occur, and when it is too large, haze of the film becomes high and transparency may be deteriorated. In addition, these antioxidants may be used individually by 1 type, and may be used in combination of 2 or more type.

The polyester used in the present invention preferably contains a dye for the purpose of preventing the light piping phenomenon. The dye to be blended for such a purpose is not particularly limited in its type, but in the production of the film, it is necessary that it has excellent heat resistance, and examples thereof include anthraquinone-based and perylene-based dyes. To be Further, as the color tone, gray dyeing is preferable as seen in general photographic light-sensitive materials. As these dyes, there are MACROLEX series manufactured by Bayer, SUMIPLAST series manufactured by Sumitomo Chemical Co., Ltd., and Diaresi manufactured by Mitsubishi Kasei.
From the n series and the like, one kind may be used alone, or two or more kinds of dyes may be mixed and used so as to obtain a necessary color tone. At this time, the dye has a spectral transmittance of 60% to 85% in the wavelength range of 400 to 700 nm and a difference between the maximum and the minimum of the spectral transmittance of 10% in the wavelength range of 600 to 700 nm. Is preferable in order to prevent the light piping phenomenon and to obtain a good photographic print.

If desired, the polyester film of the present invention may be provided with slipperiness. The slipperiness imparting means is not particularly limited, but an external particle addition method of adding inert inorganic particles to polyester, an internal particle precipitation method of precipitating a catalyst to be added during the synthesis of polyester,
Alternatively, a method of applying a surfactant or the like on the back surface of the film is common. Among these, the internal particle deposition method that can control the deposited particles relatively small,
It is preferable because slipperiness can be imparted without impairing the transparency of the film. As the catalyst, various known catalysts can be used, but Ca and Mn are particularly preferable because high transparency can be obtained. These catalysts may be used alone or in combination of two kinds.

The polyester film of the present invention may have a multilayer structure composed of different polyesters. For example,
When the above-mentioned polyester layer is the A layer and the above-mentioned other polyester layer is the B layer or the C layer, a two-layer structure consisting of the A layer and the B layer may be used.
A three-layer structure such as B layer / A layer, A layer / B layer / C layer, B layer / A layer / B layer or B layer / A layer / C layer may be used. Further, a structure having four or more layers is of course possible, but it is not preferable in practice because the manufacturing equipment becomes complicated. The thickness of the layer A is preferably 20% or more, and more preferably 30 to 70% of the total thickness of the polyester film. In this case, the thickness of the A layer is the thickness of the layer when the A layer has only one layer, and is the sum of the thicknesses when the A layer has two or more layers. The thickness of the B layer or C layer is preferably 5 to 60 μm, more preferably 10 to 50 μm. When the thickness of each layer is within the above range, transparency, mechanical strength, and dimensional stability are excellent, and further, water absorbability is provided, and thus a polyester film having excellent curl recovery property can be obtained.

The polyester constituting the B layer or the C layer is formed by laminating a polyester or copolymerized polyester layer such as polyethylene terephthalate excellent in transparency, mechanical strength, and dimensional stability to obtain the transparency of the entire film, Mechanical strength, dimensional stability, etc. can be improved.

Further, when the polyester film of the present invention has a layer structure, the above-mentioned functions such as anti-oxidation, light-piping prevention, slipperiness, and the like, or addition of various additives other than those mentioned above is applied only to the surface layer. Since it can be performed, the transparency of the film can be maintained high.

The method for synthesizing the polyester as the raw material of the polyester film of the present invention is not particularly limited, and the polyester can be produced by a conventionally known method for producing polyester. For example, a direct esterification method in which a dicarboxylic acid component is directly esterified with a diol component, first a dialkyl ester is used as a dicarboxylic acid component, and an ester exchange reaction is performed between this and the diol component, and this is heated under reduced pressure. A transesterification method in which the excess diol component is removed to perform polymerization can be used. At this time, if necessary, a transesterification catalyst or a polymerization reaction catalyst may be used, or a heat stabilizer may be added. In addition, in each process during synthesis, coloring agent, antioxidant,
A crystal nucleating agent, a slip agent, a stabilizer, an antiblocking agent, an ultraviolet absorber, a viscosity adjusting agent, a defoaming agent, a clarifying agent, an antistatic agent, a pH adjusting agent, a dye, a pigment and the like may be added.

The thickness of the polyester film of the present invention is not particularly limited. It may be set so as to have a required strength according to the purpose of use. Particularly when the polyester film is used for a photographic light-sensitive material for color negative, it is preferably 20 μm or more, and particularly preferably 40 μm or more.
In addition, when it is used for medical and printing photographic light-sensitive materials,
It is preferably 50 μm or more, and particularly preferably 60 μm or more.

In the method of laminating the same or different polyesters having different intrinsic viscosities, the difference in the intrinsic viscosities is 0.02 to
0.5 (dl / g) is preferable, and in the method of changing the thickness of both outer layers, the thickness of both outer layers is d.
_{If 1} and d ₂ , then 1.1 ≦ d ₁ / d ₂ ≦ 10, and further 2 ≦ d ₁
/ D ₂ ≦ 5 is preferable from the viewpoint of production such as stretching of the film.

