JPH0845062A - Magnetic recording media - Google Patents

Abstract

(57) [Abstract] [Purpose] To provide a magnetic recording medium capable of high density recording and particularly excellent in output characteristics. A magnetic recording medium comprising a magnetic support, at least a non-magnetic layer provided on the magnetic support, and a magnetic layer provided on the non-magnetic layer, the non-magnetic layer comprising: Contains needle-shaped non-magnetic powder, and the magnetic layer contains needle-shaped ferromagnetic powder, and the magnetic powder has an axial ratio (average major axis length / average minor axis length) of The ratio (axial ratio of ferromagnetic powder / axial ratio of non-magnetic powder) to the axial ratio (average major axis length / average minor axis length) of the magnetic powder is 0.5 to 10, and the average of the ferromagnetic powder is The ratio of the major axis length to the average major axis length of the nonmagnetic powder (average major axis length of the ferromagnetic powder / average major axis length of the nonmagnetic powder) is 0.4 or more. Magnetic recording medium.

Description

Detailed Description of the Invention

[0001]

The present invention enables high density recording,
In particular, it relates to a magnetic recording medium having excellent output characteristics.

[0002]

2. Description of the Related Art Conventionally, magnetic recording media have been widely used in the form of tapes, disks, drums or sheets. Such a magnetic recording medium is usually manufactured by coating a nonmagnetic support such as a polyester film with a magnetic coating material containing a magnetic powder and a binder as main components. In recent years, in particular, there has been a demand for miniaturization of magnetic recording media and high density recording, and in order to meet such demands, for example, an attempt to improve coercive force or saturation magnetization or a magnetic layer Proposals have been made to reduce the thickness. In addition to the above requirements, there is a strong demand for a magnetic recording medium having particularly excellent output characteristics in order to meet the demand for a high-quality magnetic recording medium. Therefore, an object of the present invention is to provide a magnetic recording medium capable of high density recording and particularly excellent in output characteristics.

[0003]

DISCLOSURE OF THE INVENTION As a result of various studies, the present inventors have used a magnetic support instead of a conventionally used non-magnetic support, and a powder used in a magnetic layer and a powder used in a non-magnetic layer. It has been found that a magnetic recording medium having a specific axial ratio can achieve the above object.

The present invention has been made on the basis of the above findings, and includes a magnetic support, at least a non-magnetic layer provided on the magnetic support, and a magnetic layer provided on the non-magnetic layer. Wherein the non-magnetic layer contains needle-shaped non-magnetic powder, the magnetic layer contains needle-shaped ferromagnetic powder, and the axial ratio of the ferromagnetic powder is The ratio of (average major axis length / average minor axis length) to the axial ratio of the nonmagnetic powder (average major axis length / average minor axis length) (ferromagnetic powder axial ratio / nonmagnetic powder axial ratio) is 0.5 to 10, which is the ratio of the average major axis length of the ferromagnetic powder to the average major axis length of the nonmagnetic powder (average major axis length of the ferromagnetic powder / average major axis length of the nonmagnetic powder). )
Is 0.4 or more, and a magnetic recording medium is provided.

The magnetic recording medium of the present invention will be described in detail below. As shown in FIG. 1, the magnetic recording medium according to the present invention includes a magnetic support 1, a non-magnetic layer 2 provided on the magnetic support 1, and a magnetic layer 3 provided on the non-magnetic layer 2. And a back coat layer 4 is provided on the back surface of the magnetic support 1 as required.

The magnetic support 1 comprises at least a magnetic portion A (see FIGS. 2a to 2e) consisting of a matrix component made of a thermoplastic resin and a filler component made of magnetic powder.

Examples of the thermoplastic resin include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexylene dimethylene terephthalate and polyethylene bisphenoxycarboxylate, polyolefins such as polyethylene and polypropylene, and cellulose acetate butyrate. Cellulose derivatives such as cellulose acetate propionate, vinyl-based resins such as polyvinyl chloride and polyvinylidene chloride, or polyamides, polyimides, polycarbonates, polysulfones, polyether / etherketones, polyurethanes and the like are used. These resin components may be used alone or in combination.

As the magnetic powder, ferromagnetic powder such as metal magnetic powder or oxide-based magnetic powder can be used. Specific examples of the above oxide-based magnetic powder include the following. Iron oxide magnetic powder such as γ-iron oxide and magnetite; Cr, Mn,
Ferromagnetic powder containing a metal such as Co or Ni added thereto; chromium dioxide; a metal such as Na, K, Fe or Mn added to the chromium dioxide;
Ferromagnetic powder to which a non-metal element such as P or an oxide thereof is added; micro tabular barium ferrite; part of Fe atoms of the barium ferrite is Ti, Co, Zn, V
Ferromagnetic powder substituted with atoms such as. In addition, specific examples of the magnetic metal powder include Fe-Co, Fe-Ni, and Fe-A.
1, Fe-Ni-Al, Co-Ni, Fe-Co-N
i, Fe-Ni-Al-Zn, Fe-Al-Si, etc. are mentioned.

