JP2005276285A - Magnetic recording medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a magnetic recording medium having excellent tape wound-up shape after running. <P>SOLUTION: The magnetic recording medium has a back coat layer. The back coat layer contains a specified compound and the surface of the back coat layer has ≤250 pieces/265×350 μm<SP>2</SP>protrusions having ≥50 nm height. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a magnetic recording medium, and more particularly relates to a magnetic recording medium for high-density recording that is excellent in electromagnetic conversion characteristics and tape winding shape after running, and is less likely to cause winding defects called radiation. .

In recent VTRs and computer drives, a so-called high transfer rate has been developed to increase the relative speed of the magnetic recording medium with respect to the magnetic head as the capacity is increased. In order to increase the capacity, it is necessary to improve the recording density, and a magnetic recording medium having excellent electromagnetic conversion characteristics is required. Therefore, fine particles, high coercive force type ferromagnetic metal fine powders and hexagonal ferrite fine powders have been used.
Further, in order to increase the capacity and transfer rate, it is necessary to increase the tape feed speed. In particular, in a drive using a rotating cylinder, it is necessary to increase the durability of the magnetic recording medium because the transfer rate is increased by increasing the number of rotations and the number of heads.

  In a digital magnetic recording medium of a type in which a signal is recorded / reproduced by sliding a magnetic head on the medium surface, the surface property of the medium magnetic layer is extremely important. In general, when the surface property is improved, the number of dropouts is reduced and the electromagnetic conversion characteristics are improved, but the contact area between the head and the medium is increased, which affects the running durability. Providing the surface of the magnetic layer with a protrusion made of an abrasive or the like improves the running durability, but conversely increases the spacing loss and deteriorates the electromagnetic conversion characteristics. Thus, it has been difficult to achieve both high electromagnetic conversion characteristics and high running performance and high durability.

  Patent Documents 1 and 2 propose that a recess is provided on the surface of the magnetic layer for the purpose of achieving both electromagnetic conversion characteristics and running performance. However, such a dent becomes a recording defect, and causes a dropout in a high-density digital magnetic recording medium with a small reproduction bit area, which causes a decrease in electromagnetic conversion characteristics.

  On the other hand, in order to improve the runnability of a magnetic recording medium having a smooth magnetic layer, it is known to use a backcoat layer provided with protrusions. However, when the backcoat layer having protrusions and the magnetic layer surface overlap, the protrusions bite into the magnetic layer surface and deep dents (so-called “reflection”) occur on the magnetic layer surface. If such a deep dent exists, the contact between the magnetic layer surface and the head becomes unstable and dropout increases, resulting in an increase in error rate. In particular, in recent years, the magnetic layer tends to be increasingly thinner for higher recording density. In a magnetic recording medium having such a thin magnetic layer, if there is a dent on the surface of the magnetic layer, the contact between the surface of the magnetic layer and the head becomes unstable, and the tape winding shape after running is disturbed. In some cases, tape deformation such as breaking of the tape edge occurs. Such tape deformation also increases the error rate. As described above, particularly in a magnetic recording medium having a thin magnetic layer, it has been extremely difficult to achieve both excellent electromagnetic conversion characteristics and good running properties.

In addition, in order to improve the smoothness of the backcoat layer, it has been proposed to use an organic dye compound as a dispersant for particulate materials such as carbon black (see Patent Document 3). However, in the current thinned magnetic recording medium, it is difficult to prevent the deterioration of the electromagnetic conversion characteristics due to the reflection of the magnetic layer due to the protrusion on the surface of the backcoat layer only by using the dispersant described in Patent Document 3. there were.
Japanese Patent Laid-Open No. 3-116413 JP-A-6-180835 JP 2002-117524 A

  An object of the present invention is to provide a magnetic recording medium suitable for high-density digital recording, which has excellent electromagnetic conversion characteristics and excellent running properties (especially excellent tape winding shape after running).

（一般式（Ｉ）中、 Ｑ；アントラキノン系色素、フタロシアニン系色素、キナクリドン系色素、ジオキサジン系色素、アントラピリミジン系色素、アサンスロン系色素、インダスロン系色素、フラバンスロン系色素、ピランスロン系色素、ペリノン系色素、ペリレン系色素、チオインジゴ系色素、イソインドリノン系色素、およびトリフェニルメタン系色素からなる群から選ばれる有機色素残基、Ｗ；直接結合、−（ＣＨ₂）_n−、−ＮＨ−、−ＣＯＮＨ−、またはＣＨ₂ＮＨ、ｎ；１〜４の整数、ｍ；１〜１０の整数、Ｘ；単結合、または下記構造式で表される二価の連結基から選択される基、

および、Ｙ：下記一般式（ＩＩ）で表される基を表す。）

（一般式（ＩＩ）中、Ｚ；低級アルキレン基、−ＮＲ₂；低級アルキルアミノ基、または窒素原子を含む５員若しくは６員飽和へテロ環、および、ａ；１または２を表す。）
［請求項２］前記磁性層表面の深さが２０ｎｍ以上である凹み個数が５０個／２６５×３５０μｍ²以下である、請求項１に記載の磁気記録媒体。
［請求項３］前記磁性層の厚さは、０．０１〜０．２μｍの範囲である、請求項１または２に記載の磁気記録媒体。
［請求項４］前記強磁性粉末は、平均板径１０〜４０ｎｍの強磁性六方晶フェライト粉末または平均長軸長２０〜７０ｎｍの強磁性金属粉末である、請求項１〜３のいずれか１項に記載の磁気記録媒体。 Means for achieving the object of the present invention is as follows.
[Claim 1] A magnetic recording medium having a magnetic layer containing a ferromagnetic powder and a binder on one surface of a nonmagnetic support, and a backcoat layer containing carbon black on the other surface,
The back coat layer contains a compound represented by the following general formula (I):
The number of protrusions having a height of 50 nm or more on the surface of the backcoat layer is 250/265 × 350 μm ² or less.

(In general formula (I), Q: anthraquinone dye, phthalocyanine dye, quinacridone dye, dioxazine dye, anthrapyrimidine dye, asanthrone dye, indanthrone dye, flavanthrone dye, pyranthrone dye, perinone Organic dye residue selected from the group consisting of dyes, perylene dyes, thioindigo dyes, isoindolinone dyes, and triphenylmethane dyes, W; direct bond, — (CH ₂ ) _n —, —NH— , -CONH-, or CH ₂ NH, n; 1~4 integer, m; 1 to 10 integer, X; group selected from divalent linking group represented by a single bond, or the following structural formula,

Y represents a group represented by the following general formula (II). )

(In the general formula (II), Z represents a lower alkylene group, —NR ₂ ; a lower alkylamino group, or a 5- or 6-membered saturated heterocyclic ring containing a nitrogen atom, and a represents 1 or 2.)
[2] The magnetic recording medium according to [1], wherein the number of recesses having a depth of 20 nm or more on the surface of the magnetic layer is 50/265 × 350 μm ² or less.
[3] The magnetic recording medium according to [1] or [2], wherein the magnetic layer has a thickness in the range of 0.01 to 0.2 [mu] m.
[Claim 4] The ferromagnetic powder is one of ferromagnetic hexagonal ferrite powder having an average plate diameter of 10 to 40 nm or ferromagnetic metal powder having an average major axis length of 20 to 70 nm. 2. A magnetic recording medium according to 1.

  According to the present invention, it is possible to provide a magnetic recording medium suitable for high density digital recording having excellent electromagnetic conversion characteristics and excellent winding shape after running.

Hereinafter, the present invention will be described in more detail.
The magnetic recording medium of the present invention is a magnetic recording medium having a magnetic layer containing a ferromagnetic powder and a binder on one side of a nonmagnetic support and a backcoat layer containing carbon black on the other side. The back coat layer contains a compound represented by the following general formula (I).

In the general formula (I), Q represents an organic dye residue. The organic dye residue Q can be a commercially available dye or pigment, such as an anthraquinone dye, phthalocyanine dye, quinacridone dye, dioxazine dye, anthrapyrimidine dye, asanthrone dye, induslon And dyes, flavanthrone dyes, pyranthrone dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindolinone dyes, and triphenylmethane dyes.
W is a direct bond, — (CH ₂ ) _n —, —NH—, —CONH—, or CH ₂ NH, n is an integer of 1 to 4, m is an integer of 1 to 10, X is a single bond, or the following structure A group selected from divalent linking groups represented by the formula:

および、Ｙは下記一般式（ＩＩ）で表される基を表す。

Y represents a group represented by the following general formula (II).

一般式（ＩＩ）中、Ｚは、低級アルキレン基を表す。Ｚは、例えば−（ＣＨ₂）_b−と表されるが、該ｂは１〜５の整数を表し、好ましくは２または３を表す。
一般式（ＩＩ）中、−ＮＲ₂が低級アルキルアミノ基を表す場合、例えば−Ｎ（Ｃ_nＨ_2n+1）₂と表され、ｎは１〜４の整数を表し、好ましくは１または２を表す。一方、該−ＮＲ₂が窒素原子を含む５員または６員飽和ヘテロ環を表す場合、下記構造式で表されるヘテロ環が好ましい。

In general formula (II), Z represents a lower alkylene group. Z is represented, for example, as — (CH ₂ ) _b —, wherein b represents an integer of 1 to 5, preferably 2 or 3.
In the general formula (II), when —NR ₂ represents a lower alkylamino group, for example, —N (C _n H _{2n + 1} ) ₂ is represented, n represents an integer of 1 to 4, preferably 1 or 2 Represents. On the other hand, when the —NR ₂ represents a 5-membered or 6-membered saturated heterocycle containing a nitrogen atom, a heterocycle represented by the following structural formula is preferred.

In the general formula (II), Z and NR ₂ may each have a lower alkyl group or an alkoxy group as a substituent.
In the general formula (II), a represents 1 or 2, preferably 2.

  Specific examples of the compound represented by formula (I) are shown below, but the present invention is not limited to these specific examples. Hereinafter, Pc represents phthalocyanine, and CuPc represents copper phthalocyanine.

  The amount of the compound represented by the above general formula (I) in the back coat layer is preferably 0.1 to 50 parts by weight with respect to the carbon black. If the addition amount is within the above range, a good dispersion effect can be obtained.

