JP4228876B2 - Magnetic recording medium - Google Patents

Description

  The present invention relates to a magnetic recording medium such as a magnetic tape or a magnetic disk.

  As magnetic tapes for audio, video, computers, etc. and disk-shaped magnetic recording media such as flexible disks, ferromagnetic fine particles such as γ-iron oxide, Co-containing iron oxide, chromium oxide, and ferromagnetic metal fine powder A magnetic recording medium in which a magnetic layer in which powder is dispersed in a binder is provided on a support is used. In general, polyethylene terephthalate, polyethylene naphthalate, or the like is used as the support used in the magnetic recording medium. Since these supports are stretched and highly crystallized, they have high mechanical strength and excellent solvent resistance.

  The magnetic layer obtained by applying a coating solution in which a ferromagnetic fine powder is dispersed in a binder to a support has a high degree of filling of the ferromagnetic fine powder, a small elongation at break, and a mechanical force is applied. May be easily broken and peeled off from the support. Therefore, an undercoat layer is provided on the support and the magnetic layer is strongly bonded onto the support.

  For example, a magnetic recording medium in which a radiation-cured layer is formed using a compound having a functional group that is cured by radiation such as an electron beam, that is, a radiation-curing compound is known (see Patent Documents 1 to 4). Radiation-cured layers using these radiation-cured compounds have insufficient smoothness of the magnetic layer, and sufficient electromagnetic conversion characteristics cannot be obtained. Further, since the peel strength of the magnetic layer is insufficient, when it is repeatedly run with a VTR or the like, a part of the magnetic layer is peeled off, which may cause a failure such as dropout. Furthermore, since the radiation-cured layer is soft, there is a problem that there are many failures that stick to the guide roller or the like in the coating process.

JP-A-57-40747 JP 58-146023 A JP-A-60-150227 Japanese Patent Publication No. 5-57647

  The problem to be solved by the present invention is to provide a magnetic recording medium excellent in productivity and excellent in smoothness and electromagnetic conversion characteristics, with less failure during web conveyance during the manufacturing process and less loss of the magnetic layer. .

In order to achieve the above object, the present invention has the following configuration. That is, the present invention
In a magnetic recording medium in which a radiation-cured material layer obtained by curing a radiation-curable compound-containing layer by radiation irradiation on a nonmagnetic support and a magnetic layer containing a ferromagnetic powder and a binder are formed in this order. The magnetic recording medium is characterized in that an epoxy ester acrylate compound or an epoxy ester methacrylate compound having a benzene ring structure, a heterocyclic structure or a cyclohexane ring structure is used as the radiation curable compound.

  Here, the number of acroyl groups or methacryloyl groups in the molecule of the epoxy ester acrylate compound or epoxy ester methacrylate compound having a benzene ring structure, a heterocyclic structure or a cyclohexane ring structure is preferably 2 or more.

  Further, a nonmagnetic layer containing a nonmagnetic powder and a binder can be further formed between the radiation cured product layer and the magnetic layer.

  According to the present invention, it is possible to obtain a magnetic recording medium excellent in productivity and excellent in smoothness and electromagnetic conversion characteristics, with less failure during web conveyance during the manufacturing process and less loss of the magnetic layer.

Hereinafter, the present invention will be described in more detail.
I. Radiation cured material layer <Radiation curable compound>
The “radiation curable compound” contained in the radiation curable layer in the present invention refers to a compound having a property of starting to polymerize or crosslink when irradiated with radiation such as ultraviolet rays or an electron beam, to be polymerized and cured. The reaction of the radiation curable compound does not proceed unless energy (ultraviolet ray or electron beam) is applied from the outside. For this reason, the coating liquid containing the radiation curable compound has a stable viscosity unless irradiated with ultraviolet rays or an electron beam, and high coating smoothness can be obtained. In addition, since the reaction proceeds instantaneously due to high energy by ultraviolet rays or electron beams, a high coating strength can be obtained with a coating solution containing a radiation curable compound.
The radiation used in the present invention includes various types of radiation such as electron beams (β rays), ultraviolet rays, X rays, γ rays, and α rays.

The radiation curable compound in the present invention is an epoxy ester acrylate compound or epoxy ester methacrylate compound (having a radiation functional double bond and an OH group) having a benzene ring structure, a heterocyclic structure or a cyclohexane ring structure. Such a compound can be obtained by an addition reaction of acrylic acid, acrylic acid chloride, methacrylic acid or methacrylic acid chloride to an epoxy compound having a benzene ring structure, a heterocyclic structure or a cyclohexane ring structure.
Examples of epoxy compounds having a benzene ring structure, a heterocyclic structure, or a cyclohexane ring structure include bisphenol A type epoxy resins, bisphenol F type epoxy resins, halogenated bisphenol A type epoxy resins, tetraphenylolethane tetraglycidyl ether, and phenol novolac type epoxies. Resin, o-cresol novolac type epoxy resin, naphthalene type epoxy resin, cardo type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, isocyanurate A type epoxy resin or the like can be used.

The number of (meth) acryloyl groups in one molecule is preferably 2 or more, more preferably 3 or more. This is because the greater the number of functional groups, the higher the curability, the fewer unreacted materials after curing, and the better the storage stability of the magnetic recording medium.
In addition, when the acrylic acid adduct and the methacrylic acid adduct are compared, the former acrylic acid adduct has a higher curability and is preferable.
Epoxy ester (meth) acrylate has an OH group together with (meth) acryloyl group in the molecule, so the hydrophilicity of the cured film is increasing, and magnetic film and non-magnetic film formed on the cured film are increased. High adhesion to the film. Here, the epoxy ester (meth) acrylate may partially leave epoxy. Residual epoxy groups, like OH groups, have the effect of increasing adhesion to magnetic and nonmagnetic films formed thereon.

In addition, the epoxy ester (meth) acrylate having the ring structure used in the present invention is advantageous in curing a thin coating film having a thickness of 1 μm or less because of little inhibition of curing by oxygen during radiation curing.
Furthermore, the epoxy ester (meth) acrylate having the above-mentioned ring structure used in the present invention has a high elastic modulus of the cured film due to the ring structure, leading to an improvement in the strength of the entire magnetic recording medium, which is advantageous in terms of running durability. It is.

  Specific compounds (compounds 1 to 14) of preferable radiation curable compounds used in the present invention are shown below.

  The glass transition temperature (Tg) after curing of the radiation cured product layer is preferably 80 to 150 ° C, more preferably 100 to 130 ° C. If the glass transition temperature is less than 80 ° C., adhesion failure may occur in the coating process. Moreover, when it exceeds 150 degreeC, a coating film may become weak.

  The thickness of the radiation cured product layer is preferably from 0.1 to 1.0 μm, more preferably from 0.3 to 0.7 μm. When the thickness is less than 0.1 μm, it is difficult to obtain sufficient smoothness. If it exceeds 1.0 μm, the adhesion to the support tends to be lowered.

