JPH02139711A - Magnetic storage body and its manufacture and magnetic storage device - Google Patents

Abstract

PURPOSE:To improve corrosion resistance of a metal medium in an environment with water or chlorine and to reduce the coefft. of friction between the storage body and a head by depositing an organic compd. layer containing substituents or derivatives of phthalocyanine or fluorinated polyether polymers on a substrate coated with a magnetic thin film. CONSTITUTION:The substrate is coated with a magnetic thin film, on which an org. compd. layer containing phthalocyanine, substituents or derivatives of phthalocyanine, or fluorinated polyether polymer is deposited. A thin film comprising carbide, nitride, oxide or carbon is provided between the magnetic thin film and the organic compound layer. Recently, magnetic heads have been made hardened more and more and the medium of this invention can endure against larger shock caused by this kind of head. By this method, crushing of a head can be avoided and such a storage body having excellent long-term mechanical reliability and storage reliability can be manufactured.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to magnetic storage devices (magnetic disk devices, magnetic drum devices, and magnetic tape devices), magnetic storage bodies (hereinafter referred to as storage bodies) used in the magnetic storage devices, and methods for manufacturing the same. Regarding. [Prior Art] A memory body having an En-containing thin film has sufficient mechanical reliability to withstand contact with a recording/reproducing head (hereinafter referred to as a head) and is resistant to harsh environments such as moisture and chlorine. Sufficient corrosion resistance is required. Conventionally, Afi alloy substrates, glass plates, ceramic plates, etc. have been used as substrates, which have been subjected to alumite treatment or non-magnetic plating treatment such as N1-P plating, and then polished to make them mirror-finished or have a surface density. After non-magnetic plating such as P, N1-Cu-P, coating with Cr, Bi, etc., a magnetic thin film is coated, and further SiO2 (including polysilicic acid), Al1
After coating with a protective film such as a solid solution of N, C, Si sN4 and 1.0 g of Al, with or without an intermediate layer using a coupling agent, it is coated with a liquid lubricant such as perfluoropolyether, a higher alcohol, or a fatty acid. A thin layer of a representative solid lubricant is applied. Although the above-mentioned memory bodies have a certain level of durability and have already begun to appear on the market, they have major drawbacks. Magnetic storage device equipped with the above storage body at 40℃80%Rf
If left in an environment of H., galling points will occur in one or two places on one memory body, leading to a defect error. Furthermore, repeated contact between the storage body and the head increased the coefficient of friction between them, often causing the spindle motor to stop. [Problem to be solved by the invention 1 With conventional technology, the corrosion resistance of magnetic thin films cannot be sufficiently ensured. Furthermore, there was a problem in that it was not possible to maintain sufficient mechanical reliability between the storage body and the head. The present invention solves the above problems, and its purpose is to dramatically improve the corrosion resistance of metal media in environments containing moisture and chlorine, and to improve the coefficient of friction between the storage body and the head. It is an object of the present invention to manufacture and provide a highly reliable memory body that can significantly reduce the amount of water and maintain its effects over a long period of time, and to provide a magnetic memory device using the memory body. [Means for Solving the Problems 1] The present invention provides a method in which a magnetic thin film is coated on a substrate, and at least phthalocyanine, a substituted product or derivative thereof based on a phthalocyanine skeleton, and/or a fluorinated polyether polymer is coated on the magnetic thin film. It is characterized by being coated with an organic compound layer containing. A thin film made of at least one substance selected from carbide, nitride, oxide, or carbon is formed between the magnetic thin film and the organic compound layer on the master mold. or,
Furthermore, a thin film of a coupling agent having different functional groups in the molecule is formed between the thin film made of at least one substance selected from carbide, nitride, oxide, or carbon and the organic compound layer. shall be. The magnetic thin film can be coated using materials and methods similar to those of the prior art. Co, Fe, Ni, Cr, Ta, P
, a coating is formed using a dry film forming method such as a wet plating method or a sputtering method using a metal made of a noble metal element or the like. Carbides, nitrides, and oxides include A2, B, Y, Si, and Ti.
It is a compound of elements selected from , Zr, Hf, Nb, Ta, Cr, Mo, and W, and the mixing and lamination thereof are arbitrary. Carbon is graphite, diamond, amorphous (
(including i-carbon) alone, in a mixture, or in a laminated manner, and a film thickness of 100 to 400 layers is appropriate for each. The above-mentioned compounds and carbon can be coated by a PVD method or CVD method such as a sputtering method or an ion blasting method, and the oxide can also be coated by a thermal decomposition method of an organometallic compound. Coupling agents having different functional groups in the molecule are, for example, organometallic compounds having a hydrolyzable group on one side of the molecule and at least one kind of functional group such as an amino group or an imino group on the other side. It is expressed by the formula. R', -M-(OR)n- Here, R' is an organic group having at least one functional group such as an amine group or an imino group, and R is an alkyl group having 1 to 5 carbon atoms. Also, M is Sl, Ti, Zr, Nb, H
These are metal elements such as f and Ta, and m is the valence of each metal element. Further, i is an integer from 1 to (m-1). Representative organometallic compounds are shown below. NH2-(CH2)2-NH-(CH2) 3S i
(OCHa) 5 NHz (CHz)z NH(CH2) 3-
H3 Si-(OCH3)2NH2-(CH2)2NH(CHz)2-NH(
CH2) 2 S i (OCHa) 3 Each of these is diluted with an alcohol medium, and a polycondensation film is formed by coating and baking by a known method such as a spray method, a spinner method, a dipping method, or a pyrosol method. The concentration is determined by the desired film thickness, and a monomolecular film thickness is sufficient, and a film thickness of around 200 molecules or less is no problem. Also, the firing temperature is 60℃~200"C
