JPH09258354A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance magnetic characteristics comparable to a videotape and to prevent occurrence of errors in the magnetic recording and its reproduction by forming an outermost transparent magnetic recording layer containing ferromagnetic grains and having a thickness smaller than a specified value and a nonmagnetic layer under this magnetic recording layer. SOLUTION: The silver halide photographic sensitive material has at least one silver halide emulsion layer on one side of a support and the transparent magnetic recording layer containing the ferromagnetic grains on the other side of the support as the uppermost layer of <0.5μm thickness and the nonmagnetic undercoat layer under this magnetic recording layer. This outermost magnetic recording layer has a thickness of <0.5μm, preferably, 0.05-0.3μm, further preferably, 0.05-0.2μm, and most preferably, 0.08-0.15μm, thus permitting the obtained photosensitive material to attain a very high magnetic recording density as high as about 5-1000 times and to be low in tendency to cause errors in the magnetic recording and its reproduction.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material having a transparent magnetic recording layer (hereinafter abbreviated as photographic light-sensitive material, light-sensitive material, photographic light-sensitive material, photographic film or light-sensitive material).

[0002]

2. Description of the Related Art Japanese Unexamined Patent Publication (Kokai) No. 4-104245 or Japanese Unexamined Patent Publication (Kokai) No. 4-215651 discloses a photosensitive material using hexagonal ferrite ferromagnetic particles in a transparent magnetic recording layer. After that, many magnetic output errors occurred, and a high-density magnetic recording layer that could be used in the personal computer era was not introduced.

[0003]

A new photographic system for a silver halide photographic light-sensitive material having a transparent magnetic recording layer (Adv.
Unlike the conventional magnetic tape (audio, video), the ancillary Photo System (hereinafter abbreviated as APS) has a “development processing step”, and thus stains composed of components in the development processing solution have a magnetic recording layer. It has been found that an unexpected failure frequently occurs that adheres to the surface of the back and is transferred to the surface of the magnetic head during magnetic recording / reproduction after development processing, resulting in a magnetic input / output error (magnetic recording / reproduction error). In addition, APS is attracting attention as a silver halide photographic film capable of magnetic recording, but the current format has a maximum linear density of only about 4 bytes / mm, and much more, it standardizes the compensation of triple writing. The writing capacity is only about 120 bytes / screen (4 tracks) at maximum. Then, in the case of APS, the recording of image processing etc. by the personal computer input is done by a floppy disk or a photo CD.
Therefore, the silver salt image information is left behind in the APS cartridge. If information such as image processing is separated on another medium, it becomes inconvenient for general users when reprocessing or other data input is not complicated.

However, if each screen has an index, the search is facilitated, which is convenient when the image is viewed on a television or viewed on a slide. Therefore, if the density of the magnetic recording layer of the APS is increased, it is possible to input Chinese characters, and it is expected that the APS will be realized in the age of the personal computer. Therefore, an object of the present invention is to provide a silver halide photographic light-sensitive material having a high-density transparent magnetic recording layer which has excellent magnetic characteristics like a video tape and does not cause magnetic recording / reproducing errors.

[0005]

SUMMARY OF THE INVENTION The present invention is a halogenated compound having at least one silver halide emulsion layer on one side of a support and a transparent magnetic recording layer on the other side of the support. In the silver photographic light-sensitive material, the transparent magnetic recording layer containing ferromagnetic particles has an outermost layer having a thickness of less than 0.5 μm,
It is achieved by a silver halide photographic light-sensitive material characterized by having a non-magnetic layer under the transparent magnetic recording layer.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The transparent magnetic recording layer of the present invention is a high-density magnetic recording layer having transparency that does not substantially affect photographic image quality, and has a blue filter transmission density of 0.
-0.5, preferably 0-0.3, more preferably 0-
0.15. The magnetic recording layer is composed of at least two layers of a non-magnetic layer mainly composed of non-magnetic particles and a binder resin on a support and a magnetic layer on which ferromagnetic particles are dispersed in a binder resin solution. The transparent magnetic recording layer used in the present invention has a thickness of the outermost magnetic recording layer of 0.5 μm.
less than m, preferably 0.05 μm or more and 0.3 μm
Less, more preferably 0.05 μm or more and 0.2
.mu.m or less, and most preferably 0.08 .mu.m or more and 0.
It is 15 μm or less.

The ferromagnetic particles used in the magnetic layer of the present invention include various types of ferromagnetic particles such as iron oxide particles, chromium oxide particles, cobalt-adhering iron oxide particles, metal particles and hexagonal ferrite particles. Particles can be used. Among them, hexagonal ferrite particles are preferable in terms of magnetic properties.
In particular, Fe or Ni or Co as a main component (75 wt%
The above-mentioned ferromagnetic metal particles are preferable for effectively achieving the object of the present invention.

