JPH0581652A - Magnetic recording material - Google Patents

Abstract

PURPOSE:To provide a magnetic material having improved dispersion stability and a silver halide photographic sensitive material having a magnetic recording layer contg. the magnetic material and having excellent transparency and magnetic characteristics. CONSTITUTION:A magnetic material dispersed in a binder and forming a magnetic recording layer is composed of internal magnetic particles and coating layers of an org. polymer having a thickness >=0.05 time as large as the particle diameter of the magnetic particles on the surfaces of the particles. A silver halide photographic sensitive material characterized by the presence of a magnetic recording layer contg. the magnetic material is formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a magnetic material, and particularly to a magnetic material having improved dispersion stability and improved transparency of a magnetic recording layer. It is another object of the present invention to provide a silver halide photographic light-sensitive material (hereinafter abbreviated as photographic light-sensitive material, photographic film, light-sensitive material) having a magnetic recording layer containing the above magnetic material.

[0002]

2. Description of the Related Art Magnetic recording has become an important and general recording method such as video tape, audio tape, floppy disk and magnetic card. These magnetic recordings
Each has different uses and usages, but basically, magnetic recording is performed by dispersing a ferromagnetic material in a binder to prepare a coating solution of a magnetic material and applying it thinly and uniformly on a support. A layer is formed. Analog signals such as voice and music and digital signals from a computer are magnetically recorded on the magnetic recording layer as a series of minute magnets via a magnetic head. Therefore, it is the mission of the magnetic recording layer to record and reproduce such information as faithfully as possible to the original signal. In that case, the quality of the magnetic recording and reproducing characteristics depends not only on the magnetic properties of the magnetic material, but also on the dispersibility of the magnetic material in the binder. That is, the arrangement of magnetic materials depending on the dispersibility, the agglomerates, the adsorptivity of the binder, and the size of the secondary agglomerates have a great influence on the magnetic properties. However, there has been little knowledge about the dispersion of magnetic materials in the past, and it was extremely difficult to use them.
In general production, a magnetic material such as acicular magnetic ferric oxide γFe ₂ O ₃ or acicular chromium oxide CrO ₂ is dispersed with a binder and a solvent in a mixing / dispersing machine (for example, a kneader or a sand mill), Apply the solution by filtering it
Used with magnetic field orientation. However, it is very difficult to miniaturize the magnetic material due to insufficient dispersion or aggregation in the coating liquid in a short time to form coarse particles.

Recently, attempts have been made to apply this magnetic recording layer to photographic films. That is, it is known that the conventional photographic film optically imprints information (for example, the date and time), but more information (for example, photographing condition, person to be photographed, number of prints, trimming information, etc.) is added. Although it could not be done, there is an advantage that the above information can be arbitrarily added by adding the magnetic recording layer to the photographic film. In order to impart a magnetic recording layer to a photographic film, it is essential that the photographic performance is not deteriorated and that the magnetic characteristics are sufficiently exhibited. For example, these are disclosed in Japanese Examined Patent Publication Nos. 42-4539 and 57-6576. The deterioration of transparency and the deterioration of graininess caused by coarse particles due to agglomeration of magnetic materials pose a serious problem, which is a particular problem in photographic performance. On the other hand, in the conventional magnetic recording layer, the stability of the coating solution of the magnetic material was stable to the extent that it could be manufactured by a method using a large amount of magnetic material and a small amount of binder and high viscosity. However, when this conventional high-viscosity magnetic material coating liquid is applied to a photographic film, it cannot be thinned and its transparency is greatly deteriorated.

Therefore, as a method of increasing the transparency of a photographic film, the required S / N ratio may be small if the magnetic recording is performed by a digital signal. In that case, the coating amount of the magnetic material is video. The amount of tape, audio tape, etc. can be reduced to 1/10 to 1/100 and transparency can be maintained. However, it is necessary to reduce the concentration of the magnetic material in the coating liquid in order to reduce the amount of the magnetic material and reduce the film thickness. In that case, the magnetic material easily coalesces and agglomerates in the coating liquid to form lumps, which is a problem in photographic performance. As a solution to these problems, surface modification of the magnetic material has been attempted (for example, imparting a very thin titanium oxide to the surface) in order to improve the dispersion stability of the magnetic material. For example, JP-A-60-196905 and 58-22243.
No. 3, No. 59-23505 and the like. Although these methods do improve some dispersion stability, they were not able to achieve the sufficient dispersion stability required for photographic films.

[0005]

Therefore, a first object of the present invention is to provide a magnetic material having excellent dispersion stability in a coating solution. The second object is to provide a magnetic material that provides a magnetic recording layer having excellent transparency. The third object is to provide a photographic film having excellent magnetic properties.

[0006]

Means for Solving the Problems The above-mentioned problems are, in a magnetic material dispersed in a binder, the magnetic material having magnetic particles inside and having a particle size of 0.0 of the particle diameter of the magnetic particles on the surface.
It has been achieved by a magnetic material characterized by having a coating layer made of an organic compound having a thickness of 5 times or more. Hereinafter, the present invention will be described in detail. First, the magnetic particles present inside the magnetic material of the present invention will be described. As the magnetic particles used in the present invention, ferromagnetic iron oxide, Co-doped ferromagnetic iron oxide, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, barium ferrite, Co-containing magnetite and the like can be used. As an example of a ferromagnetic alloy, the metal content is 75 wt
%, And 80% by weight or more of the metal content is at least one ferromagnetic metal or alloy (Fe, Co, Ni, Fe)
-Co, Fe-Ni, Co-Ni, Co-Fe-Ni, etc.) and other components (A
l, Si, S, Sc, Ti, V, Cr, Mn, Cu, Z
n, Y, Mo, Rh, Pd, Ag, Sn, Sb, B, B
a, Ta, W, Re, Au, Hg, Pd, P, La, C
e, Pr, Nd, Te, Bi, etc.) can be mentioned. Further, the ferromagnetic metal component may contain a small amount of water, hydroxide or oxide.

Methods for producing these ferromagnetic powders are known,
The ferromagnetic material used in the present invention can also be manufactured according to a known method. The shape and size of the ferromagnetic material are not particularly limited and can be widely used. The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like. The crystallite size and the specific surface area are not particularly limited, but in the case of the crystallite size and the spherical shape, 0.01 μm to 5 μm is preferable, and 0.02 to 4 μm is particularly preferable. In the case of needles, the major axis is 0.02 to 10 μm and the minor axis is 0.01 to 2 μm.
In m, the ratio of the major axis to the minor axis is preferably 100: 1 to 3: 1,
Further, the major axis is more preferably 0.4 to 8 μm, the minor axis is more preferably 0.02 to 1 μm, and the ratio of the major axis to the minor axis is more preferably 100: 1 to 5: 1. When the magnetic particles are plate-shaped such as barium ferrite, the plate-shaped maximum length is 0.1 to 20 μm and the thickness thereof is 0.02 to 3 μm, and more preferably the plate-shaped maximum length. Is 0.1 to 10 μm and its thickness is 0.0
2 to 2 μm is preferable. At this time, the plate-shaped maximum length-thickness ratio (so-called aspect ratio) is 2 to 100, and preferably 4 to 30. Further, when the magnetic particles are cubic or polyhedral, the length of one side is 0.05 to 3 μm, and more preferably 0.15 to 1.5 μm.

These magnetic particles of the present invention have a coating layer made of an organic polymer on the surface thereof, which will be described below. The organic polymer that constitutes the coating layer of the present invention is not particularly limited. Preferably, known thermoplastic resins, thermosetting resins, radiation curable resins, reactive resins, natural polymers and mixtures thereof can be used. As the thermoplastic resin, a vinyl chloride / vinyl acetate copolymer,
Vinyl system such as vinyl chloride, vinyl acetate and vinyl alcohol, maleic acid and / or acrylic acid copolymer, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / acrylonitrol copolymer, ethylene / vinyl acetate copolymer Copolymer / nitrocellulose, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose derivatives such as cellulose acetate butyrate resin, acrylic resin, polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane,
Polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin,
Examples thereof include rubber resins such as styrene butadiene resin and butadiene acrylonitrile resin, silicone resins, and fluorine resins.

