JPH06111273A - Magnetic recording medium - Google Patents

Abstract

PURPOSE:To provide a magnetic recording medium with well-balancedly improved electromagnetic conversion characteristics, product yield, and durability by improving the dispersion property and dispersion stability of a fine ferromagnetic particle and then improving the uniformity in filling state of a magnetic layer and surface smoothness. CONSTITUTION:In the medium where a magnetic layer is formed by applying magnetic application liquid containing a ferromagnetic particle, each kind of solid powder, and a binder onto a non-magnetic substrate, the above ferromagnetic powder has a specific surface 30m<2>/g or more according to the BET method and a pH of 7-11. Then, vinyl chloride resin with a polar group and silane coupling agent are contained in the above magnetic application liquid where the pH of the above solid powder is 7-11.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a magnetic recording medium, and more particularly to a magnetic recording medium for high recording density having excellent electromagnetic conversion characteristics, track quality and durability.

[0002]

2. Description of the Related Art In recent years, magnetic recording media, particularly video tapes and floppy disks, have come to use magnetic powders having a high coercive force and a small particle size in order to increase the recording density.

However, since these magnetic powders are extremely difficult to disperse and are unstable once dispersed, agglomerated particles are generated, resulting in an insufficiently filled magnetic coating film and inhomogeneity. Tend to produce a different coating surface. For this reason, the S / N ratio is deteriorated due to the deterioration of the electrical conversion characteristics, the track quality is deteriorated due to the increase of erasing defects (the production yield is deteriorated due to the increase of extra pulse errors), and the durability is further deteriorated. It has drawbacks.

With respect to such technical problems, extensive studies have been conducted from the viewpoint of improving the affinity of the binder resin for magnetic powder as a property of the binder resin. For example, a sulfonic acid group or a phosphoric acid group is added to the molecular structure. Although the introduced binder resin was put to practical use, the dispersibility and dispersion stability of the ferromagnetic powder are still insufficient by itself.

Regarding the removal of agglomerated particles, in order to achieve a high recording density, the filter pore size should be made small.
It is necessary to remove even small agglomerated particles, but as a result, the solvent concentration after filtration tends to rise compared to before filtration,
Dispersion failure due to re-aggregation of ferromagnetic powder and solid powder due to solvent shock increases, and process becomes unstable due to increase in filter clogging frequency, which is not preferable in terms of dispersibility and dispersion stability, and is still insufficient. Is the state of.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to provide BE
To improve the dispersibility and dispersion stability of a ferromagnetic powder having a specific surface area of 30 m ² / g or more by the T method to maintain a uniform filling state of the magnetic coating film and to further improve the surface smoothness. To provide a magnetic recording medium for high recording density which has improved electromagnetic conversion characteristics (improved S / N ratio), production yield (good track quality and low extra pulse error rate) and durability in a well-balanced manner. It is in.

[0007]

The above object can be achieved by the present invention described below. That is, the present invention applies a ferromagnetic powder, various solid powders such as an antistatic agent, a lubricant, and an abrasive, and a magnetic coating liquid containing a binder onto a non-magnetic substrate to form a magnetic layer. In the magnetic recording medium, the ferromagnetic powder has a BET specific surface area of 30 m ² / g or more and a pH of 7 or less.
Magnetic recording liquid containing a polar group-containing vinyl chloride resin and a silane coupling agent in the magnetic coating liquid having a pH of 7 to 11 and a weak alkali range of 7 to 11. It is a medium.

According to the present invention described above, a vinyl chloride resin containing a polar group, preferably a sulfonic acid group or a phosphoric acid group, in a vehicle containing the ferromagnetic powder and the solid powder, and a silane coupling agent, preferably a terminal. By adding a silane coupling agent whose functional group is an epoxy group or a mercapto group, improves the affinity in the liquid vehicle with the ferromagnetic powder and all solid powders to be dispersed contained in the magnetic coating liquid, Therefore, the present invention realizes a magnetic recording medium with improved dispersibility and dispersion stability and improved electromagnetic conversion characteristics (S / N ratio), product yield (extra pulse error rate) and durability.