The intrinsic viscosity is determined as follows. Film or pellet with phenol 1,1,2,
It was dissolved in a mixed solvent of 2-tetrachloroethane (weight ratio 60/40) to prepare solutions having concentrations of 0.2 g / dl, 0.6 g / dl and 1.0 g / dl, and each was measured at 20 ° C. with an Ubbelohde viscometer. Relative viscosity increment η _{SP at} concentration (C) (ratio η of increment η-η _S to η _S of solvent viscosity η _S of polymer solution viscosity η η
_SP : η _SP = (η-η _S ) / η _S ) is calculated. Then η _SP
/ C is plotted against C, and the straight line obtained by the method of least squares is extrapolated to the concentration C = 0 to obtain η at the concentration C = 0.
_{Calculate SP} / C. The intrinsic viscosity [η] is η _SP / C (C =
0). The unit is indicated by dl / g.

The Tg of the polyester film is preferably 60 ° C. or higher, more preferably 70 ° C. or higher and 150 ° C. or lower. Tg is determined by measuring with a differential scanning calorimeter. Tg
Within this range, the film is not deformed in the drying step of the development processor, and a photosensitive material with a small curl after development is obtained.

For the purpose of reducing the curling of the polyester photographic support, the methods described in JP-A-51-16358 and JP-A-6-35118 can be preferably used.

That is, it is a method of heat-treating at a temperature of 50 ° C. or higher and a glass transition point or lower for 0.1 to 1500 hours.

Since this heat treatment is carried out at a high temperature of 50 ° C. or higher, if it is carried out after coating the emulsion, it tends to cause deterioration of the performance of the emulsion layer. Therefore, it is desirable to do it before coating the emulsion layer.

The support of the present invention includes a matting agent, an antistatic agent, a lubricant, a surfactant, a stabilizer, a dispersant, a plasticizer, an ultraviolet absorber, a conductive substance, a tackifier, a softening agent and a fluidity. Additives, thickeners, antioxidants and the like can be added.

The silver halide photographic light-sensitive material of the present invention is a light-sensitive material for black and white, a light-sensitive material for color negative, a light-sensitive material for color paper, a light-sensitive material for color reversal, a light-sensitive material for movies, an X-ray light-sensitive material. , A photosensitive material for printing, a photosensitive material for microphotography, and the like.

As the hydrophobic binder used in the magnetic recording layer, a thermoplastic resin, a radiation curable resin, a thermosetting resin,
Other reactive resins can be used alone or in combination.

As the above-mentioned thermoplastic resin, vinyl chloride-
Vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, copolymer of vinyl acetate and vinyl alcohol, partially hydrolyzed vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile Copolymer, ethylene-vinyl alcohol copolymer,
Vinyl-based polymers or copolymers such as chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, and cellulose derivatives such as nitrocellulose, cellulose acetate propionate, and cellulose acetate butyrate resin. , Maleic acid and / or acrylic acid copolymer, acrylic acid ester copolymer, acrylonitrile-styrene copolymer, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer Coalesce, acrylic resin, polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, Examples thereof include rubber resins such as amino resins, styrene-butadiene resins, butadiene-acrylonitrile resins, silicone resins, and fluorine resins.

The above-mentioned thermoplastic resin has a Tg of -40 to 180 ° C,
It is preferably 30 to 150 ° C., the weight average molecular weight is preferably 5,000 to 300,000, and more preferably the weight average molecular weight is 10,000 to 200,000.

These can be usually used as a solvent-based or water-based emulsion or a water-based colloidal solution. The particle size of these synthetic resin emulsions ranges from 5 nm to 2
You can use the μm one.

The radiation-curable resin is a resin which is cured by radiation such as electron beam and ultraviolet ray, and is of maleic anhydride type, urethane acryl type, ether acryl type, epoxy acryl type, solvent type or water type emulsion type. Is mentioned.

Examples of thermosetting resins and other reactive resins include phenolic resins, epoxy resins, polyurethane-based curable resins, urea resins, alkyd resins, silicone-based curable resins, etc., which are solvent-based, water-soluble or water-based. The thing of emulsion is mentioned.

The hydrophobic binders listed above may have a polar group in the molecule. The polar group epoxy _{group, -COOM, -OH, -NR 2,} -NR 3 X, -SO 3 M, -OSO
_{3 M, -PO 3 M 2,} -OPO 3 M (M each hydrogen, an alkali metal, an ammonium, X is an acid which forms an amine salt, R
Represent hydrogen and an alkyl group, respectively. ) Is mentioned.

Besides, a hydrophilic binder may be used in the present invention. Examples of the hydrophilic binder include, for example, Research Disclosure No. 17643, page 26, and No. 187.
The water-soluble polymers, cellulose ethers and water-soluble polyesters described on pages 16 and 651 can be mentioned.

Examples of the water-soluble polymer include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, acrylic acid-based copolymers, maleic anhydride-based copolymers and the like in addition to the above-mentioned celluloses. Examples of ethers include methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like.