The above-mentioned thermosetting resin or reactive resin is a resin whose molecular weight becomes extremely large by heating, and examples thereof include phenol resin, phenoxy resin, epoxy resin,
Curable polyurethane resin, urea resin, melamine resin, alkyd resin, silicone resin, acrylic reaction resin, epoxy-polyamide resin, nitrocellulose melamine resin, mixture of high molecular weight polyester resin and isocyanate prepolymer, urea formaldehyde resin, low molecular weight glycol / High molecular weight diol / polyisocyanate mixtures, polyamine resins, and mixtures thereof.

As the radiation curable resin, a resin obtained by bonding a group having a carbon-carbon unsaturated bond as a radiation curable functional group to the thermoplastic resin is used. Preferred functional groups include an acryloyl group and a methacryloyl group. In the binder molecules listed above, polar groups (epoxy group, CO ₂ M, OH, NR ₂ , NR ₃ X, SO ₃ M, O
SO ₃ M, PO ₃ M ₂ , OPO ₃ M ₂ , wherein M is hydrogen, alkali metal or ammonium, and when there are plural Ms in one group, R may be hydrogen or (Which is an alkyl group) may be introduced. The content of the polar group is 10 ^-7 to 10 ^-3 equivalent, preferably 10 ^-6 to 1 gram per gram of the polymer.
10 ⁻⁴ equivalent is a preferable range. The above-listed organic compounds for surface coating of magnetic particles are used alone or as a mixture of several kinds, and a known epoxy-based, aziridine-based, isocyanate-based cross-linking agent, and / or a radiation-curable vinyl-based monomer are added for curing treatment. Can be used, and is a particularly preferable use form. For example, a polyisocyanate compound having two or more isocyanate groups is preferable as the isocyanate crosslinking agent, and examples thereof include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, naphthylene-1,5-diisocyanate, Isocyanates such as o-toluidine diisocyanate, isophorone diisocyanate, and triphenylmethane diisocyanate, reaction products of these isocyanates with polyalcohols, and polyisocyanates produced by condensation of these isocyanates can be mentioned.

The radiation-curable vinyl-based monomer is a compound which can be polymerized by irradiation with radiation and which has at least one carbon-carbon unsaturated bond in the molecule,
(Meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl esters, vinyl esters, vinyl heterocyclic compounds, N-vinyl compounds, styrene, (meth) acrylic acid, crotonic acid, itaconic acid, Examples thereof include olefinic acid. Of these, preferred are (meth) acrylates of polyethylene glycol such as diethylene glycol di (meth) acrylate and triethylene glycol di (meth) acrylate having two or more (meth) acryloyl groups, and trimethylolpropane tri (meth) acrylate. ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, a reaction product of a polyisocyanate and a hydroxy (meth) acrylate compound, and the like. These crosslinkers are preferably 5 to 45 wt% of the total binder including crosslinkers. Further, a hydrophilic binder can be used as the organic polymer for coating the surface of the magnetic particles of the present invention. As the hydrophilic binder to be used, Research Disclosure No. 17643, 2
6 and pp. 651, No. 18716, water-soluble polymers, cellulose esters, latex polymers, water-soluble polyesters, etc. are exemplified. Water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, maleic anhydride copolymers, etc., and carboxymethyl cellulose, hydroxyethyl cellulose as cellulose ester. And so on. As the latex polymer, vinyl chloride-containing copolymer, vinylidene chloride-containing copolymer,
Examples thereof include acrylic acid ester-containing copolymers, vinyl acetate-containing copolymers, butadiene-containing copolymers, and the like. The most preferred of these is gelatin. Gelatin is a so-called alkali-treated (lime-treated) gelatin that is immersed in an alkaline bath before extraction of gelatin in the manufacturing process thereof, an acid-treated gelatin that is immersed in an acid bath, and a double-dipped gelatin that has undergone both treatments and an enzyme treatment. Any of gelatin may be used. If necessary, a portion of colloidal albumin, casein,
Cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, agar, sodium alginate, starch derivatives, sugar derivatives such as dextran, synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymer,
Polyacrylamide or derivatives thereof, partial hydrolysates, gelatin derivatives and the like may be used in combination with gelatin.

Hardening the magnetic material coated with gelatin is preferred. Examples of hardeners that can be used in magnetic materials 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 and others U.S. Pat. No. 3,288,775
No. 2,732,303, British Patent 974,72
No. 3, 1,167,207, etc., compounds having a reactive halogen, divinyl sulfone,
5-acetyl-1,3-diacryloylhexahydro-
1,3,5-triazine and others US Pat. No. 3,63
5,718, 3,232,763, British Patent No. 9
94,869 and the like, compounds having a reactive olefin, N-hydroxymethylphthalimide, and other U.S. Pat. Nos. 2,732,316 and 2,5.
N-methylol compounds described in U.S. Pat. No. 86,168, isocyanates described in U.S. Pat. No. 3,103,437, U.S. Pat. No. 3,017,280.
No. 2,983,611 and the like, aziridine compounds described in US Pat. Nos. 2,725,294 and 2,725,295, and the like.
Examples thereof include epoxy compounds described in US Pat. No. 3,091,537 and halogen carboxaldehydes such as mucochloric acid. Alternatively, as a hardener for inorganic compounds, chrome alum, zirconium sulfate, JP-B-56-12853, JP-A-58-32699.
No., Belgian Patent No. 825,726, JP-A-60-22
5148, JP-A-51-126125, JP-B-58
Examples include carboxyl group-activating type hardeners described in JP-A-50699, JP-A-52-54427, US Pat. No. 3,321,313 and the like. The amount of the hardener used is usually 0.01 to 30% by weight based on dry gelatin,
It is preferably 0.05 to 20% by weight.

The method of coating the organic polymer of the present invention on the magnetic particles is not particularly limited. It is preferable to add the organic polymer in the previous stage to a liquid (for example, an organic solvent or an aqueous dispersion) in which the magnetic particles of the present invention are dispersed, and then add and disperse the organic polymer in a solvent in which the organic polymer is insoluble to obtain the desired magnetic material. Can be created. At this time, it is particularly preferable to fix the organic polymer on the surface of the magnetic particles by using the above-mentioned curing agent capable of curing the organic polymer. It is also preferable to add a polymerizable monomer to a liquid (for example, an organic solvent or an aqueous dispersion) in which the magnetic particles of the present invention are dispersed, and then polymerize on the surface of the magnetic particles to obtain a magnetic material coated with the organic polymer. .. In the present invention, the thickness of the organic polymer coated on the surface of the magnetic material is
It is 0.05 times or more, preferably 0.07 times or more, and more preferably 0.1 to 10 times the particle diameter of the magnetic particles. Here, the particle size of the magnetic particles indicates the diameter when the magnetic particles are spherical or polyhedral, the minor axis length when the magnetic particles are needle-like particles, and the thickness when the particles are plate-like. In the case of a cube, the length of one side is shown. The molecular weight of the organic polymer coated on the surface of the magnetic material of the present invention is 1,000 or more, and particularly preferably 3,000 to 1,000,000.