Further, in the present invention, as the magnetic powder, soft magnetic powder or iron oxide powder having a low remanent magnetization (hereinafter referred to as "low remanent magnetization iron oxide powder") used in magnetic toner is used. May be. The soft magnetic powder is a magnetic powder made of a metal, a metal oxide, an alloy, an amorphous alloy or the like and known as a powder having a high magnetic permeability and a low coercive force. In the present invention, any soft magnetic powder can be used, but those used for so-called weak electric devices such as magnetic heads and electronic circuits are particularly preferable. ) Magnetic Properties and Applications "(Shokabo, 1984), pages 368-376, soft magnetic materials can be used. Specific examples of the soft magnetic powder preferably used in the present invention include:
Iron-silicon alloy, iron-aluminum alloy, iron-nickel alloy, iron-cobalt alloy, iron-cobalt-nickel alloy,
Examples thereof include nickel-cobalt alloy, sendust, manganese-zinc ferrite, nickel-zinc ferrite, magnesium-zinc ferrite, magnesium-manganese ferrite, and the like. The low remanent magnetization iron oxide powder has a remanent magnetization of about 10 emu / g,
Examples thereof include magnetite powder having a coercive force of 150 Oe or less.

In the present invention, in order to improve the dispersibility of the magnetic powder such as the ferromagnetic powder, the soft magnetic powder and the low remanent magnetization iron oxide powder, the magnetic powder is surface-treated. May be given. The surface treatment is "Charac
terization of Powder Surfaces "; can be carried out by a method similar to the method described in Academic Press, and examples thereof include a method of coating the surface of the magnetic powder with an inorganic oxide. At this time, the inorganic oxides that can be used include Al ₂ O ₃ , SiO ₂ , and TiO ₂ .
₂ , ZrO ₂ , SnO ₂ , Sb ₂ O ₃ , ZnO and the like can be mentioned, and when used, they can be used alone or in combination of two or more. The surface treatment may be performed by an organic treatment such as a silane coupling treatment, a titanium coupling treatment and an alumina coupling treatment other than the above method.

The magnetic support 1 may be composed of a single layer having only the magnetic portion A as shown in FIG. 2a, or as shown in FIGS. 2b to 2e, the magnetic portion A and the non-magnetic portion B may be multi-layered. It may be a structure. That is, the magnetic support 1 can have the following configurations a to e. a. As shown in FIG. 2 a, a structure consisting of a single layer of magnetic portion A only. b. As shown in FIG. 2B, the nonmagnetic portion B is provided on the surface of the magnetic portion A (the surface located on the magnetic layer 3 side in the magnetic recording medium). c. As shown in FIG. 2c, the magnetic part A is provided on the surface of the non-magnetic part B. d. As shown in FIG. 2D, a non-magnetic portion B is provided on each of the front surface and the back surface of the magnetic portion A. e. As shown in FIG. 2e, the nonmagnetic portion B is provided with magnetic portions A on the front surface and the back surface, respectively.

Here, the preferable thickness of the entire magnetic support having the structure shown in FIGS. 2A to 2E is 1 to 300 μm. Further, the ratio of the thickness of the magnetic portion A to the thickness of the non-magnetic portion B in the magnetic support having the configuration shown in FIGS.
1:99 to 99: 1, preferably 2:98 to 98: 2,
More preferably, the ratio is 5:95 to 95: 5.

The material for forming the non-magnetic portion B is not particularly limited as long as it is a non-magnetic material, but the thermoplastic resin used as the matrix component of the magnetic portion A can be preferably used. Although the non-magnetic portion B can be formed only by itself, in order to control the surface property and running property of the outer surface of the non-magnetic portion B to be a predetermined value, the material for forming the non-magnetic portion B is the formation material. It is preferable to use materials to which various fillers are added. Examples of the filler used in this case include the non-magnetic powder described below used for forming the non-magnetic layer, and the particle size thereof is preferably 0.8 μm or less, more preferably 0.0
2 to 0.2 μm, and its content (blending amount)
Is preferably 5% by weight or less in the non-magnetic portion, and more preferably 0.01 to 2% by weight.

The composition of the thermoplastic resin and the magnetic powder in the magnetic portion A can be appropriately changed according to the desired coercive force, saturation magnetization, etc., but in the magnetic support having the structure shown in FIGS. Is 0.1 to 1000 parts by weight of magnetic powder, preferably 0.1 to 100 parts by weight of the thermoplastic resin.
2 to 100 parts by weight, more preferably 0.3 to 80 parts by weight is desirable.