In the magnetic recording medium of the present invention, the number of protrusions having a height of 50 nm or more on the surface of the backcoat layer is 250/265 × 350 μm ² or less. The number is preferably 200/265 × 350 μm ² or less, more preferably 170/265 × 350 μm ² or less. When the number of protrusions exceeds 250/265 × 350 μm ² , the electromagnetic conversion characteristics are remarkably deteriorated due to the show-through of the protrusions on the surface of the backcoat layer to the magnetic layer. Ideally, it is preferable that there are no protrusions having a height of 50 nm or more on the surface of the backcoat layer, but in the present invention, the lower limit value of the number of recesses is, for example, 5/265 × 350 μm ^2. it can.

In the magnetic recording medium of the present invention, the number of protrusions having a height of 50 nm or more on the surface of the backcoat layer is 250 pieces / 265 × 350 μm ² or less, so that show-through to the magnetic layer can be prevented. The number of recesses having a depth of 20 nm or more on the surface of the magnetic layer is preferably 50/265 × 350 μm ² or less. If the number of dents is 50/265 × 350 μm ² or less, an increase in dropout due to the presence of dents and a decrease in S / N (SNR) can be avoided, and the tape winding shape after running is disturbed. The increase in the dropout due to can be avoided, and high electromagnetic conversion characteristics can be obtained. The number of the recesses is more preferably 45 pieces / 265 × 350 μm ² or less, and still more preferably 40 pieces / 265 × 350 μm ² or less. Ideally, it is preferable that the magnetic layer surface does not have a dent having a depth of 20 nm or more. However, in the present invention, the lower limit value of the number of the dents can be, for example, 5/265 × 350 μm ² .

The number of protrusions and the number of recesses are measured as follows.
In the present invention, the “number of protrusions having a height of 50 nm or more on the backcoat layer surface” refers to the number of protrusions having a height of 50 nm or more from the root mean square surface of the backcoat layer. Here, the “square mean surface” is a surface in which the sum of the squares of deviations of the back coat layer surface is equal in the vertical direction. The position of the root mean square surface can be obtained by a surface roughness measuring instrument such as an atomic force microscope or an optical surface roughness meter. The number of protrusions having a height of 50 nm or more from the root mean square surface of the back coat layer was measured within a range of 265 μm × 350 μm using a surface roughness meter (NewView 5000) manufactured by ZYGO, and squared by image analysis software. It can be obtained by integrating the number of regions having a height of 50 nm or more from the average surface. The number of dents in the magnetic layer can also be measured by the same method.

  In the present invention, as a method for controlling the number of protrusions having a height of 50 nm or more on the surface of the backcoat layer, a method of adjusting the dispersion condition of the coating liquid for the backcoat layer, the number of protrusions of the support, the calendar temperature, and the calendar pressure. Can be mentioned. In general, when the calender conditions are increased (calendar pressure, temperature, roll hardness is increased, speed is decreased), the protrusions on the surface of the backcoat layer can be reduced.

In particular, in the present invention, in order to control the number of back coat layer protrusions, it is important to highly disperse the back coat layer coating solution. In the present invention, carbon black is dispersed in a solvent containing the compound represented by the general formula (I) to prepare a backcoat layer coating solution, which is coated, heated, and heated according to a conventional coating method. A back coat layer can be provided by curing. There is no restriction | limiting in particular about a solvent, Water, an organic solvent, those liquid mixture, etc. can be used.
When the compound represented by the general formula (I) and the binder are kneaded using an open kneader or the like, or dispersed using a roll mill or a sand mill, the carbon black is mixed well to disperse well. be able to. In addition, if the compound represented by the general formula (I) and the binder are mixed by heating before dispersion, the basic group of the compound represented by the general formula (I) and the binder Not only the affinity is improved, but also the carbon black is uniformly and rapidly mixed, so that an improvement in quality and productivity is achieved.

  Furthermore, in the present invention, in the step of dispersing the backcoat layer coating solution, multistage dispersion is performed while successively lowering the dispersion containing carbon black, and the dispersion medium has a high specific gravity, high hardness, and a small diameter (for example, 0 .5μmφ) dispersion media, high dispersion of the dispersion media, high peripheral speed of the disperser, and long dispersion time are appropriately combined to disperse the coating solution for the backcoat layer to a very high degree. Can do. As the disperser, for example, a media disperser such as a ball mill, an attritor or a sand grinder can be used, and a vibration mill or an ultrasonic disperser can also be used. When using a media-type disperser, it is preferable to increase the filling rate of the dispersion medium, for example, 60 to 100%. As the dispersion medium, steel balls, glass beads, ceramic beads (zirconia or the like) can be used, and it is particularly preferable to use small diameter high specific gravity ceramic beads such as zirconia beads. Furthermore, when it is desired to apply shear to the carbon black on the powder, a kneader can be used. For example, an open kneader, a pressure kneader, a helical rotor, a continuous kneader, a roll mill, a taper roll, an internal mixer, a bumper mixer, and the like can be used. The dispersed liquid is usually adjusted in viscosity so as to be easily applied and then supplied to the application section. When the liquid is sent, it is usually filtered in a circulation, single or multiple stages. The filter used at this time can be selected depending on the liquid quality, and either a depth type or a pleat type can be used. The filtration accuracy is preferably selected according to the accuracy according to the desired level.

  The protrusions existing on the surface of the backcoat layer are classified into protrusions caused by the support and protrusions related to the coating layer. Usually, fine protrusions are formed on the support surface by containing fine inorganic or organic fillers. These minute protrusions are reflected on the surface of the backcoat layer to form minute surface protrusions, but the number of protrusions on the surface of the backcoat layer can be changed by changing the particle size of the filler contained in the support. . Further, the influence of the protrusions on the support surface on the backcoat layer can be reduced by increasing the thickness of the backcoat layer.

Further, by polishing the backcoat layer surface, the number of protrusions having a height of 50 nm can be reduced, and as a result, the number of recesses having a depth of 20 nm or more on the surface of the magnetic layer can be reduced.
Examples of the method for surface treatment of the backcoat layer include a method of polishing by pressing a polishing tape or a diamond wheel against the surface of the backcoat layer. At that time, surface protrusions can be controlled by controlling the count and pressing pressure of the polishing tape and diamond wheel.
In the case of a tape, it is possible to use a polishing method using a polishing tape (wrapping tape blade method), a sapphire blade method, a diamond wheel method, etc. disclosed in JP-A-63-259830. The backcoat layer surface protrusions can be controlled by selecting these and setting each processing condition. Even when there are many surface protrusions on the support or on the backcoat layer after application, the surface treatment can reduce protrusions on the surface of the backcoat layer.

In the present invention, in order to control the number of dents on the surface of the magnetic layer, in addition to reducing the number of protrusions of the backcoat layer as described above, the particle size of the ferromagnetic powder (major axis length, etc.), It is preferable to use a method of adjusting the thickness of the magnetic layer and the dispersion conditions of the coating liquid for the magnetic layer and the coating liquid for the nonmagnetic layer.
As described above, various methods can be used to control the number of protrusions on the surface of the backcoat layer and the number of recesses on the surface of the magnetic layer. By optimizing these methods in combination, desired characteristics can be obtained. A magnetic recording medium having the same can be obtained.

[Back coat layer]
In general, a magnetic tape for recording computer data is strongly required to have repeated running characteristics as compared with a video tape and an audio tape. In the present invention, carbon black is contained in the back coat layer in order to maintain such high running durability.

In the back coat layer, it is preferable to use a combination of two types of carbon blacks having different average particle sizes. In this case, it is preferable to use a combination of fine particle carbon black having an average particle size of 5 to 50 nm and coarse particle carbon black having an average particle size of 51 to 220 nm.
In general, the addition of fine particulate carbon black as described above can set the surface electrical resistance of the backcoat layer to a low level and can also set the light transmittance to a low level. Some magnetic recording devices utilize the light transmittance of the tape and are used for the operation signal. In such a case, the addition of particulate carbon black is particularly effective. In addition, particulate carbon black is generally excellent in retention of liquid lubricants, and contributes to reduction of the friction coefficient when used in combination with lubricants.

  Specific products of the particulate carbon black include the following. In addition, the average particle size is shown in parentheses. BLACK PEARLS 800 (17 nm), BLACK PEARLS 1400 (13 nm), BLACK PEARLS 1300 (13 nm), BLACK PEARLS 1100 (14 nm), BLACK PEARLS 1000 (16 nm), BLACK PEARLS 900 (15 nm), BLACK PEARLS 8 (BLACK PEARLS 8) PEARLS 4630 (19 nm), BLACK PEARLS 460 (28 nm), BLACK PEARLS 430 (28 nm), BLACK PEARLS 280 (45 nm), MONARCH 800 (17 nm), MONARCH 14000 (13 nm), MONARCH 1300 (13 nm), MONARCH 1 MONARCH 1000 (16nm MONARCH 900 (15 nm), MONARCH 880 (16 nm), MONARCH 630 (19 nm), MONARCH 430 (28 nm), MONARCH 280 (45 nm), REGAL 330 (25 nm), REGAL 250 (34 nm), REGAL 99 (38 nm), REGAL 400 (25 nm), REGAL 660 (24 nm) (above, manufactured by Cabot), RAVEN2000B (18 nm), RAVEN1500B (17 nm), Raven 7000 (11 nm), Raven 5750 (12 nm), Raven 5250 (16 nm), Raven 500 ULTRAII 8 nm), Raven 3500 (13 nm), Raven 2500 ULTRA (13 nm), Raven 2000 (18 nm) , Raven 1500 (17 nm), Raven 1255 (21 nm), Raven 1250 (20 nm), Raven 1190 ULTRA (21 nm), Raven 1170 (21 nm), Raven 1100 ULTRA (32 nm), Raven 1080 ULTRA U28 TRA 28 ULTRA U28 30 nm), Raven 1040 (28 nm), Raven 880 ULTRA (30 nm), Raven 860 (39 nm), Raven 850 (34 nm), Raven 820 (32 nm), Raven 790 ULTRA (30 nm), Raven 780 UL 29R ULTRA (30 nm) (above, manufactured by Columbian Carbon), Asahi # 90 (19 nm), Asahi # 80 (2 nm), Asahi # 70 (28 nm), Asahi F-200 (35 nm), Asahi # 60 HN (40 nm), Asahi # 60 (45 nm), HS-500 (38 nm) (above, manufactured by Asahi Carbon Co.), # 2700 ( 13 nm), # 2650 (13 nm), # 2400 (14 nm), # 1000 (18 nm), # 950 (16 nm), # 850 (17 nm), # 750 (22 nm), # 650 (22 nm), # 52 (27 nm) , # 50 (28 nm), # 40 (24 nm), # 30 (30 nm), # 25 (47 nm), # 95 (40 nm), CF9 (40 nm), # 4350 (50 nm), # 3040 (50 nm) (above, (Mitsubishi Chemical Corporation), PRINTEX90 (14 nm), PRINTEX95 (15 nm), PRINTEX85 (16 nm), PRINTEX75 ( 17 nm) (above, manufactured by Degussa), # 3950 (16 nm) (manufactured by Mitsubishi Chemical Industries, Ltd.).