The pH value referred to here is 5 g of ferromagnetic powder or solid powder and 105 ml of pure water (evaporation loss of 5 m).
l) is weighed and added to a 300 ml beaker, boiled for 5 minutes, cooled to room temperature, and the above-mentioned supernatant liquid or strainer is added to JI.
It was determined by the method of measurement by the glass electrode method specified by S (Z-8802).

Next, the present invention will be described in detail.

The ferromagnetic powder used in the present invention has a pH of 7
The ferromagnetic powder has a specific surface area of 30 m ² / g or more by the BET method.
Of Co-containing γ-Fe known in the art
Examples thereof include ₂ O ₃ , Co-containing γ-Fe ₃ O ₄ , oxide magnetic powder such as barium ferrite, and metal magnetic powder such as iron and Fe—Co—Ni. Here, the magnetic powder having a specific surface area of less than 30 m ² / g is difficult to raise the S / N ratio, so that the purpose of increasing the recording density cannot be achieved.

The various solid powders in the present invention are all of the various solid powders contained in the magnetic layer for the purpose of improving the characteristics, except for the ferromagnetic powder. Specific examples of such solid powder include antistatic agents, lubricants, and abrasives. In the present invention, the pH of all these various types of solid powder contained in the magnetic layer must be in the range of 7 to 11 weak alkalis.

Carbon black is often used as the solid powder. Carbon black is a so-called conductive carbon black that imparts conductivity (antistatic property) to the magnetic coating film, and as a solid lubricant that reduces friction between the coating film and the drive head, if necessary. There is carbon black.

The conductive carbon black generally has a small particle size (30 nm or less) and a large specific surface area (100 m).
² / g or more), those having a developed structure structure are preferably used.

On the contrary, carbon black for lubrication has a large particle size (50 nm or more) and a small specific surface area (100 m).
² / g or less), and those with little development of structure structure are preferably used.

The total amount of these carbon blacks added is 1 to 20 parts by weight per 100 parts by weight of the ferromagnetic powder. In the present invention, the pH of any carbon black is
Used in the range of 7 to 11.

Another example of a commonly used solid powder is:
There are well-known abrasives such as α-alumina and α-iron oxide, and those having a size of 0.05 to 2 μm are usually used, and those having a size of 0.1 to 1 μm are particularly preferably used. .

The amount of the abrasive added is 1 to 20 parts by weight per 100 parts by weight of the ferromagnetic powder. In the present invention α
-Alumina, α-iron oxide, etc., all of which have a pH adjusted to the range of 7 to 11 are used.

The vinyl chloride resin having a polar group used in the present invention has a degree of polymerization of 100 to 500 and an average molecular weight of 1,000 to 10,000, and contains, for example, a vinyl chloride monomer and an alkali salt of sulfonic acid or phosphoric acid. It can be obtained by copolymerizing a copolymerization monomer, an epoxy group-containing monomer, a hydroxyl group-containing monomer and, if necessary, another copolymerization monomer. This copolymerization method is already known and disclosed in JP-A-60-235814.
No. 60-238306, No. 60-238309, Japanese Patent Publication No. 1-262626, Japanese Patent Publication No. 1-26627 and the like. However, the above-mentioned hydroxyl group may be supplied as a monomer, but may be generated by partial hydrolysis of a copolymer using a fatty acid vinyl such as vinyl acetate as another copolymer monomer.

The amount of the vinyl chloride resin added is 1 to 20 parts by weight per 100 parts by weight of the ferromagnetic powder.

The silane coupling agent used in the present invention promotes the dispersing effect in the magnetic coating liquid of the ferromagnetic powder and the solid powder having a pH of 7 to 11 and showing a weak alkali, and further the dispersion stability. From the viewpoint of maintaining the above, a silane coupling agent having a terminal functional group having an epoxy group or a mercapto group is preferable. The general formula is as follows when a specific example is shown.

[0022]

[Chemical 1]

The amount of the silane coupling agent added is 0.1 to 2 parts by weight per 100 parts by weight of the ferromagnetic powder.