As another structure of the magnetic support, a non-magnetic film may be coated with a magnetic paint as shown in FIG. 2f. In this case, the non-magnetic portion is the non-magnetic film body B'and the magnetic portion is the magnetic film body A'formed by the magnetic paint containing the magnetic powder. Figure 2f
In the constitution of the film body A ′ shown in FIG.
10 to 1500 parts by weight of magnetic powder with respect to 00 parts by weight,
Preferably 200 to 1200 parts by weight, more preferably 5
It is desirable that the amount is from 0.00 to 1000 parts by weight.

Next, a preferred method for producing the above magnetic support will be described separately for the magnetic support having the structure shown in FIG. 2a and the magnetic support having the structure shown in FIGS. A preferred method for producing a magnetic support having the structure shown in FIG. 2a;
After the thermoplastic resin and the magnetic powder are sufficiently dried, they are mixed in the above composition range and melt-mixed using an extruder to obtain a mixture of particles (raw material mixture for magnetic part). A method of molding using a molding machine capable of melt extrusion. The magnetic powder may be mixed at the same time as the reaction monomer is added during the polymerization of the thermoplastic resin, or may be added and mixed during the polymerization of the thermoplastic resin. 2b-e is a preferred method for producing a magnetic support; the raw material mixture for the magnetic portion and the raw material for the non-magnetic portion mainly composed of the thermoplastic resin are coextruded using a molding machine capable of melt extrusion. A method of molding into a desired configuration.
In addition, as the above-mentioned "co-extrusion molding method", in addition to the method of simultaneously extrusion-molding the raw material mixture for the magnetic portion and the raw material for the non-magnetic portion to form a two-layer or multi-layer magnetic support, Either one of the raw material mixture for the magnetic portion and the raw material for the non-magnetic portion is extruded first to obtain a film-like material, and then the raw material mixture for the magnetic portion and / or the non-magnetic material is further formed on the film-like material. There is a method of forming a two-layer or multi-layer magnetic support by extrusion-molding a raw material for parts.

The magnetic support having the structure shown in FIG. 2f can be manufactured by the following method. In the process of extrusion molding using only the non-magnetic part raw material, the magnetic coating material is applied at any stage of the molding process to form the magnetic film body (magnetic part) A ′, A method for producing a magnetic support. However, in this case,
The above-mentioned magnetic film body A ′ in the configuration shown in FIG.
Is preferably one that does not swell or dissolve in the solvent used when forming the nonmagnetic layer and the magnetic layer provided on the film A ′.

When manufacturing the above magnetic support,
When forming the magnetic portion A or the magnetic film A ′, a magnetic field orientation treatment and a calender treatment can be performed, if necessary.

The magnetic support used in the present invention is obtained by manufacturing the magnetic support having the structure shown in FIG. 2f by the above-mentioned method and the like, and further, magnetic properties in the magnetic support having the structure shown in FIG. 2f. It may be manufactured by extruding the above-mentioned raw material for the non-magnetic portion or the like onto the film body A ′ or the like to form the non-magnetic portion B or the like.

The non-magnetic layer provided on the magnetic support is a layer containing acicular non-magnetic powder, and is a layer formed by applying a non-magnetic coating material on the magnetic support. . The non-magnetic paint used when forming the non-magnetic layer is preferably a paint composed of needle-shaped non-magnetic powder, a binder and a solvent, or a paint composed of the binder and the solvent.

The non-magnetic powder is acicular and is not particularly limited as long as it is non-magnetic, but carbon black,
Graphite, titanium oxide, barium sulfate, zinc sulfide,
Magnesium carbonate, calcium carbonate, zinc oxide, calcium oxide, magnesium oxide, tungsten disulfide, molybdenum disulfide, boron nitride, tin dioxide, silicon dioxide,
Non-magnetic chromium oxide, alumina, silicon carbide, cerium oxide, corundum, artificial diamond, non-magnetic iron oxide,
Pomegranate, garnet, silica, silicon nitride, molybdenum carbide, boron carbide, tungsten carbide, titanium carbide, diatomaceous earth, dolomite, resinous powder and the like, among them, carbon black, titanium oxide, barium sulfate,
Calcium carbonate, alumina, non-magnetic iron oxide and the like are preferably used.

The non-magnetic powder may be subjected to the above-mentioned surface treatment in order to improve the dispersibility of the non-magnetic powder. Further, in the non-magnetic layer, in addition to the non-magnetic powder, a non-acicular powder may be mixed and used. In this case, the amount of the non-magnetic powder used in the non-magnetic layer is 50 based on the total powder content
It is preferably at least wt%. At this time, the non-acicular powder can be used without particular limitation as long as it is not needle-shaped and non-magnetic, and specifically, it is exemplified as a specific example of the non-magnetic powder. The compound can be used.

The particle size of the nonmagnetic powder is preferably 0.001 to 3 μm, more preferably 0.005 to 1 μm.
μm, most preferably 0.005-0.5 μm.
Further, the non-magnetic powder is preferably contained in the non-magnetic layer formed by applying the non-magnetic coating material in an amount of preferably 5 to 99% by weight, more preferably 30 to 95% by weight, and most preferably 50 to 95% by weight. %, It is desirable to incorporate it in the above non-magnetic paint.

