JPH07181612A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the photosensitive material superior in transparency and scratch resistance and not scratched at the time of recording and regenerating through a magnetic head in a wide temperature range by incorporating at least one of polyethylene type waxes at least in the side of a transparent magnetic recording layer. CONSTITUTION:The photosensitive material has one or more silver halide emulsion layers on one side of a support and the transparent magnetic recording layer on the tether side, and the side of the magnetic recording layer contains one of the polyethylene type waxes of polyethylene oxide type having a number average molecular weight of >=900 and an acid value of 5-55 and unsaturated bonds in the terminals of the waxes.

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 is necessary to enter various information obtained at the time of printing, such as customer information, etc., from the viewpoint of management, improvement of print quality, and efficiency of print work.

In a conventional photographic light-sensitive material, it is impossible to input all the information, and
At the time of shooting, I was only optically entering information such as the shooting date / time, aperture, and exposure time. Moreover, at the time of printing, it was impossible to input the above information into the photographic light-sensitive material because there was no means for that.

Since the magnetic recording system is easy to record / reproduce, the use of the magnetic recording system for inputting the above various information to the photographic light-sensitive material has been studied and various techniques have been proposed.

For example, a stripe-shaped magnetic recording layer in which fine particles of a ferromagnetic material are dispersed is provided on the emulsion surface or the back surface next to the image area to record information such as voice and shooting conditions. KAISHO No. 50-62627, No. 49-4503, U.S. Pat. No. 3,243,376, No. 3,220,843, etc., and the amount, size, etc. of magnetic particles on the back surface of the photographic light-sensitive material. It is described in US Pat. Nos. 3,782,947, 4,279,945, 4,302,523, etc. that a transparent magnetic recording layer having the required transparency is provided by selecting the above. Further, U.S. Pat.No. 4,947,196,
WO 90/04254 describes a photographic camera having a magnetic head together with a roll-shaped film having a magnetic recording layer containing a magnetic substance that enables magnetic recording on the back surface of a photographic film.

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 voice and image signals. is doing.

[0007]

However, the conventional technique has a problem that the film is easily scratched when recording or reproducing with the magnetic head. In particular, the scratches are remarkable under high temperature conditions, which is a serious problem with silver halide photographic light-sensitive materials used in a wide range.

Therefore, an object of the present invention is to provide a silver halide photographic which has excellent transparency required for a photographic light-sensitive material, and which has excellent scratch resistance in recording and reproducing by a magnetic head in a wide temperature range. To provide a light-sensitive material.

[0009]

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

At least in a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on one side on a support and a transparent magnetic recording layer on the other side, at least on the transparent magnetic recording layer side. A silver halide photographic light-sensitive material comprising at least one polyethylene wax.

The silver halide photographic light-sensitive material as described above, wherein the polyethylene wax has a number average molecular weight of 900 or more.

The polyethylene wax has an acid value of 5
The silver halide photographic light-sensitive material as described above or above, which is an oxidized polyethylene wax having a number of 55 or more.

The silver halide photographic light-sensitive material as described above or above, wherein the polyethylene wax has an unsaturated bond at its end.

The present invention will be described in detail below.

The term "transparent" as used in the present invention specifically means a case where the maximum optical density of the magnetic recording layer is 1.5 or less. The optical density in the present invention means an optical densitometer PDA-65.
The optical densities Db, Dg and Dr measured by using filters (manufactured by Konica Corp.) through filters B, G and R. The maximum value among them is Dmax. The maximum value Dmax of the optical density of the magnetic recording layer of the present invention may be 1.5 or less, but is preferably small considering the influence on the photographic image, and preferably 0.8.
Or less, particularly preferably 0.3 or less.

In the present invention, various supports can be used as the support. 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.

The polyester support is not particularly limited, but aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid and ethylene glycol, 1,3-propanediol, 1,4-butanediol, etc. Examples thereof include condensation polymers with alkylene glycols such as polyethylene terephthalate, polyethylene-2,6-dinaphthalate, polypropylene terephthalate, polybutylene terephthalate, and copolymers thereof.