When using a water-soluble polymer, it is preferable to use a hardener. As a hardening agent that can be used, for example, formaldehyde, aldehyde compounds such as glutaraldehyde, diacetyl, ketone compounds such as cyclopentanedione, bis (2-chloroethylurea),
2-Hydroxy-4,6-dichloro-1,3,5-triazine, U.S. Pat.Nos. 3,288,775, 2,732,303, British Patent 974,723, 1,167,207, etc. Reactive halogen-containing compounds, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, U.S. Pat.Nos. 3,635,718, 3,232,763, and British patents Compounds having a reactive olefin described in Japanese Patent No. 994,869, N-hydroxymethylphthalimide, US Pat. No. 2,73
2,316, N-methylol compounds described in 2,586,168 and the like, isocyanates described in U.S. Pat.No. 3,103,437, U.S. Pat.
3,017,280, aziridine compounds described in 2,983,611 and the like, acid derivatives described in U.S. Pat.Nos. 2,725,294 and 2,725,295, U.S. Pat.No. 3,091,537 Examples thereof include epoxy compounds and halogen carboxaldehydes such as mucochloric acid. Further, it is also possible to use an inorganic hardener, as the inorganic hardener, chrome bright vane, zirconium sulfate, and JP-B-56-12853, 58-32699. , Belgian Patent No. 825,726, JP-A-60-225148
JP-A-51-126125, JP-B-58-50699, JP-A-52-54427, U.S. Pat. Can be mentioned.

The hardener is usually added in an amount of 0.01 to the resin solid content.
-60% by weight, preferably 0.05-50% by weight.

The magnetic recording medium of the present invention can be obtained by dispersing and kneading the above components in an organic solvent, coating the mixture on a non-magnetic support, orienting it if necessary, and then drying. After drying, planar treatment may be performed if necessary.

As the solvent used in the dispersion, kneading and coating of the present invention, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone and tetrahydrofuran in any ratio; methanol, ethanol, propanol, butanol, Alcohol such as isobutyl alcohol, isopropyl alcohol, methylcyclohexanol; ester such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isopropyl acetate, ethyl lactate, glycol acetate, monoethyl ether; ether, glycol dimethyl ether, glycol Glycol ethers such as monoethyl ether and dioxane; benzenetoluene, xylene,
Tar-based compounds (aromatic hydrocarbons) such as cresol, chlorobenzene and styrene; chlorinated hydrocarbons such as methylene chloride, ethylene chloride, carbon tetrachloride, chloroform, ethylene chlorohydrin and dichlorobenzene, N, N-
Dimethyl formaldehyde, hexane, water, etc. can be used.

The method of dispersion is not particularly limited, and the order of addition of each component can be set appropriately. For the preparation of the magnetic paint, a conventional kneading machine such as a two-roll mill, a three-roll mill, a ball mill, a pebble mill, a tron mill,
Sand grinder, Szegvari attritor, high speed impeller, disperser, high speed stone mill, high speed impact mill, disper, kneader, high speed mixer, reciprocating blender, cokneader, intensive mixer,
A tumbler, a blender, a disperser, a homogenizer, a single screw extruder, a twin screw extruder, an ultrasonic disperser, etc. can be used.

The magnetic recording layer may be provided on the support by using a coater such as an extrusion coater, an air doctor coater, a blade coater, an air knife coater or a squeeze coater, an impregnation coat method, a reverse roll coat method, Transfer roll coating method, gravure coating method, kiss coating method, cast coating method, spray coating method and the like can be used. In order to perform multi-stripe coating, these coating coaters may be arranged in series. As a specific method of stripe coating, for example,
JP-A-48-25503, JP-A-48-25504, and JP-A-48-98803
No. 50-138037, No. 52-15533, No. 51-
3208, 51-6239, 51-65606, 5
1-140703 publication, Japanese Patent Publication No. 29-4221 publication, U.S. Patent 3,06
The descriptions in the Nos. 2,181 and 3,227,165 can be referred to.

In order to firmly adhere these magnetic recording layers to the support, an undercoat layer may be provided on the support, and the support may be subjected to chemical treatment, mechanical treatment, corona discharge treatment,
Flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment,
Surface activation treatment such as active plasma treatment, laser treatment, concentrated acid treatment, or ozone oxidation treatment may be performed. Furthermore, an undercoat layer may be provided after the surface activation treatment. The undercoat layer is preferably an aqueous latex type.

The ferromagnetic fine powder used in the transparent magnetic layer of the present invention includes ferromagnetic iron oxide fine powder, Co-doped ferromagnetic iron oxide fine powder, ferromagnetic chromium dioxide fine powder, ferromagnetic metal powder, and strong metal powder. Magnetic alloy powder, barium ferrite, etc. can be used.

As an example of the ferromagnetic alloy powder, the metal content is 75
wt% or more, and 80 wt% or more of the metal content is at least one kind of ferromagnetic metal or alloy (Fe, Co, Ni, Fe-Co, Fe-
Ni, Co-Ni, Co-Fe-Ni, etc.) and 20 wt% of the metal content
Other components (Al, Si, S, Sc, Ti, V, Cr, Mn, C
u, Zn, Y, Mo, Rh, Pd, Ag, Sn, Sb, B, Ba, Ta,
W, Re, Au, Hg, Pb, P, La, Ce, Pr, Nd, Te, Bi, etc.) can be included. In addition, the ferromagnetic metal component may contain a small amount of water, hydroxide or oxide.

