JPH10326408A - Magnetic recording medium and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lubricating film with lubricity stable even at a high temp. by providing the surface of a protective film contg. carbon with lubricants of two components consisting of an alkyl amine-based lubricant, which is soluble in a general-purpose solvent and has an amino group or N, N-dimethyl amino group at the molecule terminal and a lubricant, which is soluble in the general- purpose solvent, and is liquid at ordinary temp. SOLUTION: The alkyl amine-based solid lubricant 7 is applied on the surface of the carbon based protective film 5 in which a carboxyl group-COOH exists and a salt is formed between the carboxyl group-COOH and the amino group-NH2 of the solid lubricant 7 to securely and chemically bond the solid lubricant 7 to the surface of the carbon based protective film 5. Further, the denatured perfluoropolyether based liquid lubricant 5 which is liquid at ordinary temp. is applied on the solid lubricant 7. As a result, the liquid lubricant 9 acts as a boundary fluid lubricating film and is capable of exhibiting the lubricating characteristics over a wide temp. range when the solid lubricant 7 loses the nature as the boundary lubricating film at its m.p. or above.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thin-film magnetic recording medium exhibiting excellent durability over a wide temperature range, and a method for manufacturing the same.

[0002]

2. Description of the Related Art Hard disks are widely used as external storage devices for computers. Recent hard disks have increased storage capacity, and giga-level hard disks have been put to practical use.

Conventional hard disks are made of glass or NiP.
/ Al was a type in which a magnetic layer was provided on a hard non-magnetic substrate such as Al. However, hard non-magnetic substrates such as glass and NiP / Al are relatively expensive, and about 40% of the disk cost has been occupied by the hard non-magnetic substrates.

Also, with the spread of portable personal computers such as notebook computers, a conventional hard disk using a hard non-magnetic base cannot be accommodated in the personal computer itself, or even if it can be accommodated, its storage capacity is too low to be practical. Some problems have been pointed out. For this reason, in view of price competition for notebook personal computers, there is a strong demand for an increase in storage capacity and cost reduction of a built-in hard disk.

[0005] In order to satisfy such demands, plastic non-magnetic substrates (eg, amorphous polyolefin, APO) have recently been used instead of conventional rigid non-magnetic substrates.
Attempts have been made to use it. The use of a non-magnetic plastic substrate not only significantly reduces the cost of the disk but also dramatically increases the storage capacity. For example, if a 3.5-inch size is used for double-sided storage, a storage capacity of about 3 to 5 gigabytes can be achieved.

In a recording medium using a plastic nonmagnetic substrate, CoCrPt, CoCrTa, CoCrP
_{tTa, CoCrNiPt, CoCrPt-SiO x} ,
Plane thin film type magnetic recording medium material mainly composed of Co, such as CoCrPt-SiC _x is excellent in high density recording characteristics, is a very important material for future hard disk media.

In recent thin-film magnetic recording media, the flying height of the head during recording and reproduction is designed to be about 50 nm in order to realize a higher recording density, and the tribological role between the medium and the magnetic head slider is extremely important. It has become.

In the in-plane thin film type magnetic recording medium, the durability is inferior because the magnetic layer responsible for magnetic recording is a metal thin film. Therefore, the design of a protective lubricating film that sufficiently improves the reliability at a head flying height of about 50 nm is an even more important issue than the research and development of magnetic materials. Further, portable notebook personal computers, which are currently used in large quantities, have a wider operating temperature and humidity environment than conventional fixed desktop personal computers.
Therefore, it is necessary to design a new protective lubricating film having stable durability in a wide temperature and humidity range for future hard disks.

The upper surface of the conventional Co-based magnetic layer has a thickness of 50
A carbon protective film was provided in the range of 800 to 800, preferably 100 to 400. The carbon protective film is formed of, for example, sputter carbon, plasma CVD carbon, diamond-like carbon, hydrogen-containing carbon, nitrogen-containing carbon, silicon-containing carbon, or the like. The carbon protective film protects the Co-based magnetic layer,
This has the effect of improving the slidability of the magnetic head. However, it is known that the carbon protective film alone is inferior in practical durability. Therefore, attempts have been made to improve the durability of the carbon protective film by applying a liquid lubricant on the upper surface of the carbon protective film.

[0010] As a liquid lubricant which has been studied to improve the durability of a thin film type magnetic recording medium having a carbon protective film, Fomblin-Z-AM2001 manufactured by Montecatini Co., Ltd. has been used.
(Both terminals: piperonyl group), -DOL (both terminals: hydroxyl group), -DEAL (both terminal functional groups: ester group), -DIAC
(Both terminals: carboxyl group) or Daikin Industries
Demnum-SA (one end: hydroxyl group), -SH (one end: carboxyl group), -SP, -SY, or Kryt manufactured by DuPont
Perfluoropolyether-based lubricants such as ox, and aliphatic hydrocarbon-based, fluorine-substituted alkyl-based, and phosphate-based lubricants are known.

The important role of the lubricant is to prevent the magnetic head slider from directly contacting the protective film by firmly adsorbing to the surface of the protective film, and to significantly reduce the tangential force of the magnetic head slider sliding on the medium. It is to reduce. In order to realize these roles, it is first necessary for the lubricant molecules to be chemically adsorbed on the surface of the carbon protective film, and the lubricant molecules themselves have a structure capable of sufficiently reducing the tangential force as a lubricant film. There is a need.

It is known that the surface of a carbon film used as a protective film slightly contains functional groups such as alcohol, carbonyl group, ether, ester and carboxyl group. Therefore, regarding the adsorption, the perfluoropolyether-based lubricant molecule can adsorb to the surface of the carbon protective film by the interaction of the functional group at the molecular end with the functional group present on the surface of the carbon protective film. At present, little is known about its adsorption state, but it is probably weak adsorption via hydrogen bonding, and its adsorption power is considered to be an intermediate level between physical adsorption and chemical adsorption. Therefore, the perfluoropolyether-based lubricant can be adsorbed on the surface of the carbon protective film, but the adsorption is not strong chemical adsorption.

Further, perfluoropolyether-based lubricants require extremely expensive perfluoroalkyl as a solvent, which is a major factor in increasing the cost of the medium.

Further, the perfluoropolyether-based lubricant is liquid at normal temperature. Therefore, if a perfluoropolyether-based liquid lubricant having a thickness greater than the average surface roughness is present on the surface of a medium which has been increasingly smoothed in order to achieve high recording density recording, head / medium during contact / start / stop There is a problem that stiction (sticking) occurs at the interface.

However, since the lubricant molecule has many fluorine atoms in the molecule, it has the effect of greatly reducing the surface energy and simultaneously sliding the magnetic head and reducing its tangential force.

As described above, a perfluoropolyether-based lubricant requires a very expensive solvent as a diluting solvent at the time of use, which is one of the causes for increasing the production cost.
Further, the adsorption force on the surface of the carbon protective film is not large as described above.

On the other hand, aliphatic hydrocarbon-based, fluorine-substituted alkyl-based, phosphate-based lubricants and the like, which can use inexpensive general-purpose solvents, have great attractiveness for cost reduction, compared to perfluoropolyether-based lubricants. . The desired properties of the lubricant are to prevent the magnetic head slider from directly contacting the protective film surface by firmly adsorbing to the protective film surface as described above. This is to significantly reduce the tangential force. In these non-perfluoropolyether-based lubricants, there is a wide choice of functional groups at the molecular ends. For example, an aliphatic amine (terminal functional group: amino group) reacts with a carboxyl group existing on the surface of the carbon protective film by an acid-base reaction. Thus, chemical adsorption can be firmly performed on the surface of the carbon protective film (it is extremely difficult to introduce an amino group into the molecular end of the perfluoropolyether-based liquid lubricant, and it cannot be purified). Aliphatic amines are chemisorbed with their alkyl chains oriented almost vertically to the surface of the carbon protective film. Therefore, for example, stearylamine exists on the surface of the carbon protective film in a state close to a monomolecular film, and can significantly reduce the tangential force of the magnetic head slider sliding on the vertically oriented hydrocarbon chain.

However, as is well known, there is a problem that the hydrocarbon-based lubricant molecule loses the lubricating action near its melting point.
This indicates that the lateral cohesion of hydrocarbon chains is extremely important as a boundary lubrication film. When the temperature rises and the melting occurs near the melting point, the hydrocarbon chain film breaks, and the magnetic head slider penetrates the lubricating film and makes direct contact with the protective film, thereby causing a head crash.

In a hard disk drive unit, the temperature rises to around 50 ° C. during operation. Therefore, hydrocarbon-based lubricants exhibit boundary lubrication properties at temperatures lower than the melting point (around room temperature), and have the advantage of being able to use inexpensive solvents. However, there is a problem in designing a lubricating film having stable lubricity at high temperatures. is there.

[0020]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a lubricating film having a stable lubricating property even at a high temperature and a thin-film magnetic recording medium having the lubricating film.

[0021]

As described above, although the perfluoropolyether-based lubricant can reduce the tangential force when the magnetic head slides, it cannot be firmly adsorbed on the carbon protective film. In addition, since expensive perfluoroalkyl is required for the solvent, there is a problem that the cost is increased. On the other hand, aliphatic hydrocarbon-based lubricants that can use inexpensive general-purpose solvents have great appeal for cost reduction and can be chemically adsorbed firmly to the protective film surface. There is a problem in designing a lubricating film to have.

In order to solve the above problem, in a thin-film magnetic recording medium provided with a protective film containing at least carbon, the thin film magnetic recording medium is soluble on a protective film in a general-purpose solvent and has at least an amino group [-NH ₂ ] at the molecular terminal. Or N, N-dimethylamino group [-N
(CH ₃ ) ₂ ] and a two-component lubricant consisting of a lubricant that is soluble in a versatile solvent and is a liquid at room temperature. It has been found that lubricity can be increased in the range.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION At least an amino group [-
Alkylamine-based lubricants having NH ₂ ] or N, N-dimethylamino groups [-N (CH ₃ ) ₂ ] can be firmly applied to the protective film surface by acid-base reaction with carboxyl groups existing on the carbon-based protective film. Since it can be chemically bonded, it works as a good boundary lubrication film (see the following formula). R-NH ₂ (alkyl amine lubricant molecules) + HOOC-R '(carbon surface carboxyl ^{_{group) → RN + H 3 O -}} OC-R' ( salt form, R: an alkyl chain, R ': a carbon protective film)

FIG. 1A is a schematic diagram showing this chemical bond in a normal temperature state. A Co-based magnetic layer 3 is formed on the upper surface of a plastic non-magnetic substrate 1, and a carbon protective film 5 is provided on this magnetic layer. A carboxyl group -COOH exists on the surface of the carbon protective film. Now alkylamine-based solid lubricant 7 is applied to, salt between the amino group -NH ₂ carboxyl groups -COOH and alkyl amine lubricants of the carbon-based protective layer is formed on the surface of, alkylamine-based lubricant The agent 7 is firmly chemically bonded to the surface of the carbon-based protective film 5. In the present invention, the solid alkylamine-based lubricant 7 is further coated with a liquid lubricant 9 at room temperature. In a normal temperature atmosphere, the alkylamine-based lubricant 7 has a strong lateral interaction due to van der Waals force, so that the alkylamine molecules can be maintained in an upright state. Therefore, the hydrocarbon chain of the alkylamine-based lubricant 7 functions as a favorable boundary lubricant film up to its melting point, and can prevent the magnetic head 11 from directly contacting the surface of the carbon-based protective film 5.