The elastic modulus of the radiation cured product layer is preferably 1.0 to 4 GPa. If it is less than 1.0 GPa, the coating film tends to cause adhesion failure. If it exceeds 4 GPa, the coating film tends to be brittle.
As the radiation used in the present invention, an electron beam or ultraviolet rays can be used. When ultraviolet rays are used, it is necessary to add a photopolymerization initiator to the above compound. In the case of electron beam curing, a polymerization initiator is unnecessary, and the penetration depth is also deep, which is preferable.
As the electron beam accelerator, a scanning system, a double scanning system, or a curtain beam system can be adopted, but a curtain beam system that can obtain a large output at a relatively low cost is preferable. As the electron beam characteristics, the acceleration voltage is 30 to 1,000 kV, preferably 50 to 300 kV, and the absorbed dose is 0.5 to 20 Mrad, preferably 2 to 10 Mrad. When the acceleration voltage is 30 kV or less, the amount of transmitted energy is insufficient. When the acceleration voltage exceeds 300 kV, the efficiency of energy used for polymerization is reduced, which is not economical. It is preferable that the atmosphere in which the electron beam is irradiated has an oxygen concentration of 200 ppm or less by nitrogen purge. When the oxygen concentration is high, cross-linking and curing reactions near the surface are inhibited.

A mercury lamp is used as the ultraviolet light source. The mercury lamp is a 20 to 240 W / cm lamp and is used at a speed of 0.3 m / min to 20 m / min. In general, the distance between the substrate and the mercury lamp is preferably 1 to 30 cm.
A radical photopolymerization initiator is used as a photopolymerization initiator used for ultraviolet curing. For details, for example, those described in “New Polymer Experiments Vol. 2 Chapter 6 Light / Radiation Polymerization” (published by Kyoritsu Publishing 1995, edited by Polymer Society) can be used. Specific examples include acetophenone, benzophenone, anthraquinone, benzoin ethyl ether, benzyl methyl ketal, benzyl ethyl ketal, benzoin isobutyl ketone, hydroxydimethyl phenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-2 diethoxyacetophenone, and so on. The mixing ratio of the aromatic ketone is 0.5 to 20 parts by weight, preferably 2 to 15 parts by weight, and more preferably 3 to 10 parts by weight with respect to 100 parts by weight of the radiation curable compound.
Radiation curing equipment and conditions are described in “UV / EB curing technology” (published by General Technology Center Co., Ltd.) and “Applied technology of low energy electron beam irradiation” (2000, issued by CMC Co., Ltd.). Known ones can be used.

II. Magnetic layer <ferromagnetic powder>
As the ferromagnetic powder contained in the magnetic layer in the present invention, either a ferromagnetic metal powder or a ferromagnetic hexagonal ferrite powder can be used.
(Ferromagnetic metal powder)
The ferromagnetic metal powder used in the magnetic layer in the present invention is not particularly limited as long as it contains Fe as a main component (including an alloy), but may be a ferromagnetic alloy powder containing α-Fe as a main component. preferable. This ferromagnetic metal powder includes Al, Si, S, Sc, Ca, Ti, V, Cr, Cu, Y, Mo, Rh, Pd, Ag, Sn, Sb, Te, Ba, Ta, other than the 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. In addition to the α-Fe, those containing at least one selected from the group consisting of Al, Si, Ca, Y, Ba, La, Nd, Co, Ni, and B are preferable. In particular, Co, Al, and Y are included. Is preferred. 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%.
These ferromagnetic powders may be previously treated with a dispersant, lubricant, surfactant, antistatic agent, etc., which will be described later, before dispersion. Further, the ferromagnetic metal powder may contain a small amount of water, hydroxide or oxide.

The moisture content of the ferromagnetic powder is preferably 0.01-2%. It is preferable to optimize the moisture content of the ferromagnetic powder depending on the type of binder.
The crystallite size is preferably 8 to 20 nm, more preferably 10 to 18 nm, and particularly preferably 12 to 16 nm. As the crystallite size, an average value obtained by a Scherrer method from a half-value width of a diffraction peak using an X-ray diffractometer (RINT2000 manufactured by Rigaku Corporation) under the conditions of a radiation source CuKα1, a tube voltage of 50 kV, and a tube current of 300 mA is used.
The long axis length of the ferromagnetic metal powder is preferably 10 to 100 nm, more preferably 30 to 90 nm, and particularly preferably 40 to 80 nm. When the magnetic recording medium of the present invention is reproduced by a magnetoresistive head (MR head), the long axis length of the ferromagnetic metal powder is preferably 60 nm or less. The long axis length is obtained by taking a transmission electron micrograph, tracing the short axis length and the long axis length of the ferromagnetic powder directly from the photograph, and tracing the transmission electron micrograph with IBASSI manufactured by Carl Zeiss. It is required to use the method of reading in combination.

The specific surface area by the BET method of the ferromagnetic powder used in the magnetic layer in the present invention (S _BET) is preferably less than 30 m ² / g or more 50 m ² / g, more preferably 38~48m ² / g. This makes it possible to achieve both good surface properties and low noise. The pH of the ferromagnetic metal powder is preferably optimized by combination with the binder used. The range is preferably pH 4-12, more preferably pH 7-10. The ferromagnetic 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 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, the properties are not particularly affected. Further, the ferromagnetic metal powder used in the magnetic layer in the present invention preferably has fewer vacancies, and its value is 20% by volume or less, more preferably 5% by volume or less.

  In addition, the shape may be acicular, granular, rice granular, or plate-like as long as it satisfies the above-mentioned characteristics regarding the particle size, but in particular, acicular ferromagnetic powder should be used. Is preferred. In the case of acicular ferromagnetic metal powder, the acicular ratio is preferably 4 to 12, and more preferably 5 to 12.

The coercive force Hc of the ferromagnetic metal powder is preferably 159 to 239 kA / m (2,000 to 3,000 Oe), more preferably 167 to 231 kA / m (2,100 to 2,900 Oe). . The saturation magnetic flux density is preferably 150 to 300 mT (1,500 to 3,000 G), and more preferably 160 to 290 mT (1,600 to 2,900 G). Saturation magnetization σs is preferably from ^{140~170A · m 2 / kg (emu} / g), more preferably a ^{145~160A · m 2 / kg (emu} / g).

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 particle size distribution of goethite in the ferromagnetic metal powder, using monodispersed α-Fe 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 with 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 a ferromagnetic metal aqueous solution by adding a reducing agent such as sodium borohydride, hypophosphite or hydrazine, a metal at a low pressure For example, a fine powder is obtained by evaporation 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.

(Ferromagnetic hexagonal ferrite powder)
Examples of the ferromagnetic hexagonal ferrite ferromagnetic powder contained in the magnetic layer of the present invention include barium ferrite, strontium ferrite, lead ferrite, calcium ferrite substitutes, and Co substitutes. 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.