In particular, from the curl recovery property after development processing, JP-A 1-244446, 1-291248, 1-298350, 2-89045, 2-93641, Ibid 2-181749
It is preferable to use a polyester having a high water content as shown in JP-A No. 2-214852 and JP-A No. 2-291135.

Further, it is more preferable to use a support as shown in Japanese Patent Application No. 5-99649 in which two or more layers of copolyester having different water contents are laminated.

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 support is used for the purpose of neutralizing the tint of the minimum density portion, preventing the light piping phenomenon (edge fogging) that occurs when light enters the film coated with the photographic emulsion layer from the edge, and preventing halation. Dyes can be included.

The type of dye is not particularly limited, but when a polyester film is used as the support, it is preferable that it has excellent heat resistance in the film forming process, and examples thereof include anthraquinone chemical dyes. Further, as the color tone, when it is intended to prevent light piping, gray dyeing is preferable as seen in general light-sensitive materials. As the dye, one kind or a mixture of two or more kinds may be used. Mitsubishi Kasei Co., Ltd. Diaresin, Bayer MACROLEX
It is possible to achieve the target by using such dyes alone or in an appropriate mixture.

The photographic light-sensitive material having the magnetic recording layer of the present invention is a black-and-white light-sensitive material, a color negative light-sensitive material, a color paper light-sensitive material, a color reversal light-sensitive material, a movie light-sensitive material, an X-ray. Any photosensitive material such as a photosensitive material, a photosensitive material for printing, a photosensitive material for microphotography, etc. may be used.

The silver halide grain contained in the silver halide photographic emulsion may be a grain in which a latent image is mainly formed on the surface, or may be a grain in which a latent image is mainly formed inside the grain.

The binder used in the magnetic recording layer is a thermoplastic resin, a radiation curable resin, a thermosetting resin, or any other reactive resin, which may 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 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 usually be used as solvent-based or water-based emulsions or water-based colloidal solutions. 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 rays, and is a maleic anhydride type, urethane acryl type, ether acryl type, epoxy acryl type solvent-based or water-based emulsion type. Can be mentioned.

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

The binders listed above may have a polar group in the molecule. Epoxy group as polar group, -CO
_{OM, -OH, -NR 2, -NR} 3 X, -SO 3 M, -OSO 3 M, -PO
₃ M ₂ and —OPO ₃ M (M is hydrogen, an alkali metal, or ammonium, X is an acid that forms an amine salt, and R is hydrogen or an alkyl group).

Other hydrophilic binders that can be used in the present invention include, for example, Research Disclosure.
No.17643, page 26, and No. 18716, page 651 can be mentioned water-soluble polymers, cellulose ethers, latex polymers, and water-soluble polyesters.

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, etc. 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. Examples of hardeners that can be used include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethylurea), and 2-hydroxy-4,6-dichloro-. 1,3,5-triazine,
Compounds having a reactive halogen described in U.S. Pat.Nos. 3,288,775, 2,732,303, British Patent 974,723, 1,167,207, etc., divinyl sulfone, 5-acetyl-1,3 -Diacryloylhexahydro-1,3,5-triazine, U.S. Pat.Nos. 3,635,718, 3,232,763, British Patent 994,869 and the like, compounds having a reactive olefin, N- Hydroxymethylphthalimide, US Patent 2,732,
No. 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.No. 3,017,
No. 280, aziridine compounds described in 2,983,611, etc., U.S. Pat.No. 2,725,294,
Examples thereof include acid derivatives described in US Pat. No. 2,725,295, epoxy compounds described in US Pat. No. 3,091,537, and halogen carboxaldehydes such as mucochloric acid. Further, an inorganic hardener may be used, and examples of the inorganic hardener include chrome bright vane and zirconium sulfate.
JP-B-56-12853, JP-B-58-32699, Belgian patent 825,726, JP-A-60-225148, JP-A-51
-126125, Japanese Patent Publication No. 58-50699, Japanese Patent Publication No. 52-5442
The carboxyl group-activating type hardeners described in JP-A No. 7, U.S. Pat. No. 3,321,313 and the like can also be mentioned.