The binder may be a thermoplastic resin, a thermosetting resin, a reactive resin, or the like, which may be used alone or as a mixture.
As the binder, specifically, vinyl chloride resin, polyester, polyurethane, nitrocellulose,
Epoxy resin and the like can be mentioned.
Resins and the like described in JP-A No. 162128, page 2, upper right column, line 19 to page 2, lower right column, line 19 and the like can be mentioned. Further, the binder may contain a polar group for improving dispersibility and the like. The amount of the binder used is preferably about 5 to 100 parts by weight, more preferably 5 to 70 parts by weight, based on 100 parts by weight of the non-magnetic powder.

Examples of the above-mentioned solvent include ketone-based solvents, ester-based solvents, ether-based solvents, aromatic hydrocarbon-based solvents, chlorinated hydrocarbon-based solvents, and the like. The solvents described in JP-A-57-162128, page 3, lower right column, line 17 to page 4, lower left column, line 10 and the like can be used.

In addition, the non-magnetic coating material contains additives usually used in magnetic recording media, such as a dispersant, a lubricant, an abrasive, an antistatic agent, an anticorrosive agent, an antifungal agent, and a curing agent. , Can be added if necessary. As the above additives,
Specifically, it is described in JP-A-57-162128, page 2, upper left column, line 6 to page 2, upper right column, line 10 and page 3, upper left column, line 6 to third page upper right column, line 18 and the like. Various additives may be mentioned.

To prepare the above non-magnetic paint, for example,
The above non-magnetic powder and the above binder together with a part of the solvent are put into a Nauter mixer or the like and premixed to obtain a mixture, and the obtained mixture is kneaded by a continuous pressure kneader or the like, and then it is mixed with the solvent. Examples include a method of diluting with 1 part, dispersing treatment using a sand mill, mixing additives such as a lubricant, filtering, and further mixing the remaining solvent and curing agent.

The magnetic layer provided on the non-magnetic layer is a layer containing acicular ferromagnetic powder, and is a layer formed by applying a magnetic coating material on the non-magnetic layer. As the magnetic paint used when forming the magnetic layer, a paint containing a ferromagnetic powder, a binder and a solvent as main components is preferably used. Examples of the ferromagnetic powder include ferromagnetic iron oxide, ferromagnetic chromium dioxide, and ferromagnetic metal powder.

The above ferromagnetic iron oxide is FeOx (1.33).
A metal such as Cr, Mn, Co, or Ni added to ≦ x ≦ 1.5) can be used. Further, the ferromagnetic chromium dioxide is CrO ₂ or Na, K, F in the CrO _2.
Metals such as e and Mn, oxides of the metals, and nonmetal elements such as P may be used. Examples of the ferromagnetic metal powder include ferromagnetic metal powders having a metal content of 70% by weight or more, and 80% by weight or more of at least one type of ferromagnetic metal (eg, Fe, Co, Ni). . Specific examples of the ferromagnetic metal powder include, for example,
Fe-Co, Fe-Ni, Fe-Al, Fe-Ni-A
1, Co-Ni, Fe-Co-Ni, Fe-Ni-Al
-Zn, Fe-Al-Si, etc. are mentioned.

The ferromagnetic powder may contain a rare earth element or a transition metal element, if necessary. Further, as the above-mentioned ferromagnetic powder, barium ferrite in the form of a small flat plate and some of its Fe atoms are Ti and C.
Magnetic powders substituted with atoms such as o, Zn and V can also be used. The ferromagnetic powder may be subjected to the above surface treatment in order to improve the dispersibility of the ferromagnetic powder.

As the binder and the solvent used in the magnetic paint, the same binders and solvents as those used in the non-magnetic paint can be used. Also,
The binder is preferably used in an amount of about 5 to 100 parts by weight, based on 100 parts by weight of the ferromagnetic powder.
It is particularly preferable to use 70 parts by weight. Further, the above-mentioned additives used in the above-mentioned non-magnetic paint can be added to the above-mentioned magnetic paint.

To prepare the above magnetic coating material, for example, the above ferromagnetic powder and the above binder together with a part of the solvent are put into a Nauter mixer or the like and premixed to obtain a mixture, and the obtained mixture is continuously added. After kneading with a pressure kneader or the like, then diluting with a part of the solvent and dispersing treatment using a sand mill or the like, mixing additives such as a lubricant and filtering, and further curing agents such as polyisocyanate and the rest. And the like. In the magnetic recording medium according to the present invention, the dry thickness of the magnetic layer is preferably 0.
05-1.5 μm, more preferably 0.05-1.2 μm
m, most preferably 0.1 to 1 μm, and the dry thickness of the nonmagnetic layer is preferably 0.5 to 4 μm, more preferably 0.5 to 3.5 μm, and most preferably 0.5 to 3 μm.
μm.

