JP2006286074A - Magnetic recording medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a magnetic recording medium having excellent running durability and electromagnetic conversion characteristics and capable of suppressing increase of an error rate under low humidity environment. <P>SOLUTION: In the magnetic recording medium wherein a non-magnetic layer including non-magnetic powder and a binder is provided on one surface of a supporting body, a magnetic layer including ferromagnetic powder and a binder is provided on the non-magnetic layer and a back layer is provided on the other surface of the supporting body, 4.0 to 8.0 pieces/μm<SP>2</SP>abrasives and 1.0 to 2.0 pieces/μm<SP>2</SP>aggregates of the abrasives exist on the surface of the magnetic layer and ratio (mass%) of a lubricant in the magnetic layer is 1 to 5 when ratio (mass%) of the lubricant in the back layer is defined as 1. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a magnetic recording medium, and more particularly to a magnetic recording medium that has excellent running durability and can suppress an increase in error rate in a low humidity environment.

  In recent years, a means for transmitting information such as an optical fiber at a high speed has been rapidly developed, and an image or data having a huge amount of information can be transferred. In this situation, advanced techniques for recording, reproducing and storing such an enormous amount of information have been required. Examples of the recording / reproducing medium include a flexible disk, a hard disk, and a magnetic tape. In particular, magnetic tape is in great demand for computer data backup. In this magnetic tape for data backup, with the increase in capacity of the hard disk to be backed up, a recording capacity of several tens to several hundreds GB per volume has already been commercialized, and further increase in the recording capacity is required. ing.

  However, the usage environment of the magnetic tape for data backup is not always in a good state, and is often used in a severe state. Particularly in the winter, a magnetic tape having a performance that can be used without problems even under a low humidity environment of 20% RH or less (it is considered that the inside of the drive is further low humidity) is required.

  Along with the increase in recording capacity, advanced technology is required in the tribology of the drive head and magnetic tape surface, and even if a very small amount of foreign matter adheres to the head, a problem occurs in data recording and playback, which is a big problem. May be a problem.

  In the durability test under a low humidity environment, the effect of the lubricant is reduced, and foreign matters such as fatty acid metal salts are easily generated when the head and the magnetic tape slide. At this time, if the magnetic tape is poorly polished, foreign matter is not removed, which causes an increase in error rate.

  In order to remove the foreign matter, it is effective to increase the grain size of the abrasive on the surface of the magnetic tape or increase the amount of addition. However, these are not suitable for magnetic tapes for high density recording in which the magnetic layer is a thin layer. Electromagnetic conversion characteristics, especially the cause of reduced output. In order to improve the polishing properties without deteriorating the electromagnetic conversion characteristics, it is necessary to use an efficient abrasive.

In the following Patent Document 1, a magnetic recording medium in which a nonmagnetic layer and a magnetic layer are provided on one surface of a support and a backcoat layer containing carbon black is provided on the other surface, the support having a thickness of 3 is provided. Less than .9 μm, the total thickness of the media is 5.4 μm or less, and the wear width of the AlFeSil prism when the media is run under specific running conditions is a, and after that run, the same running location of the media is the same A magnetic recording medium having a wear width change rate b / a of 0.6 or more and 1.0 or less, where b is the wear width of the AlFeSil prism when the new AlFeSil prism is brought into contact with Disclosure. However, the magnetic recording medium disclosed in Patent Document 1 has a problem that the running durability is insufficient and the error rate increases in a low humidity environment.
As described above, in the development of a magnetic recording medium that requires high reliability, there has been a demand for a means that is excellent in running durability and that suppresses an increase in error rate even in a low humidity environment.

JP 2004-288332 A

  Accordingly, an object of the present invention is to provide a magnetic recording medium that is excellent in running durability, suppresses an increase in error rate in a low humidity environment, and is excellent in electromagnetic conversion characteristics.

The present invention is as follows.
1) A nonmagnetic layer containing a nonmagnetic powder and a binder is provided on one surface of the support, a magnetic layer containing a ferromagnetic powder and a binder is provided on the nonmagnetic layer, and the other side of the support is provided. In the magnetic recording medium provided with the back layer on the surface, the number of abrasives present on the surface of the magnetic layer is 4.0 to 8.0 / μm ² , and the aggregate of abrasives is 1.0 to 2. 0 / μm ² and the ratio (mass%) of the lubricant in the magnetic layer is 1 to 5 when the ratio (mass%) of the lubricant in the back layer is 1. Magnetic recording medium.
2) The magnetic recording medium as described in 1) above, wherein the indentation hardness (DH) of the magnetic layer surface defined by the following formula (1) is 25 to 80 kg / mm ² (245 to 785 MPa).
DH = 3.7926 × 10 ⁻² {Pmax / (Hmax) ² } (Kg / mm ² ) (1)
(However, Pmax is the maximum load and Hmax is the maximum displacement of the indenter.)
3) The magnetic recording medium as described in 1) or 2) above, wherein the interface variation rate defined by the following formula (2) is in the range of 5 to 30%.
Interface fluctuation rate = (standard deviation of magnetic layer thickness ÷ average value of magnetic layer thickness) × 100 (%) (2)

  According to the present invention, it is possible to provide a magnetic recording medium that is excellent in running durability, suppresses an increase in error rate in a low humidity environment, and has excellent electromagnetic conversion characteristics.

Hereinafter, the present invention will be described in more detail.
In the present invention, the number of abrasives present on the surface of the magnetic layer is 4.0 to 8.0 / μm ² , and the aggregate of abrasives is 1.0 to 2.0 / μm ^2. One feature.
Here, the “abrasive material present on the surface of the magnetic layer” in the present invention means that at least a part of the abrasive material protrudes from the surface of the magnetic layer to the air side (side contacting the head). The protrusion of the abrasive can be easily identified by microscopic observation.
The abrasive aggregate means a state in which a plurality of abrasive powders are aggregated. This abrasive aggregate can also be easily identified by microscopic observation.
Further, the number of abrasives present on the surface of the magnetic layer is determined visually, and means the total number of abrasives and single abrasives constituting the aggregate, and the number of abrasive aggregates is as described above. Count.

If the number of abrasives present on the surface of the magnetic layer is less than 4.0 / μm ² , the cleaning effect on the head is small, which causes an increase in error rate. On the other hand, if it exceeds 8.0 / μm ² , the head will be damaged or nonmagnetic parts will increase, resulting in a decrease in output. Further, if the aggregate is less than 1.0 / μm ² , the abrasiveness is decreased, and foreign matters such as fatty acid metal salts adhering to the head cannot be sufficiently removed, resulting in an increase in the error rate. Cause. On the other hand, if it exceeds 2.0 / μm ² , the polishing property is improved, but the head is damaged, the nonmagnetic portion increases in the magnetic layer, and the output is lowered, which is not preferable. More preferably, the number of abrasives present on the surface of the magnetic layer is 5 to 7 / μm ² , and the aggregate of abrasives is 1.2 to 1.7 / μm ² . Particularly preferably, the number of abrasives present on the surface of the magnetic layer is 6 to 7 / μm ² , and the aggregates of abrasives are 1.4 to 1.7 / μm ² .
In order to achieve the absolute number of abrasives present on the surface of the magnetic layer and the ratio of aggregates, as described in detail below, the type and amount of the binder and additive of the nonmagnetic layer should be selected. It is possible to control the addition amount of the abrasive, to select the size of the abrasive, and to change the degree of dispersion of the abrasive.

  The aggregate of abrasives is preferably an aggregate of 2 to 5 abrasives. More preferably, it is 2-3. Abrasiveness is further enhanced by agglomeration of the abrasive within the above range. The size of the abrasive aggregate is 0.3 to 0.7 μm, preferably 0.3 to 0.5 μm. If the size of the aggregate of the abrasive is too large, the interface between the magnetic layer and the nonmagnetic layer is disturbed, resulting in a decrease in output, which is not preferable.

In the present invention, when the ratio (mass%) of the lubricant in the back layer is 1, another feature is that the ratio (mass%) of the lubricant in the magnetic layer is 1 to 5. More preferably, the said ratio is 1-3, Most preferably, it is 1-2.
By adding a lubricant to the back layer, for example, when the cartridge is wound as a magnetic tape around the cartridge, the lubricant is stably transferred from the back layer to the magnetic layer and replenished. As a result, even if the number of runnings increases, the decrease in the lubricant is suppressed, the sliding between the magnetic layer and the head can be performed smoothly, and the generation of foreign matters such as fatty acid metal salts can be reduced. .
In addition, it is possible to simply increase the amount of lubricant in the nonmagnetic layer and the magnetic layer without adding a lubricant to the back layer, but the excess amount of lubricant causes sticking to the tape under high humidity, etc. It is not preferable. Therefore, as in the present invention, the lubricant from the back layer side can be replenished satisfactorily to the surface of the magnetic layer by adding a lubricant within the above range to the back layer that is always in contact with the magnetic layer. did it. That is, since the amount of lubricant added per unit mass of the back layer is equal to or less than that of the magnetic layer, the amount of lubricant on the surface of the magnetic layer does not increase. For example, when the magnetic tape is running, since the lubricant on the surface of the magnetic layer is replenished only (for example, about 1% of the amount of lubricant in the magnetic layer), sticking in a high humidity environment due to excessive amount of lubricant Such disadvantages do not occur.

In the magnetic recording medium of the present invention, the indentation hardness (DH) of the magnetic layer surface defined by the following formula (1) is preferably 25 to 80 kg / mm ² (245 to 785 MPa). More preferably, it is 30-60 kg / mm < ² > (294-589 MPa), Most preferably, it is 30-50 kg / mm < ² > (294-490 MPa).
DH = 3.7926 × 10 ⁻² {Pmax / (Hmax) ² } (Kg / mm ² ) (1)
(However, Pmax is the maximum load and Hmax is the maximum displacement of the indenter.)
When the DH is less than 25 kg / mm ² (295 MPa), it means that the nonmagnetic layer is soft, and the abrasive added to the magnetic layer and the aggregates thereof are, for example, a nonmagnetic layer during calendering for the purpose of smoothing. It is difficult to achieve the ratio of abrasive aggregates present on the surface of the magnetic layer and the absolute number per unit area as defined in the present invention. On the other hand, if it exceeds 80 kg / mm ² (785 MPa), the nonmagnetic layer becomes hard, and aggregates may protrude greatly on the surface of the magnetic layer, which may cause damage to the head surface.
As shown in FIG. 1, the indentation hardness (DH) of the magnetic layer surface is a triangular pyramid, the radius of curvature of the tip a is 100 nm, the blade angle (α) is 65 °, and the inter-ridge angle (β) is 115. It is obtained based on a load unloading curve when a diamond indenter having a shape of ° is pushed into the magnetic layer at a measurement temperature of 80 ° C and a load of 6 mgf.
When the indenter with the specific shape described above is pushed into the magnetic layer with a load of 6 mgf, the tip a of the indenter does not reach the depth of 0.1 μm from the surface of the magnetic layer, and the above characteristics at the pole surface of the magnetic layer are obtained. Can be measured.
The indenter having the above-described shape is known as a Berkovich indenter, and a measuring apparatus equipped with this Berkovich indenter and capable of measuring at a measurement temperature of 80 ° C. and a load of 6 mgf is an ultra-fine indentation manufactured by Elionix Co., Ltd. A hardness measuring machine (model number: ENT-1100a) or the like can be used.