The hardener is usually added in an amount of 0.01 based on 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 using an organic solvent and water, 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, a ketone system such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, tetrahydrofuran, etc. 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 preparing magnetic coating, protective layer, overcoat layer, a conventional kneading machine, for example, two-roll mill, three-roll mill, ball mill, pebble mill, tron mill, sand grinder, Sz
egvari Attritor, high speed impeller,
Disperser, High Speed Stone Mill, High Speed Impact Mill, Disper, Kneader, High Speed Mixer, Revosiblender, Cokneader, Intensip Mixer, Tumbler, Blender, Disperser, Homogenizer, Single Screw Extruder, Twin Screw Extruder and An ultrasonic disperser or the like can be used.

The magnetic recording layer, the protective layer and the overcoat layer may be provided on the support by an extrusion coater, an air doctor coat, a blade coat, an air knife coat, a squeeze coat, an impregnation coat, a reverse roll coat, Transfer roll coat, gravure coat, kiss coat, cast coat, spray coat, etc. can be used. In order to perform multi-stripe coating, these coating heads may be arranged in multiple rows. As a specific method of stripe coating, for example, Japanese Patent Application Laid-Open No. 48-255
No. 03, No. 48-25504, No. 48-98803, No. 50
-138037, 52-15533, 51-3208,
No. 51-6239, No. 51-65606, No. 51-140703, Japanese Patent Publication No. 29-4221, U.S. Pat.No. 3,062,181, No. 3,227,165 can be referred to the description. .

An undercoat layer may be provided on the support in order to firmly adhere these magnetic recording layers to the support.
The substrate is subjected to surface activation treatment such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, concentrated acid treatment and ozone oxidation treatment. Good. 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. Further, the ferromagnetic metal component may contain a small amount of water, hydroxide or oxide.

The methods for producing these ferromagnetic powders are 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 any 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, SBET is 20 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 may be treated with a substance containing an element such as titanium, silicon or aluminum, carboxylic acid, sulfonic acid, sulfuric acid ester, phosphonic acid). It may be treated with an organic compound such as an acid, a phosphoric acid ester, an adsorptive compound having a nitrogen-containing heterocycle such as 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. For these magnetic recording layers,
It is described in JP-A-47-32812 and JP-A-53-109604.

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

The thickness of the magnetic recording layer is preferably 0.01 to 20 μm, more preferably 0.05 to 15 μm, and further preferably
0.1 to 10 μm.

When forming an optically transparent magnetic recording layer, the binder is preferably used in an amount of 1 to 20 parts by weight per 1 part by weight of the magnetic powder. More preferably, it is 2 to 15 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 the layer to improve smoothness, and S of magnetic output is obtained.
It is also possible to improve the / N ratio. In this case, it is preferable to apply the silver halide photographic light-sensitive layer after the calendering treatment.

After the magnetic recording layer is provided, the surface of the layer is subjected to calendering to improve the smoothness, and the S / N ratio of the magnetic output is increased.
It is also possible to improve the ratio. In this case, it is preferable to apply the silver halide photographic light-sensitive layer after the calendering treatment.

Examples of the abrasive include non-magnetic inorganic powders having a Mohs hardness of 5 or more, preferably 6 or more. Specifically, aluminum oxides (α-alumina, γ-alumina,
Corundum, etc., Chromium oxide (Cr ₂ O ₃ ), Iron oxide (α-
Fe ₂ O ₃ ), oxides such as silicon dioxide and titanium dioxide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond. Their average particle size is 0.
01 to 1.0 μm is preferable, and it can be added in the range of 0.5 to 30 parts by weight with respect to the binder 100 of the outermost layer.