  Examples of specific products of coarse particle carbon black include BLACK PEARLS 130 (75 nm), MONARCH 120 (75 nm) (above, manufactured by Cabot), Raven 520 ULTRA (68 nm), Raven 510 ULTRA (58 nm), Raven 500 (53 nm), Raven 460 (67 nm), Raven 450 (75 nm), Raven 420 (86 nm), Raven 410 (101 nm), Raven 22 (83 nm), Raven 16 (68 nm), Raven 14 (55 nm) (and above, Colombian) Carbon)), Asahi # 55 (66 nm), Asahi 50H (85 nm), Asahi # 51 (91 nm), Asahi # 50 (80 nm), Asahi # 35 (78 nm), Asahi # 15 (122 nm) (Made by company) # 10 (75nm), # 5 (76nm), # 4010 (75nm), # 3030 (55nm) (manufactured by Mitsubishi Chemical Corporation) can be exemplified.

When two types of carbon black having different average particle sizes are used in the back coat layer, the content ratio (mass ratio) of fine particle carbon black having an average particle size of 5 to 50 nm and coarse particle carbon black having an average particle size of 51 to 220 nm. ) Is preferably in the range of the former / the latter = 1/100 to 1/1, and more preferably in the range of 1/20 (5/100) to 1/2 (50/100).
The content of carbon black in the backcoat layer (the total amount when two types are used) is usually in the range of 30 to 100 parts by mass with respect to 100 parts by mass of the binder, It is the range of 45-95 mass parts.

An inorganic powder can be used for the back coat layer. As the inorganic powder, it is preferable to use two types having different hardnesses in combination.
Specifically, it is preferable to use a soft inorganic powder having a Mohs hardness of 3 to 4.5 and a hard inorganic powder having a Mohs hardness of 5 to 9.
By adding a soft inorganic powder having a Mohs hardness of 3 to 4.5, the friction coefficient can be stabilized by repeated running. Moreover, when the hardness is within this range, the sliding guide pole is not scraped. The average particle size of the inorganic powder is preferably in the range of 30 to 50 nm.
Examples of the soft inorganic powder having a Mohs hardness of 3 to 4.5 include calcium sulfate, calcium carbonate, calcium silicate, barium sulfate, magnesium carbonate, zinc carbonate, and zinc oxide. These can be used alone or in combination of two or more. Among these, calcium carbonate is particularly preferable.
The content of the soft inorganic powder in the back coat layer is preferably in the range of 0 to 140 parts by mass, more preferably 0 to 100 parts by mass with respect to 100 parts by mass of the carbon black.

By adding a hard inorganic powder having a Mohs hardness of 5 to 9, the strength of the backcoat layer is enhanced and the running durability is improved. When these inorganic powders are used together with carbon black or the soft inorganic powder, there is little deterioration even with repeated sliding, and a strong backcoat layer is obtained. In addition, the addition of the inorganic powder provides an appropriate polishing force and reduces the adhesion of shavings to the tape guide pole and the like. In particular, when used in combination with a soft inorganic powder (especially calcium carbonate), the sliding characteristics with respect to the guide pole having a rough surface can be improved, and the friction coefficient of the backcoat layer can be stabilized.
The hard inorganic powder preferably has an average particle size in the range of 80 to 250 nm (more preferably, 100 to 210 nm).

Examples of the hard inorganic powder having a Mohs hardness of 5 to 9 include α-iron oxide, α-alumina, and chromium oxide (Cr ₂ O ₃ ). These powders may be used alone or in combination. Of these, α-iron oxide or α-alumina is preferably used. Content of hard inorganic powder is 0-30 mass parts normally with respect to 100 mass parts of carbon black, Preferably, it is 0-20 mass parts.

  When the soft inorganic powder and the hard inorganic powder are used in combination in the back coat layer, the difference in hardness between the soft inorganic powder and the hard inorganic powder is 2 or more (more preferably 2.5 or more, particularly 3 or more). It is preferable to select and use a soft inorganic powder and a hard inorganic powder.

  The back coat layer preferably contains the two types of inorganic powders having the specific average particle size and different Mohs hardness and the two types of carbon blacks having the different average particle size. In particular, in this combination, it is preferable that calcium carbonate is contained as the soft inorganic powder.

  The back coat layer can contain a lubricant. The lubricant can be appropriately selected from the above-mentioned lubricants that can be used for the nonmagnetic layer or the magnetic layer. In the backcoat layer, the lubricant is usually added in the range of 1 to 5 parts by mass with respect to 100 parts by mass of the binder.

[Magnetic layer]
In the magnetic recording medium of the present invention, the thickness of the magnetic layer is preferably in the range of 0.01 to 0.2 μm, more preferably in the range of 0.03 to 0.18 μm. It is preferable to set the optimum thickness according to the system. In general, if the magnetic layer thickness is 0.01 μm or more, high output and good C / N can be obtained. On the other hand, if the magnetic layer thickness is 0.2 μm or less, good C / N can be obtained with less noise.

The magnetic layer thickness can be determined as follows.
An ultra-thin slice (about 80 nm thick) sample in the thickness direction of the magnetic recording medium is prepared by an ultra-thin section method known as a transmission electron microscope sample preparation method, and an ultra-thin section photograph (with a transmission electron microscope) 50000 times). The upper layer surface and the upper and lower layer interfaces in the photograph are traced on the film base, and 500 straight lines parallel to the thickness direction at intervals of 0.025 μm are drawn between the upper layer surface and the upper and lower layer interfaces. It can be a thickness.

  In order to achieve high-density recording, the magnetic recording medium of the present invention has a ferromagnetic hexagonal ferrite powder having an average plate diameter of 10 to 40 nm or a ferromagnetic metal powder having an average major axis length of 20 to 70 nm as the magnetic powder contained in the magnetic layer. Is preferably used.

<Ferromagnetic hexagonal ferrite powder>
The ferromagnetic hexagonal ferrite powder has a hexagonal magnetoplumbite structure, has extremely large uniaxial crystal magnetic anisotropy, and has a very high coercive force (Hc). For this reason, magnetic recording media using ferromagnetic hexagonal ferrite powder have excellent chemical stability, corrosion resistance, and friction resistance, and can reduce magnetic spacing due to the increase in density, thereby realizing a thin film. High C / N and resolution are possible. The average plate diameter of the ferromagnetic hexagonal ferrite powder is preferably 10 to 40 nm, more preferably 13 to 35 nm, and still more preferably 15 to 32 nm. In general, when the track density is increased and reproduction is performed with a magnetoresistive head, it is necessary to reduce noise and to reduce the average plate diameter of the ferromagnetic hexagonal ferrite powder. Also, from the viewpoint of reducing magnetic spacing, it is preferable that the average plate diameter of hexagonal ferrite is as small as possible. However, if the average plate diameter of the ferromagnetic hexagonal ferrite powder is too small, the magnetization becomes unstable due to thermal fluctuation. For this reason, it is preferable that the lower limit of the average plate diameter of the ferromagnetic hexagonal ferrite powder used in the magnetic layer of the magnetic recording medium of the present invention is 10 nm. When the average plate diameter is 10 nm or more, there is little influence of thermal fluctuation, and stable magnetization can be obtained. On the other hand, the upper limit of the average plate diameter of the ferromagnetic hexagonal ferrite powder is preferably 40 nm. If the average plate diameter is 40 nm or less, noise is reduced and electromagnetic conversion characteristics are improved, and this is particularly suitable for reproduction with a magnetoresistive head (MR head).

  The average plate diameter of the ferromagnetic hexagonal ferrite powder is obtained by photographing the ferromagnetic hexagonal ferrite powder with a transmission electron micrograph, and directly reading the plate diameter of the ferromagnetic hexagonal ferrite powder from the photograph and the image analysis device curl. It can be determined from the average value of values measured in combination with a method of tracing and reading a transmission electron micrograph with IBASSI manufactured by Zeiss.

  In the present invention, as the ferromagnetic hexagonal ferrite powder contained in the magnetic layer, for example, barium ferrite, strontium ferrite, lead ferrite, calcium ferrite substitution, Co substitution, and the like can be used. 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.

As described above, the ferromagnetic hexagonal ferrite powder preferably has an average plate diameter of 10 to 40 nm, more preferably 13 to 35 nm, and still more preferably 15 to 32 nm. Moreover, it is preferable that average plate | board thickness is 1-30 nm, More preferably, it is 2-25 nm, More preferably, it is 3-20 nm. The plate ratio (plate diameter / plate thickness) can be 1 to 15, preferably 1 to 7. If the plate-like ratio is 1 to 15, sufficient orientation can be obtained while maintaining high filling properties in the magnetic layer, and noise increase can be suppressed by stacking between particles. Moreover, the specific surface area by BET method within the said particle size range is 10-200 m < ² > / g. This specific surface area is approximately the value calculated from the particle plate diameter and plate thickness.

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

  The coercive force (Hc) of the hexagonal ferrite particles can be in the range of 119.4 to 318.4 kA / m (1500 to 4000 Oe), preferably 159.2 to 278.6 kA / m (2000 to 2000). 3500 Oe), more preferably 175.1 to 238.8 kA / m (2200 to 3000 Oe). However, when the saturation magnetization (σs) of the head exceeds 1.4T, it is preferably 159.2 kA / m or less. The coercive force (Hc) can be controlled by the particle size (plate diameter / plate thickness), the type and amount of the contained element, the substitution site of the element, the particle generation reaction conditions, and the like.