Next, the magnetic material of the present invention is used as a magnetic recording layer, and the binder preferably used in that case will be described below. The binder used in the present invention is a known thermoplastic resin, a thermosetting resin, a radiation curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer which has been conventionally used as a binder for magnetic recording media. Mixtures of these can be used. The fat has a Tg of −40 ° C. to 150 ° C. and a weight average molecular weight of 10,000 to
It is 1,000,000, preferably 10,000 to 300,000. Examples of the thermoplastic resin include vinyl chloride / vinyl acetate copolymers, vinyl chloride, vinyl acetate / vinyl alcohol, maleic acid and / or acrylic acid copolymers, vinyl chloride / vinyl chloride
Vinyl-based copolymers such as vinylidene chloride copolymer, vinyl chloride / acrylonitrol copolymer, ethylene / vinyl acetate copolymer / nitrocellulose, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate resin Cellulose derivatives such as, acrylic resin, polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane, polycarbonate polyurethane resin, polyester resin,
Examples thereof include rubber resins such as polyether resins, polyamide resins, amino resins, styrene butadiene resins, butadiene acrylonitrile resins, silicone resins, and fluorine resins. The thermosetting resin or the reactive resin whose molecular weight becomes extremely large by heating, for example, phenol resin, phenoxy resin, epoxy resin, curable polyurethane resin, urea resin, melamine resin, alkyd resin, silicone resin, acrylic resin. System reaction resin, epoxy-polyamide resin, nitrocellulose melamine resin, mixture of high molecular weight polyester resin and isocyanate prepolymer, urea formaldehyde resin,
Included are low molecular weight glycol / high molecular weight diol / polyisocyanate mixtures, polyamine resins, and mixtures thereof.

As the radiation-curable resin, the above-mentioned thermoplastic resin to which a group having a carbon-carbon unsaturated bond is bonded as a radiation-curable functional group is used. Preferred functional groups include an acryloyl group and a methacryloyl group. In the binder molecules listed above, polar groups (epoxy group, CO ₂ M, OH, NR ₂ , NR ₃ X, SO ₃ M, O
SO ₃ M, PO ₃ M ₂ , OPO ₃ M ₂ , wherein M is hydrogen, alkali metal or ammonium, and when there are plural Ms in one group, R may be hydrogen or Introducing (which is an alkyl group) is preferable from the viewpoint of dispersibility and durability of the magnetic material, and the effect of adding the fluorine-based oligomer surfactant of the present invention remarkably appears. The content of polar groups is 10 ⁻⁷ to 10 per 1 gram of polymer.
^-3 equivalents, and more preferably 10 ^-6 to 10 ^-4 equivalents, are preferable ranges. The above-listed polymer binders are used alone or as a mixture of several kinds, and can be cured by adding a known epoxy-based, aziridine-based, isocyanate-based crosslinking agent, and / or a radiation-curable vinyl-based monomer. .. As the isocyanate cross-linking agent, a polyisocyanate compound having two or more isocyanate groups,
For example, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, naphthylene-
Isocyanates such as 1,5-diisocyanate, o-toluidine diisocyanate, isophorone diisocyanate, and triphenylmethane diisocyanate, reaction products of these isocyanates and polyalcohols,
And polyisocyanates produced by condensation of these isocyanates.

The radiation-curable vinyl-based monomer is a compound which can be polymerized by irradiation with radiation and has one or more carbon-carbon unsaturated bonds in the molecule,
(Meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl esters, vinyl esters, vinyl heterocyclic compounds, N-vinyl compounds, styrene, (meth) acrylic acid, crotonic acid, itaconic acid, Examples thereof include olefinic acid. Of these, preferred are (meth) acrylates of polyethylene glycol such as diethylene glycol di (meth) acrylate and triethylene glycol di (meth) acrylate having two or more (meth) acryloyl groups, and trimethylolpropane tri (meth) acrylate. ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, a reaction product of a polyisocyanate and a hydroxy (meth) acrylate compound, and the like. These crosslinkers are preferably 5 to 45 wt% of the total binder including crosslinkers. Further, a hydrophilic binder can be used in the magnetic recording material of the present invention. Examples of the hydrophilic binder used include Research Disclosure No. 17643, page 26, and No. 18 of the same.
716, 651, water-soluble polymers,
Cellulose ester, latex polymer, water-soluble polyester, etc. are exemplified. Water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, maleic anhydride copolymers, etc., and carboxymethyl cellulose, hydroxyethyl cellulose as cellulose ester. And so on. Examples of the latex polymer include a vinyl chloride-containing copolymer, a vinylidene chloride-containing copolymer, an acrylic acid ester-containing copolymer, a vinyl acetate-containing copolymer, and a butadiene-containing copolymer. The most preferred of these is gelatin. Gelatin is a so-called alkali-treated (lime-treated) gelatin that is immersed in an alkaline bath before extraction of gelatin in the manufacturing process thereof, an acid-treated gelatin that is immersed in an acid bath, and a double-dipped gelatin that has undergone both treatments and an enzyme treatment. Any of gelatin may be used. If necessary, a part of them may be colloidal albumin, casein, carboxymethylcellulose, cellulose derivatives such as hydroxyethylcellulose, agar, sodium alginate, starch derivatives, sugar derivatives such as dextran, synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinyl. Pyrrolidone,
Polyacrylic acid copolymers, polyacrylamides or their derivatives, partial hydrolysates, gelatin derivatives and the like may be used in combination with gelatin.

It is preferable to harden the magnetic recording material containing gelatin. As a hardener that can be used in the magnetic recording layer,
For example, aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,3.
5-triazine and others US Pat. No. 3,288,77
5, No. 2,732,303, British Patent No. 974,7
23, 1,167,207 and the like, compounds having a reactive halogen, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, and others. US Patent No. 3,
Compounds having reactive olefins described in 635,718, 3,232,763, British Patent 994,869, etc., N-hydroxymethylphthalimide, and other US Patents 2,732,316. Issue 2
N-methylol compounds described in US Pat. No. 3,103,437, isocyanates described in US Pat. No. 3,103,437, and US Pat. No. 3,017,28.
0, 2,983,611 and the like, aziridine compounds, US Pat. Nos. 2,725,294 and 2,725,295 and the like, acid derivatives,
Examples thereof include epoxy compounds described in US Pat. No. 3,091,537 and halogen carboxaldehydes such as mucochloric acid. Alternatively, as a hardener for inorganic compounds, chrome alum, zirconium sulfate, JP-B-56-12853, JP-A-58-32699.
No., Belgian Patent No. 825,726, JP-A-60-22
5148, JP-A-51-126125, JP-B-58
Examples include carboxyl group-activating type hardeners described in JP-A-50699, JP-A-52-54427, US Pat. No. 3,321,313 and the like.

The amount of the hardener used is usually 0.01 to 30% by weight, preferably 0.05 to 20% by weight based on dry gelatin.
% By weight. The thickness of the magnetic recording layer is 0.1 μ to 10 μ,
Preferably 0.2μ ~ 5μ, more preferably 0.5μ ~
3 μ. The weight ratio of the magnetic particles to the binder is preferably 1: 100 to 40: 100, more preferably 5: 100 to 30: 100. The magnetic recording layer having the magnetic material of the present invention is a silver halide photographic material (hereinafter,
It is preferably used for a photographic film, a photographic light-sensitive material or a light-sensitive material. This photographic material will be described below. The magnetic recording layer containing the magnetic material of the present invention can be provided on the entire back surface of the photographic support by coating or printing or in the form of stripes. It is also preferable to simultaneously apply (co-cast) a solution of a binder in which a magnetic material is dispersed and a solution of a binder for preparing a support in the form of a stripe or stripes to prepare a support having a magnetic recording layer. in this case,
The two binders may have different compositions, but it is preferable that they have the same composition. Also, multi-layer co-casting of two or more layers,
For example, as the other layer, an antistatic layer, an antihalation layer, a scratch resistant layer, a slip layer, an antiadhesive layer, a dye layer, an undercoat adhesive layer, a UV absorbing layer and the like can be mentioned. The co-casting Giessor may be a type in which the coating solutions of the respective layers join at the tip of the Giessor, or a method in which the coating solutions join inside, or a method of combining the tips and internal joining. .. Further, it may be applied to a support, and as a method for applying it, air doctor coat, blade coat, air knife coat, squeeze coat, impregnation coat, reverse roll coat, transfer roll coat, gravure coat, kiss coat, cast coat, spray coat. Etc. can be used, and other methods are also possible, and specific explanations for these can be found in "Coating Engineering", pages 253 to 277 (Showa 46.
3.20. Issued). By such a method, the magnetic recording layer coated on the support is subjected to a treatment for orienting the magnetic material in the layer immediately while drying, if necessary, and then the formed magnetic recording layer is dried. The transport speed of the support at this time is usually 2 m / min to 500 m /
The drying rate is controlled at 20 ° C to 120 ° C. If necessary, the surface is smoothed to produce the magnetic recording layer of the present invention. These are described in, for example, Japanese Patent Publication No. 40-23625, Japanese Patent Publication No. 39-28368, and US Pat. No. 3,473,960. The method disclosed in Japanese Examined Patent Publication No. 41-13181 is considered to be a basic and important technique in this field.