As the hexagonal ferrite that can be used as the ferromagnetic particles in the magnetic recording layer, a ferromagnetic powder which is typically tabular and has an easy axis of magnetization in the direction perpendicular to the tabular plane is preferable. Examples of the composition of the hexagonal ferrite include barium ferrite, strontium ferrite, lead ferrite, each substitution product of calcium ferrite, Co substitution product, and the like, specifically, magnetoplumbite-type barium ferrite and strontium ferrite, and further, Examples include magnetoplumbite-type barium ferrite and strontium ferrite containing a part of the spinel phase,
Particularly preferred is barium ferrite or a Co substitution product thereof. In addition, the above hexagonal ferrite contains Co
-Ti, Co-Ti-Zr, Co-Ti-Zn, Ni-
A material to which an element such as Ti-Zn or Ir-Zn is added can also be used. Hexagonal ferrite usually has a hexagonal shape, and the particle diameter means the width of a hexagonal plate, and is measured using an electron microscope. In the present invention, the particle diameter is 0.01 to 0.2 μm, and particularly preferably 0.03.
Is defined in the range of 0.1 μm. Further, the average thickness (plate thickness) of the fine particles is about 0.001 to 0.2 μm, and particularly preferably 0.003 to 0.05 μm. Further, the tabular ratio (particle diameter / plate thickness) is 1 to 10, preferably 3 to 7. The specific surface area (SBET) of these hexagonal ferrite fine powders by the BET method is 2
5 to 70 m @ 2 / g is preferred. Further, the saturation magnetization amount of the hexagonal ferrite fine powder is preferably 50 emu / g or more, and when it is less than 50 emu / g, sufficient reproduction output cannot be obtained and it becomes unsuitable for high density recording.

If the particle size of the magnetic particles that can be used in the present invention is expressed by the specific surface area by the BET method, it is 25 to 80 m 2 /
g, preferably 35 to 60 m2 / g. 25
If it is less than m2 / g, noise becomes high, and if it is more than 80 m2 / g, dispersion becomes difficult and the surface properties of the magnetic layer cannot be improved, which is not preferable. In addition, when expressed by the crystallite size measured by X-ray diffraction analysis, it is 450 to 10
0 angstrom, preferably 350 to 150
Angstrom.

The water content of the magnetic particles is preferably 0.01 to 2% by weight. It is necessary to optimize the water content of the magnetic material depending on the type of the binder resin. It is preferable that the pH of the magnetic particles be optimized by a combination with the binder resin used. Its range is from 4 to 12, preferably from 6 to 10. In particular, when the binder resin has a polar group in the molecule, it is desirable to pay attention to the pH. The magnetic particles may be subjected to a surface treatment with Al, Si, P or an oxide thereof, if necessary. The amount thereof is 0.1 to 10% with respect to the magnetic particles, and the surface treatment is preferable because the adsorption of a lubricant such as a fatty acid becomes 100 mg / m 2 or less.

Soluble Na, Ca and F are contained in the magnetic particles.
e may contain inorganic ions such as Ni and Sr, but 5
If it is not more than 00 ppm, there is no particular effect on the characteristics. These ferromagnetic particles include Al, Si,
S, Sc, Ti, V, Cr, Cu, Y, Mo, Rh, P
d, Ag, Sn, Sb, Te, Ba, Ta, W, Re,
Au, Hg, Pb, Bi, La, Ce, Pr, Nd,
It may contain atoms such as P, Co, Mn, Zn, Ni, Sr, and B.

These ferromagnetic fine particles may be previously treated with a dispersant, a lubricant, a surfactant, an antistatic agent or the like before dispersion. When the ferromagnetic particles are ferromagnetic metal particles, they may contain a small amount of hydroxide or oxide.

In order to enable high recording density, it is preferable that the magnetic recording layer has a coercive force of 1400 Oersteds or more. More preferably, it is 1500 ersted or more. If the coercive force is too low, the signal output is reduced due to the self-demagnetizing action, which is not preferable. Further, if it is too high, it becomes difficult to reverse the magnetization by the magnetic recording head.
It is desirable to set it to 00 oersteds or less.

The saturation magnetization and the coercive force can be measured using VSM-PI (manufactured by Toei Industry Co., Ltd.) with a maximum applied magnetic field of 10 KOe. For the measurement of the specific surface area, a cantersorb (US, manufactured by Canterchrome Co.) can be used. 250 ° C, 3
After dehydration in nitrogen atmosphere for 0 minutes, BET single point method (partial pressure 0.3
It is measured in 0). The residual magnetic flux density of the magnetic recording layer of the present invention is preferably 1500 G (gauss) or more.

The orientation ratio of the magnetic grains in the magnetic recording layer is 0.85 or more, preferably 0.90.
Further, 0.95 or more is optimal. When the orientation ratio is 0.
In order to achieve the value of 85 or more, a method in which the upper magnetic layer is in an undried state, for example, a random orientation method using a permanent magnet as disclosed in Japanese Patent Publication No. 3-41895, JP-A-63-148417. No., JP-A-1-30
For example, a method for applying an alternating magnetic field, which is disclosed in Japanese Patent Application Laid-Open No. 0427, Japanese Patent Application Laid-Open No. Hei 1-300428, and the like can be used. In this case, it is necessary that the acicular ratio of the ferromagnetic metal particles is 12 or less, preferably 10 or less in order to make the orientation ratio 0.85 or more.