FIG. 2 shows a load unloading curve showing a change in the amount of displacement of the Barcovic indenter when the load is continuously increased and the Barkovi indenter is pushed into the sample and unloaded when the load reaches 6 mgf. is there. As shown in the figure, as shown by curve A, the displacement increases as the load increases, and the maximum displacement (Hmax) is shown at 6 mgf. When the load is unloaded, the displacement amount gradually decreases as shown by the curve B, but the displacement amount shows a certain value even when the load becomes zero. At this time, the plastic deformation amount (H ₁ ) is obtained by extrapolating the tangent line b at the maximum displacement amount (Hmax) of the curve B to zero load (that is, the horizontal axis). The slope of the tangent line b at this time is dP / dH. The value obtained by subtracting the plastic deformation amount (H ₁ ) from the maximum displacement amount is the elastic deformation amount (H ₂ ).
Therefore, the indentation hardness (DH) is calculated by the above equation (1) from the maximum displacement (Hmax) and the maximum load (Pmax = 6 mgf) obtained above.
The means for setting the indentation hardness (DH) of the magnetic layer to the above range is not particularly limited, but the kind and component ratio of the binder, the ratio of the inorganic to the binder, the calender condition, the thermo condition, etc. are appropriately selected or adjusted. Can be mentioned.

  Conventionally, the Vickers hardness generally used for evaluating the characteristics of the layer surface is that a pyramid-shaped diamond indenter is pushed into the layer surface to a depth of about 0.1 to 0.2 μm with a predetermined load. It is obtained from the ratio of the surface area of the impression remaining after opening the indenter and the load, and measures surface characteristics different from the indentation hardness according to the present invention.

Furthermore, the magnetic recording medium of the present invention preferably has an interface variation rate defined by the following formula (2) within a range of 5 to 30%. More preferably, it is 5 to 20%, and particularly preferably 5 to 10%.
Interface fluctuation rate = (standard deviation of magnetic layer thickness ÷ average value of magnetic layer thickness) × 100 (%) (2)
Here, a method for measuring the thickness of the magnetic layer is well known in the art. For example, an ultrathin section of a cross section of a magnetic recording medium is photographed with a transmission electron microscope (TEM), and a photograph of the obtained cross section is obtained. Then, an ultra-thin slice method in which the interface between the magnetic layer and the non-magnetic layer is visually traced, and further processed by an image analyzer to calculate the magnetic layer thickness can be employed.
If the interface variation rate is outside the range of 5 to 30%, the aggregates may protrude greatly on the surface of the magnetic layer, and the head surface may be damaged, which is not preferable.

Next, the layer structure of the magnetic recording medium manufactured according to the present invention will be described.
[Support]
The support in the present invention is usually a nonmagnetic support, and a polyester support (hereinafter simply referred to as polyester) is preferable. Such a polyester is a polyester composed of a dicarboxylic acid and a diol, such as polyethylene terephthalate and polyethylene naphthalate.
The main constituent dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethanedicarboxylic acid, Examples thereof include cyclohexane dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl thioether dicarboxylic acid, diphenyl ketone dicarboxylic acid, and phenylindane dicarboxylic acid.
Examples of the diol component include ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis ( 4-Hydroxyphenyl) sulfone, bisphenol fluorene hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol and the like.
Among the polyesters having these as main constituents, terephthalic acid and / or 2,6-naphthalenedicarboxylic acid as a dicarboxylic acid component and ethylene glycol as a diol component from the viewpoint of transparency, mechanical strength, dimensional stability, etc. And / or a polyester mainly composed of 1,4-cyclohexanedimethanol is preferred.
Among them, a polyester mainly composed of polyethylene terephthalate or polyethylene-2,6-naphthalate, a copolymer polyester composed of terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and two or more kinds of these polyesters A polyester having a mixture as a main constituent is preferred. Particularly preferred is a polyester having polyethylene-2,6-naphthalate as a main constituent.
The polyester used in the present invention may be biaxially stretched or a laminate of two or more layers.
The polyester may be further copolymerized with other copolymerization components, or may be mixed with other polyesters. Examples of these include the dicarboxylic acid components and diol components mentioned above, or polyesters composed thereof.
In the polyester used in the present invention, an aromatic dicarboxylic acid having a sulfonate group or an ester-forming derivative thereof, a dicarboxylic acid having a polyoxyalkylene group or an ester-forming derivative thereof, in order to make it difficult for delamination during film formation. A diol having a polyoxyalkylene group may be copolymerized.
Of these, 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 4-sodium sulfophthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid, and the like in terms of polyester polymerization reactivity and film transparency. Compounds in which sodium is substituted with other metals (for example, potassium, lithium, etc.), ammonium salts, phosphonium salts, etc., or ester-forming derivatives thereof, polyethylene glycol, polytetramethylene glycol, polyethylene glycol-polypropylene glycol copolymers and their A compound obtained by oxidizing the hydroxy groups at both ends to form a carboxyl group is preferred. The proportion of copolymerization for this purpose is preferably 0.1 to 10 mol% based on the dicarboxylic acid constituting the polyester.
For the purpose of improving heat resistance, a bisphenol compound, a compound having a naphthalene ring or a cyclohexane ring can be copolymerized. The copolymerization ratio is preferably 1 to 20 mol% based on the dicarboxylic acid constituting the polyester.

In the present invention, the method for synthesizing the polyester is not particularly limited, and can be produced according to a conventionally known polyester production method. For example, a direct esterification method in which a dicarboxylic acid component is directly esterified with a diol component. First, a dialkyl ester is used as a dicarboxylic acid component, this is transesterified with the diol component, and this is heated under reduced pressure. A transesterification method of polymerizing by removing excess diol component can be used. At this time, if necessary, a transesterification catalyst or a polymerization reaction catalyst can be used, or a heat-resistant stabilizer can be added.
In addition, anti-coloring agents, antioxidants, crystal nucleating agents, slipping agents, stabilizers, anti-blocking agents, UV absorbers, viscosity modifiers, antifoaming and clearing agents, antistatic agents, pH adjustments in each process during synthesis One or more of various additives such as an agent, a dye, a pigment, and a reaction terminator may be added.

  Further, a filler may be added to the polyester. Examples of the filler include inorganic powders such as spherical silica, colloidal silica, titanium oxide, and alumina, and organic fillers such as crosslinked polystyrene and silicone resin.

  In the present invention, the thickness of the polyester as the support is preferably 3 to 80 μm, more preferably 3 to 50 μm, and particularly preferably 3 to 10 μm. The center line average roughness (Ra) of the support surface is 8 nm or less, more preferably 6 nm or less. This Ra was measured with TOPO-3D manufactured by WYKO.

  In the magnetic recording medium of the present invention, a magnetic layer formed by dispersing ferromagnetic powder in a binder as a coating layer is provided on the support, and the magnetic recording medium is substantially provided between the support and the magnetic layer. Is provided with a nonmagnetic layer which is nonmagnetic.

[Magnetic layer]
The ferromagnetic powder contained in the magnetic layer preferably has a volume of (0.1 to 8) × 10 ⁻¹⁸ ml, and more preferably (0.5 to 5) × 10 ⁻¹⁸ ml. By setting it within this range, it is possible to effectively suppress a decrease in magnetic characteristics due to thermal fluctuations, and to obtain good C / N (S / N) while maintaining low noise. The ferromagnetic powder is not particularly limited, but ferromagnetic metal powder or hexagonal ferrite powder is preferable.
The volume of the acicular powder is obtained from the major axis length and minor axis length assuming that the shape is a cylinder.
In the case of plate-like powder, the volume is determined from the plate diameter and axial length (plate thickness) assuming that the shape is a prism (hexagonal prism in the case of hexagonal ferrite powder).
As for the size of the magnetic material, an appropriate amount of the magnetic layer is peeled off. N-Butylamine is added to 30 to 70 mg of the peeled magnetic layer, sealed in a glass tube, set in a thermal decomposition apparatus, and heated at 140 ° C. for about 1 day. After cooling, the contents are taken out from the glass tube and centrifuged to separate the liquid and solids. The separated solid is washed with acetone to obtain a powder sample for TEM. This sample is photographed with a Hitachi transmission electron microscope H-9000, and the particles are photographed at a photographing magnification of 100000 times and printed on a photographic paper to obtain a total magnification of 500,000 times to obtain a particle photograph. A target magnetic substance is selected from the particle photograph and placed on an image analyzer KS-400 digitizer manufactured by kontron, and the size of each particle is measured by tracing the outline of the powder. The size of 500 particles is measured, and the measured values are averaged to obtain an average size.

<Ferromagnetic metal powder>
The ferromagnetic metal powder used for the magnetic layer in the magnetic recording medium of the present invention is not particularly limited as long as it contains Fe as a main component (including an alloy), but is ferromagnetic with α-Fe as a main component. Alloy powder is preferred. These ferromagnetic powders include Al, Si, S, Sc, Ca, Ti, V, Cr, Cu, Y, Mo, Rh, Pd, Ag, Sn, Sb, Te, Ba, Ta, other than predetermined atoms. It may contain atoms such as W, Re, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, P, Co, Mn, Zn, Ni, Sr, and B. It is preferable that at least one of Al, Si, Ca, Y, Ba, La, Nd, Co, Ni, and B is included in addition to α-Fe, and it is particularly preferable that Co, Al, and Y are included. More specifically, it is preferable that Co is contained in an amount of 10 to 40 atomic%, Fe is contained in an amount of 2 to 20 atomic%, and Y is contained in an amount of 1 to 15 atomic%.

