JPH0782635B2 - Magnetic recording medium - Google Patents

Description

Detailed Description of the Invention a. TECHNICAL FIELD The present invention relates to a magnetic recording medium such as a magnetic tape, a magnetic sheet and a magnetic disk.

B. 2. Description of the Related Art Recently, there has been a strong demand for longer recording times, higher recording densities, and higher information amounts for magnetic recording media such as magnetic tapes. In order to achieve a long recording time and an increased amount of information, it is necessary to reduce the total thickness of the magnetic recording tape and store it on a supply reel longer. However, in order to reduce the total thickness of the tape, it is necessary to reduce the thickness of the base film, but in reality, the stiffness of the tape decreases, and the tape edge is easily scratched during loading or unloading. In some cases, when a high tensile force is applied, the tape is deformed and the recording is distorted.

A biaxially oriented polyethylene terephthalate film has been conventionally used as a base film of a magnetic recording tape, and a so-called super tension film having a high Young's modulus in the running direction is used particularly for long-time recording. However, the polyethylene terephthalate film has a Young's modulus in the running direction of at most 800 kg / mm.
² is the limit. On the other hand, if the Young's modulus in the running direction is increased, the Young's modulus in the lateral direction inevitably decreases, and the tape is easily damaged at the edge during running. On the other hand, if it is attempted to increase the Young's modulus in the width direction in the production of the film, in this case too, a sufficient Young's modulus in the running direction cannot necessarily be obtained, and the touch with the magnetic head becomes poor, resulting in output fluctuation.

The base film which has been stretched at a high ratio to have a high Young's modulus has a problem that the strain generated during molding remains and the dimensional stability is low. Further, there is another problem that the high-magnification stretching process lowers the product yield.

Furthermore, in the base film manufacturing process or the tape processing process, a process for removing residual strain such as relaxation heat treatment or aging treatment is indispensable, and selection and combination of manufacturing conditions are complicated.

As described above, there is no satisfactory magnetic tape having a thin base film for long-time recording.

In particular, with the recent widespread use of VTRs with built-in cameras, tapes are often placed under severe temperature conditions such as taking them out of the door or bringing them into the car, so tape dimensional stability that does not cause distortion There is a strong demand for dimensional stability of the base film.

On the other hand, in recent years, with the increase in density and S / N of magnetic materials, especially recording media for video and computers, magnetic powders having smaller particle diameters have been used.

Generally, the S / N ratio of a magnetic recording medium is said to be proportional to the square root of the number of particles of the magnetic powder in the recording material that is related to recording / reproduction. The smaller the magnetic powder, the better the S / N ratio.

Further, when the magnetic powder is made into fine particles and the BET value thereof is increased, the surface of the magnetic layer becomes so smooth that spacing loss is reduced, which is advantageous in obtaining high electromagnetic conversion characteristics.

Further, if the surface of the magnetic layer is made smooth to increase the density, the running property of the magnetic tape or the like is rather deteriorated, which is a problem. That is, since the recording medium as described above violently comes into sliding contact with the magnetic head during recording and reproduction, the smoothness of the surface causes an increase in the sliding contact area and an increase in the friction coefficient, which deteriorates the running property. This causes undesirable results such as wear of the magnetic layer during repeated use, loss of magnetic powder and the like contained in the layer, and clogging of the magnetic head due to fallen objects. Further, even if the magnetic tape itself is thinned and the magnetic layer is made extremely smooth, sticking to a tape guide or the like easily occurs when the tape is wound or unwound, and the running property of the magnetic tape is easily deteriorated. . For this reason, the running durability of the magnetic tape or the like is deteriorated, and the electromagnetic conversion characteristics such as S / N and RF output are adversely affected.

The above problems have become more prominent due to the recent trend toward higher quality and longer magnetic tapes. Higher density of magnetic recording media, thinner tapes and running and durability of magnetic tapes, etc. A technical solution to the contradictory issue of sex was desired.

C. OBJECT OF THE INVENTION It is an object of the present invention to provide a magnetic recording medium which is excellent in durability, scratch resistance, running property, and various characteristics during repeated use and has a high level of electromagnetic conversion characteristics.

D. Structure of the invention and its effect The present invention, a support made of polyethylene naphthalate, a fatty acid, and a BET value of 40 m ² / gr or more containing a magnetic metal powder, magnetic layer having a thickness of 2.5μm or less, The present invention relates to a magnetic recording medium having a back coat layer containing carbon black.