The production method of these ferromagnetic powders is known,
The ferromagnetic powder used in the present invention can also be manufactured according to a known method.

The shape and size of the ferromagnetic powder can be widely used without particular limitation. As the shape, needle shape, rice grain,
It may be spherical, cubic, or plate-like, but needle-like or plate-like is preferable in terms of electromagnetic conversion characteristics. The crystallite size and specific surface area are not particularly limited, but the crystallite size is 400 Å or less, and the BET value is 2
0 m ² / g or more is preferable, and 30 m ² / g or more is particularly preferable. The pH of the ferromagnetic powder and the surface treatment can be used without particular limitation (the surface treatment may be performed with a substance containing an element such as titanium, silicon, aluminum, carboxylic acid,
It may be treated with an organic compound such as an adsorptive compound having a nitrogen-containing heterocyclic ring such as sulfonic acid, sulfuric acid ester, phosphonic acid, phosphoric acid ester, and benzotriazole).
The preferred pH range is 5-10. In the case of ferromagnetic iron oxide fine powder, it can be used without any particular limitation on the ratio of divalent iron / trivalent iron. These magnetic recording layers are described in JP-A-47-32812 and 53-109604.

Hc of the ferromagnetic powder can be used without any particular limitation. It is preferably 400 to 2000 Oe.

In the case of forming an optically transparent magnetic recording layer, the binder is 2 to 1 part by weight of the ferromagnetic powder.
It is preferable to use 50 parts by weight. More preferably, it is 5 to 30 parts by weight with respect to 1 part by weight of the magnetic powder. Further, the solvent is used in such an amount that the coating can be easily performed.

After providing the magnetic recording layer, calendering is performed on this layer to improve smoothness, and S of magnetic output is provided.
It is also possible to improve the / N ratio. In this case, it is preferable to apply a silver halide photographic light-sensitive layer on the side opposite to the support after calendering.

As the antistatic agent, fine particles of metal oxide are preferable. Examples of metal oxides include oxygen-rich oxides such as Nb ₂ O _{5 + X} , oxygen-deficient oxides such as RhO _2-X and Ir ₂ O _3-X , or Ni (OH) _X. Nonstoichiometric hydride, HfO
₂ , ThO ₂ , ZrO ₂ , CeO ₂ , ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In
₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₂ , V ₂ O _5, etc., or a composite oxide thereof are preferable, and ZnO, TiO ₂ and SnO ₂ are particularly preferable. Examples of containing a heteroatom include, for example, ZnO with A
Addition of l, In, etc., addition of Nb, Ta, etc. for TiO ₂ , and S
The addition of Sb, Nb, halogen elements, etc. is effective for nO ₂ . Addition amount of these hetero atoms is 0.01 mol% to 25 mol%
Is preferable, but the range of 0.1 mol% to 15 mol% is particularly preferable. The volume resistivity of these electrically conductive metal oxide powders is preferably 10 ⁷ Ωcm or less, particularly 10 ⁵ Ωcm or less. Further, it may be a sol in which fine particles of the metal oxide are mixed in an aqueous solution.

Besides these, nonionic fine particles, but nonionic surfactants such as alkylene oxide, glycerin and glycidol; higher alkyl amines, quaternary ammonium salts, salts of pyridine and other heterocyclic compounds, Cationic surfactants such as phosphonium or sulfonium compounds; anionic surfactants containing an acidic group such as carboxylic acids, phosphorus compounds, sulfate ester groups, and phosphate ester groups; amino acids, aminosulfonic acids, sulfuric acid of amino alcohols or Examples thereof include amphoteric surfactants such as phosphoric acid esters. These surfactants may be contained as a substituent of the polymer.

In the present invention, a general matting agent may be used. The matting agent may be added in the range of 1 to 400 parts by weight based on 100 of the binder in the layer. Specific examples of the matting agent are shown below, but the matting agent is not limited thereto.

[0073]

[Chemical 1]

[0074]

[Chemical 2]

A wax having an average particle diameter of 0.01 μm to 3.0 μm may be contained in the binder of the uppermost layer. To check the size of wax particles, a sample coated on a support was embedded in a room temperature curable resin and then a microtome was used to measure about 150 n.
An ultrathin section with a thickness of m can be prepared, held on a copper mesh with a carbon support film, and observed with a scanning transmission electron image by an electron microscope. When viewed by this observation method, the shape of the wax particles is generally spindle-shaped or needle-shaped, and some of the waxes having a high melting point are spherical. The diameter or major axis length of 100 or more wax particles observed by the above electron microscope was averaged to obtain the average particle diameter. In the present invention, the average particle size is preferably 0.01 to 3.0 μm, and when 0.01 μm or more, sufficient slipperiness is obtained, and when 3.0 μm or less, scratch resistance is good. And in this, 0.05-1.0 μm is more preferable,
Most preferred is 0.1-0.5 μm.