On the other hand, as shown in FIG. 1B, above the melting point, the amino group [—NH ₂ ] or the N, N-dimethylamino group [—N (CH ₃ ) ₂ ] itself is on the surface of the carbon protective film. However, the interaction between the alkylamine-based solid lubricant 7 and the alkylamine hydrocarbon chains in the lateral direction is reduced, resulting in film breakage and loss of properties as a boundary lubricating film.

However, the lubricating film used in the present invention is a two-component lubricating film in which a lubricant 9 which is liquid at room temperature is used together with a solid alkylamine-based lubricant 7. Therefore, when the solid alkylamine-based lubricant 7 loses its properties as a boundary lubricating film at a temperature equal to or higher than its melting point, the liquid lubricant 9 present at the same time acts as a boundary fluid lubricating film, and has stable lubricating properties over a wide temperature range. Can be demonstrated. In the present invention, the term “normal temperature” is used in the same meaning as terms such as “room temperature”, “ambient temperature” or “ambient temperature”, and generally refers to a temperature in the range of −20 ° C. to + 60 ° C. Is shown.

The liquid lubricant 9 alone has a poor effect as a boundary lubricating film (a liquid at room temperature means that the lubricant molecules themselves have a large steric hindrance and a small interaction between the molecules. The liquid lubricant itself cannot form a pseudo monomolecular film such as a hydrocarbon-based lubricant on the surface of the carbon protective film at around normal temperature.) However, as described above, the amino group at the terminal of the alkylamine-based lubricant
[-NH ₂ ] or N, N-dimethylamino group [-N (CH ₃ ) ₂ ] itself is chemically adsorbed to the carboxyl group present on the surface of the carbon protective film even at a temperature higher than the melting point. Therefore, at a high temperature equal to or higher than the melting point, the amino group [—NH ₂ ] or the N, N-dimethylamino group [—N (CH ₃ ) ₂ ] present at the terminal of the alkylamine-based lubricant becomes the anchor adsorption point. Since a liquid lubricant having a property of reducing the tangential force at the time of sliding of the magnetic head at a high temperature exists on the broken hydrocarbon chain, an excellent lubricating action can be exhibited in a wide temperature range.

The alkylamine-based lubricant according to the present invention is an alkylamine-based lubricant having at least an amino group [—NH ₂ ] or an N, N-dimethylamino group [—N (CH ₃ ) ₂ ] at a molecular terminal. It is desirable that the number of carbon atoms is 10 or more and the solid is at room temperature. If the number of carbon atoms is less than 10, the interaction between carbon chains in the lateral direction is weak, so that it cannot function as a stable boundary lubricating film from room temperature to its melting point. The upper limit of the number of carbon atoms is not particularly limited, but when the number of carbon atoms exceeds 36, the interaction in the lateral direction is saturated. Being a solid at normal temperature indicates that the interaction between alkyl chains is strong even at thermal energy near room temperature and does not cause film breakage, which is an important requirement required for the alkylamine-based lubricant according to the present invention. .

The alkylamine-based lubricant according to the present invention has the following formula: C _a H _{2a + 1} NH ₂ or C _a H _{2a + 1} N (CH ₃ ) ₂ (where a is an integer of 10 or more) It is a saturated alkylamine. In the case of unsaturated alkyl containing double or triple bonds, the steric hindrance of the unsaturated bond significantly reduces the lateral interaction between the alkyl chains and liquefies at around room temperature, thus acting as a boundary lubricant. I can't do it.

The alkylamine-based lubricant according to the present invention has the following formula: F (CF ₂ ) _b (CH ₂ ) _c NH ₂ or F (CF ₂ ) _b (CH ₂ ) _c N (CH ₃ ) ₂ (wherein b and c are b ≧ 1, c ≧ 1 and b + c ≧
And a partially fluorinated saturated alkylamine. Lateral interactions between partially fluorinated alkyl chains are slightly reduced compared to interactions between fluorine-free alkyl chains. However, since a fluorine atom is contained in the molecule, the surface energy can be greatly reduced, and the tangential force when the magnetic head slides can be reduced as compared with an alkylamine containing no fluorine.
In the above formula, it is desirable that b + c, that is, the total number of carbon atoms is 10 or more, and the solid is a solid at room temperature. If the number of carbon atoms is less than 10, the interaction between carbon chains in the lateral direction is weak, so that it cannot function as a stable boundary lubricating film from room temperature to its melting point.
The upper limit of the number of carbon atoms is not particularly limited, but when the number of carbon atoms exceeds 36, the interaction in the lateral direction is saturated. Being a solid at normal temperature indicates that the interaction between alkyl chains is strong even at thermal energy near room temperature and does not cause film breakage, which is an important requirement required for the alkylamine-based lubricant according to the present invention. . B must be 1 or more because it contains fluorine and has a fluorine chain at the molecular end. The carbon bonded to the amino group is preferably a -CH ₂ -chain rather than a -CF ₂ -chain in order to reduce the electron-withdrawing action and make the lone electron pair of the amino group more easily accept the proton of the carboxyl group,
c is preferably 1 or more.

In the solid / liquid two-component lubricating layer used in the magnetic recording medium according to the present invention, the lubricant which is liquid at room temperature includes an ether bond, an amide bond or an ester at one or both terminals of perfluoropolyether. A modified perfluoropolyether having a saturated or unsaturated hydrocarbon chain having 4 or more carbon atoms, a saturated or unsaturated oxygen-containing hydrocarbon chain having 4 or more carbon atoms, or a branched hydrocarbon having 4 or more carbon atoms bonded through a bond Can be used.

A saturated or unsaturated hydrocarbon chain having 4 or more carbon atoms or a saturated or unsaturated oxygen-containing hydrocarbon chain having 4 or more carbon atoms via an ether bond, an amide bond or an ester bond at one or both terminals of the perfluoropolyether. The hydrogen chain and the branched hydrocarbon chain having 4 or more carbon atoms are linked because the perfluoropolyether-based lubricant may be alcohol, such as ethanol, propanol, or isopropyl alcohol, or acetone, methyl ethyl ketone, or methyl. It is soluble in inexpensive general-purpose solvents such as ketones such as isobutyl ketone and cyclohexanone, and saturated alkyls such as hexane, pentane and heptane, and thus has the effect of greatly reducing the cost of producing a lubricant solution.

Particularly, when both ends or one end of a perfluoropolyether-based lubricant is modified with an unsaturated hydrocarbon chain having 4 or more carbon atoms, a saturated oxygen-containing hydrocarbon chain or a branched hydrocarbon chain, these Due to the steric hindrance, the interaction between the lubricant molecules is weakened, and the viscosity of the entire lubricant near normal temperature is further reduced. Therefore, there is an effect that the stiction (sticking) at the time of sliding of the magnetic head is reduced, and the friction coefficient is reduced.

The fact that the viscosity of the modified perfluoropolyether liquid lubricant decreases at around normal temperature indicates that the viscosity of the modified perfluoropolyether liquid lubricant further decreases at high temperatures due to its thermal energy. is there.
Therefore, a modified perfluoropolyether liquid lubricant having the property of decreasing the viscosity at high temperature and reducing the tangential force at the time of sliding of the magnetic head is present on the alkylamine which has lost the lubricating effect due to the film breaking at high temperature. Therefore, an excellent lubricating action can be exhibited in a wide temperature range from normal temperature to high temperature (10 to 60 ° C.).

Although the viscosity of the modified perfluoropolyether-based lubricant used in the present invention is not an essential requirement of the present invention, it is generally in the range of 10 to 100 cst at low temperatures and 5 to 100 cst at high temperatures. Preferably, it is within the range of 50 cst. If the viscosity of the modified perfluoropolyether-based lubricant at a low temperature is more than 100 cst, disadvantages such as an increase in the shearing force during fluid lubrication and an increase in the motor torque in the magnetic disk drive occur.

As already mentioned above, the alkylamine lubricant breaks at high temperatures. However, the amino group [-NH ₂ ] or N, N-dimethylamino group [-N (CH ₃ ) ₂ ] present at the terminal of the alkylamine-based lubricant and the carboxyl group [-COOH] on the carbon protective film surface The chemical bond due to the acid-base reaction is not broken. This chemical bond serves as an anchor point, and good boundary lubrication can be realized even at high temperatures by cooperating with a low-viscosity liquid lubricant existing thereon.

The evidence that the chemical bond is not broken even at a temperature higher than the melting point will be described using stearylamine. Stearylamine has a melting point of 56 ° C. and exhibits extremely excellent boundary lubrication on the surface of the carbon protective film at room temperature. It was confirmed that stearylamine loses the boundary lubricating action when the temperature rises above 56 ° C., but recovers good boundary lubricity when the temperature is returned to room temperature again. This experimental fact shows that even at a temperature higher than the melting point, the chemical bond due to the acid-base reaction between the amino group at the end of stearylamine and the carboxyl group on the surface of the carbon protective film is not broken, and merely the alkyl chain in the stearylamine is not destroyed. Indicate that the interaction in the lateral direction is weakened by thermal energy at a temperature equal to or higher than the melting point, and the lubricating film is broken. If the chemical bond is broken by the acid-base reaction at a temperature higher than the melting point, when the temperature is lowered and the stearylamine is solidified, the amino group is again oriented vertically to the surface of the carbon protective film and a pseudo monomolecular film is formed. Cannot be re-oriented. Therefore, even if the temperature is returned from the melting point to around room temperature, stearylamine should not be able to act as a boundary lubricating film. Therefore, since a low-viscosity liquid lubricant is present on the alkylamine whose film has been broken even at a temperature higher than the melting point of the alkylamine, good lubricity is exhibited even at a high temperature.

In the above modified perfluoropolyether liquid lubricant, the main chain of the modified perfluoropolyether has-(CF ₂ CF ₂ CF ₂ O) _d -or-(CF ₂ O) _e- ( A compound composed of CF ₂ CF ₂ O) _f -or-(C (CF ₃ ) FCF ₂ O) _g- can be used. The number of main chains of the perfluoropolyether, that is, d, g, and e + f is preferably an integer of 10 or more. If it is less than 10, the molecular weight is 2000
The lubricant molecules evaporate at a high temperature and cannot exist stably as a liquid.