The ferromagnetic metal powder may be previously treated with a dispersant, a lubricant, a surfactant, an antistatic agent or the like, which will be described later. The ferromagnetic metal powder may contain a small amount of water, hydroxide or oxide. The moisture content of the ferromagnetic metal powder is preferably 0.01-2%. It is preferable to optimize the moisture content of the ferromagnetic metal powder depending on the type of the binder. The pH of the ferromagnetic metal powder is preferably optimized depending on the combination with the binder used. The range is usually from 6 to 12, but preferably from 7 to 11. The ferromagnetic metal powder may contain inorganic ions such as soluble Na, Ca, Fe, Ni, Sr, NH ₄ , SO ₄ , Cl, NO ₂ and NO ₃ . These are preferably essentially absent. If the total of each ion is about 300 ppm or less, the characteristics are not affected. The ferromagnetic metal powder used in the present invention preferably has fewer vacancies, and its value is 20% by volume or less, more preferably 5% by volume or less.

  The average major axis length of the ferromagnetic metal powder is preferably 30 to 100 nm, and more preferably 35 to 60 nm. The crystallite size of the ferromagnetic metal powder is preferably 8 to 20 nm, more preferably 10 to 18 nm, and particularly preferably 12 to 16 nm. This crystallite size is an average value obtained by a Scherrer method from a half-value width of a diffraction peak using an X-ray diffractometer (RINT2000 series manufactured by Rigaku Corporation) under the conditions of a radiation source CuKα1, a tube voltage 50 kV, and a tube current 300 mA. .

The specific surface area by BET method of the ferromagnetic metal powder _{(S BET)} is preferably at least ^{50 m} 2 / g, more preferably from 55~100m ² / g, and most preferably 60~80m ² / g. Within this range, both good surface properties and low noise can be achieved. The pH of the ferromagnetic metal powder is preferably optimized depending on the combination with the binder used. The range is 4-12, preferably 7-10. The ferromagnetic metal powder may be surface-treated with Al, Si, P, or an oxide thereof as required. The amount thereof is 0.1 to 10% with respect to the ferromagnetic metal powder. When the surface treatment is performed, the adsorption of a lubricant such as a fatty acid is preferably 100 mg / m ² or less. The ferromagnetic metal powder may contain soluble inorganic ions such as Na, Ca, Fe, Ni, and Sr. However, if it is 200 ppm or less, it does not particularly affect the characteristics. Further, the ferromagnetic metal powder used in the present invention preferably has fewer vacancies, and its value is 20% by volume or less, more preferably 5% by volume or less.

The shape of the ferromagnetic metal powder may be needle-like, granular, rice-grained or plate-like as long as the particle volume shown above is satisfied, but it is particularly preferable to use a needle-like ferromagnetic powder. In the case of acicular ferromagnetic metal powder, the average acicular ratio [arithmetic average of (major axis length / minor axis length)] is preferably 4 to 12, more preferably 5 to 12. The coercive force (Hc) of the ferromagnetic metal powder is preferably 159.2 to 238.8 kA / m (2000 to 3000 Oe), more preferably 167.2 to 230.8 kA / m (2100 to 2900 Oe). . The saturation magnetic flux density is preferably 150 to 300 mT (1500 to 3000 G), and more preferably 160 to 290 mT. The saturation magnetization (σs) is preferably 140 to 170 A · m ² / kg (140 to 170 emu / g), and more preferably 145 to 160 A · m ² / kg. The SFD (switching field distribution) of the magnetic material itself is preferably small and is preferably 0.8 or less. When the SFD is 0.8 or less, the electromagnetic conversion characteristics are good, the output is high, the magnetization reversal is sharp, the peak shift is small, and it is suitable for high-density digital magnetic recording. In order to reduce the Hc distribution, there are methods such as improving the goethite particle size distribution in the ferromagnetic metal powder, using monodispersed αFe ₂ O ₃ , and preventing sintering between particles.

  As the ferromagnetic metal powder, those obtained by a known production method can be used, and the following methods can be mentioned. Reduction of hydrous iron oxide and iron oxide with anti-sintering treatment using iron or other reducing gas to obtain Fe or Fe-Co particles, reduction of complex organic acid salt (mainly oxalate) and hydrogen A method of reducing with a reactive gas, a method of thermally decomposing a metal carbonyl compound, a method of reducing by adding a reducing agent such as sodium borohydride, hypophosphite or hydrazine to an aqueous solution of a ferromagnetic metal, a metal at a low pressure For example, the powder is obtained by evaporating in an inert gas. The ferromagnetic metal powder thus obtained is subjected to a known slow oxidation treatment. A method of reducing the amount of demagnetization by reducing the hydrous iron oxide and iron oxide with a reducing gas such as hydrogen and controlling the partial pressure, temperature and time of the oxygen-containing gas and inert gas to form an oxide film on the surface. preferable.

<Hexagonal ferrite powder>
Hexagonal ferrite powders include, for example, barium ferrite, strontium ferrite, lead ferrite, calcium ferrite, and their substitutes such as Co. More specifically, magnetoplumbite type barium ferrite and strontium ferrite, magnetoplumbite type ferrite whose particle surface is coated with spinel, and magnetoplumbite type barium ferrite and strontium ferrite partially containing a spinel phase, etc. Is mentioned. In addition to predetermined atoms, Al, Si, S, Sc, Ti, V, Cr, Cu, Y, Mo, Rh, Pd, Ag, Sn, Sb, Te, Ba, Ta, W, Re, Au, Hg , Pb, Bi, La, Ce, Pr, Nd, P, Co, Mn, Zn, Ni, Sr, B, Ge, and Nb may be included. In general, elements such as Co—Zn, Co—Ti, Co—Ti—Zr, Co—Ti—Zn, Ni—Ti—Zn, Nb—Zn—Co, Sb—Zn—Co, and Nb—Zn are added. You can use things. Some raw materials and production methods contain specific impurities. Other preferable atoms and the content thereof are the same as those of the ferromagnetic metal powder.

The particle size of the hexagonal ferrite powder is preferably a size that satisfies the above-described volume, but the average plate diameter is preferably 10 to 30 nm, and more preferably 10 to 20 nm. The average plate ratio {average of (plate diameter / plate thickness)} is 1-15, and preferably 1-7. If the average plate ratio is 1 to 15, sufficient orientation can be obtained while maintaining high filling properties in the magnetic layer, and noise increase can be suppressed by stacking between particles. Further, the specific surface area (S _BET ) by the BET method within the above particle size range is preferably 40 m ² / g or more, more preferably 40 to 200 m ² / g, and 60 to 100 m ² / g. Is most preferred.

  The distribution of the particle plate diameter and plate thickness of the hexagonal ferrite powder is generally preferably as narrow as possible. Quantifying the particle plate diameter and plate thickness can be compared by randomly measuring 500 particles from a particle TEM photograph. In many cases, the distribution of the particle plate diameter and plate thickness is not a normal distribution, but when calculated and expressed as a standard deviation with respect to the average size, σ / average size = 0.1 to 2.0. In order to sharpen the particle size distribution, the particle generation reaction system is made as uniform as possible, and the generated particles are subjected to a distribution improvement process. For example, a method of selectively dissolving ultrafine particles in an acid solution is also known.

  The coercive force (Hc) of the hexagonal ferrite powder can be in the range of 159.2 to 238.8 kA / m (2000 to 3000 Oe), preferably 175.1 to 222.9 kA / m (2200 to 2800 Oe). More preferably, it is 183.1-214.9 kA / m (2300-2700 Oe). However, when the saturation magnetization (σs) of the head exceeds 1.4T, it is preferably 159.2 kA / m or less. The coercive force (Hc) can be controlled by the particle size (plate diameter / plate thickness), the type and amount of the contained element, the substitution site of the element, the particle generation reaction conditions, and the like.

The saturation magnetization (σs) of the hexagonal ferrite powder is 40 to 80 A · m ² / kg (emu / g). Higher saturation magnetization (σs) is preferable, but tends to be smaller as the particles become finer. In order to improve the saturation magnetization (σs), it is well known to combine spinel ferrite with magnetoplumbite ferrite, and to select the type and amount of contained elements. It is also possible to use W-type hexagonal ferrite. When the magnetic material is dispersed, the surface of the magnetic material particles is also treated with a material suitable for the dispersion medium and the polymer. As the surface treatment agent, inorganic compounds and organic compounds are used. Typical examples of the main compound include oxides or hydroxides such as Si, Al, and P, various silane coupling agents, and various titanium coupling agents. The addition amount is 0.1 to 10% by mass with respect to the mass of the magnetic substance. The pH of the magnetic material is also important for dispersion. Usually, about 4 to 12 has optimum values depending on the dispersion medium and polymer, but about 6 to 11 is selected from the chemical stability and storage stability of the medium. Water contained in the magnetic material also affects the dispersion. Although there is an optimum value depending on the dispersion medium and the polymer, 0.01 to 2.0% is usually selected.

The hexagonal ferrite powder is manufactured by mixing (1) barium oxide / iron oxide / metal oxide replacing iron and boron oxide as a glass forming substance so as to have a desired ferrite composition, and then melting and quenching. After being reheated, washed and ground to obtain barium ferrite crystal powder, glass crystallization method, (2) neutralizing barium ferrite composition metal salt solution with alkali, by-product Hydrothermal reaction method to obtain barium ferrite crystal powder by liquid phase heating at 100 ° C. or higher after removal of water, (3) neutralization of barium ferrite composition metal salt solution with alkali, by-product There is a coprecipitation method in which the product is removed, dried, treated at 1100 ° C. or lower, and pulverized to obtain a barium ferrite crystal powder, but the present invention does not select a production method. The hexagonal ferrite powder may be subjected to surface treatment with Al, Si, P, or an oxide thereof as required. The amount thereof is 0.1 to 10% with respect to the ferromagnetic powder, and the surface treatment is preferable because the adsorption of a lubricant such as a fatty acid is 100 mg / m ² or less. The ferromagnetic powder may contain inorganic ions such as soluble Na, Ca, Fe, Ni, and Sr. Although it is preferable that these are essentially not present, if they are 200 ppm or less, they do not particularly affect the characteristics.

<Binder>
The binder (binder) used in the magnetic layer of the present invention is a conventionally known thermoplastic resin, thermosetting resin, reactive resin, or a mixture thereof. Examples of the thermoplastic resin include vinyl chloride, vinyl acetate, vinyl alcohol, maleic acid, acrylic acid, acrylic ester, vinylidene chloride, acrylonitrile, methacrylic acid, methacrylic ester, styrene, butadiene, ethylene, vinyl butyral, vinyl acetal. And polymers or copolymers containing vinyl ether as a constituent unit, polyurethane resins, and various rubber resins.

  Examples of thermosetting resins or reactive resins include phenolic resins, epoxy resins, polyurethane curable resins, urea resins, melamine resins, alkyd resins, acrylic reactive resins, formaldehyde resins, silicone resins, and epoxy-polyamide resins. And a mixture of polyester resin and isocyanate prepolymer, a mixture of polyester polyol and polyisocyanate, a mixture of polyurethane and polyisocyanate, and the like. The thermoplastic resin, thermosetting resin and reactive resin are all described in detail in “Plastic Handbook” issued by Asakura Shoten.