The present invention is characterized in that polyethylene naphthalate is used for a support such as a base film.

That is, polyethylene naphthalate has a high Young's modulus as described later, and the rigidity of the magnetic recording medium can be sufficiently maintained even when the support is thin. Therefore, at the same time as making the magnetic recording medium thin, it is possible to prevent damage to the edge portion of the magnetic recording medium during running and improve scratch resistance, improve the durability of the magnetic recording medium, and stabilize running of the magnetic recording medium. It is possible to prevent fluctuations in the output while maintaining the property. Further, it is possible to improve skew distortion and maintain good dimensional stability of the magnetic recording medium.

In addition, since metal magnetic powder is used as the magnetic powder, it is possible to provide a high-performance medium for high-density recording, and the specific surface area is 40 m ² / g or more to increase the packing density of magnetic powder for recording. The density can be further improved. This specific surface area is preferably 90 m ² / g or less, and further 46 to 80
A range of m ² / g is recommended. In other words, this makes it possible to increase the density of magnetic recording and smooth the surface, and obtain high-level electromagnetic conversion characteristics such as high S / N and high output.

However, due to the smoothing of the surface of the magnetic layer due to the fine particles of the magnetic powder and the thinning of the magnetic recording medium described above, the running stability and running durability of the magnetic recording medium are improved as described in the section of the prior art. May decrease. In this respect, in the present invention, since a back coat layer containing a fatty acid in the magnetic layer and containing carbon black is provided, the synergistic effect of these increases the running stability and running durability of the magnetic recording medium. You can keep it good. That is, the lubrication effect of the fatty acid improves the running property on the magnetic layer side, and the dispersant effect of the fatty acid can reduce or eliminate the conventional dispersant represented by lecithin, sorbitan derivative, phosphate ester, etc. It is possible to improve the stiffness of the layer, prevent the back side from sticking by the back coat layer, and improve the running property of the magnetic recording medium in combination with the lubricating action of carbon black.
Further, the inclusion of carbon black in the back coat layer also has the effect of improving the light shielding effect of the back coat layer and improving the optical density of the magnetic recording medium. This makes it possible to reduce the thickness of the magnetic layer and the like, which is further advantageous in extending the recording time.

As described above, the adoption of the configuration of the present invention technically solves the contradictory problems of increasing the density of magnetic recording, thinning the magnetic recording medium, and improving the durability and running of the magnetic recording medium. Is done.

Further, if the thickness of the magnetic recording medium is 9 μm or less, recording can be performed for a longer time, which is advantageous. Further, if the thickness of the magnetic layer is 2.5 μm or less, the magnetic recording medium can be made thinner,
It is advantageous for long-term recording.

Further, if the thickness of the support is 6.0 μm or less, it is advantageous for thinning the magnetic recording medium. However, the thickness of the support is preferably 3.5 μm or more in order to maintain the rigidity of the medium.

Next, the polyethylene naphthalate of the present invention will be described.

An example of this is polyethylene-2,6-naphthalate. Polyethylene-2,6-naphthalene may be any polyethylene-2,6-naphthalenediene whose repeating structural unit is substantially composed of ethylene-2,6-naphthalenedicarboxylate units, and is not copolymerized. The number of repeating structural units as well as the carboxylate
It also includes a copolymer in which 10% or less, preferably 5% or less, is modified with other components, and a mixture or composition with another polymer.

That is, polyethylene-2,6-naphthalate is obtained by combining naphthalene-2,6-dicarboxylic acid, or a functional derivative thereof, and ethylene glycol or a functional derivative thereof in the presence of a catalyst under appropriate reaction conditions. Polyethylene-2,6-naphthalate is copolymerized by adding an appropriate one or two or more third components (modifiers) before the completion of the polymerization of polyethylene-2,6-naphthalate. Alternatively, a mixed polyester may be used. Suitable third component is a compound having a divalent ester forming functional group such as oxalic acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,7-dicarboxylic acid, succinic acid, diphenyl ether dicarboxylic acid. Such as dicarboxylic acids, or lower alkyl esters thereof, oxycarboxylic acids such as P-oxybenzoic acid, P-oxyethoxybenzoic acid, or lower alkyl esters thereof, or dihydric alcohols such as propylene glycol, trimethylene glycol, etc. Compounds. Polyethylene-2,6-naphthalate or a modified polymer thereof is obtained by blocking the terminal hydroxyl group and / or carboxyl group with a monofunctional compound such as benzoic acid, benzoylbenzoic acid, benzyloxybenzoic acid or methoxypolyalkylene glycol. Alternatively, it may be modified with a trifunctional or tetrafunctional ester forming compound such as glycerin or pentaerythritol in an extremely small amount within a range where a substantially linear copolymer is obtained.