In the magnetic recording medium according to the present invention, as a lubricant which is a liquid at normal temperature, (1) a partially fluorinated saturated hydrocarbon having 6 or more carbon atoms at one or both terminals of an unsaturated hydrocarbon having 10 or more carbon atoms; A compound in which alkyl is linked by an ether bond, an ester bond or an amide bond; (2) a partially fluorinated saturated alkyl having 10 or more carbon atoms has an ether bond, an ester bond, or an amide bond having an unsaturated hydrocarbon having 10 or more carbon atoms at both ends; (3) a compound in which a branched hydrocarbon having 10 or more carbon atoms is linked to both ends or one end of a partially fluorinated saturated alkyl having 10 or more carbon atoms by an ether bond, an ester bond, or an amide bond; ) An unsaturated hydrocarbon having 10 or more carbon atoms is bonded to one or both ends of a saturated hydrocarbon having 10 or more carbon atoms by an ether bond or an ester bond. Or (5) a compound in which unsaturated hydrocarbons having 10 or more carbon atoms are linked to both ends or one end of an unsaturated hydrocarbon having 10 or more carbon atoms by an ether bond, an ester bond, or an amide bond. (6) a compound in which a saturated hydrocarbon having 10 or more carbon atoms is linked to both terminals of an unsaturated hydrocarbon having 10 or more carbon atoms by an ether bond, an ester bond, or an amide bond, (7) a saturated hydrocarbon having 10 or more carbon atoms (8) a compound in which a branched hydrocarbon having 4 or more carbon atoms is linked at each end or one end thereof by an ether bond, an ester bond, or an amide bond; A compound in which four or more branched hydrocarbons are linked by an ether bond, an ester bond or an amide bond, or (9) a partially fluorinated saturated alkyl having 10 or more carbon atoms Terminal or compounds to total carbon number of 4 or more polyether at one end and connected by an ether bond or an ester bond or amide bond, or the like can be used.

Since these compounds basically have at least one double bond, triple bond, branched hydrocarbon or ether bond in the molecule, the interaction between the molecules is weakened by the steric hindrance. Therefore, it can exist as a liquid at a temperature near normal temperature. Further, since two same or different molecules are connected by an ester bond, an ether bond or an amide bond, the molecular weight is increased, and the evaporation is suppressed even at a high temperature. In particular, when one molecule contains fluorine, the surface energy can be reduced by the fluorine atom, and the characteristics as a fluid lubricant can be improved.

The partially fluorinated saturated alkyl having 6 or more carbon atoms is represented by the following formula:-(CH ₂ ) _p (CF ₂ ) _q F (where p and q are integers of 1 or more and satisfy p + q ≧ 6) It is preferable that it is shown by. The partially fluorinated saturated alkyl having 10 or more carbon atoms is represented by the following formula:-(CH ₂ ) _p (CF ₂ ) _q (CH ₂ ) _p- (where p and q are integers of 1 or more, and 2p + q ≧ Ten
Is preferable. Since it contains fluorine and has a fluorine chain at the molecular end, q is 1
Must be at least. In the partially fluorinated alkyl of the above formula, the carbon bonded to the ester bond, ether bond or amide bond must not adversely affect the ester bond, ether bond or amide bond strength.
Therefore -CH _2- rather than -CF ₂ -chains to reduce the electron withdrawing effect
It is preferably a chain. For this reason, p is preferably 1 or more. The number of carbon atoms of the above partially fluorinated alkyl linked by an ester bond, an ether bond or an amide bond, that is, p + q is preferably an integer of 6 or more. If it is less than 6, the molecular weight is small and it cannot exist stably at high temperature, and the lubricating action cannot be sufficiently exerted.

In the magnetic recording medium according to the present invention, the lubricant which is liquid at normal temperature is dimethylpolysiloxane [-(Si (CH ₃ ) ₂ O) _h- ] or hydrogen of the methyl group in dimethylpolysiloxane. Fluorinated dimethylpolysiloxane in which is partially substituted with fluorine or partially fluorinated alkyl [-(Si (CF ₃ ) ₂ O) _h -,-(Si (CF ₃ ) (CH ₃ ) O) _h -,-( Si (C ₂ H ₄ C ₆ F
₁₃ ) ₂ O) _h- ] or the following formula: CH ₃ (Si (CH ₃ ) ₂₀ ) _n -Si (NH ₂ ) ₃ , F (CF
_{2) n CH 2 -Si (NH} 2) 3 or _{F (CF 2) n CH 2} CH 2 -Si (NH 2) 3 ( in the formula,
n is an integer of 6 or more), and a modified dimethylpolysiloxane having an amino group at a terminal can also be used. In the above formula, h is preferably 6 or more because h does not evaporate at a high temperature (for example, a temperature exceeding 56 ° C.).

In the magnetic recording medium according to the present invention, as a lubricant which is liquid at normal temperature, the following formula is used: [FC ₆ H ₄ O] _m- (P ₃ N ₃ )-[OC ₆ H ₄ CF ₃ ] _{6 -m} (wherein m is an integer of 0 to 6),
Or (CF ₃ ) ₂ CF (CF ₂ ) _j CH ₂ CHOCORCH ₂ OCOR (where j is an integer of 2 to 16, and R is —CR ₁ R ₂ R
Indicated by _{3, R 1, R 2,} R 3 are each _{C s H 2s + 1, C} t H
It indicated by _{2t + 1} and _{C u H 2u + 1, s} , t and u are s ≧ 1, t ≧ 1 and u ≧ 1, respectively, and, s + t + u ≧
Or a compound represented by the formula: F (CF ₂ ) _j CH ₂ CHOCORCH ₂ OCOR (wherein j is an integer of 2 to 16, and R is —CR ₁ R ₂ R
Indicated by _{3, R 1, R 2,} R 3 are each _{C s H 2s + 1, C} t H
It indicated by _{2t + 1} and _{C u H 2u + 1, s} , t and u are s ≧ 1, t ≧ 1 and u ≧ 1, respectively, and, s + t + u ≧
8 is an integer that satisfies 8).

The compound represented by the formula [FC ₆ H ₄ O] _m- (P ₃ N ₃ )-[OC ₆ H ₄ CF ₃ ] _{6 -m} comprises three nitrogen atoms and three phosphorus atoms. A lubricant that is liquid at room temperature and has a total of six partially fluorinated benzenes or fluorinated alkylbenzenes bonded to a six-membered ring. Since it has six benzene rings, it can be dissolved in a general-purpose solvent. Also, three nitrogens and three
It can be adsorbed on the carbon-based protective film by a six-membered ring composed of individual phosphorus atoms or a benzene ring bonded to the six-membered ring, and has an effect of improving lubricity. Further, fluorine or fluorinated alkyl bonded to the benzene ring has the effect of reducing surface energy and reducing frictional force. M in the molecular formula may be any integer in the range of 0 to 6, since a 6-membered ring composed of 3 nitrogens and 3 phosphorus atoms has 6 bonds.

In the magnetic recording medium according to the present invention, (CF ₃ ) ₂ CF (CF ₂ ) _j CH ₂ CHOCORC is used as a lubricant which is liquid at normal temperature.
H ₂ OCOR or F (CF ₂ ) _j CH ₂ CHOCORCH ₂ OCOR (in each of the above formulas, j is an integer of 2 to 16, and R is -CR
₁ R ₂ R ₃ , where R ₁ , R ₂ and R ₃ are each C
It indicated by _{s H 2s + 1, C t} H 2t + 1 and _{C u H 2u + 1, s} , t and u are s ≧ 1, t ≧ 1 and u ≧ 1, respectively, and the s + t + u ≧ 8 Which are satisfactory integers) can be used. This molecule is a diester consisting of a partially fluorinated alkyl moiety and a branched saturated hydrocarbon moiety, and liquefies at room temperature due to the high steric hindrance of the branched saturated hydrocarbon. This molecule has a partially fluorinated alkyl moiety, which can lower the surface energy and improve the properties as a fluid lubricant. J in the partially fluorinated alkyl chain is preferably an integer in the range of 2 to 16. When j is less than 2, the effect of lowering the surface energy is insufficient, and since the molecular weight is too low, the lubricant tends to volatilize. On the other hand, when j is larger than 16, it becomes difficult to dissolve in a general-purpose solvent,
It is not preferable from the viewpoint of cost reduction. Also, -CR ₁ R ₂
R ₃ (wherein R ₁ , R ₂ , and R ₃ are C _s H _{2s + 1} , C _t H
In branched saturated hydrocarbon group represented by _{2t + 1,} and a _{C u H 2u + 1),} s, t and u are s ≧ 1, t ≧ respectively
It is preferable that 1 and u ≧ 1 and an integer satisfying s + t + u ≧ 8. s ≧ 1, t ≧ 1 and u ≧ 1
If this is the case, the steric hindrance of the branched saturated hydrocarbon group will increase, and it will be possible to liquefy at room temperature, and at the same time, it will be possible to protect the ester bond with the steric hindrance, thereby increasing the chemical stability of the molecule.

In the magnetic recording medium of the present invention, a high-resistance carbon protective film is used to protect the magnetic layer. This carbon protective film is, for example, sputtered carbon,
It is a carbon-based protective film such as plasma CVD carbon, diamond-like carbon, hydrogen-containing carbon, nitrogen-containing carbon, or silicon-containing carbon. It is necessary to increase the number of carboxyl groups on the surface of the carbon protective film in order to strongly adsorb the alkylamine-based lubricant on the surface of the carbon protective film. For this reason, before applying the alkylamine-based lubricant to the surface of the carbon protective film by spin coating or dip coating, the surface of the carbon-based protective film is subjected to at least 184.
It is effective to perform irradiation treatment with ultraviolet light having a wavelength of 9 nm, or at least perform plasma treatment in an atmosphere containing oxygen.

When the surface of the carbon protective film is treated by the above method in an atmosphere in which oxygen is present, ozone is first generated by the following reaction. This ozone then produces active oxygen according to the following equation: 3O ₂ + hν → 2O ₃ ; 2O ₃ + hν ′ →
2O ₂ + 2O With this active oxygen (O), the oxidation reaction of carbon proceeds on the surface of the carbon protective film, and hydrogen generated by the decomposition of water contained in the oxygen atmosphere and hydrogen generated by the following formula: C + H + O → C—OH (alcohol) C—OH + O → CO (H) (aldehyde) A carboxyl group is generated on the surface of the carbon protective film in the order of CO (H) + O → COOH (carboxyl group).

The carboxyl group formed by the above formula can form a salt in an acid-base reaction with the amino group in the alkyl amine according to the present invention according to the following formula to form a strong chemical bond. R-NH ₂ (alkylamine-based lubricant molecule) + HOOC-C (carboxyl group on carbon surface) → RN ⁺ H ₃ O ^- OC-C (salt formation, where R is an alkyl chain and C is carbon Is a protective film)

As described above, a large number of carboxyl groups can be generated on the surface of the carbon protective film by subjecting the surface of the carbon protective film to a surface treatment with ultraviolet light or oxygen plasma. It is desirably 0.1 or more using the composition ratio (O / C) of carbon and carbon.