The magnetic recording layer has improved lubricity, curl adjustment,
Functions such as antistatic and adhesion prevention may be provided together, or another functional layer may be provided to impart these functions. If necessary, a protective layer adjacent to the magnetic recording layer may be provided to improve scratch resistance. The back surface of the support having the magnetic recording layer can be subjected to calendering to improve smoothness and improve the S / N ratio of magnetic signals. In this case, it is preferable to apply the photosensitive layer on the support after the calendering treatment. Next, the support preferably used in the photographic light-sensitive material will be described. The material of the support of the light-sensitive material used in the present invention is not particularly limited, but various plastic films can be used, and preferable examples thereof include cellulose derivatives (for example, diacetyl, triacetyl, propionyl, butanoyl, acetylpropionyl-acetate, etc. ), Polyamide, polycarbonate described in U.S. Pat. No. 3,023,101, polyester (for example, polyethylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate polyethylene naphthalate, etc.) described in JP-B-48-40414, polystyrene. , Polypropylene, polyethylene, polysulfone, polyarylate, polyetherimide, etc.,
Particularly preferred are triacetyl cellulose and polyethylene terephthalate. Some of these films contain polar groups (epoxy, COOM, OH, NR ₂ , NR ₃ X,
SO ₃ M, OSO ₃ M, PO ₃ M ₂ , OP ₃ OM ₂ , where M is H, alkali metal, ammonia and R is H,
Alternatively, it may have an alkyl group having 1 to 20 carbon atoms). These supports of the present invention have a thickness of 75 μm or more and 30 μm or more.
It is 0 μm, and more preferably 90 μm to 200 μm.

If it is thinner than 75 μm, it is easily cut when a sudden tensile strength is applied, and if it is larger than 300 μm, the film strength becomes strong, but if it is stored in a film cartridge for a long time, poor contact with the magnetic head occurs. Cause In particular, when stored in a feeding type cartridge such as US Pat. No. 4,913,368, the magnetic properties are significantly deteriorated. A plasticizer may be added to these supports for the purpose of imparting flexibility and the like. Especially in cellulose ester, triphenyl phosphate, biphenyl diphenyl phosphate, dimethyl ethyl phosphate,
A plasticizer-containing material such as trimethoxyethyl trimellitate is preferred. Chemical treatment, mechanical treatment, or the like for firmly adhering a photographic layer (for example, a photosensitive silver halide emulsion layer, an intermediate layer, a filter layer, the transparent magne layer of the present invention or a conductive layer) on these supports, After surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, etc., direct photographic emulsion is applied and adhesive strength is applied. You may obtain, or after these surface treatment once,
Alternatively, an undercoat layer may be provided without surface treatment and a photographic emulsion layer may be coated thereon. At that time, for the cellulose derivative, a single layer of a gelatin solution dispersed in a methylene chloride / ketone / alcohol mixed organic solvent is applied to provide an undercoat layer. Gelatin hardeners include chromium salts (chrome alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6).
-Hydroxy-s-triazine, etc.), epichlorohydrin resin, vinyl sulfoalkyl-based curing agent, and the like. These undercoat liquids may contain various additives as required. For example surfactants,
Antistatic agents, antihalation agents, coloring dyes, pigments,
Examples include coating aids and antifoggants. When the undercoating liquid of the present invention is used, an etching agent such as resorcin, chloral hydrate, chlorophenol and the like can be contained in the undercoating liquid.

The subbing layer of the present invention comprises SiO ₂ , Ti
Inorganic fine particles such as O ₂ or polymethylmethacrylate copolymer fine particles (0.05 to 10 μm) can be contained as a matting agent. The undercoating liquid according to the present invention is a generally well-known coating method, for example, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, or US Pat. It can be applied by an extrusion coating method using a hopper described in Japanese Patent No. 294,294. As required, US Pat. Nos. 2,761,791, 3,508,947, 2,
941,898 and 3,526,528,
Two or more layers can be coated simultaneously by the method described in Yuji Harazaki, "Coating Engineering", page 253 (published by Asakura Shoten in 1973). Next, the photographic light-sensitive material will be described below. The light-sensitive material having the magnetic recording layer of the present invention is composed of a silver halide emulsion layer, a back layer, a protective layer, an intermediate layer, an antihalation layer and the like, and these are mainly used in the hydrophilic colloid layer. In that case, the binder of the hydrophilic colloid layer includes, for example, proteins such as gelatin, colloidal albumin and casein; cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose; sugar derivatives such as agar, sodium alginate and starch derivatives; synthetic hydrophilic colloids. For example, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide or derivatives and partial hydrolysates thereof, dextran, polyvinyl acetate, polyacrylic acid ester, rosin and the like can be mentioned.
Mixtures of two or more of these colloids may be used if desired. The most used of these is gelatin or its derivatives, and the gelatin referred to here is so-called lime-processed gelatin, acid-processed gelatin and enzyme-processed gelatin.

In the present invention, the anion, nonion,
A cation and a betaine fluorine-containing surfactant can be used in combination. These fluorine-containing surfactants are disclosed in JP-A-49-
No. 10722, British Patent No. 1,330,356, JP-A Nos. 53-84712, 54-14224, and 50.
-113221, U.S. Pat. No. 4,335,201,
No. 4,347,308, British Patent No. 1,417,91.
No. 5, Japanese Patent Publication No. 52-26687, No. 57-26719
No. 59-38573, JP-A-55-149938.
No. 54, No. 54-48520, No. 54-14224, No. 58-200235, No. 57-146248, No. 5
8-196544, British Patent No. 1,439,402
No., etc. Preferred specific examples of these are described below.

[0023]

[Chemical 1]

[0024]

[Chemical 2]

In the present invention, a nonionic surfactant may be used. Specific examples of the nonionic surfactant preferably used in the present invention are shown below.