In the present invention, the layer containing wax having an average particle size of 0.01 to 3.0 μm is the uppermost layer on the side where the transparent magnetic recording layer is provided, and wax may be added to a layer other than the uppermost layer. . The wax at this time can be used without any limitation on the average particle size, but it is more preferable to use a wax that can be added to the uppermost layer.

The uppermost layer may be a protective layer or a magnetic layer, but the uppermost layer is preferably a magnetic layer from the viewpoint of cost. If the top layer is a protective layer, the protective layer thickness is 0.1
It is preferably at least μm, more preferably at least 0.5 μm, and preferably at most 3 μm.

The amount of wax added can be used without particular limitation, but if it is too small, the scratch resistance tends to deteriorate, and if it is too large, the turbidity tends to increase, so that it is relative to the total weight of the binder in the layer containing the wax. 0.1 to 50 wt% is preferable, 1.0 to 20
wt% is more preferable, and 5.0 to 10 wt% is the most preferable.

When the wax used for the uppermost layer is present in a liquid state when dispersed, it is easily taken into the binder and it is difficult to obtain a sufficient effect, and when it becomes a liquid during the development processing, it easily flows out into the development processing solution. So the melting point is 38
C. or higher is preferable, and 50 ° C. or higher is more preferable in view of storage characteristics such as sticking. Further, it is preferably 150 ° C. or lower for easy handling.

The type of wax used in the present invention can be used without any particular limitation. Specific examples include carnauba wax, candelilla wax, rice wax, wood wax, beeswax, montan wax, ozokerite, ceresin, paraffin wax, and fisher wax.
Examples thereof include silicone oils such as Tropsch wax, polyethylene wax and polysiloxane, fluorine-based lubricants, higher fatty acids, higher fatty acid esters and the like.

The ceramic fine particles and glass fine particles used in the present invention may be those which are chemically stable and have sufficient hardness. For example, the ceramic fine particles are zirconia,
Ceramic fine particles made of various oxides such as alumina, titania, zircon, and mullite can be used, and glass fine particles include soda coal glass, substances containing titanium oxide, borosilicate glass, lead silicate series, quartz glass, and other hard materials. Glass fine particles such as glass and crystallized glass can be used. Further, it may be fine particles of ceramics or glass for a mixed medium used for a dispersing device such as a sand grinder or a filler for a chemical reaction device.

The average particle diameter of the fine particles of ceramics or glass is the length in the major axis direction, and the addition amount is expressed as a weight% with the binder of the layer to be added. If the average particle size and the addition amount of the fine particles exceed a predetermined value, deterioration of turbidity that adversely affects the sharpness and color reproducibility of the photosensitive material may occur, or the magnetic head may be scratched. Further, when it is less than the predetermined value, the contribution to the improvement of running durability is small. The layer containing the fine particles may be any layer on the side having the MG layer, but is preferably contained in the outermost layer, and may be contained in all layers on the side having the MG layer.

When the fine particles contained in the layer having the MG layer are glass fine particles, the average particle diameter is preferably 0.01 to 2.0 μm, and more preferably 0.01 to 1.0 μm. Further, when the glass fine particles are contained in the protective layer, it is preferably 0.01 to 0.3 μm,
When it is contained in the transparent magnetic layer, it is preferably 0.01 to 0.5 μm, and when it is contained in the antistatic layer, it is preferably 0.01 to 1.0 μm. The addition amount is preferably 0.01 to 15 wt.%, Preferably 0.05 to 10 wt.%
Is. Also, when glass particles are contained in the protective layer,
0.05 to 2 wt.% Is preferable, 0.05 to 5 wt.% When contained in the transparent magnetic layer, and 0.05 to 5 wt% when contained in the antistatic layer.
.About.8 wt.% Is preferred.

When the fine particles contained in the layer having the MG layer are ceramic fine particles, the average particle diameter is 0.01 to 1.0 μm.
Is good, and preferably 0.01 to 0.5 μm. When the ceramic fine particles are contained in the protective layer, it is preferably 0.01 to 0.1 μm, and when contained in the transparent magnetic layer, 0.01 to 0.3 μm,
When contained in the antistatic layer, it is preferably 0.01 to 0.5 μm.
Further, the addition amount is preferably 0.01 to 15 wt.%, Preferably 0.05
~ 10 wt.%. Further, when the ceramic fine particles are contained in the protective layer, 0.05 to 2 wt.% Is preferable, when the transparent magnetic layer is contained, 0.05 to 5 wt.% Is preferable, and when the antistatic layer is contained, 0.05 to 8 wt.% Is preferable. .

The shape of the ceramic fine particles or glass fine particles to be added is preferably not spherical but spherical, for example, irregular shape such as needle-like or polygonal cross-section. For example, a finely ground mixture medium of a disperser such as a sand grinder used in the step of dispersing a coating liquid may be used after adjusting the particle size and amount, or separately using fine particles of ceramic or glass. You may add.

The main component referred to in the present application is a component having the highest content rate among the constituent components, and the content rate is 40%.
It means the ingredient of wt% or more.