The composition ratio is determined by subjecting the lubricant layer physically present on the magnetic recording medium according to the present invention to ultrasonic cleaning with acetone for 30 seconds and then subjecting the carbon protective film surface to a composition ratio of oxygen and carbon (O / C). Is measured at a detection angle of 45 degrees using X-ray photoelectron spectroscopy (XPS), and the composition ratio (O / C) is 0.1 or more. If the composition ratio is less than 0.1, the carboxyl group concentration on the surface of the carbon protective film is not sufficient (that is, the oxidation of the surface of the carbon protective film is not sufficient).
The alkylamine-based lubricant according to the present invention cannot be sufficiently chemically bonded (that is, a pseudo monomolecular film of alkylamine-based lubricant molecules cannot be formed on the surface of the carbon protective film).

When processing with ultraviolet light having a wavelength of 184.9 nm, the oxygen concentration is preferably within a range of 100 ppm or more. The irradiation time required to obtain an O / C ratio of 0.1 or more is not particularly limited, but is generally preferably in the range of 10 seconds to 5 minutes. Ultraviolet light having a wavelength of 184.9 nm can be obtained by a low-pressure mercury lamp. Other sources of ultraviolet light can also be used. The low-pressure mercury lamp simultaneously generates ultraviolet light having a wavelength of 184.9 nm and a wavelength of 253.7 nm. Ozone is generated by ultraviolet light having a wavelength of 184.9 nm, and active oxygen is generated by ultraviolet light having a wavelength of 253.7 nm. The output of the ultraviolet light source is not particularly limited. For example, it is preferable to use a low-pressure mercury lamp of 45 W or more.

The plasma treatment can be performed using a conventional parallel plate type plasma CVD apparatus. The pressure in the chamber of the plasma CVD apparatus is not particularly limited, but is generally preferably in the range of 0.1 mTorr to 10 mTorr. 13.5 for the upper electrode of the plasma CVD device
Plasma is generated by applying a high-frequency power supply of 6 MHz or a commercial alternating current. The partial pressure of oxygen introduced into the chamber is not particularly limited. Generally, it is preferable to be within the range of 1 mTorr-5 mTorr. The processing time required to obtain an O / C ratio of 0.1 or more varies depending on various factors such as the output of a plasma CVD apparatus, but the optimum processing time can be easily determined by repeating experiments. it can.

In the solid / liquid two-component lubricating layer used in the magnetic recording medium according to the present invention, the alkylamine-based solid lubricant and the modified perfluoropolyether liquid lubricant are each a general-purpose solvent such as ethanol, propanol,
It is soluble in alcohols such as isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and saturated alkyls such as hexane, pentane and heptane. Therefore, the solvent used at the time of applying the lubricant is 1/10 or less of that of the conventional perfluoroalkyl-based lubricant, and the production cost of the medium of the present invention can be greatly reduced. For example, F which is a solvent of a perfluoropolyether lubricant
C77 is $ 15,000 / liter, whereas methylisobutyl ketone, a versatile solvent, is $ 1,000 / liter.

When a lubricant layer comprising a two-component system of the alkylamine-based solid lubricant according to the present invention and a lubricant which is liquid at normal temperature is applied to the surface of the carbon protective film by spray coating, dip coating or spin coating, It is desirable to adjust the concentration of each lubricant within the range of 0.005 wt% to 0.50 wt%. If it is less than 0.005 wt%, sufficient boundary lubrication properties cannot be obtained. On the other hand, if it exceeds 0.50 wt%, sticking (stiction) to the magnetic head may occur in the case of a lubricant which is liquid at normal temperature.

In the case of an alkylamine-based solid lubricant, a desired alkylamine compound is once dissolved in an appropriate general-purpose solvent to form a solution, and this solution is applied to the surface of the carbon protective film and then dried to obtain a solid lubricant. Form a layer. Thereafter, a solid / liquid two-component lubricating layer of the present invention can be formed by applying a lubricating solution which is liquid at room temperature to the surface of the solid lubricating layer. Alternatively, the two types of lubricants may be dissolved together in the same solvent and applied as a single lubricant solution.

The amount of the alkylamine-based solid lubricant applied is not particularly limited, but is generally 1.0 mg / m ^{2 to} 5.0 mg / m ² .
Preferably it is in the range of 4 mg / m ² . According to the coating amount within this range, 14 ° to 75 ° on the carbon protective film.
An alkylamine-based solid lubricant layer having a thickness in the range of 膜厚 can be formed. If the amount of the alkylamine-based solid lubricant applied is too small, the amount of bonding with the carboxyl groups on the carbon protective film is insufficient, and sufficient boundary lubrication characteristics cannot be obtained. Therefore, basically, an alkylamine-based solid lubricant should be used in excess of the amount of carboxyl groups present on the carbon protective film.

Similarly, the amount of the lubricant that is liquid at room temperature is not particularly limited. Generally, 1 mg / m ^{2 to} 10 m
It is preferably within the range of g / m ² . If the amount of the lubricant that is liquid at normal temperature is too small, the effect of improving the sliding characteristics at high temperatures may not be obtained, which is not preferable.

The overall thickness of the solid / liquid two-component lubricating layer comprising the alkylamine-based solid lubricant and the lubricant which is liquid at normal temperature according to the present invention is not particularly limited, but is generally in the range of 15 ° to 100 °. It is preferable that it is within the range.
If the film thickness is less than 15 °, sufficient boundary lubrication characteristics cannot be obtained at both normal temperature and high temperature. On the other hand, when the film thickness is 1
When it exceeds 00 °, in particular, when the thickness of the liquid lubricant component is large, inconvenience such as sticking occurs.

The magnetic recording medium according to the present invention includes not only a conventional hard disk using an Al alloy plated with glass or NiP on a non-magnetic substrate, but also PET, PEN,
Co-CoO vapor-deposited tape on which a magnetic metal such as Co is obliquely vapor-deposited in an oxygen atmosphere using an aramid or the like, and polycarbonate, amorphous polyolefin, polyetherimide, polyether sulfone or phenol resin on a non-magnetic substrate. The present invention can also be applied to a hard disk having a guide groove and a pit, or a guide groove or a pit formed on a polymer plastic.

In the magnetic recording medium according to the present invention, a non-magnetic substrate is made of a polymer plastic such as polycarbonate, amorphous polyolefin, polyetherimide, polyether sulfone or phenol resin, and a guide groove is formed on the polymer plastic. And the pit,
Alternatively, in the case of a hard disk in which one of the guide grooves or pits is formed, the mechanical strength of the surface of the non-magnetic substrate is increased to increase the durability of the medium, and to prevent water or oxygen from entering the substrate to increase the corrosion resistance of the medium. An oxide such as silicon oxide, aluminum oxide, titanium oxide, tantalum oxide, or zirconium oxide, or a nitride such as silicon nitride, boron nitride, or titanium nitride, or silicon carbide, titanium carbide, tungsten carbide, or tantalum carbide is formed on the plastic substrate. Or a buffer layer made of a carbide such as silicon, carbon, boron titanium or the like. These inorganic buffer layers can be formed by methods known to those skilled in the art (eg, sputtering, reactive sputtering, plasma CVD,
Ion beam evaporation)).

Since these oxides, nitrides, and carbides are amorphous, dense and have high hardness, they have the effect of improving the durability and corrosion resistance of a hard disk using a non-magnetic plastic substrate as a substrate. The thickness of these oxide, nitride and carbide buffer layers is preferably in the range of 25 ° to 5000 °. If the thickness of the buffer layer is less than 25 °, the non-magnetic plastic substrate cannot be sufficiently covered.
If it exceeds 000 °, the stress of the buffer layer will increase, and the warpage and undulation of the nonmagnetic plastic substrate will increase.

In the magnetic recording medium according to the present invention, a nonmagnetic substrate is made of a polymer plastic such as polycarbonate, amorphous polyolefin, polyetherimide, polyether sulfone or phenol resin, and a guide groove is formed on the polymer plastic. And the pit,
Alternatively, in a hard disk in which either a guide groove or a pit is formed, when a Co-based magnetic material is used for the magnetic layer,
It is preferable to provide a chromium or chromium alloy layer below the magnetic layer. The chromium or chromium alloy (for example, chromium, chromium titanium, chromium molybdenum, chromium vanadium, chromium aluminum, chromium zirconium) underlayer is provided below the magnetic layer because the C-axis of the Co-based magnetic layer is This is for realizing high recording density. The chromium alloy underlayer can be formed on the nonmagnetic substrate by a method known to those skilled in the art (for example, sputtering). Although the thickness of the chromium alloy underlayer itself is not an essential requirement of the present invention, it is generally preferable that the thickness be in the range of 10 ° to 2000 °. If the thickness of the chromium alloy underlayer is less than 10 °, the C-axis of the Co-based magnetic layer cannot be oriented in-plane. On the other hand, when the thickness of the chromium alloy underlayer is more than 2000 °, inconveniences such as generation of cracks due to increase in film stress occur.

A chromium alloy underlayer and / or the oxide,
Before forming the chromium alloy underlayer and / or the oxide, nitride, and carbide buffer layers on the plastic substrate, the surface of the plastic substrate is finally increased to improve the adhesion between the nitride and carbide buffer layers and the plastic substrate. It is effective to perform irradiation treatment with ultraviolet light having a wavelength of 184.9 nm in an atmosphere where oxygen is present, or plasma treatment in an atmosphere where oxygen is present.
This treatment decomposes and removes impurities such as natural oxides and fats and oils on the substrate surface, and at the same time, forms a functional group containing oxygen and hydrogen on the plastic substrate surface to increase wettability and improve the adhesion between the underlayer and the substrate. Is done.

The ferromagnetic metal constituting the thin film magnetic layer in the magnetic recording medium of the present invention is not particularly limited, but is generally preferably a Co-based magnetic material containing more than 50 at% of Co. Such Co-based magnetic materials are well known to those skilled in the art and need not be described further. Also, the method for depositing the magnetic layer is not particularly limited. Vacuum deposition,
In general, any conventional vapor deposition method such as sputtering can be used. The thickness of such a Co-based magnetic layer is not particularly limited. In the magnetic recording medium of the present invention, it is generally preferable to use a Co-based magnetic layer having a thickness in the range of 100 ° to 500 °. 100 film thickness
If the thickness is less than Å, there is a problem that a sufficient reproduction output cannot be obtained. On the other hand, if the film thickness exceeds 500 が あ る, there is a problem such as an increase in medium noise.

The thickness of the carbon protective film used in the present invention is not particularly limited, but is generally 100 to 500 °.
Is preferably within the range. When the thickness of the carbon protective film is less than 100 °, a sufficient magnetic layer protective effect may not be obtained. On the other hand, when the thickness of the carbon protective film is 50
If it exceeds 0 °, inconveniences such as an increase in spacing loss occur. The method of forming the carbon protective film used in the present invention is well known or known to those skilled in the art, and will not require any particular explanation.

FIG. 2 is a schematic sectional view of a thin-film magnetic recording medium having a buffer layer and a chromium alloy underlayer. A buffer layer 13 is provided on the upper surface of the non-magnetic substrate 1, and a chromium alloy base layer 15 is provided on the upper surface of the buffer layer. On the upper surface of the chromium alloy underlayer 15, a magnetic layer 3, a carbon protective film 5, an alkylamine-based solid lubricant 7, and a liquid lubricant 9 similar to those shown in FIG.