[0026]

[Chemical 3]

The layer to which the fluorine-containing surfactant and the nonionic surfactant used in the present invention are added is not particularly limited as long as it is at least one layer of the photographic light-sensitive material. For example, a surface protective layer, an emulsion layer, an intermediate layer, Examples thereof include an undercoat layer and a back layer. The amount of the fluorine-containing surfactant and nonionic surfactant used in the present invention may be 0.0001 g to 1 g per square meter of the photographic light-sensitive material, more preferably 0.0005 to 0.5 g, Particularly preferred is 0.0005 g to 0.2 g. Further, two or more kinds of these surfactants of the present invention may be mixed.
Also, ethylene glycol, propylene glycol, 1,
1,1-trimethylolpropane etc. JP-A-54-896
Polyomal compounds as shown in No. 26 can be added to the protective layer or other layers of the present invention. Other known surfactants may be added to the photographic constituent layer of the present invention alone or as a mixture. Although they are used as coating aids, they are sometimes applied for other purposes such as emulsion dispersion, sensitization and other improvement of photographic characteristics. Further, in the present invention, it is preferable that the lubricant is contained in the photographic film. Typical examples of the slip agent used in the present invention include, for example, US Pat.
2,522, British Patent 955,061, U.S. Patents 3,080,317, 4,004,927, 4,047,958, 3,489,567, British Patent No. No. 1,143,118, JP-A-1-234843.
Silicone sliding agents described in U.S. Pat.
54,043, 2,732,305, 2,97
6,148, 3,206,311, German Patents 1,284,295, 1,284,294, and the like, higher fatty acid-based, alcohol-based, acid amide-based slip agents, United Kingdom Patent No. 1,263,722, US Pat. No. 3,
Metal soaps described in 933,516 and the like, ester-based and ether-based sliding agents described in U.S. Pat. Nos. 2,588,765 and 3,121,060, British Patent 1,198,387, and the like. Etc. In this case, the slipperiness of the surface of the light-sensitive material containing the lubricant is preferably a static friction coefficient of 0.25 or less. According to the present invention, the coefficient of static friction of 0.25 or less means that a sample is conditioned at a temperature of 25 ° C. and a humidity of 60% RH for 2 hours, and then measured with a HEIDON-10 static friction coefficient measuring machine to measure 5 mm.
The value was measured using a φ stainless steel ball, and the smaller the value, the better the slipperiness. By reducing the coefficient of static friction, it is possible to reduce the friction between the emulsion surface and the back surface of the film or the inner surface of the film and the film, and between the film and the exit of the film cartridge when the film is sent from the film cartridge by spool rotation, which will be described later. Reduction can be achieved and scratches on the film can be prevented. The static friction coefficient of the film before and after the development treatment is preferably 0.25 or less, more preferably 0.23 or less, still more preferably 0.21 or less, and particularly preferably 0.20 or less. At this time, it is preferable that both the emulsion surface and the back surface are smaller, but the smaller the back surface is, the better. In order to reduce the coefficient of static friction after development of the present invention to 0.25 or less, a lubricant may be added to the emulsion layer and the back layer of the film, and it is particularly preferable to add a lubricant to the outermost layers on both sides. The method of containing the slipping agent can be achieved by containing the composition in a coating solution and applying the composition, or the composition may be adhered to the film after the film has been formed.
There is also a means using a spray method, a dip coating method, a bar coating method, a spin coating method, or the like. In the present invention, a matting agent may be included to prevent adhesion. At this time, the matting agent used is not particularly limited in its composition,
It may be an inorganic substance, an organic substance, or a mixture of two or more kinds. The particles used in the present invention are particles that remain in the light-sensitive material even after development processing, and are characterized in that they are insoluble in the processing liquid, and those which do not contain a large amount of groups that are significantly hydrophilic or are alkaline or acidic soluble. Is desirable.

Examples of the inorganic compounds and organic compounds of the matting agent of the present invention include fine powders of inorganic substances such as barium sulfate, manganese colloid, titanium dioxide, strontium barium sulfate, and silicon dioxide. Examples thereof include silicon dioxide such as synthetic silica obtained by gelling an acid, and titanium dioxide (rutile type or anatase type) generated by titanium slag and sulfuric acid. It can also be obtained by crushing from an inorganic material having a relatively large particle size, for example, 20 μm or more, and then classifying (vibrating filtration, air classification, etc.). Further, pulverized and classified products of organic polymer compounds such as polytetrafluoroethylene, cellulose acetate, polystyrene, polymethylmethacrylate, polypropylenemethacrylate, polymethylacrylate, polyethylenecarbonate and starch are also included. Alternatively, a polymer compound synthesized by a suspension polymerization method, a polymer compound spherically formed by a spray drying method or a dispersion method, or an inorganic compound can be used. Further, a polymer compound which is a polymer of one or more kinds of various polymerizable monomer compounds may be formed into particles by various means. Among these monomer compounds, acrylic acid esters, methacrylic acid esters, vinyl esters, styrenes, and olefins are preferably used. Further, in the present invention, JP-A No. 62-14647,
Particles having a fluorine atom or a silicone atom as described in JP-A Nos. 62-17744 and 62-17743 may be used. These matting agents preferably have an average particle size of 1 to 3.5 μm, and
The content of μm or more is preferably 5% or less. More preferably, a matting agent having an average particle size of 1.5 to 2.8 μm and a content of 3.5 μm or more and 5% or less is preferable. Further, the content of the matting agent is preferably 5 to 300 mg / m ² , and more preferably 20 to 250 mg / m ² . Furthermore, a matting agent which dissolves in the development processing step may be contained, and polar groups such as COOM, SO ₃ M, OSO ₃ M,
_{PO 3 M 2, OP 3 OM} 2, wherein M may be mentioned H, alkali metal, ammonia). The photographic light-sensitive material of the present invention has US Pat.
1,911, 3,411,912, Japanese Patent Publication No. 45-
The polymer latex described in No. 5331 may be included.

The silver halide emulsion layer and other hydrophilic colloid layers in the photographic light-sensitive material of the present invention can be hardened with various organic or inorganic hardeners (single or in combination). Particularly, typical examples of the silver halide color photographic light-sensitive material preferred in the present invention include a color reversal film and a color negative film, a white / black negative film, a movie negative and a positive film. Particularly, color negative films for general use and reversal films are preferable color photographic light-sensitive materials. Hereinafter, description will be made using a general-purpose color negative film. This light-sensitive material may have at least one silver halide emulsion layer of a blue color sensitive layer, a green color sensitive layer and a red color sensitive layer provided on a support. The number of non-photosensitive layers and the order of the layers are not particularly limited. As a typical example, a silver halide photographic light-sensitive material having at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. And the photosensitive layer is blue light,
In a multilayer silver halide color photographic light-sensitive material, which is a unit photosensitive layer having color sensitivity to either green light or red light, the unit photosensitive layers are generally arranged in order from the support side to red color Layer, green color sensitive layer, and blue color sensitive layer are arranged in this order. However, even if the above installation order is reversed depending on the purpose,
Further, the order of installation may be such that different photosensitive layers are sandwiched in the same color-sensitive layer. A non-photosensitive layer such as an intermediate layer of each layer may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