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. Non-stoichiometric hydrides, such as 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 and the} like, or composite oxides thereof are preferable, and ZnO, TiO ₂ and SnO ₂ are particularly preferable. Examples of containing different atoms include adding Al, In, etc. to ZnO, adding Nb, Ta, etc. to TiO ₂ , and adding Sb, Nb, halogen elements, etc. to SnO ₂ . It is effective. The addition amount of these heteroatoms is preferably in the range of 0.01 to 25 mol%, and particularly preferably in the range of 0.1 to 15 mol%.

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 the fine particles of the metal oxide are mixed in an aqueous solution.

In addition to these, conductive fine powders such as carbon black and carbon black graft polymers, nonionic surfactants such as alkylene oxides, glycerin and glycidols; higher alkyl amines, quaternary ammonium salts, pyridine and others. Of heterocyclic compounds, cationic surfactants such as phosphonium or sulfonium compounds; anionic surfactants containing acidic groups such as carboxylic acids, phosphorus compounds, sulfate ester groups, and phosphoric acid ester groups; amino acids, amino sulfones Examples thereof include amphoteric surfactants such as acids, sulfuric acid or phosphoric acid esters of amino alcohols.

These surfactants may be contained as a substituent of the polymer.

In the present invention, a general matting agent may be used. In that case, 100 mg / m ² or less is preferable, and 50 mg / m ² or less is more preferable. The matting agent is preferably added in a large amount for anti-blocking property and sticking, but it is preferable for it to be small because it causes an increase in turbidity and deterioration of photographic properties such as graininess.

Specific examples of the matting agent are shown below, but the matting agent is not limited thereto.

[0059]

[Chemical 1]

[0060]

[Chemical 2]

The polyethylene wax according to the present invention means polyethylene wax, polypropylene wax and the like, and includes a wax whose main chain is a polymer of ethylene or propylene.

The physical properties of polypropylene waxes are determined by the difference in molecular structure and molecular weight. The molecular structure with less branches has a higher density (density 0.96 or more), and the molecular structure with more branches has a lower density (density 0.93). Below).

The polyethylene wax is classified into a general type having no substituent and an oxidation type having a substituent such as a hydroxyl group, a carboxy group and a sulfo group.

As a concrete example, Mitsui Petrochemical Industry
Examples include high wax series manufactured by Sanyo Chemical Co., Ltd., sun wax series manufactured by Sanyo Chemical Industry Co., Ltd., and Viscole series, but the present invention is not limited thereto.

There is no limitation on the average molecular weight of the polyethylene wax, but if the average molecular weight is low, the mechanical strength will be low, and if it is high, the solution viscosity will be high and the coating properties will be adversely affected. A preferable average molecular weight is preferably Mn = 700 to 15,000,
900-11000 are more preferable, and 2000-5000 are the most preferable.

The density can be used from low density to high density without limitation. Preferred is 0.89 to 0.99, more preferably 0.
93 to 0.95.

Although the molecular structure is not limited, an oxidized type having a substituent such as a hydroxyl group, a carboxy group and a sulfo group is more preferable than a general type having no substituent because the back surface stain after development is good. A molecular structure having a carboxyl group with an acid value of 5 to 55 is more preferable.

The melting point is not particularly limited, but is preferably 100 to 150 ° C.

The polyethylene wax exhibits lubricity just by coating and improves scratch resistance, but it is preferable to heat-treat it in order to fix it more strongly to the surface. The heat treatment temperature is preferably 5 ° C. or more higher than the melting point, and the treatment time is preferably 10 seconds or more.

The polyethylene wax can be used without any limitation on the method of use and the coating amount. As a specific example, it is cooled and precipitated in a solvent, or pulverized by a mechanical force using a disperser such as a ball mill or a sand mill to form a solvent suspension or a solvent emulsion to form an overcoat layer. Apply. An amount of polyethylene wax after coating amount drying of the overcoat layer, the preferred range is preferably 0.1~80mg / m ^2, more preferably 1 to 30 mg / m ^2, and most preferably 5 to 10 mg / m ^2.