FIG. 3 shows a buffer layer 13, a chromium alloy underlayer 15, a magnetic layer 3, a carbon protective film 5, an alkylamine-based solid lubricant 7 and a liquid lubricant 9 on both surfaces of the nonmagnetic substrate 1.
1 is a schematic cross-sectional view of a thin-film magnetic recording medium provided with each.

In the magnetic recording medium according to the present invention, in order to further reduce the friction and abrasion when the magnetic head slides, in the magnetic disk drive system to be used, a high protective film is formed on the magnetic head slider for recording and reproducing in the drive. It is preferable to provide a carbon-based protective film such as resistance sputtering carbon, plasma CVD carbon, diamond-like carbon, hydrogen-containing carbon, nitrogen-containing carbon, or silicon-containing carbon. The method for forming the carbon-based protective film is well known to those skilled in the art and will not be described in particular. The thickness of the carbon protective film provided on the sliding surface of the magnetic head is not particularly limited, but is generally preferably in the range of 50 ° to 300 °. The thickness of the carbon protective film is 50
If it is less than Å, problems such as insufficient coating of the slider surface occur. On the other hand, when the thickness of the carbon protective film is more than 300 °, disadvantages such as an increase in spacing loss occur.

As in the case of the magnetic recording medium, the carbon protective film on the sliding surface of the magnetic head was 184.9 n in the presence of oxygen.
m, or plasma treatment in the presence of oxygen, and at least -COOH
Generate a group. Thereafter, the same or different alkylamine-based solid lubricant as that used in the magnetic recording medium is applied to the surface of the carboxyl group-containing carbon protective film. When this state is used for the thin film type magnetic recording medium of the present invention as shown in FIG. 1A, the liquid lubricant in the magnetic recording medium becomes an interface. Therefore, the sliding is performed between the hydrocarbons, and the friction and wear during the sliding can be remarkably suppressed, so that the traveling performance of the magnetic head is further improved. If desired, a liquid lubricant can be applied to the surface of the alkylamine-based solid lubricant of the magnetic head. FIG. 4 is a schematic configuration diagram of a drive system in which a carbon protective film 5 is provided on a sliding surface of a magnetic head 11 and an alkylamine-based solid lubricant 7 is applied to the carbon protective film 5.

When a non-magnetic substrate made of injection molded amorphous polyolefin, polycarbonate, polyetherimide, polyether sulfone or phenol resin is used, the cost of the substrate is higher than that of a conventional Al / Ni-P substrate or glass substrate. There is a merit that can be greatly reduced. In a conventional Al / Ni-P substrate or glass substrate, a mechanical texture or a laser texture is provided on the substrate in order to reduce a frictional force at the time of CSS (Contact Start and Stop). When the above-mentioned plastic substrate is used, a mechanical texture or a laser texture cannot be provided on the substrate. However, a depth of 15-40 nm and an apparent area ratio of 0.1-5.
By providing a 0% dot-shaped texture zone and injection molding a plastic substrate, the height of the inner surface of the plastic substrate is 15 to 40 nm, and the apparent area ratio is 0.1 to 40%.
5.0% dot texture zones can be provided. By introducing the dot-like texture, the contact area with the magnetic head slider is reduced, and the CSS (Contact S
It is possible to reduce the friction force at the time of “tart and stop”. The dots in the texture zone have a height of 15-40n
m, and the apparent area ratio is preferably 0.1 to 5.0%. If the dot height is less than 15 nm, it is not enough to avoid contact between the bottom of the medium and the magnetic head slider, and
If the dot height exceeds 40 nm, the magnetic head comes into contact with the dots while flying, causing a crash. If the apparent area ratio of the dots is less than 0.1%, the pressure applied to the dots increases, and the wear of the dots becomes severe. On the other hand, if the apparent area ratio of the dots exceeds 5.0%, the frictional force during CSS is increased. The effect of reducing is reduced.

[0071]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments.

Example 1 The following compounds were used as alkylamine-based lubricants. C ₁₄ H ₂₉ NH ₂

Example 2 The following compounds were used as alkylamine-based lubricants. C ₁₆ H ₃₃ NH ₂

Example 3 The following compounds were used as alkylamine-based lubricants. C ₁₈ H ₃₇ NH ₂

Example 4 The following compounds were used as alkylamine-based lubricants. C ₂₄ H ₄₉ N (CH ₃ ) ₂

Example 5 The following compounds were used as alkylamine-based lubricants. C ₃₃ H ₆₇ NH ₂

Example 6 The following compounds were used as alkylamine-based lubricants. FC ₁₂ F ₂₄ CH ₂ CH ₂ NH ₂

Example 7 The following compounds were used as alkylamine-based lubricants. FC ₁₂ F ₂₄ CH ₂ NH ₂

Example 8 The following compounds were used as alkylamine-based lubricants. FC ₁₆ F ₃₂ CH ₂ CH ₂ NH ₂

Example 9 The following compounds were used as alkylamine-based lubricants. FC ₁₆ F ₃₂ CH ₂ NH ₂

Example 10 The following compounds were used as a lubricant which is liquid at normal temperature. CH ₃ (CH ₂ ) ₁₁ O (CH ₂ ) ₃ NHCO-CF _2- (OC ₂ F ₄ ) _10- (OCF ₂ ) ₁₀ -CF ₂ -C
ONH (CH ₂ ) ₃ O (CH ₂ ) ₁₁ CH ₃

Example 11 The following compounds were used as a lubricant which is liquid at normal temperature. C ₄ H ₉ (CH ₂ CH = CH) ₂ C ₇ H ₁₄ COOCH ₂ -CF _2- (OC ₂ F ₄ ) _10- (OCF ₂ ) _10-
CF ₂ -CH ₂ OCOC ₇ H ₁₄ (CH ₂ CH = CH) ₂ C ₄ H ₉

Example 12 The following compounds were used as a lubricant which is liquid at normal temperature. C ₄ H ₉ (CH ₂ CH = CH) ₂ C ₇ H ₁₄ CH ₂ OCH ₂ -CF _2- (OC ₂ F ₄ ) _10- (OCF ₂ ) ₁₀
-CF ₂ -CH ₂ OCH ₂ C ₇ H ₁₄ (CH ₂ CH = CH) ₂ C ₄ H ₉

Example 13 The following compounds were used as a lubricant which is liquid at normal temperature. C ₁₇ H ₃₅ COOCH ₂ -CF _2- (OC ₂ F ₄ ) _10- (OCF ₂ ) ₁₀ -CF ₂ -CH ₂ OCOC ₁₇ H
₃₅

Example 14 The following compounds were used as a lubricant which was liquid at normal temperature. C ₁₇ H ₃₅ CH ₂ OCH ₂ -CF _2- (OC ₂ F ₄ ) _10- (OCF ₂ ) ₁₀ -CF ₂ -CH ₂ OCH ₂₁₇
H ₃₅

Example 15 The following compounds were used as a lubricant which is liquid at normal temperature. [(CH ₃ ) ₂ CH (CH ₃ ) CH] ₂ C (CH ₃ ) -COOCH ₂ -CF _2- (OC ₂ F ₄ ) _10- (OCF
₂ ) ₁₀ -CF ₂ -CH ₂ OCO-C (CH ₃ ) [C (CH ₃ ) HCH (CH ₃ ) ₂ ] ₂

Example 16 The following compounds were used as a lubricant which is liquid at ordinary temperature. C ₄ H ₉ O- (C ₂ H ₄ O) ₄ -CH ₂ -CF _2- (OC ₂ F ₄ ) _10- (OCF ₂ ) ₁₀ -CF ₂ -CH _2-
(OC ₂ H ₄ ) ₄ -OC ₄ H ₉

Example 17 The following compounds were used as a lubricant which was liquid at ordinary temperature. C ₄ H ₉ O- (C ₂ H ₄ O) ₆ -CH ₂ -CF _2- (OC ₂ F ₄ ) _10- (OCF ₂ ) ₁₀ -CF ₂ -CH _2-
(OC ₂ H ₄ ) ₆ -OC ₄ H ₉

Example 18 The following compounds were used as a lubricant which is liquid at ordinary temperature. C ₄ H ₉ (CH ₂ CH = CH) ₂ C ₇ H ₁₄ COOCH ₂ -CF ₂ -CF _2- (OC ₃ F ₆ ) ₁₅ F

Example 19 The following compounds were used as a lubricant which is liquid at ordinary temperature. CH ₃ (CH ₂ ) ₁₁ -O- (CH ₂ ) ₃ NHCOCH ₂ -CF ₂ -CF _2- (OC ₃ F ₆ ) ₁₅ F

Example 20 The following compounds were used as a lubricant which is liquid at ordinary temperature. C ₁₇ H ₃₅ COOCH ₂ -CF ₂ -CF _2- (OC ₃ F ₆ ) ₁₅ F

Example 21 The following compounds were used as a lubricant which is liquid at ordinary temperature. [(CH ₃ ) ₂ CH (CH ₃ ) CH] ₂ C (CH ₃ ) -COOCH ₂ -CF ₂ -CF _2- (OC ₃ F ₆ ) ₁₅ F

Example 22 The following compounds were used as a lubricant which is liquid at normal temperature. C ₄ H ₉ O- (C ₂ H ₄ O) ₄ -CH ₂ -CF ₂ -CF _2- (OC ₃ F ₆ ) ₁₅ F

Example 23 The following compounds were used as a lubricant which was liquid at ordinary temperature. C ₄ H ₉ O- (C ₂ H ₄ O) ₆ -CH ₂ -CF ₂ -CF _2- (OC ₃ F ₆ ) ₁₅ F

Example 24 The following compounds were used as a lubricant which is liquid at normal temperature. C ₆ F ₁₃ CH ₂ OCOC ₃ H ₆ (CH ₂ CH = CH) ₂ C ₇ H ₁₄ COOCH ₂ C ₆ F ₁₃

Example 25 The following compounds were used as a lubricant which was liquid at normal temperature. C ₄ H ₉ (CH ₂ CH = CH) ₂ C ₇ H ₁₄ COOCH ₂ CH ₂ C ₆ F ₁₃

Example 26 The following compounds were used as a lubricant which was liquid at ordinary temperature. C ₆ F ₁₃ CH ₂ -OC ₄ H ₈ (CH ₂ CH = CH) ₂ C ₇ H ₁₄ CH ₂ -O-CH ₂ C ₆ F ₁₃

Example 27 The following compounds were used as a lubricant which is liquid at normal temperature. C ₄ H ₉ (CH ₂ CH = CH) ₂ C ₇ H ₁₄ CH ₂ -O-CH ₂ C ₆ F ₁₃

Example 28 The following compounds were used as a lubricant which was liquid at ordinary temperature. C ₄ H ₉ (CH ₂ CH = CH) ₂ C ₇ H ₁₄ COOCH ₂ C ₆ F ₁₂ CH ₂ OCOC ₇ H ₁₄ (CH ₂ CH = C
H) ₂ C ₄ H ₉

