JPH07105528A - Magnetic recording medium - Google Patents

Abstract

PURPOSE:To improve both durability and recording-reproducing characteristics such as high-frequency characteristics. CONSTITUTION:An intermediate layer contg. at least one kind of compd. having <=0.1mum average particle diameter selected from among lanthanum oxide, samarium oxide, terbium oxide, europium oxide, yttrium oxide, lead titanate zirconate, lanthanum lead titanate zirconate, aluminum titanate and barium silicate is formed on a substrate and a magnetic layer contg. magnetic powder such as metal powder, cobalt stuck iron oxide powder or hexagonal ferromagnetic powder is formed on the intermediate layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a magnetic recording medium, and more particularly to a magnetic recording medium excellent in durability and recording / reproducing characteristics.

[0002]

2. Description of the Related Art A coating type magnetic recording medium is obtained by coating a magnetic coating material obtained by dispersing magnetic powder in a binder and an organic solvent on a substrate such as polyester and drying it. There is an increasing demand for higher density recording such as high quality video tapes and large capacity floppy disks.

To achieve this object, it is required to make the magnetic layer as thin as possible by using a magnetic powder having a high coercive force, a high saturation magnetization and a small particle size. However, the use of such fine magnetic powder causes a problem that the durability of the magnetic recording medium is lowered.

Therefore, it has been attempted to improve durability by increasing the amounts of abrasives such as carbon black and alumina, lubricants and binders in the magnetic layer.

Further, there has been proposed a magnetic recording medium in which a non-magnetic layer (intermediate layer) containing non-magnetic particles is formed on a base material and a magnetic layer is formed thereon. For example, JP-A-62-214514 discloses a magnetic recording medium having a non-magnetic layer having a specific surface roughness and a magnetic layer formed on the non-magnetic layer. Further, JP-A-62-231417 discloses a magnetic recording medium having a non-magnetic layer containing a lubricant and a magnetic layer containing a lubricant. JP-A-3-214422,
JP-A-3-214417 discloses a smooth non-magnetic layer formed on a relatively inexpensive non-magnetic support having a poor surface condition,
A magnetic recording medium having a good surface state having a magnetic layer formed on the non-magnetic layer is disclosed. Furthermore, JP-A-5
-73883 discloses that by precisely defining the state of the interface between the non-magnetic layer and the magnetic layer, it is possible to obtain a magnetic recording medium with improved runnability and excellent high-frequency output. .

[0006]

However, carbon black in the magnetic layer, an abrasive such as alumina, a lubricant,
When the amount of the binder is increased, the recording / reproducing characteristics of the obtained magnetic recording medium tend to deteriorate.

Further, the magnetic recording medium having the intermediate layer is described in JP-A-62-214514, JP-A-62-231417, JP-A-3-214422, and JP-A-3-214417. Although the described magnetic recording medium has relatively good runnability, it is necessary to further improve the electromagnetic conversion characteristics in order to achieve the high density recording required today.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have used a powder of a specific inorganic compound having a fine average particle diameter for an intermediate layer and forming a thick film on the intermediate layer. By providing a magnetic layer having a thickness of 1 μm or less, it was found that it is possible to obtain a magnetic recording medium in which both the durability and the recording / reproducing characteristics such as high frequency characteristics are improved in a well-balanced manner, and the present invention has been completed. .

That is, the present invention provides a substrate, an intermediate layer formed on the substrate, and a thickness of 1 μm formed on the intermediate layer.
In the magnetic recording medium having the following magnetic layer, the intermediate layer, lanthanum oxide, samarium oxide, terbium oxide, europium oxide, yttrium oxide, lead zirconate titanate, lead lanthanum zirconate titanate, aluminum titanate and silicic acid. Selected from the group consisting of barium,
The present invention also provides a magnetic recording medium containing at least one compound having an average particle size of 0.1 μm or less.

The magnetic layer of the magnetic recording medium of the present invention will be described.

In the present invention, the magnetic powder forming the magnetic layer may be any of those usually used in this field. Particularly preferable magnetic powders include acicular metal powders containing iron as a main component (metal powders), acicular cobalt-coated iron oxides and hexagonal ferromagnetic powders.