The average plate diameter of the ferromagnetic hexagonal ferrite ferromagnetic powder is preferably in the range of 5 to 40 nm, more preferably 20 to 35 nm, and still more preferably 20 to 30 nm. In order to increase the track density, when reproducing with a magnetoresistive head (MR head), it is necessary to reduce the noise, and the plate diameter is preferably 40 nm or less. If the average plate diameter is 5 nm or more, stable magnetization can be expected without being affected by thermal fluctuation.
The plate ratio (plate diameter / plate thickness) of the ferromagnetic hexagonal ferrite ferromagnetic powder is preferably from 1 to 15, and more preferably from 1 to 7. When the plate-like ratio is small, the filling property in the magnetic layer is preferably high, but when it is too small, sufficient orientation cannot be obtained, and it is preferably 1 or more. If the plate ratio is 15 or less, noise can be suppressed by stacking particles. The specific surface area according to the BET method in this particle size range is 10 to ²⁰⁰ m ² / g. The specific surface area roughly agrees with the arithmetic calculation value from the particle plate diameter and plate thickness. The distribution of the particle plate diameter and plate thickness is generally preferably as narrow as possible. Although numerical conversion is difficult, it can be compared by randomly measuring 500 particles from a particle TEM photograph. In many cases, the distribution 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 ferromagnetic hexagonal ferrite particles can be made up to about 39.8 to 398 kA / m (500 to 5,000 Oe). A higher coercive force (Hc) is advantageous for high-density recording, but is limited by the capacity of the recording head. In the present invention, the coercive force (Hc) is about 159.2 to 238.8 kA / m (2,000 to 3000 Oe), preferably 175.1 kA / m (2,200 Oe) to 222.9 kA / m ( 2,800 Oe). When the saturation magnetization of the head exceeds 1.4 Tessler, it is preferably 159.2 kA / m (2,000 Oe) or more. 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) is 40 to 80 A · m ² / kg (40 to 80 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), a known method such as composite of magnetoplumbite ferrite with spinel ferrite or selection of the type and amount of elements contained can be used. In the present invention, W-type hexagonal ferrite can be used in the magnetic layer.

  When dispersing the ferromagnetic hexagonal ferrite powder, the surface of the magnetic particles is also treated with a material suitable for the dispersion medium and polymer. As the surface treatment material, an inorganic compound or an organic compound is used. Typical examples of the main compound include compounds such as Si, Al, and P, various silane coupling agents, and various titanium coupling agents. The amount is 0.1 to 10% with respect to 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.

As a method for producing ferromagnetic hexagonal ferrite powder, (1) a metal oxide replacing barium oxide / iron oxide / iron and boron oxide as a glass-forming substance are mixed so as to have a desired ferrite composition and then melted; A glass crystallization method in which barium ferrite crystal powder is obtained by quenching to an amorphous body and then reheating, then washing and grinding, (2) neutralizing the barium ferrite composition metal salt solution with alkali, by-product Hydrothermal reaction method to obtain barium ferrite crystal powder after liquid phase heating at 100 ° C or higher after removing substances, washing, drying and pulverization, (3) neutralizing barium ferrite composition metal salt solution with alkali, by-product For example, a coprecipitation method for obtaining a barium ferrite crystal powder by drying and treating at 1100 ° C. or less after removing the product, and the like. It not is not particularly limited, and may be either of the method. The ferromagnetic hexagonal ferrite ferromagnetic powder may be subjected to a surface treatment with Al, Si, P, or an oxide thereof if necessary. The amount thereof is 0.1 to 10% with respect to the ferromagnetic 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 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>
Binders used in the magnetic layer include polyurethane resins, polyester resins, polyamide resins, vinyl chloride resins, acrylic resins copolymerized with styrene, acrylonitrile, methyl methacrylate, cellulose resins such as nitrocellulose, epoxy resins, A single resin or a mixture of a plurality of resins can be used from polyvinyl alkyl resins such as phenoxy resin, polyvinyl acetal, and polyvinyl butyral. Among these, polyurethane resins, acrylic resins, cellulose resins, and vinyl chloride resins are preferable.

The binder preferably has a functional group (polar group) that is adsorbed on the surface of the powder in order to improve the dispersibility of the magnetic material and nonmagnetic powder. Preferred -SO ₃ M is as a functional _{group, -SO 4 M, -PO (OM} ) 2, -OPO (OM) 2, -COOM,> NSO 3 M,> NRSO 3 M, -NR 1 R 2, -N ⁺ R ¹ R ² R ³ X- ^{and the} like. Here, M is hydrogen or an alkali metal such as Na or K, R is an alkylene group, R ¹ , R ² or R ³ is an alkyl group or a hydroxyalkyl group or hydrogen, and X is a halogen such as Cl or Br. The amount of the functional group in the binder is preferably 10 to 200 μeq / g, more preferably 30 to 120 μeq / g. Dispersibility will be reduced if this range is exceeded or less.

In addition to the adsorptive functional group, the binder is preferably provided with a functional group having an active hydrogen such as an —OH group in order to react with an isocyanate curing agent to form a crosslinked structure and improve the coating film strength. A preferred amount is 0.1 to 2 meq / g.
The molecular weight of the binder is preferably 10,000 to 200,000, more preferably 20,000 to 100,000 in terms of weight average molecular weight. If it is smaller than this range, the coating film strength is insufficient and the durability is lowered. When it is large, the dispersibility is lowered.

  Polyurethane resins which are preferable binders are described in detail in, for example, “Polyurethane Resin Handbook” (edited by Keiji Iwata, 1986, Nikkan Kogyo Shimbun). Usually, long-chain diols and short-chain diols (referred to as chain extenders) And an addition polymerization of a diisocyanate compound. Polyester diol, polyether diol, polyether ester diol, polycarbonate diol, polyolefin diol, etc. having a molecular weight of 500 to 5000 are used as the long chain diol. Depending on the type of this long-chain polyol, it is called polyester urethane, polyether urethane, polyether ester urethane, polycarbonate urethane or the like.

The polyester diol can be obtained by polycondensation of an aliphatic dibasic acid such as adipic acid, sebacic acid or azelaic acid, or an aromatic dibasic acid such as isophthalic acid, orthophthalic acid, terephthalic acid or naphthalenedicarboxylic acid with glycol. Examples of the glycol component include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl, 1,5-pentanediol, 1,6- Examples include hexanediol, 2,2-dimethyl1,3-propanediol, 1,8-octanediol, 1,9-nonanediol, cyclohexanediol, cyclohexanedimethanol, and hydrogenated bisphenol A. As the polyester diol, polycaprolactone diol and polyvalerolactone diol obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone can also be used.
The polyester diol is preferably one having a branched side chain or one obtained from an aromatic or alicyclic raw material from the viewpoint of hydrolysis resistance.

Polyether diols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, aromatic glycols such as bisphenol A, bisphenol S, bisphenol P, hydrogenated bisphenol A, and alicyclic diols, and alkylene oxides such as ethylene oxide and propylene oxide. There are those obtained by addition polymerization.
These long-chain diols can be used in combination of a plurality of types.

  The short chain diol can be selected from the same group of compounds as exemplified in the glycol component of the polyester diol. In addition, when a small amount of trifunctional or higher polyhydric alcohol such as trimethylolethane, trimethylolpropane, pentaerythritol, etc. is used in combination, a polyurethane resin having a branched structure is obtained and the viscosity of the solution is lowered, or the isocyanate group is increased by increasing the OH group at the end of the polyurethane. Curability with the system curing agent can be enhanced.