Example 29 The following compounds were used as a lubricant which was liquid at ordinary temperature. [(CH ₃ ) ₂ CH (CH ₃ ) CH] ₂ C (CH ₃ ) -COOCH ₂ C ₆ F ₁₂ CH ₂ OCO-C (CH ₃ )
[C (CH ₃ ) HCH (CH ₃ ) ₂ ] ₂

Example 30 The following compounds were used as a lubricant which was liquid at ordinary temperature. [(CH ₃ ) ₂ CH (CH ₃ ) CH] ₂ C (CH ₃ ) -COOCH ₂ C ₆ F ₁₃

Example 31 The following compounds were used as a lubricant which is liquid at ordinary temperature. C ₄ H ₉ (CH ₂ CH = CH) ₂ C ₇ H ₁₄ COOC ₄ H ₉ (CH ₂ CH = CH) ₂ C ₇ H ₁₄ OCOCH ₂ C
₇ H ₁₄ (CH ₂ CH = CH) ₂ C ₄ H ₉

Example 32 The following compounds were used as a lubricant which is liquid at normal temperature. C ₄ H ₉ (CH ₂ CH = CH) ₂ C ₇ H ₁₄ COOC ₇ H ₁₄ (CH ₂ CH = CH) ₂ C ₄ H ₉

Example 33 The following compounds were used as a lubricant which was liquid at ordinary temperature. C ₄ H ₉ (CH ₂ CH = CH) ₂ C ₇ H ₁₄ COOC ₈ H ₁₆ OCOC ₇ H ₁₄ (CH ₂ CH = CH) ₂ C ₄ H
₉

Example 34 The following compounds were used as a lubricant which was liquid at ordinary temperature. C ₄ H ₉ (CH ₂ CH = CH) ₂ C ₇ H ₁₄ COOC ₁₇ H ₃₅

Example 35 The following compounds were used as a lubricant which is liquid at ordinary temperature. C ₁₇ H ₃₅ COOC ₄ H ₈ (CH ₂ CH = CH) ₂ C ₇ H ₁₄ OCOC ₁₇ H ₃₅

Example 36 The following compounds were used as a lubricant which is liquid at ordinary temperature. [(CH ₃ ) ₂ CH (CH ₃ ) CH] ₂ C (CH ₃ ) -COOC ₈ H ₁₈ OCO-C (CH ₃ ) [C (CH ₃ )
HCH (CH ₃ ) ₂ ] ₂

Example 37 The following compounds were used as a lubricant which is liquid at ordinary temperature. [(CH ₃ ) ₂ CH (CH ₃ ) CH] ₂ C (CH ₃ ) -COOC ₄ H ₈ (CH ₂ CH = CH) ₂ C ₇ H ₁₄ OC
OC (CH ₃ ) [C (CH ₃ ) HCH (CH ₃ ) ₂ ] ₂

Example 38 The following compounds were used as a lubricant which was liquid at ordinary temperature. C ₄ H ₉ O- (C ₂ H ₄ O) ₆ -CH ₂ C ₆ F ₁₂ CH _2- (OC ₂ H ₄ ) ₆ -OC ₄ H ₉

Example 39 The following compounds were used as a lubricant which was liquid at ordinary temperature. C ₄ H ₉ O- (C ₂ H ₄ O) ₆ -CH ₂ C ₈ F ₁₇

Example 40 The following compounds were used as a lubricant which is liquid at normal temperature. CH ₃ (Si (CF ₃ ) (CH ₃ ) O) ₁₀ -Si (CF ₃ ) ₂ (CH ₃ )

Example 41 The following compounds were used as a lubricant which is liquid at normal temperature. CH ₃ (Si (CH ₃ ) ₂ O) ₁₀ -Si (NH ₂ ) ₃

Example 42 It was confirmed that the compounds of Examples 1 to 41 were soluble in isopropyl alcohol (IPA), methyl isobutyl ketone (MIBK) and normal heptane at a concentration of 1.0% by weight at room temperature.

Example 43 A 3.5-inch NiP-plated Al alloy substrate was polished and textured to obtain a substrate having a center line surface roughness Ra of 4 nm. On this substrate, a 50 nm Cr underlayer, a 30 nm CoCrPt magnetic layer, and a 20 nm carbon protective film were sequentially formed by DC magnetron sputtering in an Ar gas atmosphere.

Example 44 A 2.5-inch glass substrate was chemically etched in hydrofluoric acid to perform a chemical texture treatment, and a center line surface roughness Ra was obtained.
Was 4 nm. On this substrate, 5 DC magnetron sputtering was performed in an Ar gas atmosphere.
0 nm Cr underlayer, 30 nm CoCrPt magnetic layer, 20 n
m of carbon protective films were sequentially formed.

Example 45 3.5 inch size amorphous polyolefin (AP
O) The substrate was formed by injection molding. The surface of the APO substrate was subjected to a plasma treatment at 200 W RF for 1 minute in an atmosphere of oxygen pressure of 5 mTorr. Thereafter, a 50 nm Cr underlayer, 30 nm in an Ar gas atmosphere by DC magnetron sputtering.
A CoCrPt magnetic layer of 20 nm and a carbon protective film of 20 nm were sequentially formed.

Example 46 A 3.5-inch size amorphous polyolefin (AP
O) The substrate was formed by injection molding. The surface of the APO substrate was subjected to a plasma treatment at 200 W RF for 1 minute in an atmosphere at an oxygen pressure of 5 mTorr. Thereafter, a 50 nm Si buffer layer, a 50 nm Cr underlayer, a 30 nm CoCrPt magnetic layer,
A 20 nm carbon protective film was sequentially formed.

Example 47 3.5 inch size amorphous polyolefin (AP
O) The substrate was formed by injection molding. The surface of the APO substrate was subjected to a plasma treatment at 200 W RF for 1 minute in an atmosphere at an oxygen pressure of 5 mTorr. Thereafter, a 50 nm B buffer layer, a 50 nm Cr underlayer, a 30 nm CoCrPt magnetic layer,
A 20 nm carbon protective film was sequentially formed.

Example 48 A 3.5-inch size amorphous polyolefin (AP
O) The substrate was formed by injection molding. The surface of the APO substrate was subjected to a plasma treatment at 200 W RF for 1 minute in an atmosphere at an oxygen pressure of 5 mTorr. Thereafter, a 50 nm SiN _x buffer layer is formed in an Ar + N ₂ gas atmosphere by DC magnetron sputtering, and then a 50 nm C
An r underlayer, a 30 nm CoCrPt magnetic layer, and a 20 nm carbon protective film were sequentially formed.

Example 49 3.5 inch size amorphous polyolefin (AP
O) The substrate was formed by injection molding. The surface of the APO substrate was subjected to a plasma treatment at 200 W RF for 1 minute in an atmosphere at an oxygen pressure of 5 mTorr. Thereafter, a 50 nm TiN _x buffer layer is formed in an Ar + N ₂ gas atmosphere by DC magnetron sputtering, and then a 50 nm Cr
An underlayer, a 30 nm CoCrPt magnetic layer, and a 20 nm carbon protective film were sequentially formed.

Example 50 A 3.5-inch size amorphous polyolefin (AP
O) The substrate was formed by injection molding. The surface of the APO substrate was subjected to a plasma treatment at 200 W RF for 1 minute in an atmosphere at an oxygen pressure of 5 mTorr. Thereafter, a 50 nm SiO _x buffer layer is formed in an Ar + O ₂ gas atmosphere by DC magnetron sputtering, and then a 50 nm C
An r underlayer, a 30 nm CoCrPt magnetic layer, and a 20 nm carbon protective film were sequentially formed.

Example 51 A 3.5-inch size amorphous polyolefin (AP
O) The substrate was formed by injection molding. The surface of the APO substrate was subjected to a plasma treatment at 200 W RF for 1 minute in an atmosphere at an oxygen pressure of 5 mTorr. Thereafter, a 50 nm BN _x buffer layer is formed in an Ar + N ₂ gas atmosphere by DC magnetron sputtering, and then a 50 nm Cr
An underlayer, a 30 nm CoCrPt magnetic layer, and a 20 nm carbon protective film were sequentially formed.

Example 52 A 3.5-inch size amorphous polyolefin (AP
O) The substrate was formed by injection molding. The surface of the APO substrate was subjected to a plasma treatment at 200 W RF for 1 minute in an atmosphere at an oxygen pressure of 5 mTorr. Thereafter, SiC _x of 50 nm is used in an Ar + CH ₄ gas atmosphere by DC magnetron sputtering.
A buffer layer was formed, and then a 50 nm Cr underlayer, a 30 nm CoCrPt magnetic layer, and a 20 nm carbon protective film were sequentially formed in an Ar atmosphere.

Example 53 3.5 inch size amorphous polyolefin (AP
O) The substrate was formed by injection molding. The surface of the APO substrate was irradiated with ultraviolet light having a wavelength of 184.9 nm in the air for 5 minutes. Then, a 50 nm Cr underlayer, 30 n in an Ar gas atmosphere by DC magnetron sputtering.
A CoCrPt magnetic layer having a thickness of m and a carbon protective film having a thickness of 20 nm were sequentially formed.

Example 54 A 3.5-inch size amorphous polyolefin (AP
O) The substrate was formed by injection molding. The surface of the APO substrate was irradiated with ultraviolet light having a wavelength of 184.9 nm in the air for 5 minutes. Thereafter, a 50 nm Si buffer layer was formed by DC magnetron sputtering in an Ar gas atmosphere.
50 nm Cr underlayer, 30 nm CoCrPt magnetic layer, 20 nm
nm of a carbon protective film was sequentially formed.

Example 55 3.5 inch size amorphous polyolefin (AP
O) The substrate was formed by injection molding. The surface of the APO substrate was irradiated with ultraviolet light having a wavelength of 184.9 nm in the air for 5 minutes. Thereafter, a B buffer layer having a thickness of 50 nm was formed by DC magnetron sputtering in an Ar gas atmosphere.
0 nm Cr underlayer, 30 nm CoCrPt magnetic layer, 20 n
m of carbon protective films were sequentially formed.

Example 56 A 3.5-inch size amorphous polyolefin (AP
O) The substrate was formed by injection molding. The surface of the APO substrate was irradiated with ultraviolet light having a wavelength of 184.9 nm in the air for 5 minutes. 50 nm SiN _x buffer layer in Ar + N ₂ gas atmosphere by DC magnetron sputtering Thereafter, Cr underlayer 50 nm, CoCrPt magnetic layer of 30 nm, were sequentially formed 20nm carbon protective film.

Example 57 3.5 inch size amorphous polyolefin (AP
O) The substrate was formed by injection molding. The surface of the APO substrate was irradiated with ultraviolet light having a wavelength of 184.9 nm in the air for 5 minutes. Thereafter, a 50 nm TiN _x buffer layer, a 50 nm Cr underlayer, a 30 nm CoCrPt magnetic layer, and a 20 nm carbon protective film were sequentially formed in a Ar + N ₂ gas atmosphere by DC magnetron sputtering.