As the metal powder, conventionally known ones mainly composed of iron can be used. Iron powder, iron and cobalt,
Examples thereof include alloy powders of nickel and the like, and alloy powders containing aluminum, chromium, manganese, silicon, zinc, transition metal elements, rare earth metal elements and the like. The metal powder has an average major axis length of 0.2 μm or less and a coercive force of 1700 Oe.
Above all, 1700 to 2000 Oe is particularly preferable. The magnetic characteristics other than the coercive force are not particularly limited. Further, the metal powder used is needle-shaped, and the needle-shaped ratio is preferably 3 or more. When the acicular ratio is less than 3, the magnetic field orientation tends to decrease.

As the acicular cobalt-coated iron oxide, Co-coated
Fe ₃ O ₄ , Co-deposited Fe ₂ O ₃ , Co-deposited FeO _x (1.34 ≦ x <1.50)
Is used, and Co-deposited FeO _x is particularly preferable. Further, the cobalt-adhered iron oxide used in the present invention is produced by a conventional cobalt-adhesion method using acicular iron oxide as a nucleus. The magnetic characteristics can be adjusted to predetermined values by controlling the amount of cobalt added and the amount of Fe ²⁺ in the manufacturing conditions. The amount of cobalt added is usually 1 to 20% by weight (based on iron oxide as a raw material), preferably 2 to 15% by weight, and the amount of Fe ²⁺ is usually 0.5 to 30% by weight (total cobalt-coated iron oxide). %), Preferably 1 to 25% by weight. Further, the cobalt-coated iron oxide used in the present invention is preferably acicular and has an axial ratio of 3-10.
Are preferred. The cobalt-coated iron oxide used in the present invention has an average major axis length of 0.2 μm or less and a coercive force of 1
It is preferably 600 Oe or more, particularly 1600 to 2000 Oe. The magnetic characteristics other than the coercive force are not particularly limited.

As the hexagonal ferromagnetic powder, barium ferrite, strontium ferrite, calcium ferrite, or a part of iron atoms constituting these ferrites is used.
Examples include those substituted with at least one element selected from the group consisting of Co, Ti, Zr, Ni, In, Cu, Ge, and Nb. Here, the hexagonal ferromagnetic powder means a powder of a magnetic metal compound having a hexagonal crystal structure. It is desirable that such a hexagonal ferromagnetic powder has as uniform particle shape and particle size distribution as possible. Specifically, in the case of a hexagonal plate-shaped crystal, assuming that the length of the diagonal line is d and the thickness of the plate is t, the length (d) is 0.03 to 0.2 μm, and the thickness of the plate relative to the length of the diagonal line ( Those having a d / t of 3 to 10 are usually available.
The hexagonal ferromagnetic powder used in the present invention has a coercive force
It is preferably 1400 Oe or more, particularly 1400 to 2000 Oe.
The magnetic characteristics other than the coercive force are not particularly limited.

The thickness of the magnetic layer containing the above magnetic powder (the thickness of the dry coating film) is preferably 1 μm or less, more preferably 0.5 μm or less.

Next, the intermediate layer of the magnetic recording medium of the present invention will be described.

In the present invention, the intermediate layer on the substrate is lanthanum oxide, samarium oxide, terbium oxide, europium oxide, yttrium oxide, lead zirconate titanate, lead lanthanum zirconate titanate, aluminum titanate and barium silicate. It is formed by a binder and at least one compound selected from the group consisting of and having an average particle size of 0.1 μm or less (hereinafter abbreviated as inorganic powder). If the average particle size of these inorganic powders exceeds 0.1 μm, the surface properties of the magnetic layer formed on the intermediate layer are impaired. Further, the shape of the inorganic powder is not particularly limited.

The intermediate layer can also be formed by using the above inorganic powder in combination with other inorganic powder or organic powder. Other inorganic powders include carbon black,
Graphite carbon, alumina, iron oxide, titanium oxide, barium sulfate, calcium carbonate and the like can be mentioned. Further, as the organic powder, polystyrene beads, nylon powder, benzoguanamine resin beads, polyacrylic acid-based polymer beads, polyvinyl chloride resin beads, and other polymer beads can be used. The average particle size of these is
0.2 μm or less is preferable. Further, the weight ratio of the inorganic powder according to the present invention to the other powder is (inorganic powder of the present invention):
(Other powder) = 100: 0 to 10:90 is preferable. If the content of other powders exceeds 90% by weight, the high frequency characteristics of the magnetic recording medium deteriorate.