These ferromagnetic particles are disclosed in, for example, Japanese Patent Laid-Open No.
Surface treatment may be carried out with silica and / or alumina, such as those described in 9-23505 and JP-A-4-096052. In addition, JP-A-4-195726 and 4-1.
92116, 4-259911, 5-081652
A surface treatment with an inorganic and / or organic material as described may be applied. Furthermore, these ferromagnetic particles may be treated on their surface with a silane coupling agent or a titanium coupling agent. Examples of the coupling agent include Japanese Patent Publication No. 1-261469 and Japanese Patent Laid-Open No. 161032/1994.
3-Mercaptopropyl trimethoxysilane, 3-isocyanylpropyl
Methyldimethoxysilane, 3- (poly (degree of polymerization: 10) oxyethynyl) oxypropyl trimethoxysilane,
3-Methoxy (poly (polymerization degree 6) oxyethynyl) oxypropyl trimethoxysilane, decyltrimethoxysilane and the like are used. The addition amount of these silane coupling agent and titanium coupling agent to the magnetic particles is preferably 1.0 to 200% by weight. When the amount is less than this, the liquid stability is inferior, and if too much, the liquid stability is also poor. .
It is preferably 1 to 75% by weight, more preferably 2 to
50% by weight.

The addition of these silane coupling agent and titanium coupling agent of the present invention is applied to the magnetic particles of the present invention by a generally known method to modify the surface of the magnetic particles to stabilize the coating solution of the magnetic material. Can be given. That is, as described in Japanese Unexamined Patent Publication No. 6-161032, a direct treatment method for magnetic particles or an integral blend method is used, and the direct method includes a dry method, a slurry method, and a spray method. In the dry method, for example, magnetic particles and a small amount of water, or an organic solvent, or an organic solvent containing water and a coupling agent are mixed and stirred with an open kneader to remove water and the organic solvent, and then finely dispersed. Is preferred.

The thickness of the non-magnetic layer is 0.5 to 10 μm, preferably 0.6 to 3 μm, more preferably 0.6 to
1.0 μm, most preferably 0.6 to 0.8 μm. Nonmagnetic particles may be added to the nonmagnetic layer. Specifically, α-alumina, β-alumina, γ-alumina, silicon carbide, chromium oxide, cerium oxide, α-iron oxide, corundum, silicon nitride, titanium carbide having an α-conversion rate of 90% or more.
Bite, titanium oxide, silicon dioxide, boron nitride, zinc oxide, calcium carbonate, calcium sulfate, barium sulfate and the like are used alone or in combination. In particular, porous silicon dioxide is preferable. The particle size of these non-magnetic powders is preferably 0.01 to 2 μm.

Further, ZnO and TiO are formed under the non-magnetic layer.
_Three , SnO_Two , Al_Two O_Three , In_TwoO_Three , SiO_Two , M
gO, BaO, MoO_Three , V_Two O_Five A few selected from
At least one crystalline metal oxide or a mixture of these
An independent antistatic layer containing fine particles of compound oxide should be provided.
Is preferred. Particularly preferred is SnO._Two With the main component
And / or containing about 5-20% antimony oxide
In addition, other components (eg silicon oxide, boron, phosphorus, etc.)
It is the crystalline metal oxide contained. These conductive
The volume of crystalline oxide or its composite oxide particles
Resistivity is 10⁷ Ohm · cm or less, more preferably 10
^Five Ohm-cm or less. The particle size is also primary
The major axis diameter of the particles is 0.005 to 0.7 μm, and especially 0.
It is preferably 005 to 0.3 μm. This antistatic
It is preferable that the stopper is present below the magnetic recording layer.
Yes. In addition, the presence of these conductive metal oxides makes primary particles
A partially aggregated form is preferred. Belt containing the above antistatic agent
The volume resistivity of the photosensitive material having an antistatic layer is 10¹²Ohm c
m or less, preferably 10^TenMust be below ohm-cm
Is preferred.

Therefore, in a preferred embodiment used in the present invention, the outermost magnetic recording layer has a thickness of less than 0.5 μm, and a transparent porous non-magnetic layer is provided below the magnetic recording layer. The photosensitive material comprises a back layer in which an antistatic layer containing a non-magnetic conductive metal oxide is sequentially provided as a lower layer. When forming the magnetic layer on the non-magnetic layer, the so-called wet coating is performed in which the coating solution for the magnetic layer is applied onto the non-magnetic support while the coating layer for the non-magnetic layer is still in a wet state. It is preferable to adopt an on-wet coating method. By adopting this coating method, the adhesion of the magnetic layer to the non-magnetic layer can be improved, and even if the magnetic layer is as thin as 0.5 μm as in the present invention, the magnetic layer does not peel off. , A magnetic recording layer with excellent running durability in which drop-out hardly occurs is realized.

In order to prevent the particles dispersed in the coating liquid from aggregating, coating is carried out by the method disclosed in, for example, JP-A-62-95174 and JP-A-1-236968. It is desirable to apply a shearing force to the coating liquid inside the head. Also, what should be noted in the wet-on-wet coating method is the viscoelastic properties (thixotropic properties) of the coating liquid. That is, when the difference between the viscoelastic properties of the upper layer and the lower layer coating liquid is large, when the liquid is mixed at the interface between the upper layer and the lower layer, mixing of the liquid occurs. If the thickness is very small, problems such as a decrease in the surface properties of the magnetic layer are likely to occur.

