JPH07152100A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material excellent in transparency necessary for photographic material and good film holding characteristics by incorporating SiO2 having specified average primary particle size into a transparent magnetic recording layer. CONSTITUTION:This photographic sensitive material has at least one silver halide emulsion layer on at least one surface of a supporting body and a transparent magnetic recording layer on the other surface of the supporting body. The transparent magnetic recording layer contains SiO2 having <=0.9mum average primary particle size. The amt. of SiO2 is preferably 2 to 30wt.% of the binder in the layer to which SiO2 is added. The shape of the particle is not limited but a spherical particle is preferable, and further, a particle having a chain-shape structure is more preferable. Thereby, the obtd. transparent magnetic layer has excellent dispersion state of a magnetic powder and good electromagnetic conversion characteristics. Further, sedimentation or aggregation in the coating material to form the transparent magnetic layer is prevented and a transparent magnetic layer excellent in stability can be formed.

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 ferromagnetic fine particles are dispersed is provided on the emulsion surface or the back surface next to the image area to record information such as voice and photographing conditions. KAISHO 50-62627 publication, JP 49-4503 publication,
U.S. Pat.Nos. 3,243,376 and 3,220,843, etc., and transparent magnetic recording on the back surface of a photographic light-sensitive material to obtain the necessary transparency by selecting the amount and size of magnetizable particles. Providing layers is US license No. 3,782,947
No. 4,279,945, No. 4,302,523, and the like. Also, US Pat. No. 4,947,196 and WO90 / 04254 describe a photographing camera having a magnetic head together with a roll-shaped film having a magnetic recording layer containing a magnetic material that enables magnetic recording on the back surface of the photographic film. Has been done.

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, in the prior art, a large amount of a matting agent having a large particle size of 1 to 3 μm is added. Therefore, there is a problem that an error is likely to occur when recording and reproducing with the magnetic head. Further, since magnetic powder is added, there is a problem that turbidity becomes high.

In order to solve these problems, the matting agent having a large particle size is removed or reduced in a small amount, so that the emulsion surface is not affected when it is rolled in a cartridge or stored in a camera for a long time. It causes a fatal defect called "sticking" that sticks to the back side.

In the prior art, it was impossible to achieve both of them.

A first object of the present invention is to provide a silver halide photographic light-sensitive material having excellent transparency required for the photographic light-sensitive material and having good film storage characteristics.

A second object is to provide a silver halide photographic light-sensitive material having a transparent magnetic layer which is excellent in dispersion of magnetic powder and has good electromagnetic conversion characteristics.

A third object of the present invention is to provide a silver halide photographic light-sensitive material having a transparent magnetic layer which is excellent in stability and which prevents the coating material for the transparent magnetic layer from settling and aggregating.

[0013]

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

A silver halide photographic light-sensitive material having at least one silver halide emulsion layer provided on one side of a support and a transparent magnetic recording layer provided on the other side, wherein the transparent magnetic A silver halide photographic light-sensitive material characterized in that the recording layer contains SiO ₂ having an average primary particle diameter of 0.9 μm or less.

The silver halide photographic light-sensitive material as described above, wherein the SiO ₂ has a chain structure.

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. 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 and curl recovery 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.

Furthermore, 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 (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 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, X-rays. 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 ester copolymer, acrylonitrile-styrene copolymer, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylic resin, Polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene-
Examples thereof include rubber-based resins such as butadiene resin and butadiene-acrylonitrile resin, silicone-based resin, and fluorine-based resin.

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

These can be usually 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 or ultraviolet ray, 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.

The thermosetting resin and other reactive resins include phenol resin, epoxy resin, polyurethane-based curable resin, urea resin, alkyd resin, silicone-based curable resin, etc., 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 usable 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,
U.S. Pat.No. 3,288,775, 2,732,303,
British Patent No. 974,723, compounds having a reactive halogen described in 1,167,207 and the like,
Divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, U.S. Pat.Nos. 3,635,718, 3,232,763 and British Patent 994,869 Compounds with reactive olefins, N-hydroxymethylphthalimide, US Patent
2,732,316, 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. 3,017,280, No. 2,983,611 Compounds described in U.S. Pat. No. 2,725,29
4, acid derivatives described in 2,725,295 and the like, epoxy compounds described in U.S. Pat.No. 3,091,537, halogen carboxaldehydes such as mucochloric acid. it can.
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 and water, coating the resulting mixture on a non-magnetic support, orienting it if necessary, and then drying it. 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-based compounds such as isobutyl alcohol, isopropyl alcohol, and methylcyclohexanol; ester-based compounds 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 magnetic paints, conventional kneaders such as two-roll mill, three-roll mill, ball mill, pebble mill, tron mill,
Sand grinder, Szegvari attritor, high speed impeller, disperser, high speed stone mill, high speed impact mill, disper, kneader, high speed mixer, revosiblender, 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.