As the diisocyanate compound, MDI (diphenylmethane diisocyanate), 2,4-TDI (tolylene diisocyanate), 2,6-TDI, 1,5-NDI (naphthalene diisocyanate), TODI (tolidine diisocyanate), p-phenylene diisocyanate, XDI ( Aromatic diisocyanates such as xylylene diisocyanate), transcyclohexane 1,4-diisocyanate, HDI (hexamethylene diisocyanate), IPDI (isophorone diisocyanate), H ₆ XDI (hydrogenated xylylene diisocyanate), H ₁₂ MDI (hydrogenated diphenylmethane diisocyanate) ) And other aliphatic and alicyclic diisocyanates.

A preferred composition of the long chain diol / short chain diol / diisocyanate in the polyurethane resin is (80 to 15% by weight) / (5 to 40% by weight) / (15 to 50% by weight).
The urethane group concentration of the polyurethane resin is preferably 1 to 5 meq / g, more preferably 1.5 to 4.5. If it is less than this range, the mechanical strength is small, and if it is too large, the solution viscosity is high and the dispersibility is lowered.
The glass transition temperature of the polyurethane resin is preferably 0 to 200 ° C, more preferably 40 to 160 ° C. When it is lower than this range, the durability is lowered, and when it is too high, the calendering property is lowered and the electromagnetic conversion characteristics are lowered.

  As a method of introducing the above-mentioned adsorptive functional group (polar group) into the polyurethane resin, a method using a functional group as a part of a monomer of a long-chain diol, a method using a part of a short-chain diol, or after polymerizing a polyurethane, There is a method of introducing a polar group by molecular reaction.

As the vinyl chloride resin, those obtained by copolymerizing vinyl monomers with various monomers are used.
Copolymer monomers include fatty acid vinyl esters such as vinyl acetate and vinyl propionate, and acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and benzyl (meth) acrylate. , Methacrylates, allyl methyl ether, allyl ethyl ether, allyl propyl ether, allyl butyl ether, and other alkyl allyl ethers, styrene, α-methyl styrene, vinylidene chloride, acrylonitrile, ethylene, butadiene, acrylamide, and co-functional groups. As polymerization monomers, vinyl alcohol, 2-hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, 2-hydroxypropyl (meth) acrylate Relate, 3-hydroxypropyl (meth) acrylate, polypropylene glycol (meth) acrylate, 2-hydroxyethyl allyl ether, 2-hydroxypropyl allyl ether, 3-hydroxypropyl allyl ether, p-vinylphenol, maleic acid, maleic anhydride Acrylic acid, methacrylic acid, glycidyl (meth) acrylate, allyl glycidyl ether, phosphoethyl (meth) acrylate, sulfoethyl (meth) acrylate, p-styrene sulfonic acid, and Na salts and K salts thereof are used.
The composition of the vinyl chloride monomer in the vinyl chloride resin is preferably 60 to 95% by weight. If it is less than this, the mechanical strength is lowered, and if it is too much, the solvent solubility is lowered, the solution viscosity is high, and the dispersibility is lowered.

The preferred amount of the functional group for enhancing the curability with the adsorption functional group (polar group) and the polyisocyanate curing agent is as described above. As a method for introducing these functional groups, the above-mentioned functional group-containing monomers may be copolymerized, or functional groups may be introduced by polymer reaction after copolymerizing a vinyl chloride resin.
The polymerization degree is preferably 200 to 600, more preferably 240 to 450. If it is smaller than this range, the mechanical strength is lowered, and if it is too high, the solution viscosity is high and the dispersibility is lowered.

A curing agent can be used to crosslink and cure the binder used in the present invention to increase the mechanical strength and heat resistance of the coating film. A preferred curing agent is a polyisocyanate compound. The polyisocyanate compound is preferably a triisocyanate or higher polyisocyanate.
Specifically, a compound obtained by adding 3 moles of TDI (tolylene diisocyanate) to trimethylolpropane (TMP), a compound obtained by adding 3 moles of HDI (hexamethylene diisocyanate) to TMP, and 3 moles of IPDI (isophorone diisocyanate) to TMP Adduct type polyisocyanate compounds, such as compounds obtained by adding 3 moles of XDI (xylylene diisocyanate) to TMP. TDI condensed isocyanurate type trimer, TDI condensed isocyanurate pentamer, TDI condensed isocyanurate heptamer, and mixtures thereof. HDI isocyanurate type condensate, IPDI isocyanurate type condensate. There is also Crude MDI.
Among these, a compound obtained by adding 3 moles of TDI to TMP, an isocyanurate type trimer of TDI, and the like are preferable.

In addition to the isocyanate curing agent, a radiation curing type curing agent such as an electron beam or an ultraviolet ray may be used. In this case, a curing agent having two or more, preferably three or more acryloyl groups or methacryloyl groups in the molecule as a radiation curing functional group can be used. Examples include TMP (trimethylolpropane) triacrylate, pentaerythritol tetraacrylate, and urethane acrylate oligomer. In this case, it is preferable to introduce a (meth) acryloyl group into the binder in addition to the curing agent. In the case of UV curing, a photosensitizer is also used in combination.
It is preferable to add 0 to 80 parts by weight of the curing agent with respect to 100 parts by weight of the binder. If the amount is too large, the dispersibility decreases.

  In the case of a magnetic layer, the amount of binder added is preferably 5 to 30 parts by weight, more preferably 10 to 20 parts by weight with respect to 100 parts by weight of the ferromagnetic powder.