In the present invention, in order to improve the dispersibility of the magnetic powder and the inorganic powder, they may be surface-treated. The surface treatment of such magnetic powder and inorganic powder is described in "Characterization of Powder Surfaces"; Acad.
Emic Press can be referred to, for example, a method of coating the surface of magnetic powder or inorganic powder with an inorganic oxide. As the inorganic oxide used here,
Examples thereof include Al ₂ O ₃ , SiO ₂ , TiO ₂ , ZrO ₂ , SnO ₂ , Sb ₂ O ₃ , and ZnO. These may be used in combination,
It can also be used alone.

In the present invention, the method of forming (coating) the magnetic layer and the intermediate layer includes a method of simultaneously forming the magnetic layer and the intermediate layer (multi-layer simultaneous forming method) or a method of sequentially forming one layer at a time (sequential forming method). Any of these may be used, and when forming one layer, calendering may be performed for each layer.

In the present invention, the mixed paint for the intermediate layer and the magnetic paint for the magnetic layer are composed of inorganic powder or magnetic powder, a binder, an organic solvent and the like, and are common to both the intermediate layer and the magnetic layer. Binders and the like can be used.

As the binder used in the present invention, a polyurethane resin, particularly a sulfonic acid group, a sulfonic acid metal base, a sulfobetaine group, a carbobetaine group, an amino group,
Polyurethane resin containing polar groups such as hydroxyl group and epoxy group, vinyl chloride-vinyl acetate copolymer, vinyl chloride-
Vinylidene chloride copolymers, vinyl chloride-based copolymers such as vinyl chloride-acrylonitrile copolymers, in particular sulfonic acid groups, metal sulfonate groups, vinyl chloride copolymers containing polar groups such as amino groups, Butadiene-acrylonitrile copolymer, polyamide resin, polyvinyl butyral, cellulose derivative (cellulose acetate butyrate, cellulose propionate, nitrocellulose, etc.), styrene-butadiene copolymer, polyester resin, various synthetic rubbers, phenolic resin, Epoxy resin, urea resin, melamine resin, phenoxy resin, silicone resin, acrylic reaction resin, mixture of high molecular weight polyester resin and isocyanate prepolymer, mixture of polyester polyol and polyisocyanate, urea formaldehyde resin, low Mixture of molecular weight glycol / high molecular weight diol / isocyanate, and mixtures thereof and the like can be exemplified. Usually, the binder is 3.0-10.0 in the magnetic paint.
It is blended in the amount of about wt%. Further, the compounding paint for the intermediate layer contains 10 to 50 parts by weight per 100 parts by weight of the above-mentioned inorganic powder according to the present invention and other powders optionally mixed.
0 parts by weight, preferably 15 to 200 parts by weight are used.

As the organic solvent, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, benzene, toluene, xylene, dimethyl sulfoxide, tetrahydrofuran, dioxane and the like are suitable solvents for dissolving the binder resin used. There is no particular limitation and they may be used alone or in combination of two or more. Usually, the organic solvent is compounded in the magnetic paint or the compounded paint for the intermediate layer in an amount of about 20 to 80% by weight.

In the magnetic paint, various commonly used additives such as dispersants, abrasives and lubricants may be appropriately added and used. As the dispersant, lecithin,
Nonionic surfactants, anionic surfactants, cationic surfactants and the like can be used. As an abrasive, α-
Fine powders having an average particle size of 0.05 to 1 μm, such as alumina, fused alumina, chromium oxide (Cr ₂ O ₃ ), iron oxide, silicon carbide, corundum, and diamond can be used, and usually 100 parts by weight of the binder as described above are used. 0.5 to 100 parts by weight is added. Examples of lubricants include silicone oils such as various polysiloxanes, inorganic powders such as graphite and molybdenum disulfide, fine plastic powders such as polyethylene and polytetrafluoroethylene, higher fatty acids, higher alcohols, higher fatty acid esters, and fluorocarbons. And the like are added in a ratio of 0.1 to 50 parts by weight to 100 parts by weight of the above-mentioned binder.

The substrate used in the magnetic recording medium of the present invention includes synthetic resins (for example, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, polyolefins, cellulose derivatives), non-magnetic metals, glass, ceramics and papers. Etc., and the form thereof is used in films, tapes, sheets, cards, disks and the like.