As a method for providing a magnetic recording layer on a support, an extrusion coater, an air doctor coat, a blade coat, an air knife coat, a squeeze coat, an impregnation coat, a reverse roll coat, a transfer roll coat, a gravure coat, Kiss coat, cast coat, spray coat, etc. are available. In order to perform multi-stripe coating, these coating heads may be arranged in multiple rows. Specific methods of stripe coating include, for example, JP-A-48-25503, JP-A-48-25504, JP-A-48-98803, JP-A-50-138037, and JP-A-52-1553.
No. 3, No. 51-3208, No. 51-6239, No. 51-65
Reference can be made to the descriptions of Japanese Patent Nos. 606, 51-140703, Japanese Patent Publication No. 29-4221, US Pat. Nos. 3,062,181 and 3,227,165.

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 and barium ferrite 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. 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 any particular limitation. The shape is needle-like, 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 any particular limitation (the surface may be treated with a substance containing an element such as titanium, silicon, aluminum, carboxylic acid, sulfonic acid, sulfuric acid ester, phosphonic acid). (It may be treated with an organic compound such as an adsorptive compound having a nitrogen-containing heterocyclic ring such as an acid, a phosphoric acid ester, or 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 the magnetic recording layer is provided, the surface of this layer is subjected to a calendering process to improve the smoothness, and the magnetic output S
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 providing the magnetic recording layer, calendering is performed on the layer to improve smoothness, and S / N of 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 lubricant include silicone oils such as polysiloxane, plastic fine powders such as polyethylene and polytetrafluoroethylene, higher fatty acids, higher fatty acid esters, and fluorocarbons. These may be used alone or in combination. These may be added in an amount of 0.2 to 20 parts by weight with respect to 100 parts by weight of the binder. Those which can be dissolved or diffused in water are preferable.

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 ~ 1.0 μm is preferable, 0.5 ~ 30 per 100 magnetic powder
It can be added in the range of parts by weight.

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, etc., or a complex oxide of these is 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 , SnO
_{For 2} , it is effective to add Sb, Nb, halogen elements, etc. The added amount of these heteroatoms is preferably in the range of 0.01 mol% to 25 mol%, and particularly preferably in the range of 0.1 mol% 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 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 alkylamines, fourth
Primary ammonium salts, salts of pyridine and other heterocyclic compounds, cationic surfactants such as phosphonium or sulfonium compounds; carboxylic acids, phosphorus compounds, sulfate ester groups,
Anionic surfactants containing an acidic group such as a phosphoric acid ester group; amphoteric surfactants such as amino acids, aminosulfonic acids, sulfuric acid or phosphoric acid esters of aminoalcohol, and the like can be given.

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

In the present invention, a general matting agent may be used in combination with 0.9 μm or less of SiO ₂ . 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 blocking resistance and sticking, but it is preferable to add a small amount because it causes an increase in turbidity and deterioration in photographic properties such as graininess.

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

[0062]

[Chemical 1]

[0063]

[Chemical 2]

In the present invention, the average diameter of primary particles is 0.9 μm or less.
This can be achieved by adding SiO ₂ .

The addition amount is preferably 2 to 30% by weight, more preferably 5 to 15% by weight, based on the binder of the layer to which SiO ₂ is added. The addition amount per 1 m ² is preferably 1 to 200 mg / m ^2, more preferably 5 to 50 mg / m ^2.

The layer to which SiO ₂ is added may be any layer, but it is preferably added to a layer close to the uppermost layer, and most preferably added to the uppermost layer containing a binder.

The shape of the particles is not particularly limited, and any shape can be used, but spherical particles are preferable, and particle shapes having a chain structure are more preferable.

The particle shape having a chain structure means a shape in which 2 to 10 spherical particles are bonded, and for example, Technical Bulletin Aerosil (10), 1 issued by Nippon Aerosil Co., Ltd.
6, the shape is as seen in the transmission electron micrograph of Aerosil TT600 in FIG. An example of the spherical shape is shown in FIG. 6 on page 9 of the same.

The average particle diameter of the primary particles may be 0.9 μm or less, but the preferable range is 0.007 to 0.3 μm, more preferably 0.012 to 0.1 μm, most preferably 0.02 to 0.05 μm. The size of the chain structure is preferably 0.05 to 0.7 μm, more preferably 0.1 μm to 0.5 μm.

SiO ₂ may be surface-treated before use. The surface treatment is performed with halogenated silanes, alkoxysilanes, silazanes, siloxanes, etc., and can be made hydrophobic by introducing an alkyl group.

The method of addition is not particularly limited, and examples thereof include a method of adding powder, a method of dispersing and dispersing in a solvent, and a method of dispersing and adding in a binder. A preferred method is to add it after dispersing it in a binder.

[0072]

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 12, 14 to 18] 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) is provided on both sides of the support of this polyethylene terephthalate (a laminated type of materials having different moisture absorption).
² min) corona discharge treatment, and apply the following subbing coating solutions U-1 and U-2 to the outer side of the thin side of the copolyester so that the dry film thickness is 0.8 μm and 0.1 μm, respectively. The undercoating coating solution U-3 described below was coated on the other surface so that the dry film thickness was 0.8 μm, to prepare a support having an undercoating layer having an antistatic function.