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

Ferromagnetic hexagonal ferrite powder can be made by mixing barium oxide, iron oxide, iron oxide and metal oxide to replace boron oxide as a glass-forming substance so as to have a desired ferrite composition, and then melting and quenching. Amorphous, then reheated, washed and ground to obtain barium ferrite crystal powder; glass crystallization method; after neutralizing barium ferrite composition metal salt solution with alkali and removing by-products Hydrothermal reaction method in which barium ferrite crystal powder is obtained by liquid phase heating at 100 or more, followed by washing, drying and pulverization; neutralizing the barium ferrite composition metal salt solution with alkali, removing by-products and drying. There is a coprecipitation method in which the barium ferrite crystal powder is obtained by treating and pulverizing at a temperature of ℃ or less, but the present invention does not select a production method. The ferromagnetic hexagonal ferrite powder may be subjected to surface treatment with Al, Si, P, or an oxide thereof, if necessary. The amount is suitably 0.1 to 10% with respect to the ferromagnetic powder, and the surface treatment is preferable because adsorption of a lubricant such as a fatty acid is 100 mg / m ² or less. The ferromagnetic powder may contain inorganic ions such as soluble Na, Ca, Fe, Ni, and Sr. Although it is preferable that these are essentially absent, if they are 200 ppm or less, they do not particularly affect the characteristics.

<Ferromagnetic metal powder>
It is known that the ferromagnetic metal powder that can be used in the magnetic layer of the magnetic recording medium of the present invention is excellent in high-density magnetic recording characteristics. By using a ferromagnetic metal powder, a magnetic recording medium having excellent electromagnetic conversion characteristics can be obtained. The average major axis length of the ferromagnetic metal powder that can be used in the magnetic layer of the magnetic recording medium of the present invention is preferably 20 to 70 nm, more preferably 23 to 65 nm, and further preferably 25 to 60 nm. preferable. If the average major axis length of the ferromagnetic metal powder is 20 nm or more, the magnetic characteristics do not deteriorate due to thermal fluctuations, and if the average major axis length is 70 nm or less, noise is reduced and good C / N is obtained. (S / N) can be obtained.

  The average major axis length of the ferromagnetic metal powder is obtained by photographing the ferromagnetic metal powder with a transmission electron micrograph and directly reading the major axis length of the ferromagnetic metal powder from the photograph and using an image analysis apparatus IBASSI manufactured by Carl Zeiss. It can be determined from the average value of the values measured using the transmission electron micrograph trace and reading method.

  In the magnetic recording medium of the present invention, the ferromagnetic metal powder used in the magnetic layer can be one containing Fe as a main component (including an alloy), and a ferromagnetic alloy containing α-Fe as a main component. It is preferable to use a powder. These ferromagnetic powders include Al, Si, S, Sc, Ca, Ti, V, Cr, Cu, Y, Mo, Rh, Pd, Ag, Sn, Sb, Te, Ba, Ta, other than predetermined atoms. It may contain atoms such as W, Re, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, P, Co, Mn, Zn, Ni, Sr, and B. In particular, at least one of Al, Si, Ca, Y, Ba, La, Nd, Co, Ni, and B is preferably included in addition to α-Fe, and further includes at least one of Co, Y, and Al. preferable. The Co content is preferably 0 to 40 atomic%, more preferably 15 to 35 atomic% or less, and more preferably 20 to 35 atomic% with respect to Fe. The content of Y is preferably 1.5 to 15 atomic%, more preferably 3 to 12 atomic% with respect to Fe. The content of Al is preferably 1.5 to 15 atomic%, more preferably 3 to 12 atomic% or less with respect to Fe. These ferromagnetic powders may be previously treated with a dispersant, a lubricant, a surfactant, an antistatic agent or the like, which will be described later. Specifically, Japanese Patent Publication No. 44-14090, Japanese Patent Publication No. 45-18372, Japanese Patent Publication No. 47-22062, Japanese Patent Publication No. 47-22513, Japanese Patent Publication No. 46-28466, Japanese Patent Publication No. 46-38755. No. 47, No. 47-4286, No. 47-12422, No. 47-17284, No. 47-18509, No. 47-18573, No. 39-10307 No. 46-39639, U.S. Pat. Nos. 3,026,215, 3,031,341, 3,100,194, 3,342,005 and 3,389,014.

  The ferromagnetic metal powder may contain a small amount of hydroxide or oxide. As the ferromagnetic metal powder, those obtained by a known production method can be used, and examples of such a method include the following methods. Method of reducing complex organic acid salt (mainly oxalate) with reducing gas such as hydrogen, method of reducing iron oxide with reducing gas such as hydrogen to obtain Fe or Fe-Co particles, metal carbonyl compound A method of thermal decomposition, a method of reducing by adding a reducing agent such as sodium borohydride, hypophosphite, or hydrazine to an aqueous solution of a ferromagnetic metal, and evaporating the metal in a low-pressure inert gas to form a fine powder. How to get. The ferromagnetic metal powder thus obtained has a known gradual oxidation treatment, for example, a method of drying after immersing in an organic solvent, an oxide film is formed on the surface by sending an oxygen-containing gas after immersing in an organic solvent Thereafter, a method of drying, a method of forming an oxide film on the surface by adjusting partial pressures of oxygen gas and inert gas without using an organic solvent, and the like can be applied.

The specific surface area by the BET method of the ferromagnetic powder used in the present invention (S _BET) can be in the 40 to 80 m ² / g, preferably from 45~70m ² / g. If the specific surface area (S _BET ) by the BET method is 40 m ² / g or more, noise is reduced, and if it is 80 m ² / g or less, good surface properties can be obtained. In the present invention, the crystallite size of the ferromagnetic powder in the magnetic layer can be 80 to 180 mm, preferably 100 to 180 mm, and more preferably 110 to 175 mm. When the ferromagnetic metal powder is an acicular ferromagnetic metal powder, the average acicular ratio is preferably 5 to 15, and more preferably 6 to 12. The acicular ratio is represented by the ratio between the average major axis length measured by a transmission electron microscope and the crystallite size obtained by X-ray diffraction. The σs of the ferromagnetic metal powder can be 70 to 180 A · m ² / kg, preferably 80 to 170 A · m ² / kg. The coercive force of the ferromagnetic metal powder is preferably 119 to 318 kA / m, more preferably 159 to 279 kA / m, and particularly preferably 183 to 239 kA / m.

The moisture content of the ferromagnetic metal powder is preferably 0.1 to 2%. It is preferable to optimize the moisture content of the ferromagnetic metal powder depending on the type of the binder. The pH of the ferromagnetic metal powder is preferably optimized depending on the combination with the binder used. The range can be 6-12, preferably 7-11. The ferromagnetic metal powder may be surface-treated with Al, Si, P, or an oxide thereof as necessary. The amount thereof can be 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. Ferromagnetic metal powder SA (stearic acid) adsorption amount (a measure of the basic points of the surface) can be a 1~15μmol / m ^2, preferably 2~10μmol / m ^2, more preferably 3 to 8 [mu] mol / m ² . When a ferromagnetic metal powder having a large amount of stearic acid adsorption is used, it is preferable to produce a magnetic recording medium by modifying the surface of the ferromagnetic metal powder with an organic substance that strongly adsorbs to the surface. The ferromagnetic metal powder may contain inorganic ions such as soluble Na, Ca, Fe, Ni, and Sr. Although it is preferable that these are essentially absent, if they are 300 ppm or less, they do not particularly affect the characteristics. Further, the ferromagnetic metal powder used in the present invention preferably has fewer vacancies, and its value is 20% by volume or less, more preferably 5% by volume or less. The shape may be needle-shaped, rice-grained, or spindle-shaped as long as the above-described characteristics regarding the particle size are satisfied. The SFD (switching-field distribution) of the ferromagnetic powder itself is preferably small, and is preferably 0.6 or less. If the SFD is 0.6 or less, the electromagnetic conversion characteristics are good, the output is high, the magnetization reversal is sharp, and the peak shift is small, which is suitable for high-density digital magnetic recording. In order to reduce the Hc distribution, which is preferable to reduce the Hc distribution of the ferromagnetic metal powder, monodispersed α-Fe ₂ O ₃ that improves the particle size distribution of goethite is used in the ferromagnetic metal powder. There are methods such as preventing sintering.

As the carbon black used for the magnetic layer, furnace for rubber, thermal for rubber, black for color, acetylene black and the like can be used. The specific surface area (SBET) of carbon black is 5 to 500 m ² / g, the DBP oil absorption is 10 to 400 ml / 100 g, the average particle size is 5 to 300 nm, the pH is 2 to 10, and the water content is 0.1 to 10% by mass. The tap density is preferably 0.1 to 1 g / ml. Specific examples of carbon black used in the present invention include Cabot's BLACKPEARLS 2000, 1300, 1000, 900, 800, 700, VULCAN XC-72, Asahi Carbon Corporation # 80, # 60, # 55, # 50, # 35, Mitsubishi Chemical Industries, Ltd. # 2400B, # 2300, # 900, # 1000 # 30, # 40, # 10B, Columbia Carbon Corporation CONDUCTEX SC, RAVEN 150, 50, 40, 15 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 with a binder in advance before being added to the coating solution for the magnetic layer. 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 mass with respect to the ferromagnetic powder.
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 are different in the type, amount, and combination of the magnetic layer and the non-magnetic layer, and based on the above-mentioned characteristics such as particle size, oil absorption, conductivity, and pH. Of course, it is possible to use properly according to the purpose. For the carbon black that can be used in the magnetic layer in the present invention, for example, “Carbon Black Handbook (Edited by Carbon Black Association)” can be referred to.

  In the present invention, the magnetic layer may contain alumina. As the alumina used, those having an average particle diameter of 50 to 250 nm, preferably 100 to 250 nm are preferable. The amount of alumina is preferably 1 to 30% by mass, more preferably 3 to 15% by mass, based on the ferromagnetic powder. If the blending amount is 1% by mass or more, running durability can be ensured, and if it is 30% by mass or less, it is preferable without causing a decrease in S / N and head wear.

[Nonmagnetic layer]
The magnetic recording medium of the present invention can also have a nonmagnetic layer containing a nonmagnetic powder and a binder between the nonmagnetic support and the magnetic layer.
The thickness of the nonmagnetic layer can be, for example, in the range of 0.05 to 5.0 μm, preferably 0.1 to 3.0 μm, and more preferably 0.1 to 2.5 μm.