Further, the base polymer contains a matting agent such as titanium dioxide, phosphoric acid, phosphorous acid and their esters, or a stabilizer such as hindered phenol, fine particulate silica, a lubricant such as China clay, and the like. May be.

When the support is a polyethylene naphthalate film, this film is preferably a biaxially oriented film. As a method for obtaining a biaxially oriented film, for example, the unstretched film is stretched in the running direction (longitudinal direction) and then stretched in the width direction (transverse direction), so-called longitudinal-transverse sequential stretching method, transverse-longitudinal sequential stretching method, usually. Any of longitudinal-transverse-longitudinal, transverse-longitudinal-transverse stretching method, simultaneous biaxial stretching method and the like for re-stretching the biaxially stretched film can be applied. However, it is not limited to any of these stretching methods.

Furthermore, the heat shrinkage ratio of the base film when heat-treated at 70 ° C for 1 hour under no load is 0.09% or less, preferably 0.07%
The following is preferable. When the heat shrinkage ratio is more than 0.09%, the distortion of the magnetic tape also becomes large, and the distortion may appear on the screen depending on the receiver, and even valuable recording may be spoiled, which is not preferable.

In order to reduce the heat shrinkage rate of the high Young's modulus film in this way, the film after heat treatment is heated under low tension,
This can be done by relaxing in the running direction. As a method of relaxing in the running direction, for example, a method of relaxing in a non-contact state under heating low tension by a floating treatment method by aerodynamic force; a method of relaxing by giving a speed difference between a heating roll and a cooling roll each having a nip roll Or, there is a method in which the moving speed of the clip holding the film in the tenter is gradually slowed down to relax it in the running direction. However, any method can be used as long as it can relax in the running direction.

Next, fatty acids will be described.

The amount of fatty acid added to the magnetic layer is preferably 0.2 to 10 parts by weight, more preferably 0.5 to 8.0 parts by weight, based on 100 parts by weight of the magnetic powder.
If the amount of fatty acid deviates from this range, the dispersibility of the magnetic powder decreases, and the running property of the medium tends to decrease. If the amount of fatty acid increases, the fatty acid tends to exude or the output tends to decrease.

The fatty acid may be monobasic or dibasic.
A fatty acid having 6 to 30 carbon atoms, more preferably 12 to 22 carbon atoms, and a monobasic fatty acid is preferable. Examples of fatty acids are as follows.

(1) Caproic acid (2) Caprylic acid (3) Capric acid (4) Lauric acid (5) Myristic acid (6) Palmitic acid (7) Stearic acid (8) Isostearic acid (9) Linolenic acid (10) Linoleic acid (11) Oleic acid (12) Elaidic acid (13) Behenic acid (14) Malonic acid (15) Succinic acid (16) Maleic acid (17) Glutaric acid (18) Adipic acid (19) Pimelic acid (20) Azelaic acid (21) Sebacic acid (22) 1,12-Dodecanedicarboxylic acid (23) Octanedicarboxylic acid Metal magnetic powders include Fe, Ni, Co and Fe-Ni-Co.
System, Fe-Mn-Zn system, Fe-Ni system, Fe-Ni-Zn system, Fe-Co-
Ni-Cr system, Fe-Co-Ni-P system, Co-Ni system, etc. Fe, Ni, Co
Ferromagnetic powders such as metal magnetic powders whose main component is
BET value is 40 m ² / g or more. Among them, F in terms of electrical characteristics
The e-Ni system is preferred.

The metal magnetic powder refers to that obtained by a dry reduction method, and the magnetic powder obtained by wet reduction cannot obtain the high electric characteristics and durability of the present invention.