A small amount of a surfactant may be used for stabilization in preparing a solvent suspension or a solvent emulsion.

Further, a binder may be added to the solvent suspension or solvent emulsion to apply it as a protective layer. As the binder to be added, any binder that can be used in the transparent magnetic layer can be used, and the binders in the transparent magnetic layer and the protective layer may be the same or different. The amount of binder added is 0.
It is preferably added in an amount of 1 to 50 wt%, more preferably 1 to 30 wt%, most preferably 5 to 15 wt%.

The thickness of the protective layer after drying is preferably 0.05 to 3 μm, more preferably 0.1 to 1.5 μm, most preferably 0.3 to 1.0 μm. In the present invention, the overcoat layer does not contain a binder, and the layer containing the binder is defined as a protective layer.

The polyethylene wax may be used alone or as a mixture with a lubricant used in another magnetic recording medium. Examples of the lubricant include silicone oil such as polysiloxane, higher fatty acid, higher fatty acid ester and the like.

[0075]

EXAMPLES Specific examples of the present invention will be described below.
The embodiments of the present invention are not limited to these.

[Examples 1 to 17, 20 to 26] 1-1) Preparation of undercoating base <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, two of the three 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 (laminated type of materials having different moisture absorption)
² min) corona discharge treatment, and the following subbing coating solutions U-1 and U-2 were applied to the outer side of the thin copolyester.
Undercoat layer having an antistatic function by applying a dry film thickness of 0.8 μm and 0.1 μm, and then applying the undercoating coating solution U-3 below to the dry film thickness of 0.8 μm on the other surface. A formed support was prepared.

(Undercoating 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 liquid 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.

(Subbing coating liquid U-3) Polyester latex liquid (solid content 30%) 223 g Tin oxide fine powder (average particle size 0.1 μm) “SN100P” Ishihara Sangyo 107 g These are mixed and dispersed to prepare water / isopropanol. 1000 g of the 3/1 mixture was added.

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

[0083]

[Chemical 3]

1-2) Coating of magnetic recording layer On the coating of the undercoat layer U-3 of the above-mentioned undercoating base, a magnetic coating material having the following composition is used to form a dry film thickness of 0.8 μm by using a precision extrusion coater. Thus, the coating was dried while the coating film was not dried yet while the magnetic substance was oriented in the coating direction in the orientation magnetic field.

(Magnetic paint M-1) Cobalt-containing gamma iron oxide 3 parts by weight Average major axis length 0.8 μm Fe ²⁺ / Fe ³⁺ = 0.2, Hc 600 Oe Nitrocellulose resin 100 parts by weight BTH-1 / 2 (Asahi Kasei) Aerosil TT-600 (manufactured by Nippon Aerosil Co., Ltd.) 5 parts by weight Cyclohexanone 75 parts by weight Methyl ethyl ketone 150 parts by weight Toluene 150 parts by weight These were kneaded and dispersed to obtain a magnetic coating material.

After coating the magnetic recording layer, the following WAX solution was applied to the coating amount shown in Table 1 and dried, and heat-treated at a temperature 5 ° C. higher than the melting point of each wax shown in Table 1 for 10 seconds.

WAX liquid W-1 Polyethylene-based WAX described in Table 1 0.5 parts by weight Toluene 700 parts by weight or more are heated and dissolved, and cooled to precipitate a polyethylene-based wax, which is then dispersed in a sand mill to form a WAX liquid. did.

1-3) Coating of Photosensitive Material Layer The surface opposite to the surface having the magnetic recording layer, that is, the undercoat layer U-2.
After applying a corona discharge treatment of 25 W / (m ² · min) on the
A multilayer color light-sensitive material having the emulsion layer structure of Example 1 described in Japanese Patent Application No. 4-267697 was prepared, and a photographic light-sensitive material was prepared. This is designated as Sample No. 1.