  Further, when an electron beam curable resin is used for the magnetic layer, not only the coating film strength is improved and the durability is improved, but also the surface is smoothed and the electromagnetic conversion characteristics are further improved. These examples and their production methods are described in detail in JP-A No. 62-256219.

  The above resins can be used alone or in combination. Among them, it is preferable to use a polyurethane resin, and further, a cyclic structure such as hydrogenated bisphenol A or a polypropylene oxide adduct of hydrogenated bisphenol A, a polyol having an alkylene oxide chain with a molecular weight of 500 to 5000, and a chain extender. A polyurethane resin having a cyclic structure and a molecular weight of 200 to 500 reacted with an organic diisocyanate and having a polar group introduced, or an aliphatic dibasic acid such as succinic acid, adipic acid, or sebacic acid; Fat having no cyclic structure having an alkyl branched side chain such as dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol Polyester polyol composed of a group diol and 2 as a chain extender Reaction of an aliphatic diol having a branched alkyl side chain having 3 or more carbon atoms such as ethyl-2-butyl-1,3-propanediol and 2,2-diethyl-1,3-propanediol with an organic diisocyanate compound And a polyurethane resin into which a polar group is introduced, or a cyclic structure such as dimer diol, a polyol compound having a long-chain alkyl chain, and an organic diisocyanate, and a polyurethane resin into which a polar group is introduced are used. Is preferred.

  The average molecular weight of the polar group-containing polyurethane resin used in the present invention is preferably 5,000 to 100,000, and more preferably 10,000 to 50,000. If the average molecular weight is 5,000 or more, it is preferable because the obtained magnetic coating film is not brittle and the physical strength is not lowered, and the durability of the magnetic recording medium is not affected. Further, when the molecular weight is 100,000 or less, the solubility in the solvent does not decrease, and the dispersibility is also good. Further, since the viscosity of the paint at a predetermined concentration does not increase, the workability is good and the handling is easy.

Examples of the polar group contained in the polyurethane resin, for _{example, -COOM, -SO 3 M, -OSO} 3 M, -P = O (OM) 2, -O-P = O (OM) per ₂ (or more, M is a hydrogen atom or an alkali metal base), —OH, —NR ₂ , —N ⁺ R ₃ (R is a hydrocarbon group), an epoxy group, —SH, —CN, etc., and at least one of these polar groups One in which two or more are introduced by copolymerization or addition reaction can be used. Moreover, when this polar group-containing polyurethane-based resin has an OH group, it preferably has a branched OH group from the viewpoint of curability and durability, and preferably has 2 to 40 branched OH groups per molecule. It is more preferable to have 3 to 20 molecules per molecule. The amount of such polar group is from ¹⁰ -1 ^{to 10 -8} mol / g, preferably ¹⁰ -2 ^{to 10 -6} mol / g.

  Specific examples of the binder include, for example, VAGH, VYHH, VMCH, VAGF, VAGD, VROH, VYES, VYNC, VMCC, XYHL, XYSG, PKHH, PKHJ, PKHC, PKFE, Nissin Chemical Industry Co., Ltd. MPR-TA, MPR-TA5, MPR-TAL, MPR-TSN, MPR-TMF, MPR-TS, MPR-TM, MPR-TAO, Denki Kagaku 1000W, DX80, DX81, DX82, DX83, 100FD, Japan MR-104, MR-105, MR110, MR100, MR555, 400X-110A manufactured by ZEON Co., Ltd. NIPPOLAN N2301, N2302, N2304 manufactured by Nippon Polyurethane Co., Ltd. Pandex T-5105, T-R3080, T-5201 manufactured by Dainippon Ink, Inc. , Barnock D 400, D-210-80, Crisbon 6109, 7209, Byron UR8200, UR8300, UR-8700, RV530, RV280, Toyobo Co., Ltd. Daiferamin 4020, 5020, 5100, 5300, 9020, 9022, 7020, Mitsubishi Examples include MX5004 manufactured by Kasei Co., Ltd., Sanprene SP-150 manufactured by Sanyo Kasei Co., Ltd., and Saran F310 and F210 manufactured by Asahi Kasei.

The amount of the binder used in the magnetic layer of the present invention is in the range of 5 to 50% by mass, preferably in the range of 10 to 30% by mass with respect to the mass of the ferromagnetic metal powder. When using polyurethane, it is preferable to use a combination of 2 to 20% by mass and polyisocyanate in the range of 2 to 20% by mass. For example, when head corrosion occurs due to a small amount of dechlorination, only polyurethane or It is also possible to use only polyurethane and isocyanate. When using a vinyl chloride resin as the other resin, it is preferably in the range of 5 to 30% by mass. In the present invention, when polyurethane is used, the glass transition temperature is −50 to 150 ° C., preferably 0 to 100 ° C., the elongation at break is 100 to 2000%, and the stress at break is 0.49 to 98 MPa (0.05 to 10 kg / mm). ² ) The yield point is preferably 0.49 to 98 MPa (0.05 to 10 kg / mm ² ).

  When the magnetic recording medium used in the present invention is, for example, a flexible disk, it can be composed of two or more layers on both sides of the support. Therefore, the amount of the binder, the amount of vinyl chloride resin, polyurethane resin, polyisocyanate, or other resin in the binder, the molecular weight of each resin forming the magnetic layer, the polar group amount, or the resin described above It is of course possible to change the physical characteristics and the like between the non-magnetic layer and each magnetic layer as required, and rather it should be optimized for each layer, and a known technique relating to a multilayer magnetic layer can be applied. For example, when changing the amount of binder in each layer, it is effective to increase the amount of binder in the magnetic layer in order to reduce scratches on the surface of the magnetic layer. The amount of binder in the magnetic layer can be increased to provide flexibility.

  Examples of the polyisocyanate usable in the present invention include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, naphthylene-1,5-diisocyanate, o-toluidine diisocyanate, isophorone diisocyanate, triol. Examples thereof include isocyanates such as phenylmethane triisocyanate, products of these isocyanates and polyalcohols, and polyisocyanates generated by condensation of isocyanates. Commercially available product names of these isocyanates include: Coronate L, Coronate HL, Coronate 2030, Coronate 2031, Millionate MR Millionate MTL, Takeda Pharmaceutical Taketake D-102, Takenate D-110N, Takenate D-200, Takenate D-202, Sumika Bayer's Death Module L, Death Module IL, Death Module N, Death Module HL, etc. Each layer can be used in the above combination.

As the abrasive used in the present invention, α-alumina, β-alumina, silicon carbide, chromium oxide, cerium oxide, α-iron oxide, corundum, artificial diamond, silicon nitride, silicon carbide having an α conversion ratio of 90 to 100% , Titanium carbide, titanium oxide, silicon dioxide, boron nitride, etc., among which α-Al ₂ O ₃ is preferable. The Mohs hardness of the abrasive is 6 to 10, preferably 8 to 10, and these materials are used alone or in combination. Further, a composite of these abrasives (a product obtained by surface-treating an abrasive with another abrasive) may be used. These abrasives may contain compounds or elements other than the main component, but the effect is not affected if the main component is 90 to 100%. The average particle size of these abrasives is preferably 0.01 to 2 μm. More preferably, it is 0.2-0.3 micrometer, Most preferably, it is 0.22-0.26 micrometer. Note that, if necessary, abrasives having different average particle diameters can be combined, or even a single abrasive can have the same effect by widening the particle size distribution. The tap density is preferably 0.3 to ² g / ml, the water content is 0.1 to 5%, the pH is 2 to 11, and the specific surface area is preferably 1 to 30 m ² / g. The shape of the abrasive used in the present invention may be any of a needle shape, a spherical shape, and a dice shape, but those having a corner in a part of the shape are preferable because of high polishing properties.
The addition amount of the abrasive in the magnetic layer coating solution is 1.5 to 4 parts by mass, preferably 2 to 4 parts by mass, and more preferably 3 to 4 parts by mass with respect to 100 parts by mass of the ferromagnetic powder. Further, the abrasive can be used for the nonmagnetic layer coating solution.

Additives can be added to the magnetic layer in the present invention as necessary. Examples of the additive include a lubricant, a dispersant / dispersion aid, an antifungal agent, an antistatic agent, an antioxidant, a solvent, and carbon black. Examples of these additives include molybdenum disulfide, tungsten disulfide, graphite, boron nitride, graphite fluoride, silicone oil, silicone having a polar group, fatty acid-modified silicone, fluorine-containing silicone, fluorine-containing alcohol, fluorine-containing ester, Polyolefin, polyglycol, polyphenyl ether, phenylphosphonic acid, benzylphosphonic acid, phenethylphosphonic acid, α-methylbenzylphosphonic acid, 1-methyl-1-phenethylphosphonic acid, diphenylmethylphosphonic acid, biphenylphosphonic acid, benzylphenylphosphonic acid , Α-cumylphosphonic acid, toluylphosphonic acid, xylylphosphonic acid, ethylphenylphosphonic acid, cumenylphosphonic acid, propylphenylphosphonic acid, butylphenylphosphonic acid, heptylph Aromatic ring-containing organic phosphonic acids such as enylphosphonic acid, octylphenylphosphonic acid, nonylphenylphosphonic acid and alkali metal salts thereof, octylphosphonic acid, 2-ethylhexylphosphonic acid, isooctylphosphonic acid, isononylphosphonic acid, isodecylphosphonic acid Acids, isoundecyl phosphonic acid, isododecyl phosphonic acid, isohexadecyl phosphonic acid, isooctadecyl phosphonic acid, isoeicosyl phosphonic acid, alkylphosphonic acid and alkali metal salts thereof, phenyl phosphate, benzyl phosphate, phosphoric acid Phenethyl, α-methylbenzyl phosphate, 1-methyl-1-phenethyl phosphate, diphenylmethyl phosphate, biphenyl phosphate, benzylphenyl phosphate, α-cumyl phosphate, toluyl phosphate, xylyl phosphate, ethyl phosphate Phenyl, Li Aromatic phosphates such as cumenyl phosphate, propylphenyl phosphate, butylphenyl phosphate, heptylphenyl phosphate, octylphenyl phosphate, nonylphenyl phosphate, and alkali metal salts thereof, octyl phosphate, 2-ethylhexyl phosphate , Isooctyl phosphate, isononyl phosphate, isodecyl phosphate, isoundecyl phosphate, isododecyl phosphate, isohexadecyl phosphate, isooctadecyl phosphate, isoeicosyl phosphate, and alkali metal salts thereof, alkylsulfonic acid Esters and alkali metal salts thereof, fluorine-containing alkyl sulfates and alkali metal salts thereof, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, butyl stearate, oleic acid, linoleic acid, linolenic acid, Eleiji Monobasic fatty acids that may contain or be branched, such as acids and erucic acids, and their metal salts, or butyl stearate, octyl stearate, amyl stearate, isooctyl stearate Monobasic, which may contain or be branched, containing an unsaturated bond having 10 to 24 carbon atoms, such as octyl myristate, butyl laurate, butoxyethyl stearate, anhydrosorbitan monostearate, anhydrosorbitan tristearate Fatty acid and 1-6 hexahydric alcohol which may contain or be branched including an unsaturated bond having 2 to 22 carbon atoms, alkoxy alcohol or alkylene oxide which may contain or be branched an unsaturated bond having 12 to 22 carbon atoms Mono-fatty acid ester comprising any one of polymer monoalkyl ethers Di-fatty acid esters or polyvalent fatty acid esters, fatty acid amides having 2 to 22 carbon atoms, and aliphatic amines having 8 to 22 carbon atoms can be used. In addition to the above hydrocarbon groups, nitro groups and alkyl groups, aryl groups, and aralkyl groups in which groups other than hydrocarbon groups such as halogen-containing hydrocarbons such as F, Cl, Br, CF ₃ , CCl ₃ , and CBr ₃ are substituted. You may have something.