In the above, BET value (also called "specific surface area")
Means a surface area per unit weight, which is a physical quantity which is completely different from the average particle diameter. For example, there are one having a large specific surface area and one having a small specific surface area even if the average particle diameter is the same. The specific surface area is measured, for example, by first degassing the powder while heating it at around 250 ° C. for 30 to 60 minutes to remove what is adsorbed on the powder, and then introducing it into a measuring device to remove nitrogen. The initial pressure of is set to 0.5 kg / m ² and adsorption measurement is performed with nitrogen at liquid nitrogen temperature (−195 ° C.) (generally called BET method for measuring specific surface area. For details, see J. Ame. Chem. .Coc, 60 309 (1938)). As a measuring device for this specific surface area (BET value), a "powder and particle measuring device (canter soap)" jointly manufactured by Yuasa Battery Co., Ltd. and Yuasa Ionics Co., Ltd. can be used. A general explanation of the specific surface area and its measurement method is described in detail in "Measurement of Granules" (co-authored by JMDALLAVALLE and CLYDEORRJr, translated by Benda et al. , Pages 1170 to 1171, edited by The Chemical Society of Japan, published by Maruzen Co., Ltd. on April 30, 1966 (in the "Chemical Handbook", the specific surface area is simply the surface area (m ² / gr)). However, it is the same as the specific surface area in this specification.).

The carbon black that can be used in the present invention includes Conducte manufactured by Colombian Carbon.
^{x) -SC. (BET220m 2 /} g, DBP115ml / 100g, particle size 20mμ),
Conductex 975 (BET250m ² / g, DBP1
70ml / 100g), Vulcan 9 made by Cabot
(BET140m ² / g, DBP114ml / 100g, particle size 19mμ), Vulcan P (BET143m ² / g, DBP118ml / 100g, particle size 20m
μ), Asahi Carbon Co. # 80 (BET117m ² / g, DBP113ml / 1
00g, particle size 23mμ), HS100 (BET32m ² / g, manufactured by Denki Kagaku)
DBP180ml / 100g, particle size 53mμ), Mitsubishi Kasei's # 22B (B
ET55m ² / g, DBP131ml / 100g, particle size 40mμ), # 20B (BET56
^{m 2 / g, DBP115ml / 100g} , particle size ^{40mμ), # 3500 (BET47m 2} /
g, DBP187ml / 100g, particle size 40mμ)
CF-9, # 4000, # 40, # 30, MA-600 manufactured by Mitsubishi Kasei.
Cabot Black Pearls
L, Monarck 800, Black Pearls 70
0, Black Pearls 1000, Black Pearls 880,
Black Pearls 900, Black Pearls 1300, Black Pearls 2000, Sterling V,
Raven 410 made by Colombian Carbon,
Raven 3200, Raven 420, Raven 430, Raven 45
0, Raven 825, Raven 1255, Raven 1035, Raven 1000, Raven 2000, Raven 5000, Conductex 40-220, Ketjen Black FC and the like.

The magnetic recording medium of the present invention is, for example, as shown in FIG.
A magnetic layer 2 is provided on a support 1, and a BC layer 3 is provided on the surface opposite to the magnetic layer 2. Further, as shown in FIG. 2, an overcoat layer (OC layer) 4 may be provided on the magnetic layer 2 of the magnetic recording medium of FIG.

The magnetic recording medium shown in FIGS. 1 and 2 may have an undercoat layer (not shown) provided between the magnetic layer 2 and the support 1, or may have no undercoat layer. May be (same as below). Further, the support may be subjected to corona discharge treatment.

In the magnetic layer 2, other than the above-mentioned fatty acids, other lubricants (for example, silicone oil (which may be modified with carboxylic acid or ester), graphite, carbon fluoride, molybdenum disulfide, tungsten disulfide, fatty acid) Ester, fatty acid amide, α-olefin oxide, etc.)
Etc. may be added. Non-magnetic abrasive particles may also be added, including alumina, chromium oxide, titanium oxide,
α-iron oxide, silicon oxide, silicon nitride, silicon carbide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, boron nitride and the like are used. The content of the abrasive is preferably 20 parts by weight or less, more preferably 3 parts by weight to 12 parts by weight or less with respect to 100 parts by weight of the magnetic powder, and its average particle size is preferably 0.4 μm, more preferably 0.3 μm or less. .

Further, at least polyurethane can be used as the binder resin of the magnetic layer, which can be synthesized by the reaction of polyol and polyisocyanate. When a phenoxy resin and / or a vinyl chloride-based copolymer is contained together with polyurethane, the dispersibility of the magnetic powder when applied to the magnetic layer is improved and its mechanical strength is increased. However, the layer becomes too hard only with the phenoxy resin and / or the vinyl chloride copolymer, but this can be prevented by the inclusion of polyurethane, and the adhesion to the support or the underlayer becomes good.
In addition to the above, as the binder resin, a fibrous resin, a thermoplastic resin, a thermosetting resin, a reactive resin, or an electron beam irradiation curable resin may be used.