  The nonmagnetic powder contained in the nonmagnetic layer can be selected from inorganic compounds such as metal oxides, metal carbonates, metal sulfates, metal nitrides, metal carbides, and metal sulfides. Examples of such inorganic compounds include α-alumina, β-alumina, γ-alumina, θ-alumina, silicon carbide, chromium oxide, cerium oxide, α-iron oxide, hematite, and goethite with an α conversion rate of 90% or more. Corundum, silicon nitride, titanium carbide, titanium oxide, silicon dioxide, tin oxide, magnesium oxide, tungsten oxide, zirconium oxide, boron nitride, zinc oxide, calcium carbonate, calcium sulfate, barium sulfate, molybdenum disulfide, etc. Or they can be used in combination. Particularly preferred are titanium dioxide, zinc oxide, iron oxide and barium sulfate because of their small particle size distribution and many means for imparting functions, and more preferred are titanium dioxide and alpha iron oxide. The particle size of these non-magnetic powders is preferably 0.005 to 0.5 μm. However, if necessary, non-magnetic powders having different particle sizes can be combined, or even a single non-magnetic powder can have a wide particle size distribution. Can have the same effect. The particle size of the nonmagnetic powder is particularly preferably 0.01 μm to 0.2 μm. In particular, when the nonmagnetic powder is a granular metal oxide, the average particle diameter is preferably 0.08 μm or less, and when the nonmagnetic powder is an acicular metal oxide, the major axis length is 0.2 μm or less, preferably 0. It is suitable that it is 15 μm or less, more preferably 0.1 μm or less. The acicular ratio of the non-magnetic powder can be 2-20, preferably 3-10. The tap density can be 0.05-2 g / ml, preferably 0.2-1.5 g / ml. The water content of the nonmagnetic powder can be 0.1 to 5% by mass, preferably 0.2 to 3% by mass, and more preferably 0.3 to 1.5% by mass. The pH of the non-magnetic powder can be 2-11, but it is particularly preferred that the pH is between 5.5-10.

The specific surface area of the non-magnetic powder can be 1 to 100 m ² / g, preferably 5 to 80 m ² / g, more preferably 10 to 70 m ² / g. The crystallite size of the nonmagnetic powder is preferably 0.004 μm to 1 μm, and more preferably 0.04 μm to 0.1 μm. The oil absorption using DBP (dibutyl phthalate) can be 5 to 100 ml / 100 g, preferably 10 to 80 ml / 100 g, and more preferably 20 to 60 ml / 100 g. The specific gravity can be 1-12, preferably 3-6. The shape may be any of a needle shape, a spherical shape, a polyhedron shape, and a plate shape. The Mohs hardness is preferably 4 or more and 10 or less. The nonmagnetic powder has an SA (stearic acid) adsorption amount of 1 to 20 μmol / m ² , preferably ² to 15 μmol / m ² , and more preferably 3 to 8 μmol / m ² . The pH is preferably between 3-6.

The surface of these nonmagnetic powders is preferably surface-treated and Al ₂ O ₃ , SiO ₂ , TiO ₂ , ZrO ₂ , SnO ₂ , Sb ₂ O ₃ , ZnO, and Y ₂ O ₃ are present. Particularly preferred for dispersibility are Al ₂ O ₃ , SiO ₂ , TiO ₂ and ZrO ₂ , and 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 first treating with alumina and then treating the surface layer with silica, or vice versa. 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 non-magnetic powders used in the non-magnetic layer include Showa Denko Nano Tight, Sumitomo Chemical HIT-100, ZA-G1, Toda Kogyo α-Hematite DPN-250, DPN-250BX, DPN-245. , DPN-270BX, DPN-500BX, DBN-SA1, DBN-SA3, Ishihara Sangyo Titanium oxide TTO-51B, TTO-55A, TTO-55B, TTO-55C, TTO-55S, TTO-55D, SN-100, α-Hematite E270, E271, E300, E303, Titanium Industry Titanium Oxide STT-4D, STT-30D, STT-30, STT-65C, α-Hematite α-40, Teica MT-100S, MT-100T, MT-150W , MT-500B, MT-600B, MT-100F, MT-500HD, Chemical FINEX-25, BF-1, BF-10, BF-20, ST-M, Dowa Mining DEFIC-Y, DEFIC-R, Nippon Aerosil AS2BM, TiO2P25, Ube Industries 100A, 500A, and What was baked is mentioned. Particularly preferred nonmagnetic powders are titanium dioxide and α-iron oxide.

  By mixing carbon black with the nonmagnetic layer, the surface electrical resistance Rs, which is a known effect, can be reduced, the light transmittance can be reduced, and a desired micro Vickers hardness can be obtained. As carbon black, furnace for rubber, thermal for rubber, black for color, acetylene black and the like can be used.

The specific surface area of carbon black employed in the nonmagnetic layer (S _BET) is, 100~500m ² / g, preferably 150~400m ² / g, DBP oil absorption 20 to 400 ml / 100 g, preferably 30 to 400 ml / It can be 100 g. The average particle size of the carbon black can be 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 used for the nonmagnetic layer include BLACKPEARLS 2000, 1300, 1000, 900, 800, 880, 700, VULCAN XC-72, manufactured by Cabot Corporation, # 3050B, # 3150B manufactured by Mitsubishi Kasei Corporation. # 3250B, # 3750B, # 3950B, # 950, # 650B, # 970B, # 850B, MA-600, MA-230, # 4000, # 4010, CONDUCTEX SC manufactured by Columbia Carbon Co., RAVEN 8800, 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 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 with a binder in advance before being added to the nonmagnetic layer coating solution. These carbon blacks can be used in a range not exceeding 50% by mass relative to the nonmagnetic powder and in a range not exceeding 40% of the total mass of the nonmagnetic layer. These carbon blacks can be used alone or in combination. For the carbon black used in the nonmagnetic layer, for example, “Carbon Black Handbook (Edited by Carbon Black Association)” can be referred to.

  In addition, an organic powder can be added to the nonmagnetic layer according to the purpose. Examples of the 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 powder, Polyfluorinated ethylene resins can also be used. Examples of the production method include methods described in JP-A Nos. 62-18564 and 60-255827.

  As for the binder resin, lubricant, dispersant, additive, solvent, dispersion method and the like related to the nonmagnetic layer, those of the magnetic layer can be applied. In particular, with respect to the binder resin amount, type, additive, and dispersant addition amount and type, known techniques relating to the magnetic layer can be applied.

  In the present invention, the binder, lubricant, dispersant, additive, solvent, dispersion method, etc. used in the magnetic layer, nonmagnetic layer, and backcoat layer are the same for the magnetic layer, nonmagnetic layer, and back layer. Applicable to each. In particular, known techniques relating to the magnetic layer can be applied to the amount of binder, type, additive, and amount of dispersant added, and type. However, in the present invention, as described above, it is particularly preferable to highly disperse the backcoat layer coating solution.

Examples of the binder used in the present invention include conventionally known thermoplastic resins, thermosetting resins, reactive resins, and mixtures thereof.
The thermoplastic resin has a glass transition temperature of −100 to 150 ° C., a number average molecular weight of 1,000 to 200,000, preferably 10,000 to 100,000, and a polymerization degree of about 50 to 1000. Can be used.

Examples include vinyl chloride, vinyl acetate, vinyl alcohol, maleic acid, acrylic acid, acrylic ester, vinylidene chloride, acrylonitrile, methacrylic acid, methacrylic ester, styrene, butadiene, ethylene, vinyl butyral, vinyl acetal, Examples thereof include polymers or copolymers containing vinyl ether as a constituent unit, polyurethane resins, and various rubber resins. Thermosetting resins or reactive resins include phenolic resins, epoxy resins, polyurethane curable resins, urea resins, melamine resins, alkyd resins, acrylic reactive resins, formaldehyde resins, silicone resins, epoxy-polyamide resins, polyesters. Examples thereof include a mixture of resin and isocyanate prepolymer, a mixture of polyester polyol and polyisocyanate, a mixture of polyurethane and polyisocyanate, and the like. These resins are described in detail in “Plastic Handbook” issued by Asakura Shoten. It is also possible to use a known electron beam curable resin for each layer. These examples and their production methods are described in detail in JP-A No. 62-256219.
The above resins can be used alone or in combination, but are preferably selected from vinyl chloride resin, vinyl chloride vinyl acetate copolymer, vinyl chloride vinyl acetate vinyl alcohol copolymer, vinyl chloride vinyl acetate vinyl maleic anhydride copolymer. A combination of at least one selected from the above and a polyurethane resin, or a combination of these with a polyisocyanate.

As the structure of the polyurethane resin, known structures such as polyester polyurethane, polyether polyurethane, polyether polyester polyurethane, polycarbonate polyurethane, polyester polycarbonate polyurethane, and polycaprolactone polyurethane can be used. For all binding agents indicated herein, if necessary in order to obtain more excellent dispersibility and _{durability, -COOM, -SO 3 M, -OSO} 3 M, -P = O (OM) 2, - O—P═O (OM) ₂ (wherein M is a hydrogen atom or an alkali metal base), —OH, —NR ₂ , —N ⁺ R ₃ (R is a hydrocarbon group), epoxy group, —SH, —CN It is preferable to use those obtained by introducing at least one polar group selected from the above by copolymerization or addition reaction. The amount of such a polar group can be 10 ⁻¹ to 10 ⁻⁸ mol / g, preferably 10 ⁻² to 10 ⁻⁶ mol / g.

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

In the present invention, the binder used in the nonmagnetic layer and the magnetic layer can be used in the range of 5 to 50% by mass, preferably in the range of 10 to 30% by mass, with respect to the nonmagnetic powder or magnetic powder. When using a vinyl chloride resin, it is preferable to use 5 to 30% by mass, when using a polyurethane resin, 2 to 20% by mass, and when using a polyisocyanate, it is preferable to use a combination of these in the range of 2 to 20% by mass. For example, when head corrosion occurs due to a small amount of dechlorination, it is possible to use only polyurethane or only polyurethane and isocyanate. In the present invention, when polyurethane is used, the glass transition temperature is −50 to 150 ° C., preferably 0 to 100 ° C., the breaking elongation is 100 to 2000%, and the breaking stress is 0.05 to 10 kg / mm ² (≈0. 49 to 98 MPa) and a yield point of 0.05 to 10 kg / mm ² (≈0.49 to 98 MPa) are preferably used.