Example 58 3.5 inch size amorphous polyolefin (AP
O) The substrate was formed by injection molding. The surface of the APO substrate was irradiated with ultraviolet light having a wavelength of 184.9 nm in the air for 5 minutes. BN _X buffer layer 50nm in Ar + N ₂ gas atmosphere by DC magnetron sputtering Thereafter, Cr underlayer 50nm, CoCrPt magnetic layer of 30 nm, were sequentially formed 20nm carbon protective film.

Example 59 3.5 inch size amorphous polyolefin (AP
O) The substrate was formed by injection molding. The surface of the APO substrate was irradiated with ultraviolet light having a wavelength of 184.9 nm in the air for 5 minutes. Thereafter, a 50 nm SiO _x buffer layer, a 50 nm Cr underlayer, a 30 nm CoCrPt magnetic layer, and a 20 nm carbon protective film were sequentially formed by DC magnetron sputtering in an Ar + O ₂ gas atmosphere.

Example 60 3.5 inch size amorphous polyolefin (AP
O) The substrate was formed by injection molding. The surface of the APO substrate was irradiated with ultraviolet light having a wavelength of 184.9 nm in the air for 5 minutes. 50 nm SiC _x buffer layer in Ar + CH ₄ gas atmosphere by DC magnetron sputtering Thereafter, Cr underlayer 50 nm, CoCrPt magnetic layer of 30 nm, were sequentially formed 20nm carbon protective film.

Example 61 3.5 inch size amorphous polyolefin (AP
O) The substrate was formed by injection molding. At the time of this injection formation, pre-pits of data tracks and servo tracks are formed on the surface of the APO substrate by using a grooved stamper. The surface of the APO substrate was irradiated with ultraviolet light having a wavelength of 184.9 nm in the air for 5 minutes. After this DC
50 nm Cr underlayer, 30 nm CoCrPt magnetic layer, 20 nm in Ar gas atmosphere by magnetron sputtering
nm of a carbon protective film was sequentially formed.

Example 62 3.5 inch size amorphous polyolefin (AP
O) The substrate was formed by injection molding. At the time of this injection formation, pre-pits of data tracks and servo tracks are formed on the surface of the APO substrate by using a grooved stamper. The surface of the APO substrate was subjected to a plasma treatment at 200 W RF for 1 minute in an atmosphere of oxygen pressure of 5 mTorr. After this D
50 nm Cr underlayer, 30 nm CoCrPt magnetic layer, 2 nm in Ar gas atmosphere by C magnetron sputtering
A carbon protective film of 0 nm was sequentially formed.

Comparative Example 1 3.5 inch size amorphous polyolefin (AP
O) The substrate was formed by injection molding. After that, the DC magnetron sputtering was performed for 50 n
A Cr underlayer of 30 m, a CoCrPt magnetic layer of 30 nm, and a carbon protective film of 20 nm were sequentially formed.

The sample surfaces of Examples 43 to 62 and Comparative Example 1 were observed with a scanning electron microscope (SEM). As a result, no cracks could be observed on the medium surfaces of Examples 43 to 62. On the other hand, in Comparative Example 1, the length was 1.5 μm and the width was 0.05 μm.
Many earthworm-like cracks of about m were observed on the medium surface.

When the surface of the APO substrate before the oxygen plasma or ultraviolet irradiation treatment was examined by X-ray photoelectron spectroscopy (XPS), almost no oxygen was present on the APO surface, and the surface of the APO had only -CH ₂ -chains. It turned out that it was covered with. On the other hand, the surface after the APO surface was treated with oxygen plasma or ultraviolet light was analyzed by XPS to show 12.7 to 27.5 at%.
Of oxygen was detected. Therefore, when the APO surface is treated with oxygen plasma or ultraviolet rays (wavelength 184.9 nm), AP
Many functional groups containing oxygen are generated on the O surface, and the affinity and wettability with inorganic substances such as metals, oxides, nitrides, borides, silicides, and carbides are increased, and as a result, these inorganic substances It is considered that the occurrence of cracks on the medium surface due to an increase in the adhesive force was suppressed.

The alkylamine-based lubricants of Examples 1 to 9 and the lubricant which is liquid at room temperature of Examples 10 to 41 were lubricated in a combination shown in Table 1 below using methyl isobutyl ketone (MIBK) as a solvent. An agent solution was prepared. Table 1 Example No. Alkylamine-based lubricant concentration (wt.%) Liquid lubricant concentration (wt.%) 63 Example 3 0.05 Example 10 0.03 64 Example 3 0.05 Example 15 0.03 65 Example 3 0.05 Execution Example 17 0.03 66 Example 8 0.05 Example 10 0.03 67 Example 8 0.05 Example 15 0.03 68 Example 8 0.05 Example 17 0.03 69 Example 4 0.05 Example 10 0.03 70 Example 4 0.05 Example 15 0.03 71 Example Example 4 0.05 Example 17 0.03 72 Example 3 0.05 Example 18 0.03 73 Example 3 0.05 Example 21 0.03 74 Example 3 0.05 Example 23 0.03 75 Example 8 0.05 Example 18 0.03 76 Example 8 0.05 Example 21 0.03 77 Example 8 0.05 Example 23 0.03 78 Example 4 0.05 Example 18 0.03 79 Example 4 0.05 Example 21 0.03 80 Example 4 0.05 Example 23 0.03 81 Example 3 0.05 Example 24 0.03 82 Example 3 0.05 Example 25 0.03 83 Example 3 0.05 Example 28 0.03 84 Example 3 0.05 Example 29 0.03 85 Example 8 0.05 Example 24 0.03 86 Example 8 0.05 Example 25 0.03 87 Example 8 0.05 Example 28 0.03 88 Example 8 0.05 Example 29 0.03 89 Example 4 0.05 Example 24 0.03 90 Example 4 0.05 Example 25 0.03 91 Example 4 0.05 Example 28 0.03 92 Example 4 0.05 Example 30 0.03 93 Example 3 0.05 Example Example 29 0.03 94 Example 3 0.05 Example 36 0.03 95 Example 3 0.05 Example 38 0.03 96 Example 3 0.05 Example 40 0.03 97 Example 8 0.05 Example 32 0.03 98 Example 4 0.05 Example 32 0.03 99 Example Example 3 0.05 Example 32 0.03

COMPARATIVE EXAMPLE The alkylamine-based lubricants of Examples 1 to 9 alone or the lubricants of Examples 10 to 35 which were liquid at room temperature were used in methyl isobutyl ketone (MIBK) as a solvent. A lubricant solution was prepared. Table 2 Comparative Example No. Alkylamine-based lubricant concentration (wt.%) Liquid lubricant concentration (wt.%) 2 Example 3 0.05 None-3 Example 8 0.05 None-4 Example 4 0.05 None- 5 None-Example 10 0.03 6 None-Example 15 0.03 7 None-Example 17 0.03 8 None-Example 18 0.03 9 None-Example 21 0.03 10 None-Example 23 0.03 11 None -Example 24 0.03 12 None-Example 25 0.03 13 None-Example 28 0.03 14 None-Example 30 0.03 15 None-Example 32 0.03

Example 100 The surface of the carbon protective film of Examples 43 to 62 was exposed to air in air.
Irradiation treatment was performed with ultraviolet rays having a wavelength of 4.9 nm for 5 minutes. Thereafter, the lubricant solutions of Examples 63 to 99 were spin-coated on the surface of the carbon protective film subjected to the ultraviolet irradiation treatment.
Spin coating: substrate rotation speed 1000 rpm, liquid pressure 4 kg
Coating was performed at f / cm ² for 3 seconds, and then the excess lubricant solution was shaken off at a substrate rotation speed of 3000 rpm.

Comparative Example 16 The lubricant solution of Examples 63 to 99 was spin-coated on the surface of the carbon protective film without subjecting the surface of the carbon protective film of Examples 43 to 62 to UV irradiation treatment. The spin coating is performed at a substrate rotation speed of 1000 rpm at a liquid pressure of 4 kgf / cm ² for 3 seconds, and then an excess lubricant solution is applied at a substrate rotation speed of 300 rpm.
Shake off at 0 rpm.

Comparative Example 17 The surface of the carbon protective film of Examples 43 to 62 was
Irradiation treatment was performed with ultraviolet rays having a wavelength of 4.9 nm for 5 minutes. Thereafter, the lubricant solutions of Comparative Examples 2 to 15 were spin-coated on the surface of the carbon protective film subjected to the ultraviolet irradiation treatment. Spin coating is performed at a substrate rotation speed of 1000 rpm and a liquid pressure of 4 kgf.
/ Cm ² for 3 seconds, and then the excess lubricant solution was shaken off at a substrate rotation speed of 3000 rpm.

Example 101 The excess lubricant layer on the surface of the carbon protective film of Example 100 and Comparative Example 17 was subjected to ultrasonic cleaning with acetone for 30 seconds.
The composition ratio (O / C) of oxygen and carbon on the surface of the carbon protective film was measured at a detection angle of 45 degrees using X-ray photoelectron spectroscopy (XPS). As a result, it was confirmed that the composition ratio (O / C) was 0.1 or more on the surface of the carbon protective film of Example 93 and Comparative Example 17.

Comparative Example 18 The surplus lubricant layer on the surface of the carbon protective film of Comparative Example 16 was subjected to ultrasonic cleaning with acetone for 30 seconds, and then the composition ratio (O / C) of oxygen and carbon on the surface of the carbon protective film was determined by X-ray. The measurement was performed at a detection angle of 45 degrees using photoelectron spectroscopy (XPS). as a result,
The composition ratio (O / C) was 0.1% on the surface of the protective film.
It was confirmed that it was less than.

Example 102 The samples of Example 100 and Comparative Examples 16 to 17 were prepared using TiC.A
A CSS test was performed using a thin film head having an l ₂ O ₃ composite slider. CSS test condition is 30 ℃,
Under the condition of 80% RH, the relative speed between the head and the medium is accelerated to 7.54 m / s in 1 second under a load of 3 gf, held at 7.54 m / s in 1 second, and decelerated and stopped in 1 second. This is a test in which one cycle of CSS is held for one second and the cycle is four seconds.

Example 103 The samples of Example 100 and Comparative Examples 16 to 17 were prepared using TiC.A
A CSS test was performed using a thin film head having an l ₂ O ₃ composite slider. CSS test condition is 55 ℃,
Under a condition of 20% RH, under a load of 3 gf, the relative speed between the head and the medium is accelerated to 7.54 m / s in 1 second, held at 7.54 m / s in 1 second, and decelerated and stopped in 1 second. This is a test in which one cycle of CSS is held for one second and the cycle is four seconds.