In the magnetic recording medium of the present invention, the magnetic layer contains the needle-shaped ferromagnetic powder, the non-magnetic layer contains the needle-shaped non-magnetic powder, and the axial ratio of the ferromagnetic powder is The ratio to the axial ratio of the nonmagnetic powder (the axial ratio of the ferromagnetic powder / the axial ratio of the nonmagnetic powder) is 0.5 to 10, preferably 0.3 to 3.
5, and more preferably 0.5 to 2. By setting the ratio of the above axial ratios within the above range, the rheological characteristics of the magnetic layer and the nonmagnetic layer are approximated, and a magnetic material having a uniform output characteristic is produced without causing mixing of both layers. A recording medium can be obtained. Further, the axial ratio (average major axis length / average minor axis length) of the ferromagnetic powder is preferably 3 to 20, and the axial ratio of the nonmagnetic powder (average major axis length / average minor axis length). Is preferably 3 to 20.

The ratio of the average major axis length of the ferromagnetic powder to the average major axis length of the nonmagnetic powder (average major axis length of the ferromagnetic powder / average major axis length of the nonmagnetic powder) is It is 0.4 or more, preferably 0.4 to 5. When the ratio of the average major axis length of the ferromagnetic powder to the average major axis length of the nonmagnetic powder is less than 0.4, the variation δ in the thickness of the nonmagnetic layer and the magnetic layer The ratio (δ / t) to the thickness t increases, and the output decreases. Further, the average major axis length of the ferromagnetic powder is preferably 0.05 to 0.8, and the average major axis length of the nonmagnetic powder is 0.02 to 0.8.
It is preferred that

The coercive force Hc of the ferromagnetic powder is preferably 600 to 2400 Oe, more preferably 650.
~ 2300 Oe. The coercive force Hc is 600 Oe
If it is less than 2, it becomes unsuitable for short wavelength recording and becomes 2400 Oe.
When it exceeds, the magnetic field of the head becomes insufficient, so that it is preferable to set it within the above range.

In the magnetic recording medium of the present invention,
The thickness variation δ of the nonmagnetic layer is 0.04 to 0.25 μm, and the thickness variation δ of the nonmagnetic layer and the thickness t of the magnetic layer are
It is preferable that the ratio (δ / t) to 0.02 to 0.4. If the thickness variation δ and the ratio (δ / t) are out of the above range, the contact of the head becomes non-uniform and the output is lowered. Therefore, it is preferable to set the thickness in the above range. The thickness variation δ and the ratio (δ / t) are, as described later, using the ferromagnetic powder and the nonmagnetic powder having the ratio of the axial ratios and the ratio of the major axis lengths, The magnetic layer and the non-magnetic layer are formed by a wet-on-wet method, and the viscosity and the interfacial tension of the non-magnetic coating material and the magnetic coating material are approximated to each other as much as possible. It can be designed to fall within the above range by preventing disturbance.

The magnetic recording medium according to the present invention is mainly 8 m.
Although it is suitable as a magnetic tape such as m-video tape or DAT tape, it can also be used as another recording medium such as a floppy disk.

Next, an outline of the method for producing the magnetic recording medium of the present invention will be described. First, wet-on the non-magnetic coating material and the magnetic coating material on the magnetic support so that the dry thicknesses of the non-magnetic layer and the magnetic layer are the above-mentioned thicknesses.
Simultaneous multi-layer coating is performed by a wet method to form coating films for the non-magnetic layer and the magnetic layer. Next, the coating film is subjected to a magnetic field orientation treatment, followed by a drying treatment and winding. After that, calendering is performed if necessary, and then a back coat layer is further formed if necessary. Then, if necessary, for example, in the case of obtaining a magnetic tape, 40 to 70
Aging treatment is performed at a temperature of 6 to 72 hours for slitting to a desired width.

The above-mentioned simultaneous multilayer coating method is disclosed in JP-A-5-73.
No. 42, line 31 to column 43, line 31, etc. of Japanese Patent No. 883, the above-mentioned magnetic coating material for forming the above-mentioned magnetic layer is applied before the above-mentioned non-magnetic coating material for forming the above-mentioned non-magnetic layer is dried. In this method, since the boundary surface between the non-magnetic layer and the magnetic layer is smooth and the surface property of the magnetic layer is good, dropout is small, high density recording is possible, and the coating film (magnetic layer Also, a magnetic recording medium having excellent durability of the (and non-magnetic layer) can be obtained.

The magnetic field orientation treatment is carried out before the magnetic paint is dried. For example, when the magnetic recording medium of the present invention is a magnetic tape, the magnetic paint is applied in a direction parallel to the coated surface of the magnetic paint. About 500 Oe or more, preferably about 1000
It can be performed by a method of applying a magnetic field of 10,000 to 10,000 Oe, a method of passing a magnetic paint through a solenoid or the like of 1,000 to 10,000 Oe in a wet state.