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

  Examples of the polyisocyanate used in the present invention include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, naphthylene-1,5-diisocyanate, o-toluidine diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate. Isocyanates such as isocyanate, products of these isocyanates and polyalcohols, polyisocyanates formed by condensation of isocyanates, and the like can be used. Commercially available product names of these isocyanates include Coronate L, Coronate HL, Coronate 2030, Coronate 2031, Millionate MR, Millionate MTL, Takeda Pharmaceutical Taketake D-102, Takenate D-110N, Takenate D-200, Takenate D-202, Sumitomo Bayer's Death Module L, Death Module IL, Death Module N, Death Module HL, etc. can be mentioned, and these can be used alone or by utilizing the difference in curing reactivity. Alternatively, each layer can be used in combination.

As an abrasive used in the present invention, α-alumina, β-alumina, silicon carbide, chromium oxide, cerium oxide, α-iron oxide, corundum, artificial diamond, silicon nitride, silicon carbide having an α conversion ratio of 90% or more, Known materials having a Mohs hardness of 6 or more, such as titanium carbide, titanium oxide, silicon dioxide, and boron nitride, can be used alone or in combination. Further, a composite of these abrasives (a product obtained by surface-treating an abrasive with another abrasive) may be used. These abrasives may contain compounds or elements other than the main component, but the effect remains unchanged as long as the main component is 90% by mass or more. It is preferable that the tap density is 0.3 to 2 g / ml, the water content is 0.1 to 5% by mass, the pH is 2 to 11, and the specific surface area (SBET) is 1 to 30 m ² / g. The shape of the abrasive used in the present invention may be any of a needle shape, a spherical shape, and a dice shape, but those having a corner in a part of the shape are preferable because of high polishing properties. Specific examples of the abrasive used in the present invention include AKP-20, AKP-30, AKP-50, HIT-50, HIT-55, HIT-60A, HIT-70, and HIT-100 manufactured by Sumitomo Chemical Co., Ltd. , Nippon Chemical Industry Co., Ltd. G5, G7, S-1, Toda Kogyo TF-100, TF-140 etc. are mentioned. The abrasive used in the present invention can of course be changed depending on the purpose by changing the type, amount and combination of the magnetic layer (upper and lower layers) and the nonmagnetic layer. These abrasives may be added to the magnetic paint after being dispersed with a binder in advance.

  In the present invention, an additive can be added to the magnetic layer or the nonmagnetic layer as necessary. As the additive, those having a lubricating effect, an antistatic effect, a dispersing effect, a plasticizing effect and the like can be used. Examples of such additives include molybdenum disulfide, tungsten disulfide graphite, boron nitride, fluorinated graphite, silicone oil, silicone having a polar group, fatty acid-modified silicone, fluorine-containing silicone, fluorine-containing alcohol, fluorine-containing ester, polyolefin Polyglycol, alkyl phosphate ester and alkali metal salt thereof, alkyl sulfate ester and alkali metal salt thereof, polyphenyl ether, fluorine-containing alkyl sulfate ester and alkali metal salt thereof, monobasic fatty acid having 10 to 24 carbon atoms (unsaturated And a metal salt (Li, Na, K, Cu, etc.) or a monovalent, divalent, trivalent, or tetravalent carbon atom having 12 to 22 carbon atoms. , Pentavalent, hexahydric alcohols (including unsaturated bonds, It may be branched), an alkoxy alcohol having 12 to 22 carbon atoms, a monobasic fatty acid having 10 to 24 carbon atoms (which may contain an unsaturated bond or may be branched) and 2 to 2 carbon atoms. A mono-fatty acid ester or diester comprising any one of 12 monovalent, divalent, trivalent, tetravalent, pentavalent, and hexavalent alcohols (which may contain unsaturated bonds or may be branched). Fatty acid esters or trifatty acid esters, fatty acid esters of monoalkyl ethers of alkylene oxide polymers, fatty acid amides having 8 to 22 carbon atoms, aliphatic amines having 8 to 22 carbon atoms, and the like can be used.

  Specific examples thereof include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, butyl stearate, oleic acid, linoleic acid, linolenic acid, elaidic acid, octyl stearate, amyl stearate, isooctyl stearate, Examples include octyl myristate, butoxyethyl stearate, anhydrosorbitan monostearate, anhydrosorbitan distearate, anhydrosorbitan tristearate, oleyl alcohol, and lauryl alcohol. Also, nonionic surfactants such as alkylene oxide, glycerin, glycidol, and alkylphenol ethylene oxide adducts, cyclic amines, ester amides, quaternary ammonium salts, hydantoin derivatives, heterocyclics, phosphonium or sulfonium cations Surfactants, carboxylic acids, sulfonic acids, phosphoric acids, sulfuric acid ester groups, anionic surfactants containing acidic groups such as phosphoric acid ester groups, amino acids, aminosulfonic acids, amino alcohol sulfuric acid or phosphoric acid esters, alkylbeds An amphoteric surfactant such as in-type can also be used. These surfactants are described in detail in “Surfactant Handbook” (published by Sangyo Tosho Co., Ltd.). These lubricants, antistatic agents, and the like are not necessarily 100% pure, and may contain impurities such as isomers, unreacted materials, side reaction products, decomposed products, and oxides in addition to the main components. The amount of these impurities is preferably 30% or less, more preferably 10% or less.

  These lubricants and surfactants used in the present invention can be selectively used depending on the type and amount of the magnetic layer and the non-magnetic layer. For example, use of fatty acids with different melting points for the nonmagnetic layer and the magnetic layer to control bleeding to the surface, use esters with different boiling points and polarities to control bleeding to the surface, and adjust the amount of surfactant. Thus, it is conceivable to improve the stability of coating, and to increase the lubricating effect by increasing the amount of lubricant added to the non-magnetic layer, and of course not limited to the examples shown here. Further, all or a part of the additives used in the present invention may be added in any step of producing the magnetic layer coating solution. For example, when mixing with a ferromagnetic powder before the kneading step, adding at a kneading step with a ferromagnetic powder, a binder and a solvent, adding at a dispersing step, adding after dispersing, adding just before coating, etc. There is. Moreover, after applying a magnetic layer according to the purpose, the object may be achieved by applying a part or all of the additive by simultaneous or sequential application. Depending on the purpose, a lubricant can be applied to the surface of the magnetic layer after calendering or after completion of the slit.

  Examples of lubricants used in the present invention include NAA-102, NAA-415, NAA-312, NAA-160, NAA-180, NAA-174, NAA-175, NAA-222, manufactured by NOF Corporation. NAA-34, NAA-35, NAA-171, NAA-122, NAA-142, NAA-160, NAA-173K, castor hardened fatty acid, NAA-42, NAA-44, cation SA, cation MA, cation AB, cation BB, Nymeen L-201, Nymeen L-202, Nymeen S-202, Nonion E-208, Nonion P-208, Nonion S-207, Nonion K-204, Nonion NS-202, Nonion NS-210, Nonion HS- 206, Nonion L-2, Nonion S-2, Nonion S-4, Nonion O- Nonionic LP-20R, Nonionic PP-40R, Nonionic SP-60R, Nonionic OP-80R, Nonionic OP-85R, Nonionic LT-221, Nonionic ST-221, Nonionic OT-221, Monogly MB, Nonionic DS-60, Anone BF, anone LG, butyl stearate, butyl laurate, erucic acid, oleic acid manufactured by Kanto Chemical Co., Inc., FAL-205, FAL-123 manufactured by Takemoto Yushi Co., Ltd. TA-3, KF-96, KF-96L, KF96H, KF410, KF420, KF965, KF54, KF50, KF56, KF907, KF851, X-22-819, X-22-822, KF905, KF700, manufactured by Shin-Etsu Chemical Co., Ltd. KF393, KF-857 KF-860, KF-865, X-22-980, KF-101, KF-102, KF-103, X-22-3710, X-22-3715, KF-910, KF-3935, manufactured by Lion Armor Armide P, Armide C, Armoslip CP, Lion Oil & Fats Duomin TDO, Nisshin Oil & Chemicals BA-41G, Sanyo Chemical Profan 2012E, New Pole PE61, Ionette MS-400, Ionette MO-200, Ionette DL -200, Ionette DS-300, Ionet DS-1000, Ionet DO-200, and the like.

[Layer structure]
In the magnetic recording medium of the present invention, the thickness of the nonmagnetic support can be 2 to 100 μm, preferably 2 to 80 μm. When the magnetic recording medium of the present invention is a computer tape, the nonmagnetic support is 3.0 to 10 μm (preferably 3.0 to 9.0 μm, more preferably 3.0 to 8.0 μm). A range of thicknesses can be used. An undercoat layer may be provided between the nonmagnetic flexible support and the nonmagnetic layer or magnetic layer to improve adhesion. The undercoat layer thickness can be 0.01 to 0.5 μm, preferably 0.02 to 0.5 μm.

[Non-magnetic support]
Nonmagnetic supports used in the present invention include known polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins, cellulose triacetate, polycarbonate, polyamide, polyimide, polyamideimide, polysulfone, aramid, aromatic polyamide and the like. Can be used. These supports may be subjected in advance to corona discharge treatment, plasma treatment, easy adhesion treatment, heat treatment, dust removal treatment, and the like.

The surface roughness of the nonmagnetic support can be freely controlled by the size and amount of the filler added to the support as necessary. Examples of these fillers include oxides and carbonates such as Ca, Si, Ti, and acrylic organic fine powders. The maximum height SRmax of the support is 1 μm or less, the ten-point average roughness SRz is 0.5 μm or less, the center surface peak height is SRp of 0.5 μm or less, the center surface valley depth SRv is 0.5 μm or less, and the center surface area The rate SSr is preferably 10% or more and 90% or less, and the average wavelength Sλa is preferably 5 μm or more and 300 μm or less. For obtaining desired electromagnetic characteristics and durability, it is possible to form minute projections on these support surfaces, ranging filler usually an average particle size 0.01~0.2μm of 20000 pieces / mm ² Thus, by adding and dispersing in the resin forming the support, the fine protrusions on the support surface can be controlled. In this case, since there are usually coarse particles or aggregated particles in the particle size distribution, there may be coarse protrusions formed thereby. In the present invention, the height of the support surface is 0.273 μm. or more protrusions number 100/100 cm ² or less, more preferably 80 pieces / 100 cm ² or less, more preferably 50 pieces / 100 cm ² or less.