The magnetic coating liquid in the present invention contains the above-mentioned ferromagnetic powder, carbon black, solid powder such as abrasives, and polar groups such as sulfonic acid group or phosphoric acid group, carboxyl group, epoxy group and hydroxy group. Vinyl chloride resin, which has a terminal functional group such as an epoxy group and a mercapto group, is prepared by mixing a silane coupling agent with an organic solvent such as methyl ethyl ketone, methyl isobutyl ketone, toluene, cyclohexanone, and tetrahydrofuran. For example, thermoplastic resin, thermosetting resin,
Conventionally known additives such as a binder such as a reactive resin and a dispersant (for example, lecithin) may be added alone or in combination.

The non-magnetic substrate used in the present invention is preferably a plastic film. More preferably, a polyethylene terephthalate polymer film and a polyethylene naphthalate polymer film are mentioned. Such a film is preferably a biaxially oriented film.

For coating the surface of the non-magnetic substrate (one side or both sides) with the magnetic coating liquid, a conventionally known coating method can be used. As a coating method, for example, air doctor coat, blade coat, air knife coat, squeeze coat, impregnation coat, reverse roll coat,
Gravure coat, die coat, etc. can be used. The coating amount is preferably in a range such that the thickness of the coating film (magnetic layer) after drying and calendering is 0.3 to 6 μm. As the treatment after coating, a conventionally known treatment can be used.

The magnetic recording medium of the present invention has excellent electromagnetic conversion characteristics, product yield and durability, and is useful as, for example, a high recording density magnetic tape or floppy disk.

[0028]

EXAMPLES The present invention will be further described below with reference to examples. In addition, "part" in an example means a weight part. The characteristics of the magnetic recording medium were measured by the following methods.

1) Electromagnetic conversion characteristics The S / N ratio and the extra pulse error rate were measured for each medium using each drive described later. S / N ratio After recording the 2F signal on the innermost track by the drive described below, the peak value of 2F and the total noise were obtained and displayed in decibels with a spectrum analyzer (TR171: manufactured by Advantest Corporation). The results are represented by the average of n = 10 sheets. Extra pulse error rate After recording 2F signals on all tracks with the drive described below, DC erasure was performed and the peak value of the reproduced signal was divided by 1/2 the average amplitude of the same track to obtain the value. The 10th value from the worst is displayed, and the extra pulse error rate is set. The results are represented by the average of n = 10 sheets.

The drives used for the above measurement are as follows.・ Using iron oxide powder containing Co: 3.5 inch FDD YD-740 (1F: 125KHz, 2F: 250KHz) made by YE Data Co., Ltd. ・ Using barium ferrite powder: 3.5 inch made by Toshiba FDD PD-212 (1F: 250KHz, 2F: 500KHz) ・ Metal powder used: 3.5 inch FDD FD1335 (1F: 312.5KHz, 2F: 625KHz) made by NEC

2) Durability Using a 3.5-inch FDD FD1137C manufactured by NEC Corporation, the head was loaded on the outer circumference (track 00) of the medium at a normal rotation speed (360 rpm) and tension, and continuous rotation was performed on the same track. It was The test was carried out by placing a drive in a constant temperature bath operating in one cycle per day while taking the following four temperature and humidity conditions as an atmosphere every 6 hours.

25 ° C., 50% RH → 52 ° C., 80% RH
→ 25 ° C, 20% RH → 5 ° C free (free) The total number of revolutions (number of passes) until the peeling occurs on one side of the coating film by visually observing the coating surface at a 12-hour pitch.
Was defined as durability. In addition, the time for checking was subtracted and converted to 500,000 passes per day. The result is n =
It is represented by the average of three passes (10,000 passes).

[0033]

Example 1 Magnetic metal powder (pH 9.0, specific surface area 43 m ² / g, coercive force 1650 Oersted (oe)) 100 parts carbon black (Valcan P manufactured by Cabot Co., pH 7.5, specific surface area 143 m ² / g) 8 parts Abrasive (AKP20 manufactured by Sumitomo Chemical Co., pH 8.5, specific surface area 4.4 m ² / g, particle size 0.4 μm) 15 parts Silane coupling agent (γ-glycidoxy propyltrimethoxysilane) 1 part PVC resin ( Zeon Corporation MR-110, average degree of polymerization 300) 10 parts Polyurethane (Pandex T-5260 manufactured by Dainippon Ink and Chemicals, Inc.) 8 parts Polyisocyanate (Coronate L manufactured by Nippon Polyurethane Company) 5 parts Lubricant (butyl stearate and oleyl) Oleate mixture) 3 parts Solvent (mixed solvent of tetrahydrofuran and cyclohexanone) 400 parts The components of the above composition were mixed and dispersed to prepare a magnetic paint.