In order to make the viscoelasticity of the coating liquid as close as possible, it is effective to make the dispersed particles in the upper layer and the dispersed particles in the lower layer the same, but in the case of the present invention, this is not possible. In order to match with the structural viscosity brought about by the structure structure in which magnetic particles are formed by magnetism in the liquid, use particles such as silicon dioxide that easily form the structural viscosity as the non-magnetic particles in the coating liquid for the lower non-magnetic layer. Is desirable. Therefore, in the present invention, it is effective to use silicon dioxide having a large oil absorption and a small particle size, but it is also effective to use non-magnetic particles having a small particle size other than silicon dioxide. For example,
Particles of titanium oxide, aluminum oxide or the like having a particle size of 1 μm or less are likely to be a coating liquid having a structural viscosity of particles due to proper aggregation.

Further, a heat-resistant plastic roll such as epoxy, polyimide, polyamide or polyimide amide is used as a calendar roll used in the pressure molding treatment for smoothing the surface of the magnetic layer. Further, pressure molding can be performed between metal rolls. The processing temperature of the pressure molding is preferably 70 ° C. or more, more preferably 80 ° C.
That is all. The linear pressure is preferably 200 kg / cm, more preferably 300 kg / cm or more.

As a method of dispersing the above magnetic material in a binder, various known means other than Japanese Patent Application No. 4-189652 can be used, but a kneader, a pin type mill, an annular type mill or the like is preferable, A combination of a kneader and a pin type mill or a kneader and an annular type mill is also preferable. Examples of the kneader include an open type (open), a closed type, a continuous type, and a kneader such as a three-roll mill and a Labo Plast mill. In addition, upon dispersion,
The dispersant described in -0888283 and other known dispersants can be used.

The weight ratio of the magnetic particles to the binder is preferably 0.5: 100 to 60: 100, more preferably 1: 100 to 30: 100. The coating amount of the magnetic material is 0.005 to 1 g / m ² , preferably 0.01 to
0.5 g / m ^2, more preferably from 0.02~0.3g / m ^2.

The magnetic recording layer can be provided on the entire back surface of the photographic support or in the form of stripes. A support having a magnetic recording layer can also be prepared by co-casting a solution of a binder in which magnetic particles are dispersed and a solution of a binder for preparing a support in a striped manner. In this case, the compositions of the two kinds of polymers may be different, but it is preferable that they are the same. If necessary, the magnetic recording layer applied on the support is subjected to a process of immediately orienting the magnetic material in the layer while drying, and then the formed magnetic recording layer is dried. There is a method using a permanent magnet or a solenoid coil to orient the magnetic material. The strength of the permanent magnet is 2000 Oe
The above is preferable, and 3000 Oe or more is particularly preferable. In the case of a solenoid, it may be 500 Oe or more.

The saturation magnetic flux density of the magnetic layer of the present invention is 800 G or more and 3000 G or less when hexagonal ferrite is used. Coercive force Hc and Hr are 1000 Oe or more and 50
00 Oe or less, preferably 1500 Oe or more,
It is 3000 Oe or less. The coercive force distribution is preferably narrow, and SFD and SFDr are preferably 0.6 or less.
The squareness ratio is 0.55 or more and 0.67 for two-dimensional randomness.
In the following, preferably 0.58 or more and 0.64 or less, 0.45 or more and 0.55 or less are preferable in the case of three-dimensional random, and 0.6 or more and preferably 0.7 in the vertical direction in the case of vertical alignment. As described above, when the demagnetizing field is corrected, the value is 0.7 or more, preferably 0.8 or more. The orientation ratio is preferably 0.8 or more for both two-dimensional random and three-dimensional random. For two-dimensional random, vertical squareness ratio, Br, Hc and H
r is preferably within 0.1 to 0.5 times the in-plane direction.

The magnetic recording layer has lubricating properties, curl control,
Functions such as antistatic, antiadhesion, head polishing, and dust adhesion prevention may be combined. The binder of the back layer including the magnetic recording layer used in the present invention is a thermoplastic resin, thermosetting resin, reactive resin, acid, alkali or biodegradable polymer, natural product polymer (cellulose derivative, sugar derivative, etc.). And mixtures of these can be used. The Tg of the above resin is preferably -40 ° C to 300 ° C, and the weight average molecular weight thereof is 20,000 to 1,000,000, more preferably 5,000 to 300,000.

As the above-mentioned thermoplastic resin, vinyl chloride
Vinyl acetate copolymer, 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 Vinyl-based copolymers such as polymers, nitrocellulose, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, hydroxypropyl cellulose, ethyl cellulose, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, acetyl dibutyl acetate, tri Cellulose derivatives such as propionyl acetate and didodecyl acetate, acrylic resins, polyvinyl acetal resins, polyvinyl butyral resins, and polyethylene Examples include rubber resins such as terpolyurethane resin, polyether polyurethane, polycarbonate, polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene butadiene resin, butadiene acrylonitrile resin, silicone resin, and fluorine resin. it can.

The above-mentioned thermosetting resin or reactive resin is one 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.