[0087]

EXAMPLES Specific examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1 1-1) Preparation of base for undercoating <Preparation of support> As a polyester resin for the support, P-1: commercially available polyethylene terephthalate (intrinsic viscosity)
0.65) P-2: 0.1 part by weight of calcium acetate hydrate as an ester exchange catalyst was added to 100 parts by weight of dimethyl terephthalate and 64 parts by weight of ethylene glycol, and transesterification reaction was carried out by a conventional method. 5-sodium sulfo-di (β-hydroxyethyl) isophthalic acid (abbreviation: SI
P) ethylene glycol solution (concentration 35% by weight) 28 parts by weight (5 mol% / total ester bond), polyethylene glycol (abbreviation: PEG) (number average molecular weight: 4,000) 11 parts by weight (8.5% by weight / reaction product) Total weight), antimony trioxide 0.05 part by weight, phosphoric acid trimethyl ester 0.13 part by weight, Irganox 1010 (CIBA-GEIGY as an antioxidant
(Made by the company) was added so that it might be 1 weight% with respect to the product polymer. Then gradually raise the temperature and reduce the pressure to 280 ° C, 0.5 mm
Polymerization was carried out with Hg to obtain a copolyester (intrinsic viscosity
0.55).

After vacuum-drying P-1 and P-2 at 150 ° C. respectively, 2 out of 3 extruders were used for P-2.
Melt extruded at ℃, the film thickness ratio of the three layers is P-2: P-1: P
-2 = 1: 2: 3, the layers were joined in a T-die in a layered form, and rapidly solidified on a cooling drum to obtain a laminated unstretched film. Then, after longitudinal stretching (3.4 times) at 85 ℃, the temperature is further 95
After transverse stretching (3.4 times) at ℃, heat set at 210 ℃,
A biaxially stretched film having a thickness of 90 μm was obtained.

8 W / (m) on both sides of the support of this polyethylene terephthalate (lamination type of materials having different moisture absorption)
² min. Of corona discharge treatment, and the following subbing coating solutions U-1 and U-2 are applied to the outer side of the thin side of the copolyester.
Coating was performed so that the dry film thickness was 0.8 μm and 0.1 μm, and a support having an undercoat layer formed was prepared.

(Undercoating coating liquid U-1) Copolymer latex liquid of butyl acrylate / t-butyl acrylate / styrene / 2-hydroxy acrylate (superposition constitution ratio; 30: 20: 25: 25, solid content 30%) 270 g Compound (A-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g These were mixed and diluted with water to make 1 liter.

(Undercoating coating solution U-2) Gelatin 10 g Compound (A-1) 0.2 g Compound (A-2) 0.2 g Compound (A-3) 0.1 g Silica particles (average particle size: 3 μm) 0.1 g Was mixed and diluted with water to make 1 liter.

The structures of the compounds A-1 to A-3 used are shown below.

[0094]

[Chemical 3]

1-2) Coating of antistatic layer (ANS layer) An antistatic layer coating solution (A) having the following formulation was prepared using a sand grinder using glass beads having the following composition as a mixed medium.
NS-1) was kneaded and adjusted. (Note that the glass beads were used in an amount corresponding to a filling amount of 80% of the volume of the sand grinder.) Subsequently, the kneaded and adjusted dispersion was filtered by changing the size and the number of stages of the filter, and each dispersion was The amount of fine glass powder contained and the average particle size were adjusted. still,
If the addition amount or average particle size cannot be adjusted by this alone (when the addition amount is 10 wt.% Or the average particle size is 1.0 μm, etc.),
The shape and the amount of glass particles added to the ANS layer of each sample are obtained by separately adding irregularly shaped glass particles having the same composition as the following glass beads (spherical glass particles in the paint of Sample No. 1-64). The average particle size was adjusted to the shape, addition amount, and average particle size as shown in Tables 1 to 3.

Antistatic Layer Coating Liquid Formulation (ANS-1) (Undercoating Coating Liquid U-3) Polyester Latex Liquid (Solid Content 30%) 223 g Tin Oxide Fine Powder (Average Particle Size 0.05 μm) “SN100P” Made by Ishihara Sangyo 107 g These were mixed and dispersed, and 1000 g of a 3/1 mixture of water / isopropanol was added.

(Glass bead composition) SiO ₂ 55 wt.% CaO 23 wt.% Al ₂ O ₃ 13 wt.% B ₂ O ₃ 7 wt.% MgO 1 wt.% K ₂ O 0.5 wt.% Na ₂ O 0.5 wt.% Average Grain size 2.0mm 25W / (m ²
After the corona discharge treatment of (min), the shape and content of the glass fine particles in ANS-1 and the average particle diameter were adjusted to a dry film thickness of 0.8 μm.