This was applied to a polyethylene terephthalate film of 62 μm with a coating thickness of 2.5 after drying and calendering.
Both sides were coated so as to have a thickness of μm. Then dry it,
The surface of the magnetic layer was smoothed by calendering, and after heating and curing, a disk having a diameter of 90 mm was punched and polished, and then a floppy disk was prepared by a known method.

[0035]

[Example 2] Ferromagnetic metal powder of Example 1 (pH 9.
A floppy disk was prepared by the same method as in Example 1 except that the pH was changed from 0, specific surface area 43 m ² / g, coercive force 1650 oe) to pH 10.5, specific surface area 46 m ² / g, coercive force 1600 oe. .

[0036]

[Example 3] Carbon black of Example 1 was manufactured by Cabot Corp. Vulcan P (pH 7.5, specific surface area 143 m ² /
g) Cabot Black Pearls 2000 (p
A floppy disk was prepared in the same manner as in Example 1 except that the specific surface area was changed to H8.6 and the specific surface area was 1475 m ² / g).

[0037]

[Example 4] The abrasive was AKP2 manufactured by Sumitomo Chemical Co., Ltd. of Example 1.
0 (pH 8.5, specific surface area 4.4 m ² / g, particle size 0.4
A floppy disk was prepared in the same manner as in Example 1 except that the KN-320 (pH 9.5, specific surface area 4.3 m ² / g, particle size 0.3 μm) manufactured by Toda Kogyo Co., Ltd.

[0038]

Example 5 A floppy disk was prepared in the same manner as in Example 1 except that the silane coupling agent was changed from γ-glycidoxypropyltrimethoxysilane of Example 1 to γ-mercaptopropyltrimethoxysilane.

[0039]

Example 6 Barium ferrite powder (pH 7.4, specific surface area 35 m ² / g, coercive force 740 oe) 100 parts Carbon black (Valcan P manufactured by Cabot Co., pH 7.5, specific surface area 143 m ² / g) 5 parts Abrasive (AKP20 manufactured by Sumitomo Chemical Co., Ltd., pH 8.5, specific surface area 4.4 m ² / g, particle size 0.4 μm) 10 parts Silane coupling agent (γ-glycidoxy propyltrimethoxysilane) 1 part PVC resin (manufactured by Zeon Corporation) MR-110, average degree of polymerization 300) 8 parts Polyurethane (Pandex T-5260 manufactured by Dainippon Ink and Chemicals) 6 parts Polyisocyanate (Coronate L manufactured by Nippon Polyurethane Co.) 3 parts Lubricant (mixture of butyl stearate and oleyl oleate) 2 parts solvent (mixed solvent of tetrahydrofuran and cyclohexanone) 300 parts of the above composition The components were mixed and dispersed to prepare a magnetic paint.

This was applied to a 75 μm polyethylene terephthalate film with a coating thickness of 2.5 after drying and calendering.
Both sides were coated so as to have a thickness of μm. Then dry it,
The surface of the magnetic layer was smoothed by calendering, and after heating and curing, a disk having a diameter of 90 mm was punched and polished, and then a floppy disk was prepared by a known method.