, 5 to 20 minutes is sufficient. Phthalocyanine or its substituted products and derivatives based on a phthalocyanine skeleton are based on metal-free phthalocyanine or metal phthalocyanine, and the hydrogen element is substituted with halogens, polar groups such as amine groups, acid amide groups, hydroxyl groups, carboxyl groups, or epoxy groups. , compounds substituted with functional groups including vinyl groups, linear, branched, saturated, unsaturated hydrocarbon chains, and compounds in which the hydrogen of the hydrocarbon chain is substituted with the functional group, etc., and there are no particular limitations. ．． These can be applied by a dry method such as a vacuum evaporation method, or by a known wet method such as a spray method, a spinner method, a dipping method, a pyrosol method, etc. after diluting with a soluble solvent, and a film thickness of about 50 mm is appropriate. In addition to having the above-mentioned functional groups in the molecule, the fluorinated polyether polymer also has an organic group containing nitrogen with an unpaired electron and an organic group containing a cyclic group, and the main component thereof is perfluoroalkyl polyether. be. These can be diluted in a fluorinated solvent either singly or in combination, and if the above phthalocyanine or its substituted product or derivative based on a phthalocyanine skeleton can be diluted in the same solvent, it can be mixed with a fluorinated polyether polymer and then sprayed. After coating by a known method such as , spinner method, dipping method, or pyrosol method, baking is performed if necessary. Firing is 6
3 to 10 minutes at 0 to 150°C is sufficient. Also, the film thickness is 50
Around 1 person is enough. [Function] According to the present invention, a material selected from carbides, nitrides, oxides, or carbon having excellent adhesion, high hardness, and denseness is applied to various 5n thin films including metal magnetic thin films with poor corrosion resistance. The 6n thin film is coated with a thin film made of a substance that protects the 6n film from moisture that induces caries, such as chlorine. However, carbides, nitrides, and oxides all have poor lubricity, and even carbon, which has relatively excellent lubricity, has insufficient lubricity, and attempts have been made to coat the surface with a lubricant. As mentioned above, liquid lubricants typified by perfluoropolyether polymers and solid lubricants typified by higher alcohols and fatty acids are being considered as the above-mentioned lubricants. As a result, the film thickness decreased and the initial excellent lubricating ability was lost over time. Furthermore, the impact force of the head could not be absorbed completely and the head reached the magnetic thin film, resulting in a head crash. In the present invention, a magnetic thin film, a thin film made of a substance selected from carbides, nitrides, oxides, or carbon, a thin film of a coupling agent having affinity with fluorinated polyether polymer, and phthalocyanine are formed, The fluorinated polyether polymer and phthalocyanine, which have excellent lubrication ability, do not easily move on the storage medium due to impact wear of the head or rotational centrifugal force of the storage medium. In addition, both fluorinated polyether polymers and phthalocyanine are substances with excellent heat resistance, and phthalocyanine in particular has excellent impact resistance absorption, so it can withstand strong impact from increasingly hard heads, eliminating head crashes. It is now possible to As described above, it has become possible to manufacture and provide a memory body with excellent long-term mechanical reliability and storage reliability, and furthermore, by using this memory body, the long-term reliability of a magnetic memory device has been significantly improved. [Example] After applying non-magnetic N1-P alloy plating to a thickness of about 15 μm on a mirror-finished disc-shaped aluminum alloy substrate, the surface roughness was polished to Rf = 50 to 100, Rf
,,, = 500 to 1000 people were marked with streaks, and Co
-N1-P alloy plating was applied to a thickness of about 0.05 μm. Using the above substrate, a thin film of each substance was coated as shown in Table 1 using a magnetron sputtering device. The degree of vacuum achieved is 1x1
Below 0-'torr, pre-heating the substrate at 80°C for 10 minutes.
The power was 4 W/cm2. On the other hand, using the above substrate, various organic metal compounds were applied by dipping as shown in Table 2, and then baked to cover the polycondensation film. The processing liquid solvent is methanol and Freon 113.
(volume ratio 1:3) with a concentration of 1. OW/V%,
The liquid temperature was 25°C. Also, the pulling speed is locm/mi
The firing time was 150° C. for 30 minutes. Next, combine the coupling agent in Table 3 with methanol and Freon 11.
3 (volume ratio 1:3) and diluted to 0.005 W/V%, applied by a dipping method, baked, and coated with the polycondensation film. The liquid temperature is 25°C, and the pulling speed is locm/min.
The firing was performed at 110° C. for 10 minutes. The phthalocyanine and/or fluorinated polyether polymers listed in Table 3 were then coated. Since both materials were expressed by trade names or abbreviations, the details will be described later.6 Among the phthalocyanines, types that are difficult to dissolve in solvents were coated by vapor deposition. Samples were deposited from a resistive heating source after preheating at 80°C for 10 minutes in a vacuum below 1 x 10-'torr. The solvent-soluble type was mixed with a fluorinated polyether polymer, diluted with a soluble solvent, and applied by dipping. Samples coated with phthalocyanine by vapor deposition were coated by dipping using a dilute solution of fluorinated polyether polymer in Freon 113 (concentration 0.OIW/V%). In both dipping methods, the liquid temperature was 25° C. and the pulling rate was 10 cm/min. Finally, it was fired at 110°C for 10 minutes. Table 1 Pc, Metal-free phthalocyanine N 1-Pc Nickel phthalocyanine u-Pc Copper phthalocyanine N 1-PcD: 2 [Krytox is a DuPont product, 157FS/
LZM is a monofunctional group type at the molecular end (-C00H), PSL is a general formula A, and GLA and ML are a general formula B.
This is the type of Fomblin Z-D IAC is a product of Montegisson and has functional groups at both ends of the molecule. FC-A is CF, -CF, O-(C,F.-(-C,F2O), CF, 0-CF.・Sodo (Fly No Hite 0.15LLm, 9
A 171 magnetic self-memory device was manufactured using 171 m/5ec) and evaluated by the following tests. Nichijimon 10se
c) Find the change in appearance before and after, the static friction coefficient, and the rate of decrease in output by f. (2) Corrosion resistance test: leave the hinge in an environment of 80°C, 190% RfH, and measure the number of mis-singing bits after the leaving time has elapsed.
The point at which this increase was observed was cut off at half the lifespan.