  In addition, nonionic surfactants such as alkylene oxide, glycerin, glycidol, and alkylphenol ethylene oxide adducts, cyclic amines, ester amides, quaternary ammonium salts, hydantoin derivatives, heterocyclics, phosphonium or sulfoniums, etc. Amphoteric interfaces such as cationic surfactants, anionic surfactants containing acidic groups such as carboxylic acid, sulfonic acid, and sulfate ester groups, amino acids, aminosulfonic acids, sulfuric or phosphate esters of aminoalcohols, and alkylbetaines An activator or the like can also be used. These surfactants are described in detail in “Surfactant Handbook” (published by Sangyo Tosho Co., Ltd.).

  The above-mentioned lubricant, antistatic agent and the like are not necessarily pure and may contain impurities such as isomers, unreacted materials, side reaction products, decomposition products, oxides, etc. in addition to the main components. These impurities are preferably 30% by mass or less, more preferably 10% by mass or less.

  Specific examples of these additives include, for example, NAF-102, castor oil hardened fatty acid, NAA-42, cation SA, Naimine L-201, Nonion E-208, Anon BF, Anon LG, Takemoto, manufactured by NOF Corporation. Oil and fat: FAL-205, FAL-123, Shin Nippon Chemical Co., Ltd .: NJ Lube OL, Shin-Etsu Chemical: TA-3, Lion: Armido P, Lion: Duomin TDO, Nisshin Oilio BA-41G, Sanyo Kasei Co., Ltd .: Profan 2012E, New Pole PE61, Ionette MS-400, etc. are mentioned.

In addition, carbon black can be added to the magnetic layer in the present invention as necessary. Examples of carbon black that can be used in the magnetic layer include rubber furnace, rubber thermal, color black, and acetylene black. Specific surface area is 5 to 500 m ² / g, DBP oil absorption is 10 to 400 ml / 100 g, particle diameter is 5 to 300 nm, pH is 2 to 10, water content is 0.1 to 10%, tap density is 0.1 to 1 g / ml is preferred.

  Specific examples of carbon black used in the present invention include BLACKPEARLS 2000, 1300, 1000, 900, 905, 800, 700, VULCAN XC-72, manufactured by Cabot Corporation, # 80, # 60, # 55 manufactured by Asahi Carbon Co., Ltd. # 50, # 35, Mitsubishi Chemical # 2400B, # 2300, # 900, # 1000, # 30, # 40, # 10B, Columbian Carbon Corporation CONDUCTEX SC, RAVEN150, 50, 40, 15, RAVEN- MT-P, Ketjen Black International Ketjen Black EC, etc. are mentioned. Carbon black may be surface-treated with a dispersant, or may be used after being grafted with a resin, or may be obtained by graphitizing a part of the surface. Carbon black may be dispersed with a binder in advance before being added to the magnetic coating. These carbon blacks can be used alone or in combination. When using carbon black, it is preferable to use 0.1-30 mass% with respect to the mass of a magnetic body. Carbon black functions to prevent the magnetic layer from being charged, reduce the coefficient of friction, impart light-shielding properties, and improve the film strength. These differ depending on the carbon black used. Therefore, these carbon blacks used in the present invention have different types, amounts, and combinations in the magnetic layer and the nonmagnetic layer, and are based on the above-mentioned characteristics such as particle size, oil absorption, conductivity, pH, etc. Of course, it is possible to use them properly according to the purpose, but rather they should be optimized in each layer. For the carbon black that can be used in the magnetic layer of the present invention, for example, “Carbon Black Handbook” edited by Carbon Black Association can be referred to.

  Known organic solvents can be used in the present invention. The organic solvent used in the present invention is an arbitrary ratio of ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, isophorone, tetrahydrofuran, methanol, ethanol, propanol, butanol, isobutyl alcohol, isopropyl alcohol, methyl Alcohols such as cyclohexanol, esters such as methyl acetate, butyl acetate, isobutyl acetate, isopropyl acetate, ethyl lactate, glycol acetate, glycol ethers such as glycol dimethyl ether, glycol monoethyl ether, dioxane, benzene, toluene, xylene, Aromatic hydrocarbons such as cresol and chlorobenzene, methylene chloride, ethylene chloride, carbon tetrachloride, chloroform, ethyl Nkuroruhidorin, chlorinated hydrocarbons such as dichlorobenzene, N, N- dimethylformamide, may be used hexane.

  These organic solvents are not necessarily 100% pure, and may contain impurities such as isomers, unreacted materials, side reaction products, decomposition products, oxides, and moisture in addition to the main components. These impurities are preferably 30% or less, more preferably 10% or less. The organic solvent used in the present invention is preferably the same in the magnetic layer and the nonmagnetic layer. The amount added may be changed. Use non-magnetic layers with high surface tension solvents (cyclohexanone, dioxane, etc.) to increase coating stability. Specifically, the arithmetic average value of the upper layer solvent composition may not fall below the arithmetic average value of the nonmagnetic layer solvent composition. It is essential. In order to improve dispersibility, it is preferable that the polarity is somewhat strong, and it is preferable that 50% or more of a solvent having a dielectric constant of 15 or more is included in the solvent composition. Moreover, it is preferable that a solubility parameter is 8-11.

  These dispersants, lubricants, and surfactants used in the present invention can be properly used in the magnetic layer and further in the nonmagnetic layer described later as needed. For example, of course, the dispersant is not limited to the example shown here, but the dispersant has a property of adsorbing or binding with a polar group, and in the magnetic layer, mainly on the surface of the ferromagnetic metal powder and nonmagnetic. In the layer, it is presumed that the organic phosphorus compound adsorbed or bonded mainly to the surface of the non-magnetic powder with the polar group, for example, is difficult to desorb from the surface of the metal or metal compound. Accordingly, the surface of the ferromagnetic metal powder or the nonmagnetic powder of the present invention is in a state of being coated with an alkyl group, an aromatic group, etc., so that the binder resin component of the ferromagnetic metal powder or nonmagnetic powder is used. The affinity is improved and the dispersion stability of the ferromagnetic metal powder or nonmagnetic powder is also improved. In addition, since the lubricant exists in a free state, fatty acids with different melting points are used in the nonmagnetic layer and magnetic layer to control the bleeding to the surface, and leaching to the surface using esters with different boiling points and polarities. It is conceivable to improve the coating stability by controlling the amount of the surfactant, to improve the lubrication effect by increasing the additive amount of the lubricant in the nonmagnetic layer. All or part of the additives used in the present invention may be added in any step during the production of the coating solution for the magnetic layer or nonmagnetic layer. For example, when mixing with a ferromagnetic powder before the kneading step, when adding at a kneading step with a ferromagnetic powder, a binder and a solvent, when adding at a dispersing step, when adding after dispersing, when adding just before coating, etc. There is.

[Nonmagnetic layer]
Next, detailed contents regarding the nonmagnetic layer will be described. The magnetic recording medium of the present invention can have a nonmagnetic layer containing a binder and a nonmagnetic powder on a support. The nonmagnetic powder that can be used in the nonmagnetic layer may be an inorganic substance or an organic substance. Carbon black or the like can also be used. Examples of the inorganic substance include metals, metal oxides, metal carbonates, metal sulfates, metal nitrides, metal carbides, and metal sulfides.

Specifically, titanium oxide such as titanium dioxide, cerium oxide, tin oxide, tungsten oxide, ZnO, ZrO ₂ , SiO ₂ , Cr ₂ O ₃ , α-alumina, β-alumina having an α conversion of 90 to 100%, γ-alumina, α-iron oxide, goethite, corundum, silicon nitride, titanium carbide, magnesium oxide, boron nitride, molybdenum disulfide, copper oxide, MgCO ₃ , CaCO ₃ , BaCO ₃ , SrCO ₃ , BaSO ₄ , silicon carbide Titanium carbide or the like is used alone or in combination of two or more. Preferable are α-iron oxide and titanium oxide.

  The shape of the nonmagnetic powder may be any of acicular, spherical, polyhedral and plate shapes. The crystallite size of the nonmagnetic powder is preferably 4 nm to 1 μm, and more preferably 40 to 100 nm. A crystallite size in the range of 4 nm to 1 μm is preferred because it does not become difficult to disperse and has a suitable surface roughness. The average particle size of these non-magnetic powders is preferably 5 nm to 2 μm. However, if necessary, non-magnetic powders having different average particle sizes may be combined, or even a single non-magnetic powder may have a wide particle size distribution. It can also have an effect. The average particle size of the particularly preferred nonmagnetic powder is 10 to 200 nm. The range of 5 nm to 2 μm is preferable because the dispersion is good and the surface roughness is suitable.

The specific surface area of the nonmagnetic powder is 1 to 100 m ² / g, preferably 5 to 70 m ² / g, and more preferably 10 to 65 m ² / g. A specific surface area in the range of 1 to 100 m ² / g is preferred because it has a suitable surface roughness and can be dispersed with a desired amount of binder. The oil absorption using dibutyl phthalate (DBP) is 5 to 100 ml / 100 g, preferably 10 to 80 ml / 100 g, and more preferably 20 to 60 ml / 100 g. The specific gravity is 1 to 12, preferably 3 to 6. The tap density is 0.05 to 2 g / ml, preferably 0.2 to 1.5 g / ml. When the tap density is in the range of 0.05 to 2 g / ml, there are few particles to be scattered, the operation is easy, and there is a tendency that it is difficult to adhere to the apparatus. The pH of the nonmagnetic powder is preferably 2 to 11, but is particularly preferably between 6 and 9. When the pH is in the range of 2 to 11, the friction coefficient does not increase due to high temperature, high humidity, or liberation of fatty acids. The moisture content of the nonmagnetic powder is 0.1 to 5% by mass, preferably 0.2 to 3% by mass, and more preferably 0.3 to 1.5% by mass. A water content in the range of 0.1 to 5% by mass is preferable because the dispersion is good and the viscosity of the paint after dispersion is stable. The ignition loss is preferably 20% by mass or less, and the ignition loss is preferably small.