The centerline surface roughness of the surface on which the magnetic layer of the nonmagnetic support (nonmagnetic layer when a nonmagnetic layer is provided) can be 10 nm or less and 0.1 nm or more, preferably 6 nm or less. .2 nm or more, more preferably 4.5 nm or less and 0.5 nm or more. The Young's modulus in the longitudinal direction of the nonmagnetic support can be 5 GPa or more, preferably 6 GPa or more, more preferably 8 GPa or more, and the Young's modulus in the width direction can be 3 GPa or more, preferably 4 GPa or more. Further, the heat shrinkage rate of the support at 100 ° C. for 30 minutes can be preferably 3% or less, more preferably 1.5% or less, and the heat shrinkage rate at 80 ° C. for 30 minutes is preferably 1%. Hereinafter, it may be more preferably 0.5% or less. The breaking strength is preferably 5 to 100 kg / mm ² (≈49 to 980 MPa), and the elastic modulus is preferably 100 to 2000 kg / mm ² (≈0.98 to 19.6 GPa). The temperature expansion coefficient can be 10 ⁻⁴ to 10 ⁻⁸ / ° C., preferably 10 ⁻⁵ to 10 ⁻⁶ / ° C. The humidity expansion coefficient can be 10 ⁻⁴ / RH% or less, preferably 10 ⁻⁵ / RH% or less. These thermal characteristics, dimensional characteristics, and mechanical strength characteristics are preferably substantially equal with a difference within 10% in each in-plane direction of the support.

[Method of manufacturing magnetic recording medium]
The magnetic recording medium of the present invention can be produced by applying and drying a coating solution for forming each layer. The process for producing the coating liquid comprises at least a kneading process, a dispersing process, and a mixing process provided as necessary before and after these processes. Each process may be divided into two or more stages. All raw materials such as ferromagnetic powder, binder, carbon black, abrasive, antistatic agent, lubricant and solvent used in the present invention may be added at the beginning or during any step. In addition, individual raw materials may be added in two or more steps. For example, polyurethane may be divided and added in a kneading step, a dispersing step, and a mixing step for adjusting the viscosity after dispersion.

  As an organic solvent used in the method for producing a magnetic recording medium of the present invention, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, isophorone and tetrahydrofuran, methanol, ethanol, propanol and butanol can be used at any ratio. , Alcohols such as isobutyl alcohol, isopropyl alcohol and methylcyclohexanol, esters such as methyl acetate, butyl acetate, isobutyl acetate, isopropyl acetate, ethyl lactate and glycol acetate, glycol ethers such as glycol dimethyl ether, glycol monoethyl ether and dioxane Series, aromatic hydrocarbons such as benzene, toluene, xylene, cresol, chlorobenzene, methylene chloride, ethylene chloride, Carbon tetrachloride, chloroform, ethylene chlorohydrin, chlorobenzene, or dichlorobenzene, N, N- dimethylformamide, hexane and the like can be used. These organic solvents do not necessarily have to be 100% pure, and may contain impurities such as isomers, unreacted products, side reaction products, decomposition products, oxides and moisture in addition to the main components. The amount of these impurities is preferably 30% or less, more preferably 10% or less. The organic solvent used in the present invention is preferably the same type 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 improve coating stability. Specifically, it is important that the arithmetic average value of the upper layer solvent composition does not fall below the arithmetic average value of the lower layer solvent composition. is there. 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.

  In order to produce the magnetic recording medium of the present invention, it is of course possible to use a conventional known production technique as a part of the process, but in the kneading process, a strong kneading force such as a continuous kneader or a pressure kneader is used. By using the recording medium, a magnetic recording medium having a high residual magnetic flux density (Br) can be obtained. When a continuous kneader or a pressure kneader is used, the ferromagnetic powder and the binder are all or a part thereof (however, 30% or more of the total binder is preferable) and 15 to 500 parts by mass with respect to 100 parts by mass of the ferromagnetic powder. It is kneaded in the range. Details of these kneading treatments are described in JP-A-1-106338 and JP-A-64-79274. Further, when preparing the nonmagnetic layer coating solution, it is desirable to use a dispersion medium having a high specific gravity, and zirconia beads are preferred.

  A nonmagnetic layer coating solution containing a nonmagnetic powder and a binder and a magnetic layer coating solution containing a ferromagnetic powder and a binder are applied to a nonmagnetic support so that the magnetic layer is formed on the nonmagnetic layer. It is possible to use a method in which the coating is applied simultaneously or sequentially, and smoothing treatment and magnetic field orientation are performed while the coating layer is in a wet state.

Examples of the apparatus and method for applying a magnetic recording medium having a multilayer structure as described above include the following methods and apparatuses.
1. First, a nonmagnetic layer is applied by a gravure coating, a roll coating, a blade coating, an extrusion coating device or the like generally used for coating a magnetic layer coating solution. The magnetic layer is applied by a support pressure type extrusion coating apparatus disclosed in Japanese Patent No. 46186, Japanese Patent Laid-Open No. 60-238179, and Japanese Patent Laid-Open No. 2-265672.
2. The upper and lower layers are substantially separated by one coating head having two slits for passing coating liquid as disclosed in JP-A-63-88080, JP-A-2-17971, and JP-A-2-265672. Apply at the same time.
3. The upper and lower layers are applied almost simultaneously by an extrusion coating apparatus with a backup roll disclosed in JP-A-2-174965.

In order to prevent a decrease in electromagnetic conversion characteristics and the like of the magnetic recording medium due to aggregation of the ferromagnetic powder, a method such as disclosed in Japanese Patent Application Laid-Open Nos. 62-95174 and 1-2236968 can be used. It is desirable to apply shear to the coating solution. Furthermore, it is appropriate for the viscosity of the coating solution to satisfy the numerical range disclosed in JP-A-3-8471.
Furthermore, the smoothing treatment can be performed, for example, by applying a stainless steel plate to the surface of the coating layer on the web. Besides this, a method using a solid smoother as described in JP-B-60-57387, Or a method of scraping and measuring the coating liquid with a rod rotating in the direction opposite to the web traveling direction, a method of smoothing the surface of the coating liquid film by contacting a flexible sheet, etc. it can.
For magnetic field orientation, it is preferable to use a solenoid of 1000 G (0.1 T) or more and a cobalt magnet of 2000 G (0.2 T) or more in the same pole facing each other. When the magnetic recording medium of the present invention is a disk-like medium, it is preferable to use an orientation method that randomizes the orientation.

As the calendering roll, a heat-resistant plastic roll such as epoxy, polyimide, polyamide, polyimide amide or the like can be used. Moreover, it can also process with metal rolls. The treatment temperature is preferably 30 ° C. or higher, more preferably 35 ° C. or higher and 100 ° C. or lower. The linear pressure is preferably 200 kg / cm, more preferably 300 kg / cm or more. The friction coefficient with respect to SUS420J on the magnetic layer surface and the opposite surface of the magnetic recording medium of the present invention is preferably 0.5 or less, more preferably 0.3 or less, the surface resistivity is preferably 10 ⁴ to 10 ¹² ohm / sq, and the magnetic layer The elastic modulus at 0.5% elongation is preferably 100 to 2000 kg / mm ² (≈0.98 to 19.6 GPa) in both the running direction and the width direction, and the breaking strength is preferably 1 to 30 kg / cm ² (≈0). 0.098-2.94 MPa), the elastic modulus of the magnetic recording medium is preferably 100-1500 kg / mm ² (≈49-735 MPa) in both the running direction and the longitudinal direction, and the residual elongation is preferably 0.5% or less, 100 The thermal shrinkage at any temperature below 0 ° C. 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 in dynamic viscoelasticity measurement measured at 110 Hz) is preferably 50 ° C. or higher and 120 ° C. or lower, and that of the nonmagnetic layer is 0 ° C. to 100 ° C. Is preferred. The loss elastic modulus is preferably in the range of 1 × 10 ⁸ to 8 × 10 ⁹ dyne / cm ² (1 × 10 ⁷ to 8 × 10 ⁸ Pa), and the loss tangent is preferably 0.2 or less. If the loss tangent is too large, adhesion failure is likely to occur.

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 magnetic layer is preferably 30% by volume or less, and more preferably 20% by volume or less for both the nonmagnetic layer and the magnetic layer. In order to achieve high output, it is preferable that the porosity is small, but it may be better to ensure a certain value depending on the purpose. For example, in a data recording magnetic recording medium in which repetitive use is important, a larger porosity is often preferable for running durability. When the magnetic characteristics of the magnetic recording medium of the present invention are measured at a magnetic field of 398 kA / m (5 KOe), the squareness ratio in the tape running direction can be 0.70 or more, preferably 0.80 or more, more preferably 0.8. 90 or more.
The squareness ratio in the two directions perpendicular to the tape running direction is preferably 80% or less of the squareness ratio in the running direction. As described above, the SFD (Switching Field Distribution) of the magnetic layer is preferably 0.6 or less.

  The magnetic recording medium of the present invention can have a nonmagnetic layer and a magnetic layer, and it is easily estimated that these physical characteristics can be changed between the nonmagnetic layer and the magnetic layer according to the purpose. That is. For example, the elastic modulus of the magnetic layer is increased to improve running durability, 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. There can be two or more magnetic layers, and it is possible to refer to a known technique related to the magnetic layer multilayer to determine what physical characteristics are brought about by each of the two or more magnetic layers. For example, making Hc of the upper magnetic layer higher than Hc of the lower magnetic layer is described in many documents including Japanese Patent Publication No. 37-2218, Japanese Patent Application Laid-Open No. 58-56228, and the like. Further, by making the magnetic layer thin, recording can be performed even with a magnetic layer having a higher Hc.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the examples, the display of “parts” represents “parts by mass”.
[Experimental Example 1]
Nonmagnetic layer coating solution α-Fe ₂ O ₃ (nonmagnetic powder hematite) 80 parts
Average long axis length: 0.15 μm
Specific surface area by BET method: 52 m ² / g
pH: 8
Tap density: 0.8g / ml
DBP oil absorption: 7 to 38 g / 100 g
Surface treatment agent: Al ₂ O ₃ , SiO ₂
20 parts of carbon black
Average primary particle size: 16 nm
DBP oil absorption: 76ml / 100g
pH: 8
Specific surface area by BET method: 250 m ² / g
Volatile content: 1.5%
12 parts of vinyl chloride copolymer MR-104 manufactured by Nippon Zeon
Polyester polyurethane resin 5 parts
Neopentyl glycol / Caprolactone polyol / MDI
= 0.9 / 2.6 / 1, -SO 3 Na group: 1 × 10 ^-4 eq / g
α-Al ₂ O ₃ (average particle size 0.2 μm) 1 part butyl stearate 1 part stearic acid 1 part methyl ethyl ketone 100 parts cyclohexanone 50 parts toluene 50 parts