Additives can be added to the magnetic layer in the present invention as necessary. Examples of the additive include an abrasive, 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 group, phenethylphosphonic acid, α-methylbenzylphosphonic acid, 1-methyl-1-phenethylphosphonic acid, diphenylmethylphosphonic acid, biphenylphosphonic acid, benzylphenylphosphon Acid, α-cumylphosphonic acid, toluylphosphonic acid, xylylphosphonic acid, ethylphenylphosphonic acid, cumenylphosphonic acid, propylphenylphosphonic acid, butylphenylphosphonic acid, heptyl Aromatic ring-containing organic phosphonic acids such as phenylphosphonic acid, octylphenylphosphonic acid, nonylphenylphosphonic acid and alkali metal salts thereof, octylphosphonic acid, 2-ethylhexylphosphonic acid, isooctylphosphonic acid, isononylphosphonic acid, isodecyl Alkylphosphonic acids such as phosphonic acid, isoundecylphosphonic acid, isododecylphosphonic acid, isohexadecylphosphonic acid, isooctadecylphosphonic acid, isoeicosylphosphonic acid and alkali metal salts thereof, phenyl phosphate, benzyl phosphate, phosphorus Phenethyl phosphate, α-methylbenzyl phosphate, 1-methyl-1-phenethyl phosphate, diphenylmethyl phosphate, biphenyl phosphate, benzylphenyl phosphate, α-cumyl phosphate, toluyl phosphate, xylyl phosphate, phosphate Ethylpheny , Phenyl ester phosphate, propylphenyl phosphate, butylphenyl phosphate, heptylphenyl phosphate, octylphenyl phosphate, nonylphenyl phosphate, and alkali metal salts thereof, octyl phosphate, phosphate 2 -Ethylhexyl, isooctyl phosphate, isononyl phosphate, isodecyl phosphate, isoundecyl phosphate, isododecyl phosphate, isohexadecyl phosphate, isooctadecyl phosphate, isoeicosyl phosphate, and alkali metal salts thereof, alkyl Sulfonic 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, linoleic acid Monobasic fatty acids which may contain or be branched, such as acids, elaidic acid, erucic acid and the like, and their metal salts, or butyl stearate, octyl stearate, amyl stearate, Contains 10 to 24 carbon unsaturated bonds such as isooctyl stearate, octyl myristate, butyl laurate, butoxyethyl stearate, anhydrosorbitan monostearate, anhydrosorbitan distearate, anhydrosorbitan tristearate However, it may be branched even if it contains a monobasic fatty acid that may be branched, an unsaturated bond having 2 to 22 carbon atoms or a 1 to 6-valent alcohol that may be branched, or an unsaturated bond having 12 to 22 carbon atoms. Monoalkoxy of alkoxy alcohol or alkylene oxide polymer which may be Mono-fatty acid esters consisting of any one of ether, 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, alkyl groups, aryl groups, and aralkyl groups substituted with nitro groups and groups other than hydrocarbon groups such as halogen-containing hydrocarbons such as F, Cl, Br, CF ₃ , CCl ₃ , and CBr ₃ 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, heterocycles, 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 dispersant, lubricant, and the like are not necessarily pure, and may contain impurities such as isomers, unreacted materials, side reaction products, decomposition products, and oxides in addition to the main components. These impurities are preferably 30% by weight or less, more preferably 10% by weight or less.
Specific examples of these additives include, for example, manufactured by NOF Corporation: NAA-102, castor oil hardened fatty acid, NAA-42, cation SA, Naimine L-201, Nonion E-208, Anon BF, Anon LG, Takemoto Oil and fat: FAL-205, FAL-123, Shin Nippon Chemical Co., Ltd .: NJ Lube OL, Shin-Etsu Chemical: TA-3, Lion Armor: Armide P, Lion: Duomin TDO, Nisshin Oil : BA-41G, Sanyo Kasei Co., Ltd .: Profan 2012E, New Pole PE61, Ionette MS-400, and the like.

  Known organic solvents can be used in the magnetic layer of the present invention. The organic solvent is an arbitrary ratio of ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, isophorone and tetrahydrofuran, alcohols such as methanol, ethanol, propanol, butanol, isobutyl alcohol, isopropyl alcohol and methylcyclohexanol. , 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, cresol, chlorobenzene, etc. Aromatic hydrocarbons, methylene chloride, ethylene chloride, carbon tetrachloride, chloroform, ethylene chlorohydrin 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 magnetic layer of the present invention can be properly used in the magnetic layer and 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 powder, as will be described later. In the nonmagnetic layer, it is presumed that the organophosphorus compound adsorbed or bonded to the surface of the nonmagnetic powder mainly by the polar group and once adsorbed is difficult to desorb from the surface of metal or metal compound. Accordingly, the surface of the ferromagnetic powder of the present invention or the nonmagnetic powder surface described later is in a state of being coated with an alkyl group, an aromatic group, etc., so the affinity of the ferromagnetic powder or nonmagnetic powder for the binder resin component And the dispersion stability of the ferromagnetic powder or non-magnetic powder is also improved. In addition, since it exists in a free state as a lubricant, the non-magnetic layer and the magnetic layer use fatty acids with different melting points to control the bleeding to the surface, and use esters with different boiling points and polarities to bleed to the surface. It is conceivable that the stability of coating is improved by controlling the amount of the surfactant, and the lubricating effect is improved by increasing the amount of lubricant added in the nonmagnetic layer. All or a 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.

In addition, carbon black can be added to the magnetic layer in the present invention as necessary.
As the type of carbon black, furnace for rubber, thermal for rubber, black for color, acetylene black and the like can be used. The carbon black of the radiation-cured layer should be optimized for the following characteristics depending on the desired effect, and the effect may be obtained more when used in combination.

100 to 500 m ² / g, specific surface area of carbon black is preferably 150~400m ² / g, DBP oil absorption 20 to 400 ml / 100 g, preferably 30 to 200 ml / 100 g. The particle size of carbon black is 5 to 80 mμ, preferably 10 to 50 mμ, and more preferably 10 to 40 mμ. 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 used in the present invention include BLACKPEARLS 2000, 1300, 1000, 900, 800, 880, 700, VULCAN XC-72, manufactured by Cabot Corporation, # 3050B, # 3150B, # 3250B manufactured by Mitsubishi Kasei Kogyo Co., Ltd. , # 3750B, # 3950B, # 950, # 650B, # 970B, # 850B, MA-600, MA-230, # 4000, # 4010, CONDUCTEX SC, Raven 8800, 8000, 7000, 5750, 5250, manufactured by Columbia Carbon Co., Ltd. , 3500, 2100, 2000, 1800, 1500, 1255, 1250, Ketjen Black EC manufactured by Akzo Corporation, and the like.

  Carbon black may be surface-treated with a dispersant or the like, or may be used after being grafted with a resin, or may be obtained by graphitizing a part of the surface. Further, carbon black may be dispersed in advance with a binder before it is added to the paint. The carbon black that can be used in the present invention can be referred to, for example, “Carbon Black Handbook” (edited by Carbon Black Association).

  These carbon blacks can be used alone or in combination. When carbon black is used, it is preferably used in an amount of 0.1 to 30% by weight based on the weight of the magnetic material. 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 change the type, amount, and combination in the magnetic layer, and depending on the purpose based on the above-mentioned various characteristics such as particle size, oil absorption, conductivity, and PH. Of course, it is possible to use them properly, but they should be optimized in each layer.

III. Nonmagnetic Layer The magnetic recording medium of the present invention may have a nonmagnetic layer containing a binder and a nonmagnetic powder on a nonmagnetic support. The nonmagnetic powder that can be used in the nonmagnetic layer may be an inorganic substance or an organic substance. Moreover, you may mix carbon black with a nonmagnetic powder as needed with a nonmagnetic layer.

(Non-magnetic powder)
Next, detailed contents regarding the nonmagnetic layer will be described.
The magnetic recording medium of the present invention may have a nonmagnetic layer (lower layer) containing a binder and nonmagnetic powder on a nonmagnetic support provided with a smoothing layer.
For the nonmagnetic layer, magnetic powder may be used as long as the lower layer is substantially nonmagnetic, but it is preferable to use nonmagnetic powder.
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 non-magnetic powder is preferably 1 to 100 m ² / g, more preferably 5 to 70 m ² / g, and still 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 preferably 5 to 100 ml / 100 g, more preferably 10 to 80 ml / 100 g, and still more preferably 20 to 60 ml / 100 g.
The specific gravity is preferably 1 to 12, more preferably 3 to 6. The tap density is preferably 0.05 to 2 g / ml, more 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 the pH 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 water content of the nonmagnetic powder is preferably 0.1 to 5% by weight, more preferably 0.2 to 3% by weight, and still more preferably 0.3 to 1.5% by weight. A water content in the range of 0.1 to 5% by weight is preferable because the dispersion is good and the viscosity of the paint after dispersion is stable.
The ignition loss is preferably 20% by weight 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 ^{20 to} 60 μJ / cm ² (200 to 600 erg / cm 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.