When the nonmagnetic powder is an inorganic powder, the Mohs hardness is preferably 4-10. If the Mohs hardness is in the range of 4 to 10, durability can be ensured. The nonmagnetic powder has a stearic acid adsorption amount of 1 to 20 μmol / m ² , more preferably ² to 15 μmol / m ² . The heat of wetting of the nonmagnetic powder into water at 25 ° C. is preferably in the range of 200 to 600 erg / cm ² (200 to 600 mJ / m ² ). Moreover, the solvent which exists in the range of this heat of wetting can be used. The amount of water molecules on the surface at 100 to 400 ° C. is suitably 1 to 10 / 100Å. The pH of the isoelectric point in water is preferably between 3 and 9. It is preferable that Al ₂ O ₃ , SiO ₂ , TiO ₂ , ZrO ₂ , SnO ₂ , Sb ₂ O ₃ , and ZnO are present on the surface of these nonmagnetic powders by surface treatment. Particularly preferred for dispersibility are Al ₂ O ₃ , SiO ₂ , TiO ₂ , and ZrO ₂ , but more preferred are Al ₂ O ₃ , SiO ₂ , and ZrO ₂ . These may be used in combination or may be used alone. Further, a surface-treated layer co-precipitated according to the purpose may be used, or a method of treating the surface layer with silica after first treating with alumina, or vice versa may be employed. The surface treatment layer may be a porous layer depending on the purpose, but it is generally preferable that the surface treatment layer is homogeneous and dense.

  Specific examples of the non-magnetic powder used in the non-magnetic layer of the present invention include, for example, Showa Denko Nanotite, Sumitomo Chemical HIT-100, ZA-G1, Toda Kogyo DPN-250, DPN-250BX, DPN-245, DPN-270BX, DPB-550BX, DPN-550RX, Ishihara Sangyo Titanium oxide TTO-51B, TTO-55A, TTO-55B, TTO-55C, TTO-55S, TTO-55D, SN-100, MJ -7, α-iron oxide E270, E271, E300, STT-4D, STT-30D, STT-30, STT-65C manufactured by Titanium Industry, MT-100S, MT-100T, MT-150W, MT-500B manufactured by Teika T-600B, T-100F, T-500HD, etc. are mentioned. FINEX-25, BF-1, BF-10, BF-20, ST-M, Dowa Mining DEFIC-Y, DEFIC-R, Nippon Aerosil AS2BM, TiO2P25, Ube Industries 100A, 500A, Titanium Industry Y-LOP manufactured and what baked it are mentioned. Particularly preferred nonmagnetic powders are titanium dioxide and α-iron oxide.

Carbon black can be mixed in the nonmagnetic layer together with nonmagnetic powder to lower the surface electrical resistance, reduce the light transmittance, and obtain a desired micro Vickers hardness. The micro-Vickers hardness of the nonmagnetic layer is generally 25~60Kg ^/ mm 2 (245~588MPa), preferably in order to adjust the head ^contact, a 30~50Kg / mm 2 (294~490MPa), thin film hardness meter ( Using a HMA-400 manufactured by NEC, measurement can be performed using a diamond triangular pyramid needle having a ridge angle of 80 degrees and a tip radius of 0.1 μm at the tip of the indenter. It is standardized that the light transmittance is generally 3% or less for absorption of infrared rays having a wavelength of about 900 nm, for example, 0.8% or less for a VHS magnetic tape. For this purpose, rubber furnace, rubber thermal, color black, acetylene black and the like can be used.

Non specific surface area of the carbon black used in the magnetic layer is 100 to 500 m ² / g, preferably 150~400m ² / g, DBP oil absorption of the present invention are 20 to 400 ml / 100 g, preferably 30 to 200 ml / 100 g . The particle size of carbon black is 5 to 80 nm, preferably 10 to 50 nm, and more preferably 10 to 40 nm. Carbon black preferably has a pH of 2 to 10, a water content of 0.1 to 10%, and a tap density of 0.1 to 1 g / ml.

  Specific examples of carbon black that can be used in the nonmagnetic layer of the present invention include BLACKPEARLS 2000, 1300, 1000, 900, 800, 880, 700, VULCAN XC-72, manufactured by Cabot Corporation, # 3050B, manufactured by Cabot Corporation. # 3150B, # 3250B, # 3750B, # 3950B, # 950B, # 650B, # 970B, # 850B, MA-600, Columbia Carbon Corporation CONDUCTEX SC, RAVEN8800, 8000, 7000, 5750, 5250, 3500, 2100, 2000, 1800, 1500, 1255, 1250, and Ketjen Black EC manufactured by Ketjen Black International.

  Carbon black may be surface-treated with a dispersant, or may be grafted with a resin, or may be obtained by graphitizing a part of the surface. Moreover, before adding carbon black to a coating material, you may disperse | distribute with a binder beforehand. These carbon blacks can be used in a range not exceeding 50% by mass with respect to the inorganic powder and in a range not exceeding 40% of the total mass of the nonmagnetic layer. These carbon blacks can be used alone or in combination. The carbon black that can be used in the nonmagnetic layer of the present invention can be referred to, for example, “Carbon Black Handbook” edited by Carbon Black Association.

  Further, an organic powder can be added to the nonmagnetic layer according to the purpose. Examples of such organic powder include acrylic styrene resin powder, benzoguanamine resin powder, melamine resin powder, and phthalocyanine pigment, but polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin, and the like. Resin powder and polyfluorinated ethylene resin can also be used. As the production method, those described in JP-A Nos. 62-18564 and 60-255827 can be used.

As the binder resin, lubricant, dispersant, additive, solvent, dispersion method and the like of the nonmagnetic layer, those of the magnetic layer can be applied. In particular, with respect to the binder resin amount, type, additive, and dispersant addition amount and type, known techniques relating to the magnetic layer can be applied.
Among them, as the binder for the nonmagnetic layer, a polyurethane resin having a Tg of 50 to 200 ° C., for example, a polyurethane resin B described in paragraph (0032) is preferable.

  The magnetic recording medium of the present invention may be provided with an undercoat layer. By providing the undercoat layer, the adhesive force between the support and the magnetic layer or the nonmagnetic layer can be improved. As the undercoat layer, a polyester resin that is soluble in a solvent is used.

[Layer structure]
In the thickness structure of the magnetic recording medium used in the present invention, the preferable thickness of the support is 3 to 80 μm. When an undercoat layer is provided between the support and the nonmagnetic layer or the magnetic layer, the thickness of the undercoat layer is 0.01 to 0.8 μm, preferably 0.02 to 0.6 μm.

  The thickness of the magnetic layer is optimized depending on the saturation magnetization amount, head gap length, and recording signal band of the magnetic head to be used, but is generally 10 to 150 nm, preferably 20 to 120 nm, and more preferably. Is 30 to 100 nm, particularly preferably 30 to 80 nm. Further, the thickness variation rate of the magnetic layer is preferably within ± 50%, and more preferably within ± 40%. There may be at least one magnetic layer, and the magnetic layer may be separated into two or more layers having different magnetic characteristics, and a configuration related to a known multilayer magnetic layer can be applied.

  The thickness of the nonmagnetic layer of the present invention is 0.5 to 2.0 μm, preferably 0.8 to 1.5 μm, and more preferably 0.8 to 1.2 μm. The non-magnetic layer of the magnetic recording medium of the present invention exhibits its effect if it is substantially non-magnetic. For example, even if it contains a small amount of magnetic material as an impurity or intentionally, This shows the effect of the invention and can be regarded as substantially the same configuration as the magnetic recording medium of the invention. Note that “substantially the same” means that the residual magnetic flux density of the nonmagnetic layer is 10 mT or less or the coercive force is 7.96 kA / m (100 Oe) or less, and preferably has no residual magnetic flux density and coercive force. Means.

[Back layer]
The magnetic recording medium of the present invention is preferably provided with a back layer on the other surface of the support. The back layer preferably contains carbon black and inorganic powder. For the binder and various additives, the formulation of the magnetic layer and the nonmagnetic layer is applied. The thickness of the back layer is preferably from 0.1 to 1.0 μm, more preferably from 0.4 to 0.6 μm.
In addition, when the ratio (mass%) of the lubricant in the back layer is 1, the ratio (mass%) of the lubricant in the magnetic layer is 1 to 5 as described above.

[Production method]
The step of producing the magnetic layer coating liquid for the magnetic recording medium used in the present invention comprises at least a kneading step, a dispersing step, and a mixing step provided before and after these steps. Each process may be divided into two or more stages. All raw materials such as ferromagnetic metal powder, non-magnetic powder, binder, carbon black, abrasive, antistatic agent, lubricant, and solvent used in the present invention may be added at the beginning or middle of any step. In addition, individual raw materials may be added in two or more steps. For example, polyurethane may be divided and added in a kneading step, a dispersing step, and a mixing step for adjusting the viscosity after dispersion. In order to achieve the object of the present invention, a conventional known manufacturing technique can be used as a partial process. In the kneading step, it is preferable to use a kneading force such as an open kneader, a continuous kneader, a pressure kneader, or an extruder. Details of these kneading treatments are described in JP-A-1-106338 and JP-A-1-79274. Further, glass beads can be used to disperse the magnetic layer coating liquid and the nonmagnetic layer coating liquid. Such glass beads are preferably zirconia beads, titania beads, and steel beads, which are high specific gravity dispersion media. The particle diameter and filling rate of these dispersion media are optimized. A well-known thing can be used for a disperser. In addition, the aggregate of the abrasive | polishing material too large can be removed by performing filtration suitably after a dispersion | distribution process.

  In the method for producing a magnetic recording medium of the present invention, for example, the magnetic layer coating liquid is formed on the surface of the support under running so as to have a predetermined film thickness. Here, a plurality of magnetic layer coating solutions may be applied sequentially or simultaneously, and a nonmagnetic layer coating solution and a magnetic layer coating solution may be applied sequentially or simultaneously. The coating machine for applying the above magnetic coating solution or non-magnetic layer coating solution includes air doctor coat, blade coat, rod coat, extrusion coat, air knife coat, squeeze coat, impregnation coat, reverse roll coat, transfer roll coat, gravure coat Kiss coat, cast coat, spray coat, spin coat, etc. can be used. As for these, for example, “Latest Coating Technology” (May 31, 1983) issued by General Technology Center Co., Ltd. can be referred to.