For the intermediate layer, Japanese Patent Application Laid-Open No. 61-43748.
No. 59-113438, No. 59-113440
No. 61-20037, No. 61-20038, couplers such as those described in the specification, DIR compounds, etc. may be contained, and a color mixing inhibitor may be contained as is commonly used. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470.
No. or British Patent No. 923,045, JP-A-57-
No. 112751, No. 62-200350, No. 62-2
06541, 62-206543, 56-25
No. 738, No. 62-63936, No. 59-20246.
No. 4, Japanese Patent Publication No. 55-34932, No. 49-15495
No. specification. Silver halide grains include those having regular polyhedral crystals such as cubes, octahedra and tetradecahedrons, those having irregular crystal shapes such as spheres and plates, and crystal defects such as twin planes. Or a composite form thereof. The grain size of silver halide is about 0.
Fine particles of 2 microns or less or large size grains having a projected area diameter of up to about 10 microns may be used, and a polydisperse emulsion or a monodisperse emulsion may be used. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No. 17643 (December 1978), 22-2.
Page 3, "I. Emulsion preparation and ty
pes) ”, and No. 18716 (November 1979),
648, Graphide, "Physics and Chemistry of Photography," published by Paul Montel (P.Glafkides, Chemie et PhisiquePhotog.
raphique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photo
graphic Emulsion Chemistry (FocalPress, 196
6)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VLZelikman et al., Makingand
Coating Photographic Emulsion, Focal Press, 196
It can be prepared using the method described in 4) or the like. US Pat. Nos. 3,574,628 and 3,655.
Monodisperse emulsions described in, for example, 394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering (Gutoff, Photogr
aphic Science and Engineering), Volume 14, 248-
257 (1970); U.S. Pat. No. 4,434,22.
No. 6, No. 4,414, 310, No. 4,433, 048
No. 4,439,520 and British Patent No. 2,11.
It can be easily prepared by the method described in No. 2,157. The crystal structure may be uniform, may have a different halogen composition between the inside and the outside, may have a layered structure, and may have a different composition by epitaxial bonding. Often,
Further, it may be bonded with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The efficiency of the present invention is particularly remarkable when an emulsion sensitized with a gold compound and a sulfur-containing compound is used. Additives used in such processes are Research Disclosure No.
17643 and No. 18716, and the relevant parts are summarized in the table below. Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table. Additive type RD17643 RD18716 1 Chemical sensitizer Page 23 Page 648 Right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, Page 23 to 24 Page 648 Right column to Supersensitizer page 649 Right column 4 Whitening agent 24 Page 5 Antifoggant, pages 24 to 25, page 649, right column ~ and stabilizer 6 Light absorber, pages 25 to 26, page 649, right column ~ Filter dye, page 650, left column UV absorber 7 Stain inhibitor, page 25, right column Page 650 Left to right column 8 Dye image stabilizer Page 25 9 Hardener 26 page 651 Left column 10 Binder page 26 Same as above 11 Plasticizer, lubricant 27 page 650 Right column 12 Coating aid, pages 26 to 27 Same as above Surfactant Also, in order to prevent deterioration of photographic performance due to formaldehyde gas, compounds capable of being immobilized by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. It is preferably added to the light-sensitive material. Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.
No. etc.

Specific examples of the high boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used for the oil-in-water dispersion method include phthalic acid esters, phosphoric acid or phosphonic acid esters, and benzoic acid esters. Examples thereof include amides, alcohols or phenols, aliphatic carboxylic acid esters, aniline derivatives and hydrocarbons. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide. The steps of latex dispersion method, effects and specific examples of latex for impregnation are described in US Pat. No. 4,199,363.
It is described in West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is 28 μm or less, and the film swelling speed T1 / 2 is preferably 30 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T1 / 2 can be measured according to a method known in the art. For example, A. Green et al., Photographic Science and Engineering (Photogr.Sci.Eng.), 1
It can be measured by using a swellometer (swelling meter) of the type described in Vol. 9, No. 2, pp. 124-129, T1 / 2
Is 90% of the maximum swollen film thickness reached when the film is processed with a color developing solution at 30 ° C. for 3 minutes and 15 seconds, and the saturated film thickness is defined as the time until the film thickness of T1 / 2 is reached.

The film swelling speed T1 / 2 can be adjusted by adding a film hardening agent to gelatin as a binder or by changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness. The color photographic light-sensitive material according to the present invention has the RD. No.
Development can be carried out by a usual method described on pages 28 to 29 of 17643 and 615 left column to right column of No. 18716. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, Schiff base type compounds described in U.S. Pat. Nos. 3,342,597, indoaniline compounds, 3,342,599, Research Disclosures 14,850 and 15,159, and 13,924. No. listed. Next, the photosensitive material of the present invention is preferably a roll-shaped film capable of easily inputting a signal to the transparent magnetic recording layer when the film is conveyed by a camera or a printer. In this roll-shaped film, the area of one frame of the image exposure part is 350 mm ² or more and 1200 mm ² or less,
The magnetic information recordable space is preferably 15% or more of the area of one frame of the image exposure unit. In particular,
It is preferable that the number of perforations per screen is less than 135 formats. It is particularly preferable that the number of perforations per frame is 4 or less.

Information can be optically input to the magnetic information recordable space by using a light emitting body such as an LED. It is also preferable to input magnetic information and optical information so as to overlap in the space. The magnetic recording format preferably follows the system disclosed in World Publication No. 90-04205. When this photosensitive material is used in the form of a roll, it is preferable that it be housed in a cartridge.
The most common cartridge is the current 135
It is a format patrone. Other cartridges proposed in the following patents can also be used. (Actual development 58-6
7329, JP-A-58-181035, and JP-A-58
No. 182634, No. 58-195236, U.S. Pat. No. 4,221,479, Japanese Patent Application No. 63-57785.
No. 63-183344, Japanese Patent Application No. 63-325
No. 638, Japanese Patent Application No. 1-21862, Japanese Patent Application No. 1-253.
62, Japanese Patent Application No. 1-30246, Japanese Patent Application No. 1-2022
No. 2, Japanese Patent Application No. 1-21833, Japanese Patent Application No. 1-38171
Japanese Patent Application No. 1-33108, Japanese Patent Application No. 1-85198
Japanese Patent Application No. 1-172595, Japanese Patent Application No. 1-172559
No. 4, Japanese Patent Application No. 1-172593, US Pat.
18, US Pat. No. 4,848,693, US Pat.
(275) A cartridge having a means for controlling the attitude of the cartridge in the camera is particularly preferable. (Patent application 1
No. 214896) The cartridge used next has a synthetic plastic as a main component. In molding the plastics of the present invention, a plasticizer is mixed with the plastics as necessary. As the plasticizer, for example, trioctyl phosphate, tributyl phosphate, dibutyl phthalate, diethyl sebacate, methyl amyl ketone, nitrobenzene, γ-valerolactone, di-n-octyl succinate, bromonaphthalene, butyl palmitate, etc. are typical. It is something. Specific examples of the plastic material are shown below, but the invention is not limited thereto.

Specific examples include polystyrene, polyethylene,
Polypropylene, polymonochlorotrifluoroethylene, vinylidene chloride resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, methyl methacryl resin, vinyl formal resin, vinyl butyral resin, polyethylene terephthalate, Teflon , Nylon, phenol resin, melamine resin, etc. Particularly preferred plastic materials are polystyrene, polyethylene, polypropylene and the like. Further, the cartridge of the present invention may contain various antistatic agents. The antistatic agent is not particularly limited, but carbon black, metal oxide particles, nonion, anion, cation, betaine-based surfactant, nonion,
Anions, cations, betaine polymers and the like can be preferably used. As these anti-static cartridges, JP-A 1-312537 and 1-3125 are known.
No. 38. Usually, the cartridge is manufactured by using plastic in which carbon black, a pigment, etc. are kneaded in order to impart a light shielding property. Furthermore, the shape may be the same as the present size, but the diameter of the cartridge of 25 m / m is 22 m / m or less, preferably 20 m / m or less,
Setting it to 8 m / m or more is effective for downsizing the camera. Further, in the current cartridge, the tip of the spool on the side that engages with the film drive portion of the camera is exposed, which is an obstacle to downsizing of the camera, so it is preferable to eliminate this portion.
As a result, the volume of the cartridge, which is currently about 35 cm ³ , can be reduced. The volume of the cartridge case is 30 cm ³
Preferably not more than 25 cm ³ and more preferably not more than 20 cm ³
The following is preferable. The weight of the plastic used for the cartridge and the cartridge case is 1 g or more and 25 g or less, preferably 5 g or more and 15 g or less.

The ratio of the inner volume of the cartridge case to the plastic used in the cartridge and the cartridge case is 4 to 0.7, preferably 3 to 1. In the case of the cartridge containing the color light-sensitive material of the present invention, the total weight of the plastic used in the cartridge and the cartridge case is usually 1 g or more and 25 g or less, preferably 5 g or more and 15 g or less. Next, the form of the cartridge containing the color sensitive material will be described. The form of the cartridge is not particularly limited, but it is preferable that the cartridge be compatible with commercially available cameras. Furthermore, it may be used for a new camera that fits a cartridge containing a color sensitive material. An example of these specific cartridges is shown in FIG.
FIG. 4 shows the magnetic recording track of the film in FIG. 5). In FIG. 5, t-0, t-1, t-2, t-
_{3, t 00, t 29,} f 00 ~f 29 shows a magnetic recording track.