(Undercoating coating solution U-1) Copolymer latex solution 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.

(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.

[0080]

[Chemical 3]

1-2) Coating of magnetic recording layer On the coating of the undercoat layer U-3 of the 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 BET-1 / 2 (Asahi Kasei) (Manufactured by Co., Ltd.) Solid content 70% SiO ₂ powder Cyclohexanone 75 parts by weight Methyl ethyl ketone 150 parts by weight Toluene 150 parts by weight These were kneaded and dispersed to prepare a magnetic paint.

After coating the magnetic recording layer, the following WAX liquid is wetted.
It was applied and dried to a film thickness of 10 μm.

(WAX Solution) Carnauba WAX 0.5 parts by weight Toluene 700 parts by weight The above was heated and stirred at about 70 ° C. in a water bath to dissolve carnauba WAX to prepare a WAX solution.

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

[Example 13] A magnetic paint M-1 of Example 1 was prepared in the same manner as in Example 1 except that the magnetic paint M-1 was changed to the following M-2.

(Magnetic paint M-2) 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 80 parts by weight BET-1 / 2 (Asahi Kasei) (Manufactured by Co., Ltd.) Solid content 70% SiO ₂ dispersion S-1 29 parts by weight Cyclohexanone 75 parts by weight Methyl ethyl ketone 150 parts by weight Toluene 150 parts by weight (SiO ₂ dispersion S-1) SiO ₂ powder 100 parts by weight TT-600 Japan Aerosil Co., Ltd. nitrocellulose resin 75 parts by weight BET-1 / 2 (Asahi Kasei Co., Ltd.) Solid content 70% Cyclohexanone 70 parts by weight Methyl ethyl ketone 140 parts by weight Toluene 140 parts by weight These are kneaded and dispersed to form a SiO ₂ dispersion. Obtained.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the SiO ₂ powder of Example 1 was changed to have an average particle size of 1.0 μm.

[Comparative Example 2] The same procedure as in Example 1 was carried out except that the SiO ₂ powder of Example 1 was omitted.

<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 Bleach 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 treatment liquid 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 150.0g Ammonium nitrate 10.0g Water added 1.0l pH 6.0 Fixer Ethylenediaminetetraacetic acid disodium 1.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0mg Sodium bisulfite 4.6g Water added 1.0l 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) Evaluation of sticking (adhesion resistance) Each of the samples 100 to 106 was 35 mm wide and 70 mm long.
Cut at 30 ℃, 80 ℃ so that they do not touch each other.
Store in an atmosphere of% RH for 1 day. Then, four sheets are piled up with the emulsion layer on top, sandwiched with cardboard of the same size, applied with a load of 800 g, and stored under an atmosphere of 55 ° C. and 80% RH for 3 days and 7 days.

Therefore, the sample was peeled off, the areas of three bonded portions were measured, and the average value was used to measure the adhesion resistance.

Rank Area of bonded portion A 0 to 10% B 10 to 30% C 30 to 50% D 50 to 80% E 80 to 100% (2) Turbidity SEP-PT- manufactured by Mitsubishi Kasei Kogyo Co., Ltd. The turbidity before applying the emulsion layer was measured using 501D type. If it is 20ppm or less, there is no problem as a product. The smaller the value, the better.

(3) Evaluation of magnetic recording output error In the signal input method disclosed in World Publication No. 90-04205, a photographic film magnetically input only once from the back layer before development is output 500 times with the developing magnetic head. And showed the number of times the error occurred. Note that the error means that the first output value is 10
It is 0% and it is less than 70%.

(4) Evaluation of Magnetic Paint Sedimentation Rate 100 ml of each magnetic paint was placed in a graduated cylinder, and after standing for 10 hours, the separation position of the liquid was directly read on the scale from the liquid surface. The closer it is to 100, the better the stability.

(5) Surface Roughness Ra A surface roughness measuring instrument model SE-3FK manufactured by Kosaka Laboratory Ltd. was used and measured under the following conditions in accordance with JIS surface roughness BO601.

Cut-off R0.25 Measurement length 2.5 mm Longitudinal magnification 50,000 times or more The results are shown in Table 1.

[0101]

[Table 1]

From the results shown in Table 1, it can be seen that the present invention has excellent transparency, excellent storage characteristics of the film, and excellent electromagnetic conversion characteristics and dispersion stability.

[0103]

According to the present invention, firstly, it is possible to provide a silver halide photographic light-sensitive material having excellent transparency required for a photographic light-sensitive material and having good film storage characteristics.

Secondly, it is possible to provide a transparent magnetic layer having excellent dispersion of magnetic powder and good electromagnetic conversion characteristics.

Thirdly, it is possible to provide a transparent magnetic layer having excellent stability by preventing sedimentation and aggregation of the coating material for the transparent magnetic layer.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer provided on one side of a support and a transparent magnetic recording layer provided on the other side, wherein A silver halide photographic light-sensitive material characterized in that the transparent magnetic recording layer contains SiO ₂ having an average primary particle size of 0.9 μm or less. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the SiO ₂ has a chain structure.