The surface of these nonmagnetic powders is preferably surface-treated with Al ₂ O ₃ , SiO ₂ , TiO ₂ , ZrO ₂ , SnO ₂ , Sb ₂ O ₃ , and ZnO. 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 nonmagnetic powder used in the nonmagnetic 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 Titanium oxide made by Ishihara Sangyo 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, T manufactured by Teica -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 μ Vickers hardness. Μ Vickers hardness of the nonmagnetic layer is normally 25 to 60 kg / mm ^2, preferably in order to adjust the head contact, and a 30 to 50 kg / mm ^2, using a thin film hardness meter (manufactured by NEC Corporation HMA-400) Measurement can be made using a diamond triangular pyramid needle with 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 Mitsubishi Kasei Kogyo Co., Ltd. 3050B, # 3150B, # 3250B, # 3750B, # 3950B, # 950, # 650B, # 970B, # 850B, MA-600, Columbia Carbon Corporation CONDUCTEX SC, RAVEN8800, 8000, 7000, 5750, 5250, 3500, 2100 2000, 1800, 1500, 1255, 1250, Ketjen Black EC manufactured by Akzo Corporation, and the like.

  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. Further, carbon black may be dispersed in advance with a binder before it is added to the paint. These carbon blacks can be used in a range not exceeding 50% by weight and not exceeding 40% of the total weight of the nonmagnetic layer with respect to the inorganic powder. 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.

IV. Nonmagnetic Supports Examples of the nonmagnetic support that can be used in the present invention include known ones such as biaxially stretched polyethylene terephthalate, polyethylene naphthalate, polyamide, polyamideimide, and aromatic polyamide. Among these, polyethylene terephthalate, polyethylene naphthalate, and polyamide are preferable.
These supports may be subjected in advance to corona discharge, plasma treatment, easy adhesion treatment, heat treatment and the like. The surface roughness of the nonmagnetic support that can be used in the present invention is preferably a center average roughness Ra of 3 to 10 nm at a cutoff value of 0.25 mm.

V. Backcoat layer Generally, magnetic tape for computer data recording is strongly required to have repeated running characteristics as compared with video tape and audio tape. In order to maintain such high storage stability, a backcoat layer can be provided on the surface of the nonmagnetic support opposite to the surface on which the nonmagnetic layer and the magnetic layer are provided. The coating material for the back coat layer disperses a particle component such as an abrasive and an antistatic agent and a binder in an organic solvent. Various inorganic pigments and carbon black can be used as the particulate component. Moreover, as a binder, resin, such as a nitrocellulose, a phenoxy resin, a vinyl chloride resin, a polyurethane, can be used individually or in mixture, for example.

VI. Layer Configuration In the configuration of the magnetic recording medium used in the present invention, the thickness of the radiation cured product layer is preferably in the range of 0.3 to 1.0 μm as described above. Moreover, the preferable thickness of a nonmagnetic support body is 3-80 micrometers. When an undercoat layer is provided between the nonmagnetic support and the nonmagnetic layer or 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 backcoat layer provided on the surface opposite to the surface on which the nonmagnetic layer and the magnetic layer of the nonmagnetic support are provided is 0.1 to 1.0 μm, preferably 0.2 to 0.8 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 0.01 to 0.10 μm or less, preferably 0. It is 02 μm or more and 0.08 μm or less, and more preferably 0.03 to 0.08 μm. The thickness variation rate of the magnetic layer is preferably within ± 50%, 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 0.2 to 3.0 μm, preferably 0.3 to 2.5 μm, and more preferably 0.4 to 2.0 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. “Substantially the same” means that the residual magnetic flux density of the nonmagnetic layer is 10 T · m (100 G) or less or the coercive force is 7.96 kA / m (100 Oe) or less, preferably the residual magnetic flux density It means no coercive force.

VII. Manufacturing Method The process of manufacturing the magnetic layer coating liquid for the magnetic recording medium used in the present invention comprises at least a kneading process, a dispersing process, and a mixing process provided before and after these processes as necessary. Each process may be divided into two or more stages. Hexagonal ferrite ferromagnetic powder or ferromagnetic metal powder used in the present invention, non-magnetic powder, benzenephosphonic acid derivative, π-electron conjugated conductive polymer, binder, carbon black, abrasive, antistatic agent, lubrication All raw materials such as agents and solvents may be added at the beginning or middle of any process. 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. In the case of using a kneader, the magnetic powder or non-magnetic powder and all or a part of the binder (however, preferably 30% or more of the total binder) and 100 parts by weight of the magnetic material are kneaded in the range of 15 to 500 parts by weight. It is processed. 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 liquid for the magnetic layer and the liquid for the nonmagnetic layer. 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 the method for producing a magnetic recording medium of the present invention, for example, a coating solution for a magnetic layer is applied to the surface of a nonmagnetic support under running so as to have a predetermined film thickness. Here, a plurality of coating solutions for magnetic layers may be applied sequentially or simultaneously, and a lower magnetic layer coating solution and an upper magnetic layer coating solution may be applied sequentially or simultaneously. As a coating machine for applying the magnetic layer coating liquid or the lower magnetic layer coating liquid, an air doctor coat, blade coat, rod coat, extrusion coat, air knife coat, squeeze coat, impregnation coat, reverse roll coat, transfer roll A coat, a gravure coat, a kiss coat, a cast coat, a spray coat, a spin coat and the like 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 liquid coating layer is formed by subjecting the ferromagnetic powder contained in the magnetic layer coating liquid coating layer to a magnetic field orientation process in the longitudinal direction using a cobalt magnet or a solenoid. 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 fine powder, the isotropic orientation is generally preferably in-plane two-dimensional random, but can also be three-dimensional random with a vertical component. In the case of hexagonal ferrite, in general, it tends to be in-plane and vertical three-dimensional random, but in-plane two-dimensional random is also possible. 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, it is good also as circumferential orientation using a spin coat.
It is preferable to be able to control the drying position of the coating film by controlling the temperature, air volume, and coating speed of the drying air, the coating speed is preferably 20 to 1,000 m / min, and the temperature of the drying air is preferably 60 ° C. or higher. . Moreover, moderate preliminary drying can also be performed before entering a magnet zone.