The BC layer 3 may also use the above-mentioned lubricant, non-magnetic abrasive particles, and binder resin, and the magnetic layer 2 may contain carbon black.

In FIG. 2, the OC layer 4 is provided in order to protect the magnetic layer 2 from damage and the like, and therefore, it is necessary that the OC layer 4 has sufficient lubricity. Therefore, as a binder resin for the OC layer 4,
The urethane resin used for the above-mentioned magnetic layer 2 can be used (preferably in combination with a phenoxy resin and / or a vinyl chloride copolymer).

Further, as a binder resin for the magnetic layer, the following (A)-
Those of (D) are preferably used. According to these binder resins, due to the action of the polar functional group in the molecular chain,
The dispersibility of magnetic powder can be improved to prevent gelation of the coating film, and the amount of low-molecular weight dispersant added can be reduced to improve coating strength and prevent head contamination due to additive bleed-out. Can be planned.

(A) Polyurethane Resin Having Metal Sulfonate Base The method for introducing the metal sulfonate base into the polyurethane resin includes, for example, the following methods.

(1) A method of previously introducing the hydrophilic group into a dibasic acid, a polyol or the like which is a raw material of polyurethane.

(2) A method of modifying a polyurethane resin having a bifunctional or trifunctional or higher functional —OH group. For example, a compound containing the above-mentioned hydrophilic group and chlorine in the molecule, such as (a), ClCH ₂ CH ₂ SO ₃ M (M represents a base, but an alkali metal is particularly preferable) and polyfunctional --OH. Polyurethane resin is dissolved in a solvent such as dimethylformamide (DMF) and dimethylsulfoxide (DMSO) in which both components are soluble, and amines such as pyridine, picoline and triethylamine; epoxy compounds such as ethylene oxide and propylene oxide -OH in the presence of dehydrochlorinating agent
A method of introducing the hydrophilic group by a dehydrochlorination reaction of a group and chlorine.

(A-1) R-OH + ClCH 2 CH 2 SO 3 M → R-OCH 2 CH 2 SO 3 M + HCl ( where, R: polyurethane resin) but results in a slight-products, can also be synthesized by the following method. That is, (b), HOCH ₂ CH ₂ SO ₃ M and dimethylformamide (DM
F), a difunctional isocyanate compound in a solvent such as dimethyl sulfoxide (DMSO), such as 4,4′-diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (H
MDI) is reacted in an equimolar amount to obtain a reaction product by the reaction between one isocyanate group of diisocyanate and the —OH group in the molecule. Next, the -OH group of the polyurethane resin is reacted with the remaining -NCO group to obtain a binder usable in the present invention.

(However, R is polyurethane resin, R'is hydrocarbon group)
Alternatively, the following method may be used.

(C), urethane prepolymer with NCO at both ends and HOCH ₂ CH
A method of reacting with ₂ SO ₃ M.

This resin has a number average molecular weight of 10,000 to 100,000, a degree of polymerization of about 200 to 2,000, and a glass transition temperature of 0 ° C to
90 ° C., 10-1,000 equivalents / 100 g of metal sulfonate base. In addition, the mechanical properties have an initial elastic modulus of 20 to 200 kg / mm ² ,
It has a breaking strength of ^{2 to} 10 kg / mm ² and a breaking elongation of 3 to 800%.

(B) Vinyl chloride-vinyl acetate copolymer resin containing maleic acid This resin has a number average molecular weight of 8,000 to 100,000, an average degree of polymerization of about 250 to 1,000, and a maleic acid content of 0.
2% to less than 1.5% by weight. Specifically, product name VM
CH VMCC (manufactured by UCC) and trade name MPR-TM (manufactured by Nisshin Chemical Co., Ltd.) are available.

In addition to the above vinyl chloride-vinyl acetate-maleic acid terpolymer, vinyl alcohol, maleic anhydride, acrylonitrile,
Monomers such as acrylic acid, methacrylic acid, and acrylic acid ester may be copolymerized or graft-polymerized. These monomers may be contained in 0.1 to 25% by weight of the total.