【Effect of the invention】

Magnetic storage devices using thin-film storage materials have been on the market for a long time as storage devices compatible with high recording densities, but their use has been limited to a limited number of people due to concerns about long-term reliability. According to the present invention, even if the storage body is used under heating, 6f
Uniform thin films are not affected in any way in practical use, and have high mechanical reliability even with heads that are becoming increasingly hard and have low fly-hide properties, so they can be used in magnetic storage devices that can be further miniaturized and used in harsh environments. Even when installed in a computer, there is almost no noticeable deterioration in the characteristics of both the memory and the head. As described above, manufacturing of highly durable memory bodies compatible with high recording density,
By providing and using the storage body, it has become possible to provide a highly reliable magnetic storage device. Applicant: Seiko Epson Corporation

Claims (11)

[Claims] (1) A substrate coated with a magnetic thin film is coated with an organic compound layer containing at least phthalocyanine, its substituted product or derivative based on a phthalocyanine skeleton, and/or a fluorinated polyether polymer. magnetic memory. (2) The magnetic material according to claim 1, wherein a thin film made of at least one substance selected from carbide, nitride, oxide, or carbon is formed between the magnetic thin film and the organic compound layer. Memory body. (3) The magnetic memory according to claim 1 or 2, wherein the fluorinated polyether polymer is a compound represented by general formula A, B, or C. General formula A: R_f-X-Y-X-R_f B: R_f-X-Y C: Y-X-R_f-X-Y Here, R_f is CF_3-(C_2F_4O)_m
-(CF_2O)_n-, -(C_2F_4O)_m-
(CF_2O)_n-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, - ▲There are mathematical formulas, chemical formulas, tables, etc.▼, etc., and m represents an integer. Further, X represents an organic group containing nitrogen having an unpaired electron, and Y represents an organic group containing a cyclic group. The molecular weight is 1000-8000. (4) A thin film of a coupling agent having different functional groups in the molecule is formed between the organic compound layer and a thin film made of at least one substance selected from carbide, nitride, carbide, or carbon. The magnetic storage body according to claim 2 or claim 3, characterized in that: (5) A step of coating a magnetic thin film on a substrate, a step of coating the magnetic thin film with an organic compound layer containing at least phthalocyanine, its substituted product or derivative based on a phthalocyanine skeleton, and/or a fluorinated polyether polymer. A method for manufacturing a magnetic memory body, comprising: (6) The method further comprises the step of forming a thin film made of at least one substance selected from carbides, nitrides, oxides, and carbon between the magnetic thin film and the organic compound layer. A method for manufacturing a magnetic storage body. (7) Forming a thin film of a coupling agent having different functional groups in the molecule between the organic compound layer and a thin film made of at least one substance selected from carbides, nitrides, oxides, or carbon. 7. The method of manufacturing a magnetic memory body according to claim 6, further comprising: (8) A magnetic storage device characterized by using the magnetic storage body according to claim 1. (9) A magnetic storage device characterized by using the magnetic storage body according to claim 2. (10) A magnetic storage device characterized by using the magnetic storage body according to claim 3. (11) A magnetic storage device characterized by using the magnetic storage body according to claim 4.