Generally, when an intermediate layer is provided between the magnetic layer and the base material, the durability of the magnetic recording medium is improved, but in the present invention, the durability is further improved. Further, if the magnetic layer is made thin, the stiffness of the magnetic recording medium becomes weak and the envelope characteristics may deteriorate. However, in the present invention, the addition of a specific inorganic powder improves the envelope characteristics. As described above, the magnetic recording medium of the present invention has improved durability and recording / reproducing characteristics, and also has good high frequency output.

[0027]

According to the present invention, it is possible to obtain a magnetic recording medium which is improved in both durability and recording / reproducing characteristics and has a good high frequency output.

[0028]

The present invention will be further described in the following examples, but the present invention is not limited to these examples.

Examples 1 to 10 and Comparative Examples 1 to 6 (1) Intermediate Layer Coating Material and Magnetic Coating Material Compound coating materials A to C (hereinafter referred to as intermediate layer coating material) for the intermediate layer and magnetic layer coating material shown below. The magnetic paints I to III of Table 1 are shown in Table 1.
An 8 mm video cassette was produced by using the combination shown in.

<Intermediate layer paint A> 100 parts by weight of inorganic powder (see Table 1) 2 parts by weight of dispersant (GAFAC RE 610 manufactured by Toho Chemical Co., Ltd.) 30 parts by weight of vinyl chloride / vinyl acetate copolymer Parts (containing sulfonic acid group) -Polyester polyurethane resin 30 parts by weight (containing sulfonic acid group) -Butyl stearate 1 part by weight-Polyisocyanate 5 parts by weight [Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd. Curing agent] -Oleic acid 1 part by weight-Solvent 160 parts by weight (methyl ethyl ketone / toluene / cyclohexanone = 3/3/1).

<Intermediate layer paint B> In the formulation of the intermediate layer paint A, the amount of the inorganic powder is 80 parts by weight, 20 parts by weight of carbon black (average particle diameter 22 nm) is added, and butyl stearate is added. Not paint.

<Intermediate Layer Paint C> A paint in which the inorganic powder, the dispersant, and butyl stearate are not added in the formulation of the intermediate layer paint A.

<Magnetic Paint I> 100 parts by weight of needle-shaped metal powder mainly composed of iron [Fe: Al: Ca: Si: Ni: Co = 92: 2: 1: 1: 2: 2, coercive force = 1730 Oe, saturation magnetization 132emu / g, average major axis length = 0.13 μm] ・ Alumina (average particle size 0.3 μm) 7 parts by weight ・ Carbon black (average particle size 20 nm) 3 parts by weight ・ Sulfonic acid group-containing vinyl chloride-acrylic acid Copolymer resin 8 parts by weight Sulfonic acid group-containing polyurethane resin 6 parts by weight Stearic acid 1 part by weight 2-Ethylhexyl myristate 2 parts by weight Polyisocyanate 4 parts by weight [Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd. Curing agent] -Solvent 230 parts by weight (methyl ethyl ketone / toluene / cyclohexanone = 2/1/2).

<Magnetic Paint II> In the composition of Magnetic Paint I, in place of the acicular metal powder mainly composed of iron, cobalt-coated iron oxide [Co-γ-FeO _x (1.34 ≦ x <1.50), coercive force was obtained. = 1650 Oe, saturation magnetization 81 emu / g, average major axis length = 0.15μ
m] is a magnetic paint.

<Magnetic Paint III> In the composition of Magnetic Paint I, hexagonal plate-shaped barium ferrite powder [plate diameter = 0.05 μm, plate-form ratio = instead of iron-like needle-shaped metal powder]
5, magnetic coercive force = 1450 Oe, saturation magnetization = 55 emu / g]

(2) Preparation of 8 mm video cassette (i) In the case of Examples 1 to 10 and Comparative Examples 1, 3 and 5, the above intermediate layer coating materials were selected as shown in Table 1 and dried with a gravure roll. Polyethylene terephthalate (PET) with a thickness of 7 μm so that the thickness afterwards will be as shown in Table 1.
It is coated on a film and dried to form an intermediate layer, and then the above-mentioned magnetic coating material is selected as shown in Table 1 so that the thickness after drying with a gravure roll becomes the thickness shown in Table 1. It is coated on the intermediate layer, longitudinally oriented with a magnetic field strength of 5000 G, and then dried to form a magnetic layer.
C.) and then aged at 50 ° C. for 24 hours.