The drying treatment is carried out, for example, at 30 to 120 ° C.
The heating can be performed by supplying the gas heated to the above temperature. At this time, the drying degree of the coating film can be controlled by controlling the temperature of the gas and the supply amount thereof.

The calendering can be carried out by a super calendering method in which two rolls such as a metal roll and a cotton roll, a synthetic resin roll, a metal roll and a metal roll are passed. Also,
The conditions for the calendar treatment are 60 to 140 ° C. and 100
It can be up to 500 kg / cm.

The backcoat layer, which is provided if necessary, is provided on the back surface (the surface on which the nonmagnetic layer and the magnetic layer are not provided) of the magnetic support and is usually a backcoat. It is obtained by applying the back coat paint used for forming the layer on the magnetic support. The back coat paint is obtained by appropriately selecting and mixing the non-magnetic powder, the binder, the dispersant, the lubricant, the curing agent, the solvent and the like described in detail in the non-magnetic paint. The back coat paint can be prepared by a generally known back coat paint manufacturing method.

In the production of the magnetic recording medium of the present invention, finishing steps such as polishing and cleaning of the magnetic layer surface may be carried out if necessary. The non-magnetic coating material and the magnetic coating material can be applied by a generally known sequential multi-layer coating method.

[0045]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

<Example 1> [Production of magnetic support] (Production of magnetic support c) ... 2 layers (upper layer is magnetic part) Granules of polyethylene terephthalate having an intrinsic viscosity of 0.60 and barium ferrite magnetic powder The body and the magnetic powder are 10
The mixture was adjusted to be wt% and melt-mixed using an extruder to obtain a mixture of particles. Then, the mixture and a polyethylene terephthalate granular material containing no magnetic material were coextruded to obtain a double-layer film. The obtained film was stretched 3.3 times in the longitudinal direction and 3.3 times in the width direction, and then heat-treated to give a total magnetic support thickness of 13 μm.
A magnetic support c having the structure shown in FIG. 2c (having a thickness of the magnetic portion A of 1.5 μm) was obtained.

(Production of magnetic support d) ... 3 layers (sandwich magnetic part) Granules of polyethylene terephthalate having an intrinsic viscosity of 0.60 and acicular γ-Fe ₂ O ₃ magnetic powder 1 powder
The mixture was adjusted to be 5 wt% and melt-mixed using an extruder to obtain a mixture of particles. Then, the above mixture and a polyethylene terephthalate granular material containing no magnetic material were co-extruded to obtain a triple-layer film having nonmagnetic portions on both sides of the magnetic portion. The obtained film was stretched 3.3 times in the longitudinal direction and 3.3 times in the width direction, and then heat-treated to give a total thickness of the magnetic support of 10 μm (the thickness of the magnetic portion A was 1.5 μm, and the magnetic portion was 1.5 μm). A nonmagnetic portion B provided on the front surface of A has a thickness of 1.5 μm, and a nonmagnetic portion B provided on the back surface.
To obtain a magnetic support d having a structure shown in FIG.

[Production of Nonmagnetic Support] A film having a thickness of 10 μm was obtained in the same manner as the magnetic support d except that only polyethylene terephthalate was used, and this was used as a nonmagnetic support.

[Preparation of Magnetic Paint, Non-Magnetic Paint, and Backcoat Paint] Into each of the following paint formulations, components except polyisocyanate, fatty acid, and fatty acid ester were put into a Nauta mixer together with a part of the solvent. The mixture was premixed to obtain a mixture, and the obtained mixture was kneaded by a continuous pressure kneader. Then, after diluting each with a part of the solvent and dispersing with a sand mill, the fatty acid and the fatty acid ester are mixed and filtered, and the remaining solvent and polyisocyanate are further mixed to obtain a magnetic paint and a non-magnetic paint. And a back coat paint was obtained.

(Composition of Magnetic Paint A) Co-γ-FeOx (Coercive force Hc; 720 Oe, major axis length l ₂ ; 0.28 μm, axial ratio α ₂ ; 18,) 100 parts by weight Alumina (average particle size: 0. 3 μm) 9 parts by weight Carbon black (average primary particle size 20 nm) 1 part by weight Sulfonic acid group-containing vinyl chloride resin (sulfonic acid group content 1.5 × 10 ⁻⁴ eq / g) 7 parts by weight Sulfonic acid group-containing polyurethane (GPC number average molecular weight 25000, sulfonic acid group content 1.9 × 10 ⁻⁴ eq / g) 6 parts by weight stearic acid 1.5 parts by weight 2-ethylhexyl oleate 2 parts by weight Polyisocyanate [Nippon Polyurethane Industry Co., Ltd. , Trade name "Coronate L"] 3 parts by weight Methyl ethyl ketone 100 parts by weight Toluene 50 parts by weight Cyclohexanone 100 parts by weight

(Composition of Magnetic Paint B) The above Co-γ-Fe
Ox is Fe: Al: Ca: Si: Ni: Co = 73:
Metal powder having a composition of 3: 1: 1: 2: 20 (coercive force Hc;
1810 Oe, major axis length l ₂ ; 0.08 μm, axial ratio α ₂ ;
The same as the composition of the above-mentioned magnetic paint A except that it was replaced with 5).