[0037]

The present invention will be described in more detail with reference to specific examples, but the invention is not limited to the examples as long as the gist of the invention is not exceeded. Example 1 (Preparation of Magnetic Material) 10 g of a Co-containing magnetite (coercive force 850 Oe, saturation magnetization 65 emu / g), which is a cube having a side of 0.25 μm, was placed in 200 cc of water.
Ethylhexyl sulfosuccinate sodium salt 0.
Using 2 g, well dispersed with a homogenizer at 1000 rpm for 2 hours, and then divinylbenzene / styrene (molar ratio 1
0:90, the addition amount was adjusted so as to obtain the coating amount shown in Table 1), and the mixture was further stirred at 2000 rpm for 10 minutes. After heating this dispersion to 80 ° C., 0.1 g of potassium persulfate and sodium bisulfite were simultaneously added to copolymerize divinylbenzene / styrene. 8
After stirring at 0 ° C and 1000 rpm for 2 hours, another 9
The mixture was stirred at 0 ° C for 2 hours (1000 rpm). This solution was cooled to room temperature, poured into 1 liter of methanol, and the precipitated fine particles were filtered and thoroughly washed with methanol. The average particle size of the obtained fine particles is listed in Table 1. (Preparation of magnetic recording layer) 2.5 g of the Co-containing magnetite magnetic material coated with divinylbenzene / styrene thus obtained was added to vinyl chloride / vinyl acetate (molar ratio 1:
1) Add 25 g of copolymer and 150 g of butyl acetate, add C
Coating amount of o-containing magnetite magnetic particles is 0.1g / m2
Cellulose triacetate (thickness 113μ
m). Immediately after coating, a magnetic field of 3000 gauss was applied by a solenoid to orient the magnetic field. In addition, Co-containing magnetite 2.5 which is not coated with divinylbenzene / styrene is vinyl chloride / vinyl acetate (molar ratio 1: 1).
A sample prepared by adding 25 g of the copolymer and 150 g of butyl acetate and dispersing in a ball mill in the same manner was prepared as a control sample. The following evaluations were also performed on the coating solutions of the obtained samples. B) Stability evaluation of coating liquid A part of the coating liquid was sampled and its particle size was measured and evaluated with an electrophoretic light scattering photometer (Otsuka Electronics ELS-800). The coating solution was evaluated immediately after dispersion and after standing for 24 hours at 25 ° C. B) Evaluation of transparency The transmittance of the obtained coated film was measured. In the evaluation, the sample immediately after the dispersion of sample 1-1 was set to 100% and the relative evaluation was performed. The larger the value, the better the transparency. C) Evaluation of magnetic characteristics A recording density signal of 500 bpi was recorded at a feed rate of 30 mm / s using a head with a track width of 1.5 mm, a head gap of 5 μm, and a turn count of 1000, which can be input and output from the coated surface side of the film sample. After that, the S / N ratio when signals were read at the same head and the same speed was obtained. The larger the S / N ratio, the better the magnetic properties. The evaluation results are shown in Table 1.

[0038]

[Table 1]

As can be seen from Table 1, the coating solutions and the film samples 1-2 to 1-5 using the Co-containing magnetato coated with the organic polymer (divinylbenzene / styrene copolymer) of the present invention were coated. It was excellent in liquid stability, transparency and magnetic properties. On the other hand, the control sample 1-1 not coated with the organic polymer at all and the comparative samples 1-6 and 1-7 coated with the organic polymer but having a small amount thereof
Was poor in stability of the coating solution, and was significantly inferior in terms of transparency with time and magnetic properties. Sample 1-2 of the present invention
The coating surface states of Control Sample 1-1 and Comparative Samples 1-6 and 1-7 were excellent, while the coating liquids of Control Sample 1-1 and Comparative Samples 1-6 and 1-7 were rough at room temperature for 24 hours. It occurred remarkably. From the above, the magnetic particles coated with the organic polymer of the present invention in a certain amount or more provided excellent dispersibility, transparency of the coating film and magnetic properties.

Example 2 The hexagonal plate barium ferrite (the thickness of the magnetic particles was 0.15 μm) was used as the Co-containing magnetite of the magnetic particles in Example 1.
m, length 0.4 μ, coercive force 850 Oe, magnetization 80 emu / g
A magnetic material coated with divinylbenzene / styrene was prepared in exactly the same manner as in Example 1 except that
1 g of barium ferrite whose surface was coated with the obtained organic compound was added to 25 g of triacetyl cellulose and 150 g of methylene chloride and dispersed by a ball mill. This coating solution was applied to polyethylene terephthalate (thickness 100 μm) immediately after dispersion and after standing at 25 ° C. for 24 hours to obtain a film having a thickness of 2 μm. The obtained coating liquid and film were obtained in Example 1
The performance was evaluated in exactly the same manner as.

[0041]

[Table 2]

As can be seen from Table 2, Samples 2-2 to 2-5 prepared from barium ferrite coated with divinylbenzene / styrene having the thickness of the present invention have excellent coating solution stability, transparency and magnetic properties. The coated surface was also good. In contrast, control sample 2
-1, and Comparative Samples 2-6 and 2-7 having a small coating thickness of divinylbenzene / styrene were inferior in stability of the coating solution and were extremely inferior in transparency and magnetic properties.

Example 3 Samples shown in Table 3 were obtained in exactly the same manner as in Example 1 except that methyl methacrylate was used instead of styrene.

[0044]

[Table 3]

As shown in Table 3, the coating solution and film made of Co-containing magnetite having the surface coated with divinylbenzene / methyl acrylate, which is an organic compound of the present invention, are excellent in stability, transparency and magnetic properties of the coating solution. It was a thing. On the other hand, the control sample 3-1 not coated with divinylbenzene / methyl acryl at all and the comparative samples 3-6 and 3-7 with a small coating amount have poor stability of the coating solution and poor transparency and magnetic properties. Therefore, it is clear that the present invention is remarkably excellent.

Example 4 Instead of cellulose triacetate in Example 1, terephthalic acid / adipic acid / 5-sulfoisophthalic acid /
Ethylene glycol (88 / 5.3 / 6.7 / 100)
Sample 4 was prepared in the same manner as in Example 1 except that the condensate was used.
-1 to 4-7 were created. The produced film has excellent transparency and magnetic properties in Samples 4-2 to 4-5 of the present invention, whereas Control Sample 4-1 and Comparative Sample 4
In Nos. -6 and 4-7, both the transparency and the magnetic properties were remarkably poor after 24 hours of application of the coating solution.