  In the case of a magnetic tape, the magnetic layer coating solution is subjected to magnetic field orientation treatment in the longitudinal direction using a cobalt magnet or a solenoid on the ferromagnetic metal powder contained in the magnetic layer coating solution. In the case of a disk, a sufficiently isotropic orientation may be obtained even without non-orientation without using an orientation device, but known random methods such as alternately arranging cobalt magnets obliquely and applying an alternating magnetic field with a solenoid. It is preferable to use an alignment device. In the case of a ferromagnetic metal powder, the isotropic orientation is generally preferably in-plane two-dimensional random, but can also be three-dimensional random with a vertical component. Further, isotropic magnetic characteristics can be imparted in the circumferential direction by using a well-known method such as a counter-polarized magnet and making it vertically oriented. In particular, when performing high density recording, vertical alignment is preferable. Moreover, circumferential orientation can also be achieved using spin coating.

  It is preferable that the drying position of the coating film can be controlled by controlling the temperature, air volume, and coating speed of the drying air, the coating speed is preferably 20 m / min to 1000 m / min, and the temperature of the drying air is preferably 60 ° C. or higher. Also, moderate pre-drying can be performed before entering the magnet zone.

After drying, the coating layer is usually subjected to a surface smoothing treatment. For the surface smoothing process, for example, a super calendar roll or the like is used. By performing the surface smoothing treatment, voids generated by the removal of the solvent during drying disappear and the filling rate of the ferromagnetic metal powder in the magnetic layer is improved, so that a magnetic recording medium having high electromagnetic conversion characteristics can be obtained. Can do. As the calendering roll, a heat-resistant plastic roll such as epoxy, polyimide, polyamide, polyamideimide or the like is used. Moreover, it can also process with a metal roll.
The magnetic recording medium of the present invention has a surface having extremely excellent smoothness with a center surface average roughness of 0.1 to 4 nm, preferably 1 to 3 nm at a cutoff value of 0.25 mm. preferable. As the method, for example, as described above, a magnetic layer formed by selecting a specific ferromagnetic metal powder and a binder is subjected to the calendar treatment. As calendering conditions, the temperature of the calender roll is in the range of 60 to 100 ° C., preferably in the range of 70 to 100 ° C., particularly preferably in the range of 80 to 100 ° C., and the pressure is 100 to 500 kg / cm (98 to 490 kN). / M), preferably 200 to 450 kg / cm (196 to 441 kN / m), particularly preferably 300 to 400 kg / cm (294 to 392 kN / m). Is preferably carried out by

  The obtained magnetic recording medium can be cut into a desired size using a cutting machine or the like. The cutting machine is not particularly limited, but is preferably provided with a plurality of pairs of rotating upper blades (male blades) and lower blades (female blades). The slitting speed, the meshing depth, and the upper blade (male blade) are appropriately selected. The peripheral speed ratio (upper blade peripheral speed / lower blade peripheral speed) of the blade and the lower blade (female blade), the continuous use time of the slit blade, and the like are selected.

[Physical properties]
The saturation magnetic flux density of the magnetic layer of the magnetic recording medium used in the present invention is preferably 100 to 300 mT. The coercive force (Hr) of the magnetic layer is preferably 143.3 to 318.4 kA / m (1800 to 4000 Oe), more preferably 159.2 to 278.6 kA / m (2000 to 3500 Oe). The coercive force distribution is preferably narrow, and SFD and SFDr are 0.6 or less, more preferably 0.2 or less.

The friction coefficient with respect to the head of the magnetic recording medium used in the present invention is 0.50 or less, preferably 0.3 or less in the range of temperature -10 to 40 ° C. and humidity 0 to 95%. The surface resistivity is preferably 10 ⁴ to 10 ¹² Ω / sq of the magnetic surface, and the charging position is preferably within −500 V to +500 V. The elastic modulus at 0.5% elongation of the magnetic layer is preferably 0.98 to 19.6 GPa (100 to 2000 Kg / mm ² ) in each in-plane direction, and the breaking strength is preferably 98 to 686 MPa (10 to 70 Kg). / Mm ² ), the elastic modulus of the magnetic recording medium is preferably 0.98 to 14.7 GPa (100 to 1500 Kg / mm ² ) in each in-plane direction, and the residual spread is preferably 0.5% or less, 100 ° C. The thermal shrinkage at any of the following temperatures is preferably 1% or less, more preferably 0.5% or less, and most preferably 0.1% or less.

The glass transition temperature of the magnetic layer (maximum point of loss elastic modulus measured by dynamic viscoelasticity measured at 110 Hz) is preferably 50 to 180 ° C, and that of the nonmagnetic layer is preferably 0 to 180 ° C. The loss elastic modulus is preferably in the range of 1 × 10 ⁷ to 8 × 10 ⁸ Pa (1 × 10 ⁸ to 8 × 10 ⁹ dyne / cm ² ), and the loss tangent is preferably 0.2 or less. If the loss tangent is too large, adhesion failure is likely to occur. These thermal characteristics and mechanical characteristics are preferably almost equal within 10% in each in-plane direction of the medium.

The residual solvent contained in the magnetic layer is preferably 100 mg / m ² or less, more preferably 10 mg / m ² or less. The porosity of the coating layer is preferably 30% by volume or less, more preferably 20% by volume or less for both the nonmagnetic layer and the magnetic layer. The porosity is preferably small in order to achieve high output, but it may be better to ensure a certain value depending on the purpose. For example, in the case of a disk medium in which repeated use is important, a larger void ratio is often preferable for running durability.

The maximum height SR _max of the magnetic layer is 0.5 μm or less, the ten-point average roughness SRz is 0.3 μm or less, the center plane peak height SRp is 0.3 μm or less, and the center plane valley depth SRv is 0.3 μm or less. The center surface area ratio SSr is preferably 20 to 80%, and the average wavelength Sλa is preferably 5 to 300 μm. These can be easily controlled by controlling the surface properties with the filler of the support or the surface of the calendered roll. The curl is preferably within ± 3 mm.

  When the magnetic recording medium of the present invention is composed of a nonmagnetic layer and a magnetic layer, these physical characteristics can be changed between the nonmagnetic layer and the magnetic layer according to the purpose. For example, the elastic modulus of the magnetic layer can be increased to improve running durability, and at the same time, the elastic modulus of the nonmagnetic layer can be made lower than that of the magnetic layer to improve the contact of the magnetic recording medium with the head.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to the following example.
In addition, the display of "part" in an Example shows "mass part".

Example 1
Preparation of coating solution for nonmagnetic layer 80 parts of nonmagnetic powder α-Fe ₂ O ₃ hematite Surface treatment layer: Al ₂ O ₃ , SiO ₂ , average major axis diameter: 0.15 μm,
Tap density: 0.8 g / ml, BET specific surface area: 52 m ² / g,
pH 8, DBP oil absorption: 27-38ml / 100g
Carbon black 20 parts Average primary particle size: 16 nm, DBP oil absorption: 80 ml / 100 g,
pH: 8, BET specific surface area: 250 m ² / g, volatile content: 1.5%
Vinyl chloride copolymer (MR-110: manufactured by Nippon Zeon Co., Ltd.) 12 parts -SO ₃ Na content: 1 × 10 ⁻⁴ mol / g, polymerization degree: 300
Polyurethane B 5 parts Structure: Dimerdiol / hydrogenated bisphenol A /
Sulfoisophthalic acid ethylene oxide adduct /
Diphenylmethane diisocyanate = 15/85/2/100
(Molar ratio)
Mass average molecular weight 47500
Glass transition point Tg: 160 ° C.
Butyl stearate 1 part stearic acid 5 parts methyl ethyl ketone / cyclohexanone = 1/1 60 parts toluene 50 parts

Preparation of magnetic layer coating solution Ferromagnetic powder 100 parts Composition (atomic ratio): Fe / Co / Al / Y = 100/30/12/7
Hc: 175 kA / m, average long axis length: 45 nm
Average needle ratio: 4.1, BET specific surface area: 64 m ² / g
σs: 110 A · m ² / kg (emu / g)
Was pulverized with an open kneader for 10 minutes, and then carbon black (average particle size 90 nm) 2 parts vinyl chloride copolymer (MR-110: manufactured by Nippon Zeon Co., Ltd.) 12 parts -SO ₃ Na content: 1 × 10 ⁻⁴ mol / G, degree of polymerization: 300
Polyurethane (UR8300: manufactured by Toyobo Co., Ltd.) (solid content) 10 parts Glass transition point Tg: 37 ° C
The following abrasive dispersion A 1.5 parts butyl stearate 1 part stearic acid 5 parts methyl ethyl ketone / cyclohexanone = 1/1 60 parts toluene 50 parts

Abrasive dispersion A
α-Al ₂ O ₃ (HIT-60: manufactured by Sumitomo Chemical Co., Ltd.) 100 parts Average particle diameter: 0.24 μm
Vinyl chloride copolymer (MR-110: manufactured by Nippon Zeon Co., Ltd.) 10 parts —SO ₃ Na content: 1 × 10 ⁻⁴ mol / g, polymerization degree: 300
90 parts of methyl ethyl ketone / cyclohexanone = 1/1 Abrasive dispersion A was placed in a vessel coated with zirconium oxide (ZrO ₂ ) and dispersed for 1 hour with a 1.5 mm diameter sand grinder made of zirconium oxide. Prepared. Note that the dispersion dispersed and strengthened with a sand grinder for 2 hours was used as an abrasive dispersion B.

100 parts of back layer coating liquid fine particle carbon black (BP-800 manufactured by Cabot Corporation, average particle diameter: 17 nm)
Coarse particle carbon black 10 parts (Thermal black manufactured by Kern Calp, average particle size: 270 nm)
α-Fe ₂ O ₃ 15 parts (TF-100 manufactured by Toda Kogyo Co., Ltd., average particle size: 110 nm,
Mohs hardness: 5.5)
Nitrocellulose resin 140 parts Polyurethane resin 15 parts Polyester resin 5 parts Dispersant: Copper oleate 5 parts Copper phthalocyanine 5 parts Barium sulfate (precipitation) 5 parts Butyl stearate 1.3 parts Stearic acid 6 parts Methyl ethyl ketone 2200 parts Butyl acetate 300 parts 600 parts of toluene

  Each component of the nonmagnetic layer coating solution and the magnetic layer coating solution was kneaded with an open kneader and then dispersed using a sand mill. Polyisocyanate (Coronate L manufactured by Nippon Polyurethane Co., Ltd.) is added to the resulting dispersion, 5 parts to the non-magnetic layer coating liquid, 8 parts to the magnetic layer coating liquid, and 40 parts each of methyl ethyl ketone and cyclohexanone mixed solvent are added. Filtration was performed using a filter having an average pore size of 1 μm to complete a nonmagnetic layer coating solution and a magnetic layer coating solution, respectively. Further, 5 parts of polyisocyanate was added to the back layer coating solution, kneaded with a continuous kneader, dispersed using a sand mill, and filtered using a filter having an average pore diameter of 1 μm as described above. Was completed.