(Non-magnetic coating composition) -Non-magnetic coating composition (B) Amorphous α-Fe ₂ O ₃ (major axis length l ₁ ; 0.18 μm, axial ratio α ₁ ; 1 to 1.5) 90 parts by weight Carbon black (average primary particle size 0.023 μm) 7 parts by weight Alumina (average particle size 0.2 μm) 3 parts by weight Sulfonic acid group-containing vinyl chloride resin (sulfonic acid group content 1.5 × 10 ⁻⁴ eq / g ) 5 parts by weight Sulfonic acid group-containing polyurethane (GPC number average molecular weight 25,000, sulfonic acid group content 1.9 x 10 ^-4 eq / g) 8 parts by weight Polyisocyanate [Nippon Polyurethane Industry Co., Ltd., trade name "Coronate" HX "] 2 parts by weight Oleyl oleate 2 parts by weight Myristic acid 1 part by weight Methyl ethyl ketone 60 parts by weight Toluene 30 parts by weight Cyclohexanone 90 parts by weight

・ Composition of non-magnetic paint (b) Amorphous α-Fe₂O₃Needle-shaped α-Fe₂O₃(Long axis length l₁;
0.07 μm, axial ratio α ₁; Except the above 3)
Same as the composition of magnetic paint b.

・ Composition of non-magnetic coating material C Amorphous α-Fe₂O₃Needle-shaped α-Fe₂O₃(Long axis length l₁;
0.24 μm, axial ratio α ₁; Except for the above 8)
Same as the composition of magnetic paint b.

Mixing of non-magnetic paint D The above amorphous α-Fe₂O₃Needle-shaped α-Fe₂O₃(Long axis length l₁;
0.18 μm, axial ratio α ₁The above, except that 15)
Same as the composition of non-magnetic paint b.

(Blending of back coat paint) Carbon black (average primary particle size 0.028 μm) 32 parts by weight Carbon black (average primary particle size 0.062 μm) 8 parts by weight “Nipporan 2301” [trade name, Nippon Polyurethane Industry ( Polyurethane manufactured by Co., Ltd.] 20 parts by weight nitrocellulose (viscosity display made by Hercules Powder Co. of 1/2 second) 20 parts by weight polyisocyanate (trade name “D-250N” manufactured by Takeda Pharmaceutical Co., Ltd.) 4 parts by weight Copper phthalocyanine 5 parts by weight Stearic acid 1 part by weight Methyl ethyl ketone 120 parts by weight Toluene 120 parts by weight Cyclohexanone 120 parts by weight

[Production of Magnetic Recording Medium] The magnetic support c
The non-magnetic coating material (C) and the magnetic coating material (A) are applied simultaneously on the surface of the non-magnetic coating material (A) and the magnetic coating material (A) by a wet-on-wet method so that the dry thicknesses are 0.8 μm and 2.5 μm, respectively. A coating film for the magnetic layer was formed. Then, while the coating film was in a wet state, the coating film was passed through a solenoid of 5000 Oe for magnetic field orientation treatment, dried at 80 ° C., and then wound. Next, 85 ℃, 350kg
After performing a calendering treatment under the condition of / cm to form a non-magnetic layer and a magnetic layer, a back coat paint is applied on the back surface of the magnetic support so that the dry thickness becomes 0.5 μm.
After being dried at 0 ° C., it was wound up. Then 5
Aged at 0 ° C for 16 hours, 12.65mm
The width was slit to obtain a magnetic tape having a width of 12.65 mm. The output (4 MHz) and the output fluctuation (%) of the obtained magnetic tape were measured according to the following measuring methods. The results are shown in [Table 1]. The thickness variation δ of the non-magnetic layer and the ratio (δ / t) of the thickness variation δ of the non-magnetic layer and the thickness t of the magnetic layer were also measured by the method shown in the following measuring method. The results are also shown in [Table 1].

[Measurement Method] Output (4 MHz) The obtained 12.65 mm wide magnetic tape was loaded into a DAT cassette to obtain a VHS tape cassette for testing. The test VHS tape cassette thus obtained was loaded into a commercially available VHS VCR that was modified to record and reproduce, and a 4 MHz signal was recorded on the magnetic tape, and the output when this was reproduced (reproduction output) Was measured. The recording wavelength at 4 MHz was 1.45 μm.