Example 5 The following coating layer was applied on the coating layer of the film sample obtained in Example 1. 5-1) Application of first layer of photographic film back-Cellulose diacetate 0.1 g / m ² -Ethylene glycol 0.08 〃-SnO ₂ / Sb ₂ O ₃ / SiO ₂ (molar ratio 90/10/1, average Particle size 0.12 μm) 0.1 g / m ²

[0048]

[Chemical 4]

5-2) Coating of back second layer-Diacetyl cellulose 0.2 g / m ² -Colloidal silica (aerosil) 0.02 〃 ・ C ₁₅ H ₃₁ COOC ₄₀ H ₈₁ 0.02 〃 ・ C ₂₁ H ₄₃ COO (CH ₂ CH ₂ O) ₃ --COC ₉ H ₁₉ 0.01 〃 ・ C ₂₁ H ₄₃ OOC (CH ₂ ) ₁₈ -COOC ₁₈ H ₃₇ 0.01 〃 ・ Poly (vinylidene difluoride / tetrafluoride) Vinylidene) (Molar ratio 9: 1) 0.01 〃 ・ Poly (methyl methacrylate / divinylbenzene) (Molar ratio 9: 1 ・ Average particle size 1.0 μm) 0.03 〃 ・ Silica (Average particle size 1.0 μm) 0.005〃

5-3) Preparation of Photosensitive Material After the corona discharge treatment was performed on the side opposite to the back layer obtained above, each layer having the following composition was multilayer coated to prepare a color lagger photographic film. (Photosensitive layer composition) A photosensitive material was prepared in exactly the same manner as the photosensitive material described in Example 1 of JP-A-2-93641. That is, the first layer is an antihalation layer, the second layer is an intermediate layer,
The third to thirteenth layers are photosensitive layers, and the fourteenth to fifteenth layers.
The layer is a constituent of the protective layer. 5-4) Development processing of photographic film The obtained photographic film was subjected to the following method when development was required in the evaluation described below. The developing machine used was a cine type automatic developing machine FNCP-900 manufactured by Fuji Photo Film Co., Ltd. Development of these samples was performed as follows. Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 2 minutes 10 seconds Settling 4 minutes 20 seconds Water washing 3 minutes 15 seconds Stability 1 minute 05 seconds The treatment liquid composition used in each step is as follows. It was

Color developer Diethylenetriamine pentaacetic 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 g Hydroxylamine Sulfate 2.4 g 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulphate 4.5 g Water is 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 salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate aqueous solution (70%) 17 0.0 g Sodium bisulfite 4.6 g Water was added 1.0 l pH 6.6 Stabilizing solution Formalin (40%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g Water Then, the performance of the obtained sample was evaluated.

5-5) Evaluation of output error of magnetic recording In the signal input method disclosed in World Patent Publication No. 90-04205, the sensitive material magnetically input from the back side after development processing is output 500 times by the magnetic head. And showed the number of times the error occurred. The temperature and humidity in the evaluation are 25 ° C and 30% RH.
I did it in. The performance of the obtained samples 5-1 to 5-7 was evaluated, and the results are shown in Table 4.

[0053]

[Table 4]

As can be seen from Table 4, the photographic films 5-2 to 5-5, which are the samples of the present invention, are excellent with very few magnetic recording output errors, whereas the control sample 5-1 and the comparative sample 5 are excellent. Photographic films prepared from magnetic particles having no or a small amount of the organic polymer of the present invention such as -6 and 5-7 had a remarkably inferior magnetic recording output error after dispersion. The photographic images obtained from the photographic films 5-2 to 5-5 of the present invention were excellent in sharpness, gradation, color reproducibility and sharpness. In contrast, control sample 5-1 and comparative sample 5-
In Nos. 6 and 5-7, the sharpness (after dispersion aging) was extremely poor, and the images were poor. The coefficient of static friction on the magnetic recording layer side was 0.10 both before and after the development treatment, and was excellent in slipperiness and scratch-resistant even in a scratch test with a nylon scrubbing brush.

Example 6 In Example 5, the light-sensitive material was changed to JP-A-2-854 and Example 1.
Samples 6-1 to 6-7 were prepared in exactly the same manner as in Example 5 except that the reverse color emulsion layer described in Sample 101 was applied. With respect to the layer structure of the emulsion layer, the first layer is an antihalation layer, the second layer is an intermediate layer, the third to fifth layers are red-sensitive emulsion layers, and the seventh to ninth layers are green-sensitive emulsion layers. The 11th to 13th layers are blue-sensitive emulsion layers, the 14th to 15th layers are protective layers, and the 6th and 10th layers are intermediate layers. The development processing was performed by Fuji Photo Film Co., Ltd. and color reversal processing CR-56 processing. The developing machine used was E-6 manufactured by Noritsu Koki Co., Ltd.
360 was used. The samples 6-2 to 6-5 of the present invention were excellent with almost no magnetic recording output error, whereas the control sample 6-1 and the comparative samples 6-6 and 6-7.
Had a remarkably poor magnetic recording output error after dispersion. The photographic films 6-2 to 6-5 of the present invention gave excellent images. Example 7 Except that a support is prepared in the same manner as in Example 5, except that the photographic film back first layer and back second layer are cast simultaneously with the magnetic recording layer and the triacetyl cellulose of the support (four layers are simultaneously coated). Samples 7-1 to 7-7 were prepared in exactly the same manner as in Example 5. The samples 7-2 to 7-5 of the present invention were excellent with almost no magnetic recording output error, whereas the control sample 7-1 and the comparative samples 7-6 and 7-7 were magnetic samples after dispersion aging. The recording output error was extremely bad. The photographic films 7-2 to 7-5 of the present invention provided excellent images. Further, it also provided excellent transportability, scratch resistance and adhesion resistance even in the inside of the cartridge transported by sending out the spool shown in FIGS.

[0056]

The present invention provides a magnetic material having improved dispersion stability, and further provides a silver halide photographic light-sensitive material having a magnetic recording layer containing the magnetic material, which is excellent in transparency and magnetic properties. ..

[Brief description of drawings]

FIG. 1 is a perspective view of a photographic film cartridge according to the present invention.

FIG. 2 is a plan view showing a state of a front end portion of the photographic film in FIG.

FIG. 3 shows a sectional view of the cartridge of FIG.

4 is a partially cutaway view of the cartridge of FIG.

FIG. 5 shows a plan view of a magnetic recording track layer of a photographic film back layer.

[Explanation of symbols]

 1 photographic film patrone 2 spool 3 photographic film 4 patrone main body 5 film outlet 7 perforation 8 raised portion 9 protrusion 10 hole 11 notch 12 film withdrawal passage 13 step 14 emulsion constituent layer 15 support 16 transparent magnetic layer 17 Antistatic layer + Scratch resistant layer + Lubrication layer 18 1 frame 19 Perforation

Claims (10)

[Claims] 1. A magnetic material dispersed in a binder, wherein the magnetic material has magnetic particles inside and the particle size of the magnetic particles is smaller than the diameter of the magnetic particles. A magnetic material having a coating layer made of an organic polymer having a thickness of 05 times or more. 2. The magnetic particles are ferromagnetic iron oxide fine powder, Co
Containing ferromagnetic iron oxide fine powder, ferromagnetic chromium dioxide fine powder,
The magnetic material according to claim 1, which is a ferromagnetic metal fine powder, a ferromagnetic alloy fine powder, barium ferrite, or Co-containing magnetite. 3. The magnetic material according to claim 1, wherein the organic polymer is a synthetic or natural high molecular weight polymer having a molecular weight of 1000 or more. 4. A silver halide photosensitive material having a magnetic recording layer containing the magnetic material represented by claim 1, claim 2 or claim 3. Description: 5. The weight ratio of the magnetic particles to the binder is 1 :.
The silver halide photosensitive material according to claim 4, which has a magnetic recording layer of 100 to 30: 100. 6. The silver halide light-sensitive material according to claim 4, wherein the silver halide light-sensitive material is developed. 7. A photographic support, wherein a magnetic recording layer having a magnetic material dispersed in a binder and at least one layer having no magnetic material are simultaneously applied and formed into a photographic support. ~ The silver halide photosensitive material according to claim 6. 8. The magnetic recording layer having a magnetic material is oriented by a magnetic field to be formed.
The silver halide light-sensitive material described in 1. 9. The static friction coefficient on the magnetic recording layer side having a magnetic material is 0.25 or less.
The silver halide photosensitive material according to claim 8. 10. A cartridge in which the tip of the silver halide photosensitive material wound on the spool is sent to the outside from the film withdrawing port of the cartridge body by rotating a spool freely rotatably provided in the cartridge body in the film feeding direction. A silver halide light-sensitive material having a system and having a magnetic recording layer on at least one surface in a front surface or in a stripe shape, wherein the silver halide light-sensitive material is a silver halide light-sensitive material according to any one of claims 4 to 9.