[0041]

Example 7 Co-Containing Iron Oxide Powder (pH 7.8, Specific Surface Area 44 m ² / g, Coercive Force 810 oe) 100 Parts Carbon Black (Cabot Vulcan P, pH 7.5, Specific Surface Area 143 m ² / g) 8 Parts Abrasive (AKP20 manufactured by Sumitomo Chemical Co., Ltd., pH 8.5, specific surface area 4.4 m ² / g, particle size 0.4 μm) 15 parts Silane coupling agent (γ-glycidoxypropyltrimethoxysilane) 1 part PVC resin (Nippon Zeon Co., Ltd.) Company's MR-110, average degree of polymerization 300) 10 parts Polyurethane (Pandex T-5260 manufactured by Dainippon Ink and Chemicals Co., Ltd.) 8 parts Polyisocyanate (Coronate L manufactured by Nippon Polyurethane Company) 5 parts Lubricant (butyl stearate and oleyl oleate) Mixture) 3 parts Solvent (mixed solvent of tetrahydrofuran and cyclohexanone) 300 parts Composition of the above composition The components were mixed and dispersed to prepare a magnetic paint.

This was applied to a polyethylene terephthalate film of 75 μm with a coating thickness of 0.7 after drying and calendering.
Both sides were coated so as to have a thickness of μm. Then dry it,
The surface of the magnetic layer was smoothed by calendering, and after heating and curing, a disk having a diameter of 90 mm was punched and polished, and then a floppy disk was prepared by a known method.

[0043]

[Comparative Example 1] Ferromagnetic metal powder was used as in Example 1 (pH 9.
5, with a specific surface area of 43 m ² / g, coercive force of 1650 oe) (pH 6.1, specific surface area of 44 m ² / g, coercive force of 1)
A floppy disk was prepared in the same manner as in Example 1 except that the floppy disk was changed to 630 oe).

[0044]

[Comparative Example 2] manufactured by Cabot Vulcan P (pH 7.5 preferred carbon black Example 1, a specific surface area of 143m ² /
g), TB # 5500 (pH 6.
0, specific surface area 215 m ² / g) Example 1
I made a floppy disk by the same method as.

[0045]

[Comparative Example 3] AKP2 manufactured by Sumitomo Chemical Co., Ltd. of Example 1 was used as an abrasive.
0 (pH 8.5, specific surface area 4.4 m ² / g, particle size 0.4
A floppy disk was prepared in the same manner as in Example 1, except that the KN-V (pH 6.0, specific surface area 4.3 m ² / g, particle size 0.3 μm) manufactured by Toda Kogyo Co., Ltd.

[0046]

Comparative Example 4 A floppy disk was prepared in the same manner as in Example 1 except that the silane coupling agent was changed from γ-glycidoxypropyltrimethoxysilane of Example 1 to γ-aminopropyltrimethoxysilane.

[0047]

Comparative Example 5 A floppy disk was prepared in the same manner as in Example 1 except that the silane coupling agent was not added.

[0048]

Comparative Example 6 Barium ferrite powder was used in Example 6 (p
H7.4, specific surface area 35m ² / g, coercive force 740oe)
A floppy disk was prepared in the same manner as in Example 6 except that the pH value was changed from that of (pH 5.7, specific surface area of 37 m ² / g, coercive force of 720 oe).

[0049]

Comparative Example 7 A floppy disk was prepared in the same manner as in Example 7, except that the silane coupling agent was not added.

The characteristics of the floppy disk obtained in each of the above examples are shown in Tables 1, 2 and 3.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

INDUSTRIAL APPLICABILITY As described above, the present invention provides a magnetic recording medium for high recording density having excellent electromagnetic conversion characteristics, track quality and durability by improving the dispersibility of the magnetic coating and making the inside and the surface of the coating uniform. This will be realized, and will make a great contribution to increasing the density of the magnetic recording medium.

Claims (3)

[Claims] 1. A magnetic recording medium comprising a non-magnetic substrate coated with a magnetic coating liquid containing a ferromagnetic powder, various solid powders and a binder to form a magnetic layer. The ferromagnetic powder is a ferromagnetic powder having a specific surface area of 30 m ² / g or more by the BET method and a pH of 7 to 11, and all the solid powders have a pH in the range of 7 to 11 and a polarity. A magnetic recording medium comprising a vinyl chloride resin having a group and a silane coupling agent. 2. The magnetic recording medium according to claim 1, wherein the polar group of the vinyl chloride resin is a sulfonic acid group or a phosphoric acid group. 3. The magnetic recording medium according to claim 1, wherein the terminal functional group of the silane coupling agent is an epoxy group or a mercapto group.