Magnetic layer coating solution 100 parts of ferromagnetic metal powder
Composition Fe / Co = 100/30
Hc: 183 kA / m (2300 Oe)
Specific surface area by BET method: 68 m ² / g
Crystallite size: 125Å
Surface treatment agent: Al ₂ O ₃ , Y ₂ O ₃
Particle size (major axis length): 60nm
σs: 125 A · m ² / kg
Polyester polyurethane resin 12 parts Neopentyl glycol / Caprolactone polyol / MDI
= 0.9 / 2.6 / 1, -SO 3 Na group: 1 × 10 ^-4 eq / g
α-Al ₂ O ₃ (average particle size 0.15 μm) 5 parts Carbon black (average particle size 0.08 μm) 0.5 part Butyl stearate 1 part Stearic acid 5 parts Methyl ethyl ketone 90 parts Cyclohexanone 30 parts Toluene 60 parts

  About each of said coating liquid, after kneading | mixing each component with an open kneader, it was disperse | distributed using the sand mill. Then, 5 parts of polyisocyanate (Coronate L manufactured by Nippon Polyurethane Co., Ltd.) is added to the non-magnetic layer coating solution and 5 parts to the magnetic layer coating solution, and each is further mixed with methyl ethyl ketone and cyclohexanone mixed solvent (mixing ratio). 40 parts of 5: 5) was added and filtered using a filter having an average pore diameter of 1 μm to prepare a nonmagnetic layer coating solution and a magnetic layer coating solution, respectively.

Back coat layer Fine particle carbon black powder (average particle diameter: 38 nm) 100 parts Coarse particle carbon black powder (average particle diameter 80 nm) 5 parts Dispersant (see Table 1) 3 parts Nitrocellulose resin 67 parts Polyurethane resin 47 parts Poly Isocyanate 25 parts Methyl ethyl ketone 1330 parts Cyclohexanone 420 parts

After kneading fine particle carbon black powder, coarse carbon black powder, dispersant, and prescribed amount of 50% polyurethane resin with 300 parts of methyl ethyl ketone and 200 parts of cyclohexanone, using a sand mill (dispersion medium: zirconia φ0.5 μm) Primary dispersion for 6 hours.
Subsequently, a 50% polyurethane resin in a prescribed amount and 130 parts of methyl ethyl ketone were added, followed by secondary dispersion for 6 hours using a sand mill (dispersion medium: zirconia φ0.5 μm).
Nitrocellulose resin and 200 parts of methyl ethyl ketone were further added to the obtained secondary dispersion, followed by tertiary dispersion for 3 hours using a sand mill (dispersion medium: zirconia φ0.5 μm).
After adding polyisocyanate, 700 parts of methyl ethyl ketone, and 220 parts of cyclohexanone to the resulting tertiary dispersion, quaternary dispersion was performed for 1 hour using a sand mill (dispersion medium: zirconia φ0.5 μm). The obtained dispersion was filtered using a filter having an average pore diameter of 1 μm to prepare a backcoat layer coating solution.

The non-magnetic layer coating solution is 6 μm thick so that the thickness after drying is 1 μm and immediately after that the magnetic layer thickness is 0.12 μm. Simultaneous layering on a polyethylene naphthalate support having a linear surface roughness of 0.002 μm, a Young's modulus in the longitudinal direction of 6.86 GPa (700 kg / mm ² ), and a Young's modulus in the width direction of 4.9 GPa (500 kg / mm ² ) While the two layers were still wet, they were oriented and dried by a cobalt magnet having a magnetic force of 3000 G (0.3 T) and a solenoid having a magnetic force of 1500 G (0.15 T). Thereafter, a seven-stage calendar composed of a metal roll and an epoxy resin roll at a temperature of 40 ° C. and a speed of 200 m / min. The process was performed. Thereafter, a backcoat layer having a thickness of 0.5 μm was applied. Next, the roll was slit to a width of 1/2 inch, and the tape after slitting was wound around a DLT type system compatible cartridge (Compact Tape IV) by 557 m to produce a DLT4000 computer data recording magnetic tape.

[Example 2]
It was produced in the same manner as in Experimental Example 1 except that the average particle size of coarse particulate carbon black used for the backcoat layer was changed to 90 nm.

[Comparative Example 1]
No dispersant was used in the backcoat layer. The backcoat layer coating solution was prepared as follows.
Fine particle carbon black powder, coarse particle carbon black powder, prescription amount of polyurethane resin and nitrocellulose resin, 630 parts of methyl ethyl ketone, 200 parts of cyclohexanone and stirred with a disper, then 6 using a sand mill (dispersion media: glass beads φ2 μm) Dispersed primarily by time. After adding 700 parts of polyisocyanate, methyl ethyl ketone and 220 parts of cyclohexanone to the obtained dispersion, the mixture was stirred for 30 minutes using a disperser (dispersion medium: zirconia φ0.5 μm). A backcoat layer coating solution was prepared by filtering using a filter having an average pore diameter of 1 μm.

[Comparative Example 2]
It was prepared in the same manner as in Example 1 except that the dispersant was changed to the basic polymer dispersant Azisper PB711 (Ajinomoto Fine Techno Co., Ltd.).

[Comparative Example 3]
Comparative Example 1 except that the dispersant shown in Table 1 was used, and the average particle size of the fine particle carbon black powder used in the backcoat layer was changed to 17 nm, and the average particle size of the coarse particle carbon black powder was changed to 270 nm. Created in the same way.

  The structural formulas of the dispersants used in Examples 1 and 2 and Comparative Example 3 are shown below.

Evaluation Method (1) Number of Back Layer Protrusions and Number of Magnetic Layer Recesses The number of protrusions having a height of 50 nm or more from the root mean square surface of the backcoat layer was 265 μm using a surface roughness meter (NewView 5000) manufactured by ZYGO. The range of 350 μm was measured, and the number of regions having a height of 50 nm or more from the root mean square surface was calculated by image analysis software. The number of dents in the magnetic layer was also measured by the same method.
(2) SNR
Using an LTO drive, SNRsk was measured according to ECMA standards. As the reproducing head, an MR element having a width of 3 μm was used. The measured value of Comparative Example 1 was set to 0 dB.
(3) Winding form The tape was wound up on a cartridge tape of LTO1 by 600 m, and the full length was recorded with the same drive (manufactured by IBM) at a conveyance speed of 5 m / sec, and the wound surface of the wound tape was observed. The protruding part of the tape winding surface was counted. The case where the number of jumping out points was 3 or less was determined as “good”, and the case where the number of popping out points exceeded 3 was determined as “bad”.
The measurement results are shown in Table 1.

Examples 1 and 2 in which the backcoat layer contains the compound represented by the general formula (I) and the number of protrusions having a height of 50 nm or more on the surface of the backcoat layer is 250/265 × 350 μm ² or less are magnetic layers The number of recesses having a surface depth of 20 nm or more was 50/265 × 350 μm ² or less, the SNR was high, and the winding shape after running was also good.
In Comparative Example 1 in which the backcoat layer does not contain a dispersant and the dispersion method is different from those in Examples 1 and 2, the number of protrusions having a height of 50 nm or more on the surface of the backcoat layer exceeds 250/265 × 350 μm ² . It was. In Comparative Example 1, the number of recesses having a depth of 20 nm or more on the surface of the magnetic layer exceeded 50/265 × 350 μm ² , and the SNR was lower than those in Examples 1 and 2.
In Comparative Example 2 using a dispersant other than the compound represented by the general formula (I), the number of protrusions having a height of 50 nm or more on the surface of the backcoat layer exceeded 250/265 × 350 μm ² . In Comparative Example 2, the number of recesses with a depth of 20 nm or more on the surface of the magnetic layer exceeds 50/265 × 350 μm ² , the SNR is lower than those in Examples 1 and 2, and the tape winding surface after running has a lot of protrusion. The running performance was inferior.
In Comparative Example 3 produced by the same dispersion method as in Comparative Example 1 except that the carbon black used in the backcoat layer was changed, the number of protrusions having a height of 50 nm or more on the surface of the backcoat layer was 250 pieces / 265 × 350 μm. ² exceeded. In Comparative Example 3, the SNR was very low, and the tape winding surface after running was often popped out, resulting in poor running performance.

  The magnetic recording medium of the present invention can be suitably used as a magnetic recording medium for high density digital recording.

Claims (4)

A magnetic recording medium having a magnetic layer containing a ferromagnetic powder and a binder on one side of a nonmagnetic support and a backcoat layer containing carbon black on the other side,
The back coat layer contains a compound represented by the following general formula (I):
The number of protrusions having a height of 50 nm or more on the surface of the backcoat layer is 250/265 × 350 μm ² or less.

(In general formula (I), Q: anthraquinone dye, phthalocyanine dye, quinacridone dye, dioxazine dye, anthrapyrimidine dye, asanthrone dye, indanthrone dye, flavanthrone dye, pyranthrone dye, perinone Organic dye residue selected from the group consisting of dyes, perylene dyes, thioindigo dyes, isoindolinone dyes, and triphenylmethane dyes, W; direct bond, — (CH ₂ ) _n —, —NH— , -CONH-, or CH ₂ NH, n; 1~4 integer, m; 1 to 10 integer, X; group selected from divalent linking group represented by a single bond, or the following structural formula,

Y represents a group represented by the following general formula (II). )

(In the general formula (II), Z represents a lower alkylene group, —NR ₂ ; a lower alkylamino group, or a 5- or 6-membered saturated heterocyclic ring containing a nitrogen atom, and a represents 1 or 2.) ^2. The magnetic recording medium according to claim 1, wherein the number of recesses having a depth of 20 nm or more on the surface of the magnetic layer is 50/265 × 350 μm ² or less. The magnetic recording medium according to claim 1, wherein a thickness of the magnetic layer is in a range of 0.01 to 0.2 μm. The magnetic recording according to any one of claims 1 to 3, wherein the ferromagnetic powder is a ferromagnetic hexagonal ferrite powder having an average plate diameter of 10 to 40 nm or a ferromagnetic metal powder having an average major axis length of 20 to 70 nm. Medium.