After being dried, the coating layer is 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 removing the solvent during drying disappear and the filling rate of the ferromagnetic powder in the magnetic layer is improved, so that a magnetic recording medium having high electromagnetic conversion characteristics can be obtained. it can.
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 very excellent smoothness with a center surface average roughness of 0.1 to 4.0 nm, preferably 0.5 to 3.0 nm, at a cutoff value of 0.25 mm. It is preferable that it is the surface which has. As the method, for example, as described above, a magnetic layer formed by selecting a specific ferromagnetic 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 in the range of 100 to 500 kg / cm, preferably Is in the range of 200 to 450 kg / cm, particularly preferably performed by operating under conditions in the range of 300 to 400 kg / cm.

  As heat shrinkage reduction means, there are a method of heat treatment in a web shape while handling at low tension, and a method of heat treatment in a form in which a tape is laminated such as a state of being incorporated in a bulk or a cassette (thermo treatment), both of which can be used. The former is less affected by protrusions on the surface of the backcoat layer, but the heat shrinkage rate cannot be greatly reduced. On the other hand, the latter thermo-treatment can greatly improve the heat shrinkage ratio, but is strongly affected by the projection of the projection on the surface of the backcoat layer, so that the magnetic layer becomes rough and causes a decrease in output and an increase in noise. In particular, a high-output, low-noise magnetic recording medium can be supplied as a magnetic recording medium with a thermo process. The obtained magnetic recording medium can be cut into a desired size using a cutting machine, a punching machine, or the like.

VIII. Physical Properties The saturation magnetic flux density of the magnetic layer of the magnetic recording medium used in the present invention is 100 to 300 T · m (1,000 to 3,000 G). The coercive force (Hr) of the magnetic layer is 143.3 to 318.4 kA / m (1,800 to 4,000 Oe), preferably 159.2 to 278.6 kA / m (2,000 to 3). , 500 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 0.5 or less, preferably 0.3 or less in the range of temperature -10 to 40 ° C. and humidity 0 to 95%. The charging position is preferably within −500 to + 500V. The elastic modulus at 0.5% elongation of the magnetic layer is preferably 0.98 to 19.6 GPa (100 to 2,000 kg / mm ² ) in each in-plane direction, and the breaking strength is preferably 98 to 686 MPa (10 ˜70 kg / mm ² ), the elastic modulus of the magnetic recording medium is preferably 0.98 to 14.7 GPa (100 to 1,500 kg / mm ² ) in each in-plane direction, and the residual spread is preferably 0.5%. Hereinafter, the thermal contraction rate at any temperature of 100 ° C. or less 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, the storage stability is often preferable when the porosity is large.

The center surface roughness Ra of the magnetic layer measured by the TOPO-3D mirau method is 4.0 nm or less, preferably 3.0 nm or less, and more preferably 2.0 nm or less. 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. The surface protrusions of the magnetic layer can be arbitrarily set in the range of 0 to 2,000 μm having a size of 0.01 to 1 μm, which can optimize the electromagnetic conversion characteristics and the friction coefficient. preferable. These can be easily controlled by controlling the surface properties by the filler of the support, the particle size and amount of the powder added to the magnetic layer, the roll surface shape of the calendering treatment, and the like. The curl is preferably within ± 3 mm.

It is easily estimated that these physical characteristics can be changed between the nonmagnetic layer and the magnetic layer in the magnetic recording medium of the present invention depending on the purpose. For example, the elastic modulus of the magnetic layer is increased to improve the storage stability, and at the same time, the elastic modulus of the nonmagnetic layer is made lower than that of the magnetic layer to improve the contact of the magnetic recording medium with the head.
The magnetic recording medium of the present invention is not particularly limited with respect to a head for reproducing a signal magnetically recorded on the magnetic recording medium, but is preferably used for an MR head. When the MR head is used for reproducing the magnetic recording medium of the present invention, the MR head is not particularly limited, and for example, a GMR head or a TMR head can be used. The head used for magnetic recording is not particularly limited, but the saturation magnetization is 1.0 T or more, preferably 1.5 T or more.

In the present invention, an epoxy ester acrylate having a benzene ring structure, a heterocyclic structure, or a cyclohexane ring structure that can be cured by irradiation on a (nonmagnetic) support such as polyethylene terephthalate, polyethylene naphthalate, and aromatic polyamide. By forming a compound or epoxy ester methacrylate compound-containing layer and then curing it by irradiation, a magnetic layer is provided on the layer, so that the protrusions on the surface of the support can be filled. It is possible to reduce the fine protrusions of the magnetic layer derived from the protrusions of the support that are considered to have a large influence on the conversion characteristics, and to obtain a magnetic recording medium that is extremely smooth and excellent in electromagnetic conversion characteristics.
In the present invention, when an epoxy ester acrylate compound or an epoxy ester methacrylate compound-containing layer having the above ring structure that can be cured by radiation irradiation is first formed on a nonmagnetic support, a paint (before drying; radiation) Since the viscosity before irradiation) can be adjusted to a relatively low viscosity, it is considered that the horizontality when the paint is applied is excellent, and the effect of filling the fine protrusions on the support surface is great.

Moreover, the epoxy ester acrylate compound or epoxy ester methacrylate compound having the ring structure has high affinity with the support and high adhesion. Moreover, since these compounds have high adhesiveness with a magnetic layer containing a ferromagnetic powder and a binder and a nonmagnetic layer containing a nonmagnetic powder and a binder, the coating film can be prevented from falling off due to repeated running.
Moreover, these compounds have high curability when irradiated with radiation. This is considered to prevent the unreacted compound from migrating to the surface of the magnetic layer, thus preventing the mechanical strength of the magnetic layer from being lowered and preventing the running durability of the magnetic recording medium from being deteriorated.
Moreover, since these compounds can form a hard coating film with high mechanical strength (after curing), the coefficient of friction when contacting the guide roller during the coating process from after radiation curing to applying the magnetic layer is low, Difficult to cause problems such as sticking during the coating process. Therefore, the productivity of the magnetic recording medium is improved.

Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, “part” means “part by weight” unless otherwise specified.
Example 1
(1) Preparation of magnetic paint Ferromagnetic alloy powder (Composition: Fe 89 atm%, Co 5 atm%, Y 6 atm%, Hc 151.2 kA / m (1,900 Oe), crystallite size 15 nm, BET specific surface area 60 m ² / g , 100 parts of a major axis diameter of 0.08 μm, needle ratio of 7, σs 150 A · m ² / kg (emu / g)) was pulverized for 10 minutes with an open kneader, and then a vinyl chloride resin (Nippon Zeon Corporation MR110, 10 parts of polymerization degree 300) and 50 parts of polyester polyurethane solution (SO ₃ Na content 100 μeq / g, weight average molecular weight 40,000, Tg 70 ° C., 30% cyclohexanone solution) were added and kneaded for 60 minutes.
Next, 2 parts of an abrasive (Al ₂ O ₃ particle size 0.3 μm), 2 parts of carbon black (particle size 40 μm), and 200 parts of methyl ethyl ketone / toluene (1/1) were added and dispersed for 120 minutes in a sand mill. To this was added 2 parts of butyl stearate, 1 part of stearic acid, and 50 parts of methyl ethyl ketone, and the mixture was further stirred and mixed for 20 minutes, followed by filtration using a filter having an average pore size of 1 μm to prepare a magnetic paint.