In the above binder, polar groups (epoxy group, CO ₂ M, OH, NR ₂ , NR ₃ X, SO ₃ M, O are included.
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 binders may be used alone or as a mixture of several kinds, and a known crosslinking agent of epoxy type, aziridine type or isocyanate type, which is not the present invention, may be added. Known isocyanate-based crosslinking agents are polyisocyanate compounds having two or more isocyanate groups, such as tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, naphthylene-
Isocyanates such as 1,5-diisocyanate, o-toluidine diisocyanate, isophorone diisocyanate, and triphenylmethane diisocyanate, and reaction products of these isocyanates and polyalcohols (for example, 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane). Products), and polyisocyanates produced by condensation of these isocyanates.

In the present invention, the degree of substitution is 1.7 due to heat resistance and the like.
It is preferred to use a cellulose ester of ˜2.9. The degree of substitution here means the number of ester-substituted groups out of the three hydroxyl groups that cellulose has per monomer unit, and the degree of substitution 2.0 means that one hydroxyl group remains per monomer. Is shown. The degree of substitution is preferably 1.7 to 2.9, more preferably 2.0 to
2.8, and more preferably 2.2 to 2.7. The cellulose ester in the present invention, cellulose acetate, such as cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate, and cellulose nitrate,
Examples include cellulose sulfate and mixed esters thereof. Specifically, they are cellulose diacetate, cellulose acetate butyrate, cellulose acetate propionate, and cellulose nitrate.

Various plastic films can be used as the film support in the present invention, and preferred are cellulose derivatives (for example, diacetyl-, triacetyl-, propionyl-, butanoyl-, acetylpropionyl-acetate, etc.), polyamide, Polyester and polycarbonate are available. In the present invention, it is preferable to use a polyester support. The polyester used in the present invention is a diol, particularly ethylene diglycol and an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, naphthalene dicarboxylic acid (naphthalene ring 2,6-, 1,5- , 1,4
-, 2,7- is substituted with a carboxy group).

It is preferable that at least 50 mol% of 2,6-naphthalenedicarboxylic acid is contained in at least 50 mol% of all dicarboxylic acids.
Polyester containing 70 mol% or more is preferable. Particularly preferred is polyethylene 2,6-naphthalene dicarboxylate. These homopolymers and copolymers can be synthesized according to a conventionally known polyester production method. The average molecular weight of these polyesters is in the range of about 5,000 to 200,000 and o-at 35 ° C.
Intrinsic viscosity is 0.4 when measured in chlorophenol
It is 1.0 or more, preferably 0.45 or more and 0.75 or less.

These supports used in the present invention are 5
The thickness is preferably 0 to 200 μm, more preferably 80 to 115 μm, and particularly preferably 85 to 105 μm. The polyester support used in the present invention is preferably subjected to heat treatment.

The heat treatment temperature is 40 ° C. or higher and lower than Tg, more preferably Tg-20 ° C. or higher and lower than Tg. The required time is 0.1 to 1500 hours. If the temperature is lower than 40 ° C., it takes a long time to obtain a sufficient curling effect, resulting in poor industrial productivity. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. The average cooling rate of cooling is −0.01 to −20 ° C./hour, more preferably −0.1 to −5 ° C./hour.

These heat treatments may be carried out at any stage after the support film formation, UV / glow discharge / corona / flame treatment, back layer coating (antistatic agent, lubricant, etc.), and undercoat coating. Good. Preferred is after coating the antistatic layer. As a result, it is possible to prevent the attachment of dust due to electrification, which causes a surface failure of the support during heat treatment.

The support may contain a dye for the purpose of neutralizing the base tint, preventing light piping, preventing halation and the like. In order to firmly adhere a photographic layer (eg, a photosensitive silver halide emulsion layer, an intermediate layer, a filter layer, a magnetic recording layer, a conductive layer) on these supports, chemical treatment, mechanical treatment, corona discharge treatment After applying surface activation treatment such as flame treatment, ultraviolet treatment, high-frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, etc., even if a photographic emulsion is directly applied to obtain adhesive strength. After the surface treatment, the undercoat layer may be provided without the surface treatment and the photographic emulsion layer may be coated thereon. The undercoat layer may contain various additives as required. For example,
Surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids, antifoggants and the like. The undercoat layer of the present invention comprises inorganic fine particles such as SiO ₂ and TiO ₂ or polymethylmethacrylate copolymer fine particles (1 to 1).
0 μm) can be contained as a matting agent.

A matting agent may be added to the back layer of the present invention. Examples of the inorganic compound used as a matting agent include fine powders of inorganic substances such as barium sulfate, manganese colloid, titanium dioxide, strontium barium sulfate, and silicon dioxide, and synthetic silica obtained by, for example, a wet method or gelation of silicic acid. Titanium dioxide (rutile type or anatase type) produced by silicon dioxide or titanium slag and sulfuric acid. In addition, after crushing from an inorganic material having a relatively large particle size, for example, 20 μm or more,
It can also be obtained by performing classification (vibration filtration, wind classification, etc.).

Further, as the polymer compound, polytetra
Fluoroethylene, cellulose acetate, polystyrene
, Polymethylmethacrylate, polypropylmethacrylate
Rate, polymethyl acrylate, polyethylene carbo
Nate, starch, etc. These matting agents are primary particles
Even if it exists in the coating film as a child, the coating film as secondary agglomerated particles
May be present inside. The average particle size at that time is 0.1
To 1.5 μm, more preferably 0.3 to 1.0 μm
You. Further, the content is 1 to 1000 mg / m ^Two And
Preferably 3 to 300 mg / m^Two And more preferably
Is 5 to 100 mg / m^Two It is.