Subsequently, a back coat layer coating material prepared by mixing the following components in a sand mill was applied to the surface of the film opposite to the surface on which the magnetic layer was provided so as to have a dry thickness of 0.5 μm. Aged at 50 ° C for 24 hours. <Coating ingredients for back coat layer> ・ Carbon black (average particle size 0.02 μm) 32 parts by weight ・ Carbon black (average particle size 0.06 μm) 8 parts by weight ・ Polyurethane resin 20 parts by weight (Nipporan 2301 manufactured by Nippon Polyurethane Co., Ltd.) ) ・ Nitrocellulose 20 parts by weight (viscosity indication by Hercules Powder CO. Is 1/2 second) ・ Polyisocyanate 4 parts by weight [Coronate HX, a curing agent manufactured by Nippon Polyurethane Industry Co., Ltd.] ・ Stearic acid 1 part by weight -320 parts by weight of solvent.

As described above, the film on which the intermediate layer, the magnetic layer and the back coat layer are formed is cut into a tape having a width of 8 mm and loaded into an 8 mm cassette case to record for 120 hours.
8mm video cassette was made.

(Ii) In the case of Comparative Examples 2, 4 and 6 In (i) above, the intermediate layer was omitted and the thickness of the magnetic layer was 2.
An 8 mm video cassette was produced in the same manner except that the thickness was 8 μm or 2.9 μm.

[0040]

[Table 1]

(3) Performance evaluation of 8 mm video cassette With respect to the 8 mm video cassette obtained as described above, durability, 7 MHz output and envelope were measured by the following methods. The results are shown in Table 2.

Durability 8mm video cassette, commercially available Hi8VTR device 7MH
The z signal was recorded, and a 50-pass running test was conducted using another Hi8VTR device. The 7MHz output before and after the running test was measured, and the value of the 7MHz output after the running test was shown as a relative value (%) with respect to the value of the 7MHz output before the running test.

Output of 7 MHz An 8 mm video cassette was attached to a commercially available Hi8VTR modified device, and recording / reproducing characteristics of 7 MHz were measured, and the reproducing output was shown as a relative value with respect to a reference. The numerical values in Table 1 are based on Comparative Example 1 for Examples 1 to 3 and Comparative Example 2 (0d
B) as a relative value, Examples 4 to 7 and Comparative Example 4 are relative values based on Comparative Example 3, and Examples 8 to 10 and Comparative Example 6 are based on Comparative Example 5 as a reference (0 dB). Is a relative value. Envelope characteristics In the measurement of the recording / reproducing characteristics at 7 MHz, the value of output fluctuation between tracks defined by the following equation was measured. Output fluctuation (%) = B / A × 100 A: maximum value of output between 1 tracks [V] B: minimum value of output between tracks [V] That is, the larger the value obtained by the above equation is the output It exhibits good envelope characteristics with little fluctuation.

[0044]

[Table 2]

Claims (4)

[Claims] 1. A magnetic recording medium having a base material, an intermediate layer formed on the base material, and a magnetic layer having a thickness of 1 μm or less formed on the intermediate layer, wherein the intermediate layer is oxidized. Selected from the group consisting of lanthanum, samarium oxide, terbium oxide, europium oxide, yttrium oxide, lead zirconate titanate, lead lanthanum zirconate titanate, aluminum titanate and barium silicate, and having an average particle size of 0.1 μm or less. A magnetic recording medium containing at least one compound. 2. The magnetic recording medium according to claim 1, wherein the magnetic layer comprises an acicular metal powder mainly composed of iron having an average major axis length of 0.2 μm or less and a coercive force of 1700 Oe or more, and a binder. 3. The magnetic recording medium according to claim 1, wherein the magnetic layer comprises an acicular cobalt-coated iron oxide having an average major axis length of 0.2 μm or less and a coercive force of 1600 Oe or more, and a binder. 4. The magnetic recording medium according to claim 1, wherein the magnetic layer comprises a hexagonal ferromagnetic powder having a coercive force of 1400 Oe or more and a binder.