  Further, the nonmagnetic layer coating solution was applied to a 6 μm thick biaxially stretched polyethylene terephthalate (PET) base so that the thickness after drying was 1.5 μm, and immediately thereafter, the magnetic layer coating solution was dried. Was simultaneously applied so that the thickness was 0.12 μm. Seven layers consisting of a metal roll and a heat-resistant plastic after both layers are magnetically oriented by a 300mT (3,000 gauss) cobalt magnet and a 150mT (1,500 gauss) solenoid with both layers undried. After performing surface smoothing with a calender of 100 m / min, a linear pressure of 250 Pa, and a temperature of 80 ° C., the back layer coating solution is applied to the other surface of the base so that the thickness after drying becomes 0.5 μm. Applied and dried. A heat curing treatment (thermo treatment) was performed at 70 ° C. for 24 hours, and a magnetic tape was prepared by slitting to a 1/2 inch width using a cutting device.

(Example 2)
Example 1 was repeated except that the amount of abrasive dispersion A used in the magnetic layer coating solution was changed to 2 parts.

(Example 3)
Example 1 was repeated except that the changes were as follows.
The amount of abrasive dispersion A used in the magnetic layer coating solution is changed to 2 parts;
Change polyurethane UR8300 in the magnetic layer coating solution to 12 parts polyurethane B used in the nonmagnetic layer coating solution;
The amount of vinyl chloride copolymer MR-110 used in the nonmagnetic layer coating solution was changed to 14 parts;
Change the amount of polyurethane B used in the non-magnetic layer coating solution to 14 parts;
The calendar processing conditions were changed to a conveyance speed of 150 m / min, a linear pressure of 277 Pa, and a temperature of 85 ° C.

Example 4
Example 1 was repeated except that the changes were as follows.
Instead of abrasive dispersion A in the magnetic layer coating solution, change to abrasive dispersion B and change the amount used to 4 parts;
Changed the amount of vinyl chloride copolymer MR-110 used in the magnetic layer coating solution to 14 parts;
Change the polyurethane UR8300 in the magnetic layer coating solution to 10 parts of polyurethane B used in the nonmagnetic layer coating solution;
As an abrasive in the nonmagnetic layer coating solution, 1 part of α-Al ₂ O ₃ (HIT-55: Sumitomo Chemical Co., Ltd., average particle size: 0.28 μm) was added and added; / Min, linear pressure 277Pa, temperature 85 ° C.

(Example 5)
Example 1 was repeated except that the changes were as follows.
The amount of abrasive dispersion A used in the magnetic layer coating solution is changed to 4 parts;
Change polyurethane UR8300 in the magnetic layer coating solution to 12 parts polyurethane B used in the nonmagnetic layer coating solution;
Changed the amount of vinyl chloride copolymer MR-110 used in the magnetic layer coating solution to 14 parts;
The amount of vinyl chloride copolymer MR-110 used in the nonmagnetic layer coating solution was changed to 14 parts;
Changed the amount of polyurethane B used in the non-magnetic layer coating solution to 7 parts;
The calendar processing conditions were changed to a conveyance speed of 150 m / min, a linear pressure of 277 Pa, and a temperature of 85 ° C.

(Example 6)
Example 1 was repeated except that the changes were as follows.
Change polyurethane UR8300 in the magnetic layer coating solution to 12 parts polyurethane B used in the nonmagnetic layer coating solution;
Changed the amount of vinyl chloride copolymer MR-110 used in the magnetic layer coating solution to 14 parts;
The amount of vinyl chloride copolymer MR-110 used in the nonmagnetic layer coating solution was changed to 14 parts;
Changed the amount of polyurethane B used in the non-magnetic layer coating solution to 7 parts;
The calendar processing conditions were changed to a conveyance speed of 150 m / min, a linear pressure of 300 Pa, and a temperature of 90 ° C.

(Comparative Example 1)
In Example 3, Example 3 was repeated except that butyl stearate and stearic acid were removed from the back layer coating solution.

(Comparative Example 2)
Example 1 was repeated except that the changes were as follows.
Change polyurethane UR8300 in the magnetic layer coating solution to 12 parts polyurethane B used in the nonmagnetic layer coating solution;
Changed the amount of vinyl chloride copolymer MR-110 used in the magnetic layer coating solution to 14 parts;
Changed the amount of polyurethane B used in the non-magnetic layer coating solution to 7 parts;
The calendar processing conditions were changed to a conveyance speed of 150 m / min, a linear pressure of 277 Pa, and a temperature of 85 ° C.

(Comparative Example 3)
Example 1 was repeated except that the changes were as follows.
Instead of abrasive dispersion A in the magnetic layer coating solution, change to abrasive dispersion B and change the amount used to 1.5 parts;
Change the polyurethane UR8300 in the magnetic layer coating solution to 10 parts of polyurethane B used in the nonmagnetic layer coating solution;
Changed the amount of polyurethane B used in the non-magnetic layer coating solution to 7 parts;
The calendar processing conditions were changed to a conveyance speed of 150 m / min, a linear pressure of 277 Pa, and a temperature of 85 ° C.

(Comparative Example 4)
Example 1 was repeated except that the changes were as follows.
The amount of abrasive dispersion A used in the magnetic layer coating solution is changed to 4 parts;
Change polyurethane UR8300 in the magnetic layer coating solution to 12 parts polyurethane B used in the nonmagnetic layer coating solution;
Changed the amount of vinyl chloride copolymer MR-110 used in the magnetic layer coating solution to 14 parts;
Changed the amount of polyurethane B used in the non-magnetic layer coating solution to 7 parts;
As an abrasive in the nonmagnetic layer coating solution, 1 part of α-Al ₂ O ₃ (HIT-55: Sumitomo Chemical Co., Ltd., average particle size: 0.28 μm) was added and added; / Min, linear pressure 300Pa, temperature 90 ° C.

  The following evaluation was performed on the obtained magnetic tape.

<Number of abrasives present on the surface of the magnetic layer>
The number of abrasives present on the surface of the magnetic layer and the number of aggregates of the abrasives were examined by microscopic observation. The microscope was observed using a S-800 FE-SEM manufactured by Hitachi, Ltd. at a magnification of 10,000 times. The number of samples (the number of viewing fields) n = 5, and the average value was the number.

<Measurement of indentation hardness (DH)>
The indentation hardness (DH) defined by the following formula (1) was determined.
DH = 3.7926 × 10 ⁻² {Pmax / (Hmax) ² } (Kg / mm ² ) (1)
(However, Pmax is the maximum load and Hmax is the maximum displacement of the indenter.)
The details of the measurement method are as described above.

<Interface variation rate>
An ultra-thin section of the magnetic tape cross section is photographed with a transmission electron microscope (TEM), the interface between the magnetic layer and the non-magnetic layer is visually traced on the photograph of the obtained cross section, and further processed with an image analyzer to be magnetic The layer thickness was calculated. From the calculation results, the standard deviation and average value of the magnetic layer thickness were determined, and the interface variation rate defined by the following formula (2) was determined. The number of samples n = 10.
Interface fluctuation rate = (standard deviation of magnetic layer thickness ÷ average value of magnetic layer thickness) × 100 (%) (2)
<Measurement method of lubricant>
The magnetic layer or the back layer was peeled off using a blade of an NT cutter, the lubricant was extracted from the peeled piece, and measured by Shimadzu gas chromatography <model GC-MA>.

<Change rate of wear width>
The wear width of the AlFeSil prisms when the magnetic recording medium is run under the following running conditions is a, and after the running, the same part of the magnetic recording medium is the same as the above for the same AlFeSil prisms under the same conditions as above. The increment b of the wear width of the AlFeSil prism when the contact running was performed under the same running conditions, and the change rate b / a of the wear width was calculated.
<Running conditions>:
The surface of the magnetic layer is brought into contact with one ridge of the AlFeSil prism at a wrap angle of 12 degrees so as to be orthogonal to the longitudinal direction of the AlFeSil prism (the prism defined in ECMA-288 / AnnexH / H2). The recording medium is run for 50 m at a speed of 0.3 m / sec under a tension of 52.5 N / m.

<Error rate>
Output during driving: A magnetic tape was set in a DDS-4 drive under an environment of 23 ° C. and 10% RH, and an initial error rate and an error rate after 300 passes were examined.

  The results are shown in Table 1.

From Table 1, the number of abrasives present on the surface of the magnetic layer is 4.0 to 8.0 / μm ² , of which 1.0 to 2.0 / μm ² is an aggregate of abrasives. And when the ratio (mass%) of the lubricant in the back layer is 1, the ratio (mass%) of the lubricant in the magnetic layer is 1 to 5, the magnetic recording medium of the example of the present invention is It can be seen that the increase in error rate is suppressed in a low humidity environment as compared with the comparative example.

It is a figure for demonstrating the shape of the indenter used by this invention. It is a figure for demonstrating the definition of indentation hardness.

Claims (3)

A nonmagnetic layer containing nonmagnetic powder and a binder is provided on one surface of the support, a magnetic layer containing ferromagnetic powder and a binder is provided on the nonmagnetic layer, and the other surface of the support is provided. In the magnetic recording medium provided with the back layer, the number of abrasives present on the surface of the magnetic layer is 4.0 to 8.0 / μm ² , and aggregates of abrasives are 1.0 to 2.0. / Μm ² and the ratio (mass%) of the lubricant in the magnetic layer is 1 to 5 when the ratio (mass%) of the lubricant in the back layer is 1. Magnetic recording medium. The magnetic recording medium according to claim 1, wherein the indentation hardness (DH) of the magnetic layer surface defined by the following formula (1) is 25 to 80 kg / mm ² (245 to 785 MPa).
DH = 3.7926 × 10 ⁻² {Pmax / (Hmax) ² } (Kg / mm ² ) (1)
(However, Pmax is the maximum load and Hmax is the maximum displacement of the indenter.) 3. The magnetic recording medium according to claim 1, wherein an interface variation rate defined by the following formula (2) is within a range of 5 to 30%.
Interface fluctuation rate = (standard deviation of magnetic layer thickness ÷ average value of magnetic layer thickness) × 100 (%) (2)

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