(2) Preparation of non-magnetic paint 100 parts of α-Fe ₂ O ₃ (average particle size 0.15 μm, S _BET 52 m ² / g, surface-treated Al ₂ O ₃ , SiO ₂ , pH 6.5 to 8.0) , Pulverized with an open kneader for 10 minutes, and then 10 parts of a PVC resin MR110 (degree of polymerization 300) manufactured by ZEON CORPORATION and a polyester polyurethane solution (SO ₃ Na content 100 μeq / g, weight average molecular weight 40,000, Tg 70 ° C., 50 parts of cyclohexanone (30% solution) was added and kneaded for 60 minutes.
Subsequently, 200 parts of methyl ethyl ketone / cyclohexanone (6/4) was added and dispersed for 120 minutes by a sand mill. To this was added 2 parts of butyl stearate, 1 part of stearic acid, and 50 parts of methyl ethyl ketone, and the mixture was further stirred and mixed for 20 minutes, followed by filtration using a filter having an average pore diameter of 1 μm to prepare a coating material for a nonmagnetic layer.

(3) Preparation of radiation curable compound-containing coating 2 parts of compound 4 shown in Chemical Formula 1, 60 parts of methyl ethyl ketone, 10 parts of cyclohexanone and 10 parts of toluene were mixed and stirred for 20 minutes. It filtered using the filter with a particle size of 1 micrometer, and was set as the radiation hardening type compound containing coating material.

(4) Preparation of magnetic tape The thickness after drying the radiation-curable compound-containing paint is 0.5 μm on the surface of a polyethylene terephthalate support having a thickness of 7 μm and a center average surface roughness Ra of 6.2 nm. After coating with a coil bar and drying, the surface of the coating is irradiated with an electron beam with an acceleration voltage of 100 KV so that the absorbed dose is 1 Mrad to cure the radiation-curable compound-containing layer, and immediately thereafter, the cured product On the layer, the non-magnetic paint obtained in the above (2), and further on the magnetic paint obtained in the above (1), the thickness after drying was 1.5 μm and 0.1 μm, respectively. Thus, simultaneous multilayer coating was performed using a reverse roll. In a state in which the magnetic coating material is not dried, magnetic field orientation is performed with a 5,000 gauss Co magnet and a 4,000 gauss solenoid magnet, and the solvent is dried to obtain a metal roll-metal roll-metal roll-metal roll- After performing calendar processing by a combination of metal roll-metal roll-metal roll (speed: 100 m / min, linear pressure: 300 / cm, temperature: 90 ° C.), it was slit into a width of 3.8 mm to produce a magnetic tape.

Example 2
A magnetic tape was produced in the same manner as in Example 1 except that the compound 5 of Chemical Formula 2 was used as the radiation curable compound to obtain a radiation curable compound-containing coating.

Example 3
A magnetic tape was produced in the same manner as in Example 1 except that Compound 6 (n = 2) of Chemical Formula 2 was used as the radiation curable compound to obtain a radiation curable compound-containing coating.

Example 4
A magnetic tape was produced in the same manner as in Example 1 except that the compound 12 of Chemical formula 3 was used as the radiation curable compound to obtain a radiation curable compound-containing coating.

Example 5
A magnetic tape was produced in the same manner as in Example 1 except that the compound 14 of Chemical formula 4 was used as the radiation curable compound to obtain a radiation curable compound-containing coating.

Comparative Example 1
A magnetic tape was produced in the same manner as in Example 1 except that pentaerythritol tetraacrylate was used as the radiation curable compound to obtain a radiation curable compound-containing coating.

Comparative Example 2
A magnetic tape was produced in the same manner as in Example 1 except that a radiation curable compound-free liquid not containing only the radiation curable compound was used instead of the radiation curable compound-containing coating.

  Table 1 shows the characteristic evaluation results of the magnetic tapes obtained in Examples 1 to 5 and the magnetic tapes obtained in Comparative Examples 1 and 2.

Various measurement methods are as follows.
(1) Surface roughness Ra of radiation-cured layer
After applying a radiation-cured hardened layer, irradiating with electron beam, sampling without coating the non-magnetic layer and magnetic layer, and using a digital optical profilometer (manufactured by WYKO) with a light interference method and a cut-off of 0.25 mm The center average roughness was defined as Ra.
(2) Magnetic layer surface roughness Ra
The surface roughness Ra of the tape sample was measured by the same method as in (1).
(3) Electromagnetic conversion characteristics A single frequency signal of 4.7 MHz was recorded with an optimum recording current using a DDS4 drive, and the reproduction output was measured. The relative output when the reproduction output of Comparative Example 3 is 0 dB is shown.
(4) Friction coefficient of radiation-cured layer After radiation curing, a sample prepared without applying non-magnetic paint and magnetic paint is slit, and the surface of the radiation-cured layer is brought into contact with a 5 mmφ rod made of SUS420J by sliding 180 degrees. The coefficient of friction when sliding at a moving speed of 10 cm / sec was measured. The measurement environment was 23 ° C. and 50% RH.
(5) Generation of scratches on the surface of the radiation-cured layer in the coating machine The scratches generated on the surface of the radiation-cured layer when 3000 m long was applied were examined.
(6) Adhesiveness Adhesive tape is applied to the surface of the magnetic layer and peeled off 180 degrees. The magnetic layer does not peel off is considered excellent. The magnetic layer is partially peeled off, but the magnetic layer remains partially on the sample. A sample that was completely peeled off without any magnetic layer remaining on the sample was regarded as defective.
(7) Running durability A DDS4 drive was used to repeatedly run 1000 passes for 5 minutes in a 23 ° C 70% RH environment, and then a magnetic layer falling off around the cylinder and head inside the drive. Those that were not defective or could not be seen were considered good.
(8) Failure of sticking to the guide roller After applying the radiation-cured coating layer, drying and electron beam irradiation, the web runs on the guide roller that is in direct contact with the surface of the radiation-cured material layer before applying the non-magnetic paint or magnetic paint. The phenomenon that the web running becomes unstable due to sticking inside is regarded as a sticking failure to the guide roller.

Claims (3)

In a magnetic recording medium in which a radiation-cured material layer obtained by curing a radiation-curable compound-containing layer by radiation irradiation on a nonmagnetic support and a magnetic layer containing a ferromagnetic powder and a binder are formed in this order.
A magnetic recording medium comprising an epoxy ester acrylate compound or an epoxy ester methacrylate compound having a benzene ring structure, a heterocyclic structure or a cyclohexane ring structure as the radiation curable compound. 2. The magnetic recording medium according to claim 1, wherein the number of acroyl groups or methacryloyl groups in the molecule of the epoxy ester acrylate compound or epoxy ester methacrylate compound having a benzene ring structure, a heterocyclic structure or a cyclohexane ring structure is 2 or more. 3. The magnetic recording medium according to claim 1, wherein a nonmagnetic layer containing a nonmagnetic powder and a binder is further formed between the radiation cured product layer and the magnetic layer.