In the multi-layer emulsion layer, 13.7 g of gelatin, 2.3 g of 0.3-0.4 μm and 0.7-0.8 μm silver halide grains per m ² , respectively, an oil drop amount of 2.8 g, and a film thickness of 27 μm
Is.

[Examples 18 and 19] WAX liquid W- of Example 1
It was produced in the same manner as in Example 1 except that 1 was changed to W-2 below.

WAX liquid W-2 Polyethylene-based WAX 2.0 parts by weight shown in Table 1 700 parts by weight or more of toluene are heated and dissolved, and cooled to precipitate a polyethylene-based wax, which is then dispersed by a sand mill to obtain a WAX liquid. did.

[Examples 27 to 29] WAX liquid W- of Example 1
It was produced in the same manner as in Example 1 except that 1 was changed to W-3 below.

WAX liquid W-3 Polyethylene-based WAX shown in Table 1 7 parts by weight Water emulsion (solid content 20 wt%) Water 700 parts by weight Surfactant 3 parts by weight (Compound K-1) The above was sufficiently stirred with a dissolver. Then, a WAX liquid was obtained.

[Example 30] A WAX liquid W-1 of Example 1 was prepared in the same manner as in Example 1 except that the following W-4 was used.

WAX liquid W-4 Polyethylene-based WAX described in Table 1 28 parts by weight Water emulsion (solid content 20% by weight) Water 700 parts by weight Surfactant 3 parts by weight (Compound K-1) The above was thoroughly stirred with a dissolver. Then, a WAX liquid was obtained.

[0096]

[Chemical 4]

[Comparative Example 1] The procedure of Example 1 was repeated except that the polyethylene wax of Example 1 was omitted.

Comparative Example 2 Example 1 was repeated except that the polyethylene wax of Example 1 was changed to the wax shown in Table 1.
It was made in the same manner as.

<Development Treatment> The produced film base and photographic light-sensitive material were subjected to development treatment with the treatment process shown below and the treatment liquid having the composition shown below.

Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing with water 2 minutes 10 seconds Fixing 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Stability 1 minute 05 seconds The processing solution composition used in each step is as follows. It was on the street.

Color developer Diethylenetriaminepentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine sulfate 2.4 g 4- (N-Ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 g Water was added to 1.0 l pH 10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0 g Ethylenediaminetetraacetic acid disodium salt 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Water added 1.0 l pH 6.0 Fixer Ethylenediaminetetraacetic acid disodium 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 mg Sodium bisulfite 4.6 g Water added 1.0 l pH 6.6 Stabilizer Formalin (40%) 2.0mg Polyoxyethylene-p-monononylphenyl ether Tell (average degree of polymerization: 10) 0.3 g Water was added, and the following evaluation was performed on the sample obtained as described above in 1.0 liter.

(1) Turbidity Turbidity before applying an emulsion 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 Using a HEIDON Tribogear type 14DR surface measuring device, a stainless steel ball (10 mmφ) was loaded with a load of 50 g, and 5 cm / se.
Sliding was repeated 100 times at a speed of c. The degree of scratches thereafter was evaluated according to the ranks shown below.

5: No scratches 4: There is a slight trace of sliding 3 ... There is a trace of scratching 2 ... There is scratching 1 ... There is film peeling. There is no problem.

(3) Density Measured according to JIS K6760.

(4) Average molecular weight It was measured by the GPC method (number average).

(5) Acid value Measured according to JIS K5902.

(6) Coating Property The coating property of the overcoat layer was visually evaluated according to the ranks shown below.

A: A level that is clean and does not indicate that it has been applied B ... A level that indicates that the application is faint due to light reflection C ... A level that indicates that the application has been applied by transmitted light There is no problem and there is no problem.