The non-spherical inorganic particles having a Mohs hardness of 5 or more are preferable as the abrasive added to the back layer in the present invention in order to efficiently clean the stains on the magnetic head. The composition of the non-spherical inorganic particles includes aluminum oxide (α-alumina, γ-alumina, corundum, etc.), chromium oxide (Cr ₂ O ₃ ), iron oxide (α-Fe ₂
O ₃ ), silicon dioxide, titanium dioxide, oxides such as silicon carbide (SiC), carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable, and aluminum oxide and chromium oxide are more preferable. These abrasives may be present as primary particles in the coating film or may be present as secondary agglomerated particles (chain structure) in the coating film. The average particle size at that time is 0.1 to 1.5 μm, and more preferably 0.3 to 1.0 μm. Moreover, the content is 1 to 1.
000 mg / m ² , preferably 3 to 300 mg /
m ² and more preferably 5 to 100 mg / m ² .

Further, by introducing a fluorine-based compound (fluorine-containing compound) into the back layer of the present invention, dirt is less likely to adhere to the surface of the back magnetic recording layer, and thus dirt is less likely to be transferred to the surface of the magnetic head. It is preferable in that magnetic input / output trouble can be reduced.

The slip agent is added to the photosensitive layer side of the photosensitive material, the surface of the back layer or the non-magnetic layer. When added to the non-magnetic layer, it has a sustained release property, the lubricant is stably supplied to the back surface, and the effect is large. As the slip agent used in the present invention, polyorganosiloxane, higher fatty acid amide,
Higher fatty acid ester (ester of fatty acid having 12 to 60 carbon atoms and alcohol having 12 to 60 carbon atoms), higher fatty acid metal salt, ester of linear higher fatty acid and linear higher alcohol, higher fatty acid containing branched alkyl group- Higher alcohol esters and the like are preferable. Its content is sufficient slip,
0.001-0.1 g / m ² for developing scratch resistance
Is preferred, and more preferably 0.005-0.05 g /
m ² .

Since the compounds of the above-mentioned general formula have high hydrophobicity, they often have poor solubility in solvents. Therefore, there is a method of dissolving in a non-polar organic solvent such as toluene or xylene or a method of dispersing in a coating liquid, but the method of dispersing is preferable because the non-polar organic solvent is difficult to handle. As a method of dispersing the slip agent, a generally known emulsification / dispersion method can be used. Specifically, there are a method of dissolving in an organic solvent and emulsifying in water, a method of melting a lubricant at a high temperature and emulsifying in water, a solid dispersion method using a ball mill, a sand grinder, and the like. Such emulsifying and dispersing methods are described in books such as cut rice, pebbles, edited by Hidaka, and "Handbook for Application of Emulsifying and Dispersing Technology" (Science Forum Edition).

The slipping agent used in the present invention can be dispersed in an organic solvent by various methods. As the disperser used for dispersion, a normal stirrer can be used,
Ultrasonic dispersers and homogenizers are particularly preferable.

As the diluting solvent used for coating, any solvent may be used as long as it does not deteriorate the dispersion stability or the solubility of the lubricant, for example, water, water containing various surfactants, alcohols (methanol, ethanol). , Isopropanol, butanol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), and esters (acetic acid, formic acid, oxalic acid, maleic acid, succinic acid, and other methyl, ethyl, propyl, butyl esters, etc.) are preferable.

In order to effectively achieve the object of the present invention, the surface roughness of the non-magnetic support is determined by determining the center line average surface roughness (Ra).
(Cutoff value 0.25 mm) of 0.03 μm or less, preferably 0.02 μm or less, more preferably 0.01 μm or less.
It is desirable to use one having a size of μmμ or less. Further, it is preferable that these non-magnetic supports not only have a small center line average surface roughness but also have no coarse protrusions of 1 μm or more. The surface roughness can be freely controlled by the size and amount of the filler added to the non-magnetic support as needed. Examples of these fillers include oxides and carbonates such as Ca, Si, and Ti,
An organic resin fine powder such as an acrylic resin may be used. The F-5 value in the web running direction of the non-magnetic support used in the present invention is preferably 5 to 50 kg / mm @ 2, and the F in the web width direction is F-5.
The -5 value is preferably 3 to 30 kg / mm @ 2, and the F-5 value in the long direction of the web is generally higher than the F-5 value in the width direction of the web, but especially the strength in the width direction is increased. This is not the case when it is necessary. The heat shrinkage of the support in the web running direction and the width direction at 100 ° C. for 30 minutes is preferably 3% or less, more preferably 1.5% or less, and the heat shrinkage at 80 ° C. for 30 minutes is preferably 1%. %Less than,
More preferably, it is 0.5% or less. Breaking strength is 5 to 100 kg / mm2 in both directions, elastic modulus is 100 to 20
00 kg / mm2 is desirable.