1-3) Coating of transparent magnetic recording layer (MG layer) -Preparation of sample Nos. 1-1 to 26, 34, 57, 72, 73, 75 and 76 Glass beads having the above composition were mixed with each other. The transparent magnetic recording layer coating material (MG-1) having the following formulation was kneaded and adjusted with the sand grinder used as above. (Note that the glass beads were used in an amount corresponding to a filling amount of 80% of the volume of the sand grinder.) Subsequently, the kneaded and adjusted dispersion was filtered by changing the size and the number of stages of the filter, and each dispersion was The amount of fine glass powder contained and the average particle size were adjusted.
If the addition amount or average particle size cannot be adjusted by itself (when the addition amount is 10 wt.% Or the average particle size is 1.0 μm, etc.)
In addition, by adding a glass microparticle of a different shape having the same composition as that of the above glass beads, the shape and the amount of the glass microparticle added to the MG layer of each sample, and the average particle diameter are shown in Tables 1 to 3. The shape, amount added, and average particle size were adjusted.

Transparent Magnetic Layer Coating Liquid Formulation (MG-1) Cobalt-containing gamma iron oxide (average major axis length 0.8 μm, Fe ²⁺ / Fe ³⁺ = 0.2, Hc 600 Oe) 3 parts by weight Nitrocellulose resin (BTH- 1/2 (Asahi Kasei Co., Ltd.), solid content 70% 100 parts by weight Cyclohexanone 75 parts by weight Methyl ethyl ketone 150 parts by weight Toluene 150 parts by weight.

On the ANS layer of the support coated with the ANS layer, a liquid in which the shape and content of the fine glass particles in the transparent magnetic layer coating material MG-1 and the average particle diameter were adjusted was applied using a precision extrusion coater. Then, the coating was applied so that the dry film thickness would be 0.8 μm, and the coating was dried while the magnetic material was oriented in the coating direction in an orientation magnetic field while not dried.

Sample No. 1-27 to 33, 35 to 56, 58 to 71, 7
Preparation of 4 A coating material (MG-2) for transparent magnetic recording layer having the following formulation was kneaded and adjusted with a sand grinder using glass beads having the above composition as a mixing medium. (Note that the glass beads were used in an amount corresponding to a filling amount of 80% of the volume of the sand grinder.) Subsequently, the kneaded and adjusted dispersion was filtered by changing the size and the number of stages of the filter, and each dispersion was The amount of fine glass powder contained and the average particle size were adjusted.
If the addition amount or average particle size cannot be adjusted by itself (when the addition amount is 10 wt.% Or the average particle size is 1.0 μm, etc.)
To the MG layer of each sample, by additionally adding irregularly shaped glass particles having the same composition as the above glass beads (spherical glass particles in the paint of Sample No. 1-46). The addition amount and average particle size were adjusted to the shape, addition amount and average particle size as shown in Tables 1 to 3.

Transparent magnetic layer coating liquid formulation (MG-2) Cobalt-containing gamma iron oxide (average major axis length 0.8 μm, Fe ²⁺ / Fe ³⁺ = 0.2, Hc 600 Oe) 3 parts by weight Nitrocellulose resin (BTH- 1/2 (Asahi Kasei Co., Ltd.), solid content 70% 100 parts by weight Cyclohexanone 75 parts by weight Toluene 150 parts by weight Methyl ethyl ketone 150 parts by weight Carnauba WAX (made by Kato Yoko Co., Ltd.) 10 parts by weight Matting agent M-1 1 part by weight Department.

On the ANS layer of the support coated with the ANS layer, a liquid in which the shape and content of the fine glass particles in the transparent magnetic layer coating material MG-2 and the average particle diameter were adjusted was applied using a precision extrusion coater. Then, the coating was applied so that the dry film thickness would be 0.8 μm, and the coating was dried while the magnetic material was oriented in the coating direction in an orientation magnetic field while not dried.

1-4) Coating of protective layer (OC layer) -Preparation of sample Nos. 1-1 to 26, 34, 57, 72, 73, 75, 76 Use glass beads having the above composition as a mixed medium. With a sand grinder, use the following formulation for the protective layer paint (OC-
1) was kneaded and adjusted. (Note that the glass beads were used in an amount corresponding to a filling amount of 80% of the volume of the sand grinder.) Subsequently, the kneaded and adjusted dispersion was filtered by changing the size and the number of stages of the filter, and each dispersion was The amount of fine glass powder contained and the average particle size were adjusted. If the addition amount or average particle size cannot be adjusted by itself (when the addition amount is 10 wt.% Or the average particle size is 1.0 μm, etc.), the irregular glass fine particles having the same composition as the above glass beads are used. By adding (spherical glass fine particles to the paint of Sample No. 1-20) separately, the shape and amount of glass fine particles added to the OC layer of each sample, and the average particle size are shown in Tables 1 to 3. The shape, amount added, and average particle size were adjusted.

Protective layer coating liquid formulation (OC-1) Nitrocellulose resin (BTH-1 / 2 (manufactured by Asahi Kasei), solid content 70% 100 parts by weight Carnauba WAX (manufactured by Kato Yoko) 10 parts by weight Matting agent: M-1 1 part by weight Cyclohexanone 75 parts by weight Toluene 150 parts by weight Methyl ethyl ketone 150 parts by weight.

Subsequently, the protective layer coating material O is formed on the MG layer.
A liquid in which the shape and content of the glass fine particles in C-1 and the average particle diameter were adjusted was applied to give a dry film thickness of 0.3 μm.