The mixing ratio of vinyl chloride and vinyl acetate is 60 by weight.
˜95: 40-5, preferably 70-90: 30-10.

(C) Polymerizing vinyl chloride, a monomer having an epoxy group, and optionally another monomer copolymerizable therewith in the presence of a radical generator having a strong acid radical containing sulfur or phosphorus. The obtained vinyl chloride content is 60% by weight or more, and strong acid radicals bonded to this copolymer are
A vinyl chloride resin having a content of 0.1 to 4.0% by weight can be used.

This resin is vinyl chloride, a monomer having an epoxy group,
If necessary, other monomers copolymerizable with them may be added to the radical generator having a strong acid radical containing sulfur or phosphorus such as ammonium persulfate, potassium persulfate, ammonium perphosphate, and sodium perphosphate. It is obtained by polymerizing below. The amount of the radical generator used is usually 0.3 to 9.0% by weight, preferably 1.0 to 5.0% by weight, based on the monomer.

This resin can be produced by a known method. However, since many radical generators having a strong acid radical containing sulfur or phosphorus are water-soluble, emulsion polymerization or suspension using a lower alcohol typified by methanol as a polymerization medium. Advantageously, by turbid polymerization. Furthermore, solution polymerization using a ketone as a solvent is also a suitable method.

In the production of this resin, in addition to the radical generator having a strong acid radical containing sulfur or phosphorus, it is also possible to use a radical generator usually used for polymerization of vinyl chloride. Examples of these radical generators include lauroyl peroxide, benzoyl peroxide, 3,5,
5-trimethylhexanoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, t-butyl peroxypiparate, t-butyl peroxycineodeca Organic peroxides such as Noate: 2,2'-azobisisobutyronitrile,
2,2'-azobis-2,4-dimethylvaleronitrile, 4,
Examples thereof include azo compounds such as 4'-azobis-4-cyanovaleric acid. In addition, as a radical generator having a strong acid radical, sodium formaldehyde sulfoxylate,
It is also possible to combine reducing agents such as sodium sulfite, sodium thiosulfate and the like.

Examples of the monomer having an epoxy group include glycidyl ethers of unsaturated alcohols such as allyl glycidyl ether and methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, glycidyl-P.
-Glycidyl esters of unsaturated acids such as vinyl benzoate, methyl glycidyl itaconate, glycidyl ethyl malate, glycidyl vinyl sulfonate, glycidyl (meth) allyl sulfonate, butadiene monooxide, vinylcyclohexene monooxide, 2-
Examples thereof include epoxide olefins such as methyl-5,6-epoxyhexene. This monomer is generally used in a range such that the amount of epoxy groups in the copolymer is 0.5% by weight or more. If this proportion is less than 0.5% by weight,
It becomes difficult to select the conditions for introducing strong acid radicals.

In addition to vinyl chloride and a monomer having an epoxy group, examples of a monomer that can be used as necessary include vinyl acetate, carboxylic acid vinyl ester such as vinyl propionate, methyl vinyl ether, isobutyl vinyl ether, cetyl. Vinyl ethers such as vinyl ether:
Vinylidene chloride such as vinylidene chloride and vinylidene fluoride: diethyl maleate, butylbenzyl maleate, di-2-hydroxyethyl maleate, dimethyl itaconate,
Unsaturated carboxylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, lauryl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate: olefins such as ethylene and propylene: (meth) acrylonitrile Unsaturated nitriles such as: aromatic vinyl such as styrene, α-methylstyrene, P-methylstyrene, and the like. These monomers have the purpose of improving the solubility of the resin while controlling the compatibility and softening point of the above resin and other resin when mixed with each other, and the characteristics of the coating film and the coating process. Is appropriately selected according to the need for improvement of

The resin of this example thus obtained has an average degree of polymerization of 10
0-900, preferably 200-500, vinyl chloride content 60
It is more than weight%. If the degree of polymerization is less than 100, the abrasion resistance of the magnetic layer is insufficient, and if it exceeds 900, the viscosity of the coating is high and the dispersion of the magnetic powder tends to be insufficient. On the other hand, if the content of vinyl chloride is less than 60% by weight, the compatibility with the flexible material is lowered, and the solvent separation of the coating film is significantly reduced, which causes inconvenience.