The residual solvent contained in the magnetic layer is preferably 100 mg / m 2 or less, more preferably 10 mg / m 2.
It is preferably 2 or less, and the residual solvent contained in the magnetic layer is preferably smaller than the residual solvent contained in the non-magnetic layer. The porosity of the magnetic layer is preferably 30 for both the magnetic layer and the non-magnetic layer.
It is not more than 10% by volume, more preferably not more than 10% by volume.
The porosity of the non-magnetic layer is preferably larger than the porosity of the magnetic layer, but may be small as long as the porosity of the non-magnetic layer is 5% or more. The coercive force of the magnetic recording layer is preferably 1400 oersteds or more, and the orientation ratio is preferably 0.85 or more.

Particularly, representative examples of the silver halide color photographic light-sensitive material preferable in the present invention include a color reversal film and a color negative film. In particular, a color negative film for general use is a preferred color photographic light-sensitive material. Hereinafter, a general-purpose color negative film will be described. The light-sensitive material of the present invention only needs to have at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on a support. There is no particular limitation on the number of layers and the order of the non-photosensitive layers. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, it is generally a unit photosensitive layer. The array is a red color-sensitive layer in order from the support side,
It is often installed in the order of green-sensitive layer and blue-sensitive layer.

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, pages 23 to 24, page 648, right column ~ Supersensitizer, page 649, right column 4, whitening agent 24 Page 5 antifoggant page 24-25 page 649 right column-and stabilizer 6 light absorber, page 649 right column-filter dye, page 25-26 page 650 left column ultraviolet absorber 7 stain inhibitor page 25 right column 650 Page left to right column 8 dye image stabilizer page 25 9 hardening agent page 26 651 page left column 10 binder page 26 same as above 11 plasticizer, lubricant page 27 650 page left column 12 coating aid, page 26-27 page 650 Right column Surfactant

[0051]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. (Example 1-A) 1) Adhesive (undercoat) layer A 90 μm thick polyethylene naphthalate support was exposed to ultraviolet rays (UV) at a dose of 1000 mJ / cm ² using a high pressure mercury lamp having a main wavelength of 365 nm on both sides. Then, an adhesive layer having the following composition was provided on the emulsion surface side. The coating amount was 10.4 cc / m ² . The irradiation with ultraviolet rays was carried out by the method as shown in the example of JP-B-45-3828. Gelatin 10.0 parts by weight Distilled water 12.6 parts by weight Salicylic acid 2.4 parts by weight Methanol 920 parts by weight p-Chlorophenol 105 parts by weight Polyamide epichlorohydrin resin 0.5 parts by weight (described in JP-A-51-3619) According to Synthesis Example 1)

2) First back layer The first back layer was the same as the above-mentioned undercoat layer.

3) Back second layer 230 parts by weight of stannic chloride hydrate and antimony trichloride 2
3 parts by weight were dissolved in 3000 parts by weight of ethanol to obtain a homogeneous solution. To this solution, a 1N aqueous solution of sodium hydroxide was added dropwise until the solution reached pH 3 to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a red-brown colloidal precipitate. The reddish brown colloidal precipitate was separated by centrifugation.
Water was added to the precipitate to remove excess ions, and the precipitate was washed with water by centrifugation. This operation was repeated three times to remove excess ions.

Colloidal precipitate 20 with excess ions removed
0 parts by weight of water was redispersed in 1500 parts by weight of water and sprayed in a baking furnace heated to 500 ° C. to obtain a bluish average particle size of 0.00
Fine particles of stannic oxide antimony monoxide composite having a size of 5 μm were obtained. The resistivity of this fine particle powder was 25 Ω · cm. PH of a mixed solution of 40 parts by weight of the fine powder and 60 parts by weight of water
It was adjusted to 7.0, coarsely dispersed with a stirrer, and then dispersed with a horizontal sand mill (Dynomill, manufactured by Willy A. Backfen AG) until the residence time reached 30 minutes, and some of the primary particles were agglomerated. A dispersion liquid having a size of 0.05 μm as the next aggregate was prepared.

A liquid having the following formulation was applied so that the dry film thickness was 0.3 μm, and dried at 110 ° C. for 30 seconds.・ 10 parts by weight of the above conductive fine particle dispersion (SnO ₂ / Sb ₂ O ₃ , 0.15 μm) ・ 1 part by weight of gelatin ・ 27 parts by weight of water ・ 60 parts by weight of methanol ・ 2 parts by weight of resorcinol ・ Polyoxyethylene nonylphenyl ether (Polymerization degree 10) 0.01 parts by weight

4) Third layer of bag-Preparation of sliding layer The following 1 solution was dissolved by heating at 90 ° C, added to 2 solutions, and dispersed by a high pressure homogenizer to prepare a slip dispersion stock solution. 1 solution C ₉ H ₁₉ C (OH) (C ₉ H ₁₉ ) CH ₂ COOC ₄₀ H ₆₁ 0.7 g nC ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H 1.1 g xylene 2.5 g 2 Liquid Propylene glycol Mo 24.0 g Nomethyl ether Silicon dioxide (Aerosil R972) 10.0 g The following binder and solvent were added to the above slip dispersion stock solution to prepare a coating solution. Diacetyl cellulose 50.0 g Acetone 553.0 g Cyclohexanone 350.0 g The above coating solutions were simultaneously coated at a coating amount of 10.4 cc / m ² . 5) Back fourth layer Barium ferrite magnetic powder (with respect to Ba molar ratio composition: Fe
9.10%, Co0.20%, Zn0.77%, Hc2
500 Oe, specific surface area 50 m ² / g, σs 58 emu / g plate diameter 3
0 nm, plate ratio 3.5) 1650 parts by weight, water 220 parts by weight and silane coupling agent, (CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ (OCH ₂ C
H _{2) 8} OCH ₃ (Shin-Etsu Chemical Co., Ltd. X-12-641)
165 parts by weight was added, and the mixture was well kneaded in an open kneader for 3 hours. At 70 ° C., the coarsely dispersed viscous liquid is
After drying for 24 hours to remove water, the particles were heated at 110 ° C. for 1 hour for treatment to prepare surface-treated magnetic particles.