1-5) Coating of Photosensitive Material Layer After applying a corona discharge treatment of 25 W / (m ² · min) on the surface opposite to the surface having the MG layer, that is, on the undercoat layer U-2. A multi-layer color light-sensitive material having the emulsion layer structure of Example 1 described in Japanese Patent Application No. 4-267697 was prepared to prepare a photographic light-sensitive material.

The samples obtained as described above were evaluated as follows, and the results are shown in Tables 1 to 3.

(1) Turbidity Turbidity before applying a photosensitive material layer was measured using SEP-PT-501D type manufactured by Mitsubishi Kasei Co., Ltd. If it is 20ppm or less, there is no problem as a product. The smaller the value, the better.

(2) Scratch resistance and head scratch The obtained sample of silver halide color photographic light-sensitive material was
Applying 100g load to a commercially available audio magnetic head (magnetic head for compact cassette: material Permalloy) using HEIDON Tribogear type 14DR
Sliding was repeated 200 times at a speed of m / sec. After that, the degree of scratches on the film (scratch resistance) and the degree of scratches on the tracks of the magnetic head (head scratches) were evaluated according to the following ranks.

Scratch resistance A: No scratch B: There is a slight sliding mark C: There is a sliding mark D: There is scratch E: Film is peeled off. It is at a level with no practical problems.

Head scratches A ... No scratches B ... Slight scratches C ... Weak scratches D ... Several strong scratches E ... Severe strong scratches C ... Magnetic recording It does not affect re-production and is at a level with no practical problems.

[0113]

[Table 1]

[0114]

[Table 2]

[0115]

[Table 3]

As is clear from Tables 1 to 3, the sample of the present invention has good transparency and does not damage the photosensitive material and the magnetic head even after repeated use.

Example 2 The same operation was performed except that the glass bead composition of Example 1 was changed to the ceramic bead composition of the following composition, and Tables 4 to 6 were used.
The addition amount of the ceramic fine particles and the average particle size as shown in (3) were used.

Ceramic bead composition ZrO ₂ 99.6 wt.% SiO ₂ 0.4 wt.% Average particle size 2.0 mm A silver halide color photographic light-sensitive material was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The results are shown in Tables 4-6.

[0119]

[Table 4]

[0120]

[Table 5]

[0121]

[Table 6]

From the table, as in the case of Example 1, the sample of the present invention exhibits excellent effects even in the sample in which the glass bead composition is changed to the ceramic bead composition.

Example 3 When the same operation as in Example 2 was carried out except that the ceramic bead composition of Example 2 was changed to the following ceramic bead composition, the same result as in Example 2 was obtained.

Ceramic bead composition TiO ₂ 78 wt.% Al ₂ O ₃ 17 wt.% SiO ₂ 4 wt.% K ₂ O 1 wt.% Average particle size 2.0 mm

[0125]

According to the present invention, it is so transparent that it does not adversely affect printing and has good scratch resistance to the magnetic head.
It was possible to provide a silver halide photographic light-sensitive material that is hard to damage the magnetic head.

Claims (8)

[Claims] 1. A silver halide having at least one silver halide emulsion layer on one side on a support, and at least one antistatic layer and at least one transparent magnetic recording layer on the other side. In the photographic light-sensitive material, at least one layer on the side having the transparent magnetic recording layer has an average particle size of 0.01 to 1.
0 ~ 15 μm ceramic fine particles to binder 0.01 ~ 15
A silver halide photographic light-sensitive material characterized by containing wt.%. 2. Ceramic fine particles are ZrO ₂ , Al ₂ O ₃ and TiO _2.
Of these, one of the main components is Al ₂ O ₃ , TiO ₂ , S
_{iO 2, Fe 2 O 3,} K 2 O The silver halide photographic material of claim 1, wherein it is characterized in containing one or or several selected from among. 3. A silver halide having at least one silver halide emulsion layer on one side on a support and at least one antistatic layer and at least one transparent magnetic recording layer on the other side. In the photographic light-sensitive material, the average particle size of 0.01 to 2.at least one layer on the side having the transparent magnetic recording layer.
0.01 to 15 wt.
% Of silver halide photographic light-sensitive material. 4. The glass fine particles are mainly composed of SiO ₂ and Ca
1 selected from O, Al ₂ O ₃ , Na ₂ O, B ₂ O ₃ , MgO and K ₂ O
4. A silver halide photographic light-sensitive material according to claim 3, which contains one or several kinds. 5. The silver halide photographic light-sensitive material according to claim 1, wherein the shape of the ceramic fine particles and / or the glass fine particles has an irregular shape such as a needle shape or a polygonal cross section. 6. A silver halide photograph according to claim 1, wherein the layer containing ceramic fine particles and / or glass fine particles is a protective layer on the side having a transparent magnetic recording layer. Photosensitive material. 7. The silver halide photographic light-sensitive material according to claim 1, wherein the layer containing fine ceramic particles and / or fine glass particles is a transparent magnetic layer. 8. The silver halide according to claim 1, wherein the layer containing fine ceramic particles and / or fine glass particles is an antistatic layer on the side having a transparent magnetic recording layer. Photographic material.