The amount of strong acid radical bonded to the resin is -SO _3, -SO _4,
-It is necessary that the content of PO _{4 and the} like be 0.1 to 4.0% by weight. If it is less than 0.1% by weight, the dispersibility of the magnetic powder will be insufficient, and if it exceeds 4.0% by weight, the hydrophilicity of the strong acid radical will be strong.
Not only the solubility in a solvent becomes insufficient, but also the moisture resistance of the coating film decreases, and further, the aggregation of the magnetic powder occurs, which rather deteriorates the dispersibility.

Since the resin of this example has an epoxy group, it can exhibit excellent heat resistance stability. Therefore, it is possible to manufacture a magnetic recording medium having excellent reliability and less likely to cause head corrosion. Further, by utilizing the reactivity of the epoxy group, it is possible to crosslink the coating film with a polyamine compound or a polycarboxylic acid compound as a crosslinking agent. Moreover, when these cross-linking agents are used, the rate of cross-linking is faster than that for a normal epoxy group-containing vinyl chloride copolymer having no strong acid radical,
Crosslinking proceeds extremely effectively. The reason is not clear,
It is thought to be due to the promoting action of the strong acid roots that are bound.

(D) 0.1 meq / gr of one or more functional groups selected from the group consisting of carboxyl group, epoxy group and hydroxyl group
Modified polyurethane having the above content and containing an average of 3 or more (preferably 5 or more) functional groups in one molecule has an average molecular weight of 5,000 to 100,000, preferably 8,000.
~ 60,000. These modified polyurethane resins have conventional thermoplastic polyurethane resins only at the end of the molecule,
Since it does not contain a hydroxyl group, but has a polar functional group in the middle of the molecule side, it can be adsorbed particularly well to fine magnetic particles to improve wetting and contribute to the dispersibility of the magnetic powder. In particular, as a hydroxyl group-containing modified polyurethane resin, the number of functional groups containing 0.1 meq / g or more of a hydroxyl group in the molecular chain that has generated an hydroxyl group by ring-opening the epoxy group of an epoxy-modified polyurethane resin with amines and / or carboxylic acids. Three or more, preferably five or more modified polyurethane resins having an average molecular weight of 5,000 to 100,000, preferably 8,000 to 60,000 and an epoxy resin component of the following general formula [I] (R ¹ and R ² are each hydrogen or a methyl group, and n is a number of 0 or 1 or more), and the compound is suitable for this purpose.

In particular, the action of the bisphenol skeleton structure can appropriately control the hydrolysis resistance of the coating film and the hardness of the coating film of the magnetic tape. If the functional group is less than 0.1 meq / g, the fine magnetic particles cannot be sufficiently dispersed, and this purpose cannot be achieved.

As the modified polyurethane resin containing a carboxyl group,
Modified products with lysine or lysine salts (lysine salts with lysine alkali salts and other organic cations), general formula [II] (Wherein R ³ is an alkyl group having 1 to 6 carbon atoms) 2
-Hydroxypropanediol 1,3 or a modified product thereof with a salt (carboxylate). Details of lysine modification and modification with 2-carboxypropanediols are described in JP-B-46-15517 and JP-B-53-38760.
Other modified products are described in JP-B-55-41607.

Among the resins (A) to (D), it is preferable to use the urethane resin (A) or (D) and the vinyl chloride resin (C) or the vinyl chloride-vinyl acetate copolymer resin (B) in an appropriate combination. . The urethane resin (A) or (D) and the vinyl chloride type (C) or the vinyl chloride-vinyl acetate copolymer resin (B) has a ratio of (A) or (D) / (C) or (B) = 20/80 to It is preferably used in a ratio of 80/20 (wt%). Incidentally, (C) may be a vinyl chloride-vinyl acetate copolymer.

Next, at the time of coating and forming the magnetic layer and the like, it is desirable to add a predetermined amount of polyfunctional isocyanate as a cross-linking agent to the sample in order to strengthen the magnetic layer and the like. Examples of such a crosslinking agent include triphenylmethane triisocyanate, tris- (p-isocyanatophenyl) thiophosphite, polymethylene polyphenyl isocyanate and the like. Methylene diisocyanate type and tolylene diisocyanate type are preferable. When the magnetic layer is cured by electron beam irradiation or the like, the addition of the isocyanate compound may be omitted or may be added.

E. Examples Hereinafter, examples of the present invention will be described.

The components, ratios, operation sequences and the like shown below can be variously modified without departing from the spirit of the present invention. In the following examples, all "parts" represent "parts by weight".