Further, the following formulation was kneaded again in the open kneader for 4 hours. The surface-treated magnetic particles 855 g Diacetyl cellulose 25.3 g Methyl ethyl ketone 136.3 g Cyclohexanone 136.3 g

Further, a sand mill (1 /
4G) and finely dispersed at 2000 rpm for 4 hours. The above kneading liquid 45 g Diacetyl cellulose 23.7 g Methyl ethyl ketone 127.7 g Cyclohexanone 127.7 g

Further, with the following formulation, the back fourth layer coating solution was applied to the back third layer so that the coating amount was 30.0 cc / m ² .
The layer was applied undried. Drying was performed at 120 ° C. Fine dispersion 50.0 g Diacetyl cellulose 2.0 g Crosslinking agent [1]: Millionate MR-400 2.33 g (manufactured by Nippon Polyurethane Co., Ltd.) Methyl ethyl ketone 398.9 g Cyclohexanone 398.9 g ERC-DBM 0 .49 g (α-alumina abrasive manufactured by Reynolds Co., Ltd., USA, average particle size 0.5 μm)

Furthermore, while both layers are still in a wet state, permanent magnets are placed vertically above and below the non-magnetic support so that 2500 G (Gauss) is applied to the application surface in a direction perpendicular to the application surface. During this time, the coated surface was passed through for vertical alignment. The thickness of the magnetic recording layer was measured and found to be 0.27 μm. Further, a comparative sample was prepared in which the amount of the binder added to the fourth layer was increased and the thickness of the magnetic recording layer was 2.0 μm.

6) Coating of photosensitive layer A sample, which is a multilayer color photosensitive material, was prepared in which the same photosensitive layer as that described in Example 1 of JP-A-6-118561 was provided on a support having an undercoat. 7) Development processing of photographic film As for the development processing of the obtained photographic film, the developing machine is a cine type automatic developing machine FNCP-90 manufactured by Fuji Photo Film Co., Ltd.
0 (development processing was performed by CN-16X).

8) Evaluation of magnetic recording / reproduction after development processing A prepared sample (raw film) slit into a width of 24 mm and a length of 200 m was magnetically recorded in advance with an FM signal of 6 kHz at a conveying speed of 100 mm / sec. , Gap 5μm,
A general-purpose magnetic reproducing head with 2000 turns was used to reproduce a recording signal using an amplifier having a gain of about 95 dB, and the average magnitude of the reproducing signal was obtained (at this time,
I confirmed that there was no "error when recording". afterwards,
Development processing was performed, and in the same manner, each reproduced signal was examined as follows, and the magnetic recording / reproduction properties after the development processing were evaluated. If a large amount of dirt, which is a component contained in the development processing liquid, adheres to the back surface of the photosensitive material, a large amount of it will be transferred to the surface of the magnetic head, so the space loss will reduce the signal amplitude and increase the number of dropouts. Adopted from. As a result of the measurement, the sample of the present invention showed no dropout, but the comparative sample had 10 or more dropouts. Also, as a result of measuring the magnetic characteristics, it is 0.6 to 120 as compared with the conventional photosensitive material.
Approximately 5-10, realized with kilobytes / screen (4 tracks)
High-density magnetic recording of 00 times became possible.

[0063]

The silver halide photographic light-sensitive material of the present invention enables high density magnetic recording of about 5 to 1000 times. That is, simply 0.6 to 120 kilobytes / screen (4
Truck) was realized. When multi-channeling is performed by combining with a magnetic head, a maximum of 600 kilobytes can be obtained in 20 tracks, for example. Then, a digital image of 200,000 pixels can be captured. In that case,
Both silver salt images and CCD digital images can be recorded. Further, it is possible to provide a silver halide photographic light-sensitive material in which magnetic recording / reproduction errors are less likely to occur after development processing.

Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on one side of a support and a transparent magnetic recording layer on the other side of the support. The thickness of the transparent magnetic recording layer containing particles is 0.5.
A silver halide photographic light-sensitive material comprising an outermost layer having a thickness of less than μm and having a non-magnetic layer below the transparent magnetic recording layer. 2. The ferromagnetic particles contained in the transparent magnetic recording layer are barium ferrite.
The silver halide photographic light-sensitive material as described above. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the barium ferrite as the ferromagnetic particles is vertically aligned with respect to the support. 4. The silver halide photographic light-sensitive material according to claim 1, wherein the binder layer is transparent and porous. 5. The silver halide photographic light-sensitive material according to claim 4, which has an antistatic layer below the transparent porous binder layer.