Output fluctuation In the measurement of the recording / reproducing characteristics, 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 can be said that the envelope characteristics are good with little fluctuation.

The thickness t of the magnetic layer The thickness t of the magnetic layer was measured by the following method. First,
The obtained magnetic tape is cut out to a thickness of about 0.1 μm with a diamond cutter in the longitudinal direction, observed with a transmission electron microscope at a magnification of 10,000 to 100,000 times, preferably 20,000 to 50,000 times, and after taking a photograph thereof, It was printed on commercially available photographic paper. Then, the interface was visually judged on the photograph by paying attention to the difference in the shapes of the magnetic powder and the non-magnetic powder in the magnetic layer and the non-magnetic layer, and a black border line was drawn on the interface. Further, edging lines were also drawn on the surface of the magnetic layer, and then the distance between these edging lines was measured by an image processing device. The distance between the edging lines was measured by segmenting a space having a length of 21 cm into 100 to 300.

◎ Variation of thickness of non-magnetic layer δ In the obtained magnetic tape, the peak of the peak of the interface between the magnetic layer and the non-magnetic layer in the length of 20 μm (actual length) was drawn. The distance in the thickness direction of the bottom of the valley was determined at 10 to 20 places (all in 20 μm), and the average value of the sums was defined as the variation δ of the thickness of the nonmagnetic layer.

<Example 2 and Comparative Examples 1 and 2> The support, the magnetic paint and the non-magnetic paint shown in [Table 1] are used, and the thickness of the magnetic paint and the non-magnetic paint is shown in [Table 1]. Each of the magnetic tapes obtained in the same manner as in Example 1 except for the above was evaluated according to the method of Example 1. The results are shown in [Table 1].

[0063]

[Table 1]

<Example 3 and Comparative Examples 3 to 5> The support, the magnetic paint and the non-magnetic paint shown in [Table 2] are used, and the thickness of the magnetic paint and the non-magnetic paint is shown in [Table 2]. A magnetic tape having a width of 8 mm was obtained in the same manner as in Example 1 except that the width of the slit was 8 mm. Each of the obtained magnetic tapes was evaluated according to the method of Example 1 except that the output was measured as follows. The results are shown in [Table 2].

Output (7 MHz) The obtained 8 mm wide magnetic tape was loaded into a VTR cassette to obtain a test VTR tape cassette. The VTR tape cassette was loaded into a commercially available Hi8 VTR modified device, a signal of 7 MHz was recorded on the magnetic tape, and the output (reproduction output) when the signal was reproduced was measured. Incidentally, 7
The recording wavelength of MHz was 0.54 μm.

[0066]

[Table 2]

As is clear from the results shown in [Table 1],
It can be seen that the magnetic tapes obtained in Examples 1 and 2 are more excellent in output and output fluctuation than the magnetic tapes obtained in Comparative Examples 1 and 2. Further, as is clear from the results shown in [Table 2], the magnetic tapes obtained in Example 3 are excellent in output and output fluctuation as compared with the magnetic tapes obtained in Comparative Examples 3 to 5. It turns out that

[0068]

INDUSTRIAL APPLICABILITY The magnetic recording medium of the present invention is capable of high density and is particularly excellent in output characteristics.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing the structure of a magnetic recording medium according to the present invention.

2A and 2B are schematic diagrams showing a structure of a magnetic support of the magnetic recording medium, FIG. 2A is a schematic view showing a structure in which only a magnetic portion is a single layer, and FIG. Schematic showing a structure in which a non-magnetic portion is provided on the surface of the portion to form two layers, (c)
Is a schematic diagram showing a configuration in which a magnetic portion is provided on the surface of a non-magnetic portion to form two layers, and (d) is a schematic diagram showing a configuration in which a non-magnetic portion is provided on each of the front surface and the back surface of the magnetic portion and forming three layers,
(E) is a schematic view showing a structure in which a magnetic portion is provided on each of the front surface and the back surface of the non-magnetic portion to form three layers, and (f) shows a configuration in which the magnetic portion is formed on the surface of the non-magnetic portion and formed into two layers. It is a schematic diagram.

Claims (1)

[Claims] 1. A magnetic recording medium comprising a magnetic support, at least a non-magnetic layer provided on the magnetic support, and a magnetic layer provided on the non-magnetic layer. The magnetic layer contains acicular non-magnetic powder, the magnetic layer contains acicular ferromagnetic powder, and the axial ratio (average major axis length / average minor axis length) of the ferromagnetic powder and The ratio (axial ratio of ferromagnetic powder / axial ratio of nonmagnetic powder) to the axial ratio (average major axis length / average minor axis length) of the non-magnetic powder is 0.5 to
And the ratio of the average major axis length of the ferromagnetic powder to the average major axis length of the nonmagnetic powder (average major axis length of the ferromagnetic powder / average major axis length of the nonmagnetic powder) is 0. A magnetic recording medium having a size of 4 or more.