First, magnetic layers were formed on a support in the following manner, and a back coat layer was further formed to prepare each magnetic tape shown in FIG. However, in Comparative Example-4, no back coat layer was provided.

That is, first, a base film having a thickness of 4.3 μm, which is a support, is polyethylene naphthalate (PE
N) or polyethylene terephthalate (PET).

Next, after dispersing each component shown in the following table, this magnetic paint was filtered through a 1 μm filter, 5 parts of polyfunctional isocyanate was added, and the mixture was coated on a support and supercalendered, and displayed in the table below. The magnetic layer (2.5 μm thick) having the various characteristics and compositions described above was obtained.

Thereafter, a BC layer coating material having the following composition was applied to the surface opposite to the magnetic layer so that the dry thickness was 0.4 μm.

Carbon black Predetermined amount Titanium oxide 10 parts Nitrocellulose 25 parts N-2301 (Nippon Polyurethane) 25 parts Coronate L (〃) 10 parts Cyclohexanone 400 parts Methyl ethyl ketone 250 parts Toluene 250 parts Magnetic properties of the specified thickness A wide magnetic film having a layer and a BC layer was obtained and was wound. This film
It was cut into 8 mm width (however, when measuring the frequency of scratches on the tape, it was cut into 1/2 inch (12.65 mm) width) and used as each video tape in the following table (Examples, Comparative Examples) Corresponding to the number.). However, the numerical values after the second column in the table below represent parts by weight.

The following table shows the results of measuring the performance of the tapes obtained as described above. However, the evaluation items are measured and displayed according to the following criteria.

Lumi S / N: Measured with a color video noise meter "Shibasoku 925D / 1". The high pass filter was 4.2MHz and the low pass filter was 10KHz. V
The TR used an 8mm VCR.

RF output drop: Measure RF output using 8mm VCR,
It showed a value that was lower than the original output after 100 playbacks. (Unit: dB) Still image life: The time until the still image decreases by 2 dB,
Shown in minutes. The larger the value, the higher the durability and wear resistance of the magnetic recording medium.

Frequency of scratches on tape: A commercially available VHS VTR was used and the tape was set and run for 1 minute. After that, stop running, take out the tape,
Visually inspect the running part, the part used for loading and unloading, and investigate whether there is a scratch on the tape surface. Frequency of scratches on the tape = number of scratches / number of tests x 100 ( %). The number of tests was 20 or more.

However, the Lumi S / N and the RF output reduction were expressed as relative values when the value of Comparative Example 3 was set to 0 dB.

From the results shown in the table, it is understood that the tape performance is remarkably improved by forming the magnetic tape according to the present invention. That is, the base film is molded with polyethylene naphthalate (PEN), the fatty acid is contained in the magnetic layer, the magnetic metal powder is used, and the BET value is 40 m ² / gr or more, the carbon black is contained. It can be seen that the provision of the back coat layer (BC layer) brings about a remarkable improvement in tape performance.

Further, in the same manner as in Example 1 except that the thickness of the magnetic layer was 3.0 μm (Comparative Example 6), Lumi S / N (dB) was +1.5, and RF output reduction (dB) was +1. .0, still image life (mi
n) is 40, the frequency (%) of scratches on the tape is 40, support (polyethylene naphthalate), fatty acid, metallic magnetic powder (BET value is 40 m ² / gr or more), back coat layer (containing carbon black) Even if the condition (1) is satisfied, the magnetic layer thickness does not satisfy the conditions of the present invention, and the features of the present invention cannot be achieved.

That is, all the constituents of the support (polyethylene naphthalate), fatty acid, metal magnetic powder (BET value is 40 m ² / gr or more), magnetic layer thickness (2.5 μm or less), back coat layer (containing carbon black). It turns out that must be met.

[Brief description of drawings]

1 and 2 are partially enlarged sectional views showing an example of the magnetic recording medium of the present invention. In the reference numerals shown in the drawings, 1 ... Nonmagnetic support 2 ... Magnetic layer 3 ... Backcoat layer (BC layer) 4 ... Overcoat layer (OC layer).

Claims (1)

[Claims] 1. A backing containing a support made of polyethylene naphthalate, a fatty acid, and a magnetic magnetic layer having a BET value of 40 m ² / gr or more and a thickness of 2.5 μm or less, and carbon black. A magnetic recording medium having a coat layer.