(7) Backside stain after development The produced photographic light-sensitive material was cut into a width of 35 mm, subjected to normal development processing by a film hanger automatic development processor (HM-55S: manufactured by Noritsu Koki Co., Ltd.), and visually inspected. Shown below is the backside dirt. 4
Graded.

A: No stain on the back surface B: Spotted stains are visible C: Traces of the developing solution are slightly visible D: Traces of the developing solution are clearly visible C or more In that case, there is no problem in printing and there is no problem.

The above results are shown in Tables 1 and 2.

[0113]

[Table 1]

[0114]

[Table 2]

Wax No. Wax 2 High Wax 100 Mitsui Petrochemical Industry Co., Ltd. Wax 3 Sun Wax 171-P Sanyo Chemical Industry
Wax 4 Sun Wax 151-P Sanyo Chemical Industry Co., Ltd.
Wax 5 Sun Wax 131-P Sanyo Kasei Co., Ltd.
Wax 6 Sun Wax 161-P Sanyo Kasei Co., Ltd.
Wax 7 Sun Wax 165-P Sanyo Kasei Co., Ltd.
Wax 8 Sun Wax LEL-250-P Sanyo Kasei Co., Ltd.
Wax 9 Sun Wax LEL-400-P Sanyo Chemical Industry Co., Ltd.
Wax 10 High Wax 1100 Mitsui Petrochemical Co., Ltd. Wax 12 High Wax 210M Mitsui Petrochemical Co., Ltd. Wax 15 Sun Wax E-310 Sanyo Chemical Industries
Wax 16 Sun Wax E-250-P Sanyo Kasei Co., Ltd.
Wax 17 High Wax 2203A Mitsui Petrochemical Co., Ltd. Wax 19 High Wax 1105A Mitsui Petrochemical Co., Ltd. Wax 20 Viscor 660-P Sanyo Kasei
Wax 21 Viscole 550-P Sanyo Kasei Co., Ltd.
Wax 22 Yumex 110TS Sanyo Chemical Industry Co., Ltd.
Wax 23 Permarin KUE-16 Sanyo Kasei Co., Ltd.
Wax 24 Permarin KUE-8 Sanyo Kasei Co., Ltd.
Wax 25 Carnauba Wax No. 1 manufactured by Kato Hiroyuki Kato Co., Ltd. From the results shown in Tables 1 and 2, it can be seen that the room temperature scratch resistance of Example is superior to that of Comparative Example 1 having no wax.

Further, it can be seen that the polyethylene wax of the example is superior to the wax of the comparative example 2 in high temperature scratch resistance. It can be seen that polyethylene wax having an average molecular weight of 900 or more is more excellent, and polyester having an average molecular weight of 900 or more and having an unsaturated terminal group is most excellent.

Further, it can be seen that the backside stain after development is superior in Example as compared with Comparative Example 2. Among them, the acid value is 5.0m
It can be seen that g-KOH / g or more is more excellent.

The oxidized polyethylene wax having a molecular weight of 900 or more, an unsaturated terminal group and an acid value of 5.0 to 55 mg-KOH / g is the most excellent.

[0119]

According to the present invention, a silver halide photographic which has excellent transparency required for a photographic light-sensitive material, has no scratches during recording and reproduction of a magnetic head in a wide temperature range, and has excellent scratch resistance. A photosensitive material can be provided.

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on one side of a support and a transparent magnetic recording layer on the other side, and at least a transparent magnetic recording layer. A silver halide photographic light-sensitive material characterized in that it contains at least one type of polyethylene wax on its side. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the polyethylene wax has a number average molecular weight of 900 or more. 3. The polyethylene wax has an acid value of 5
The silver halide photographic light-sensitive material according to claim 1 or 2, which is an oxidized polyethylene wax having a number of 55 or more. 4. The silver halide photographic light-sensitive material according to claim 1, 2 or 3, wherein the polyethylene wax has an unsaturated bond at an end thereof.