Embodiment 104 In the CSS test of Embodiment 102 (30 ° C., 80% RH), the maximum value of stiction and C at the beginning of disk rotation were measured.
The SS durability is shown in Table 3 below. Table 3 Sample of CSS characteristics at 30 ° C. and 80% RH Maximum value of stiction (gf) CSS durability (Cycles) Example 100 0.5 to 1.5> 20,000 Comparative Example 16 1.5 to 2.0 10,000 to 15,000 Comparative Example 2 0.5 to 1.5 > 20,000 Comparative Example 3 0.5-1.5> 20,000 Comparative Example 4 0.5-1.5> 20,000 Comparative Example 5-15 1.5-2.0 3,000-8,000

Even when a two-component mixed lubricant of an alkylamine-based lubricant and a liquid lubricant at room temperature is used, the surface of the carbon protective film is not irradiated with ultraviolet light, or the surface of the carbon protective film is irradiated with ultraviolet light. No amine lubricant
It can be seen that stiction is large only with the lubricant that is liquid at normal temperature, and the CSS durability is inferior to the sample of Example 100. Further, a sample in which the surface of the carbon protective film was subjected to ultraviolet irradiation treatment and only an alkylamine-based lubricant was applied thereon exhibited CSS characteristics equivalent to those of the sample of Example 100 in an environment of 30 ° C. and 80% RH. .

Embodiment 105 In the CSS test of Embodiment 103 (55 ° C., 20% RH), the maximum value of stiction at the initial stage of disk rotation and C
The SS durability is shown in Table 4 below. Table 4 Sample of CSS characteristics at 55 ° C. and 20% RH Maximum value of stiction (gf) CSS durability (Cycles) Example 100 0.3 to 1.0> 20,000 Comparative Example 16 1.0 to 1.5 15,000 to 20,000 Comparative Example 2 2.0 to 3.5 2,000 Comparative Example 3 2.0 to 3.5 2,000 Comparative Example 4 2.0 to 3.5 2,000 Comparative Example 5 to 15 0.5 to 1.5 5,000 to 13,000

In the sample of Example 100, the temperature was 55 ° C.
The stiction decreases even when the temperature reaches ℃, and the CSS durability is equivalent to that at 30 ° C. It is considered that the stiction decreases at 55 ° C. because the viscosity of the liquid lubricant at normal temperature decreases at high temperature. At high temperatures, the samples of Comparative Example 16 and Comparative Examples 5 to 15 having a liquid lubricant at room temperature also show reduced stiction and improved CSS durability. On the other hand, Comparative Examples 2 to 4 having only an alkylamine-based solid lubricant showing good CSS characteristics at 30 ° C
Shows that stiction increases at a high temperature of 55 ° C. and CSS durability also decreases. This is because, as described in detail in the prior art, alkylamine-based lubricants lose boundary lubricity near their melting points.

The surface of the carbon protective film according to the present invention is irradiated with ultraviolet rays and the surface thereof has a two-component lubricant of an alkylamine-based solid lubricant and a lubricant which is liquid at room temperature. It can be seen that good CSS characteristics are exhibited in a wide temperature and humidity range of 20 ° C. and 20% RH.

Embodiment 106 A diamond-like carbon protective film was formed on the surface of a TiC.Al ₂ O ₃ composite slider by a plasma CVD method.
0 nm was formed.

Example 107 A diamond-like carbon protective film was formed on the surface of a TiC.Al ₂ O ₃ composite slider by a plasma CVD method.
0 nm was formed. Next, the surface of this DLC protective film was set to 184.
Ultraviolet irradiation was performed for 5 minutes in the air using a low-pressure mercury lamp generating a wavelength of 9 nm. X-ray photoelectron spectroscopy (XPS) of oxygen / carbon composition ratio (O / C) on carbon protective film surface
Was measured at a detection angle of 45 degrees. As a result, it was confirmed that the composition ratio (O / C) was 0.1 or more on the surface of the carbon protective film.

Embodiment 108 A diamond-like carbon protective film was formed on the surface of a TiC.Al ₂ O ₃ composite slider by a plasma CVD method.
0 nm was formed. Next, the surface of this DLC protective film was set to 184.
Ultraviolet irradiation was performed for 5 minutes in the air using a low-pressure mercury lamp generating a wavelength of 9 nm. Thereafter, stearylamine (concentration: 0.05 wt%, solvent: methyl isobutyl ketone) was spray-coated on the DLC protective film. After the excess lubricant layer on the surface of the carbon protective film is ultrasonically cleaned with acetone for 30 seconds, the composition ratio (O / C) of oxygen and carbon on the surface of the carbon protective film is detected by X-ray photoelectron spectroscopy (XPS). Measured at 45 degrees. As a result, it was confirmed that the composition ratio (O / C) was 0.1 or more on the surface of the protective film.

Example 109 The medium obtained in Example 100 was replaced with TiC.A without the magnetic head slider and DLC protective film of Examples 106 to 108.
A CSS test was performed using an l ₂ O ₃ composite slider. The CSS test conditions were 55 ° C., 20% RH, a head vertical load of 3.5 g, a measurement radius of 19 mm, a disk rotation speed of 5400 rpm in 3 seconds, a relative speed of 12.4 m / s, and a floating for 10 seconds. , Deceleration and stop for 6 seconds, and rest for 11 seconds.

Example 110 Table 5 summarizes the maximum value of stiction and CSS durability. As can be seen from the table, a DLC protective film was provided on the magnetic head slider, the surface of the DLC protective film was irradiated with ultraviolet light having a wavelength of 184.9 nm, and then an alkylamine-based lubricant was applied to the surface of the DLC protective film. It can be seen that the application reduces the stiction particularly as compared with the magnetic head slider without the DLC protective film. This is because the carbon-based protective film DLC is also provided on the magnetic head slider, so that the alkylamine-based lubricant is chemically adsorbed on the DLC on the surface of the magnetic head slider at the beginning of sliding or during sliding, as shown in FIG. It is considered that the friction between the hydrocarbon chains was caused by the liquid lubricant. Table 5 CSS characteristics at 55 ° C and 20% RH ──────────────────────────────────── Medium Magnetic head {slicer} Maximum value of stiction (gf) CSS durability (cycle) Example 100 TiC / Al ₂ O ₃ 0.3 to 1.0> 20,000 Example 100 Example 106 0.2 to 0.8> 20,000 Example 100 Example 107 0.2 to 0.6> 20,000 Example 100 Example 108 0.1 to 0.4> 20,000 ────────────────────────────────────

Example 111 Co was obliquely deposited to a thickness of 0.15 μm on a surface of a 6.3 μm thick PET film in an oxygen atmosphere.
_The gas for film formation was controlled to ₂ H ₄ : 60 ml / min and H ₂ : 120 ml / min, and RF at 13.56 MHz and 1 kW was used.
A DLC (diamond-like carbon) protective film having a thickness of 20 nm was formed on the magnetic layer by a plasma polymerization method using a power supply. The produced medium was cut into a width of 8 mm to obtain a magnetic tape. The surface of the carbon protective film of this magnetic tape was
Irradiation treatment was performed with ultraviolet light having a wavelength of 84.9 nm for 5 minutes. Thereafter, a lubricant solution was prepared from the amine of Example 3 (concentration: 0.05 wt%) and the liquid lubricant of Example 10 (concentration: 0.03 wt%) using methyl isobutyl ketone as a solvent. Was applied to the magnetic tape.

Example 112 Co was obliquely vapor-deposited on an aramid film having a thickness of 3.8 μm to a thickness of 0.15 μm in an oxygen atmosphere.
C ₂ H ₄ : 60 ml / min, H ₂ : 120 ml / min
13.56 MHz, 1 kW R
DLC on magnetic layer by plasma polymerization using F power supply
(Diamond-like carbon) A protective film having a thickness of 20 nm was formed. The produced medium was cut into a width of 8 mm to obtain a magnetic tape. The surface of the carbon protective film of this magnetic tape was
Irradiation treatment was performed with ultraviolet light having a wavelength of 84.9 nm for 5 minutes. Thereafter, a lubricant solution was prepared from the amine of Example 3 (concentration: 0.05 wt%) and the liquid lubricant of Example 10 (concentration: 0.03 wt%) using methyl isobutyl ketone as a solvent. Was applied to the magnetic tape.

Example 113 Co was obliquely vapor-deposited on a surface of a PEN film having a thickness of 6.0 μm to a thickness of 0.15 μm in an oxygen atmosphere.
_The gas for film formation was controlled to ₂ H ₄ : 60 ml / min and H ₂ : 120 ml / min, and RF at 13.56 MHz and 1 kW was used.
A DLC (diamond-like carbon) protective film having a thickness of 20 nm was formed on the magnetic layer by a plasma polymerization method using a power supply. The produced medium was cut into a width of 8 mm to obtain a magnetic tape. The surface of the carbon protective film of this magnetic tape was
Irradiation treatment was performed with ultraviolet light having a wavelength of 84.9 nm for 5 minutes. Thereafter, a lubricant solution was prepared from the amine of Example 3 (concentration: 0.05 wt%) and the liquid lubricant of Example 10 (concentration: 0.03 wt%) using methyl isobutyl ketone as a solvent. Was applied to the magnetic tape.

Comparative Example 19 Co was obliquely deposited to a thickness of 0.15 μm on the surface of a PET film having a thickness of 6.3 μm in an oxygen atmosphere.
_The gas for film formation was controlled to ₂ H ₄ : 60 ml / min and H ₂ : 120 ml / min, and RF at 13.56 MHz and 1 kW was used.
A DLC (diamond-like carbon) protective film having a thickness of 20 nm was formed on the magnetic layer by a plasma polymerization method using a power supply. The produced medium was cut into a width of 8 mm to obtain a magnetic tape. The surface of the carbon protective film of this magnetic tape was
Irradiation treatment was performed with ultraviolet light having a wavelength of 84.9 nm for 5 minutes. Thereafter, a lubricant solution was prepared from the amine of Example 3 (concentration: 0.05 wt%) using methyl isobutyl ketone as a solvent, and the lubricant solution was applied to the magnetic tape.

Example 114 The samples of Examples 111 to 113 and Comparative Example 19 were prepared by using 8 samples.
A still test was performed using an mmVTR. At this time, the motor load current of the cylinder and the reproduction output were monitored, and the time during which the reproduction output became half of the initial value was defined as the still life. The still test was performed at 55 ° C. and 20% RH under a tape tension of 1
2.5g / cm, relative speed between head and tape 11.3m
Per second. Table 6 shows the cylinder load current value and still life measurement results. Table 6 Sample of still test measurement result at 55 ° C. and 20% RH Cylinder load current value (mA) Still life (hr) Example 111 25> 150 Example 112 24> 150 Example 113 25> 150 Comparative example 19 63 0 .5

Example 115 The following compounds were used as a lubricant which is liquid at ordinary temperature. [FC ₆ H ₄ O] _2- (P ₃ N ₃ )-[OC ₆ H ₄ CF ₃ ] ₄

Example 116 The following compounds were used as a lubricant which is liquid at ordinary temperature. [FC ₆ H ₄ O] _3- (P ₃ N ₃ )-[OC ₆ H ₄ CF ₃ ] ₃

Example 117 The following compounds were used as lubricants which were liquid at room temperature. _{[FC 6 H 4 O] 4} - (P 3 N 3) - [OC 6 H 4 CF 3] 2

Example 118 The following compounds were used as a lubricant which was liquid at ordinary temperature. (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ C (H) (OCOC (CH ₃ ) ₂ (C ₆ H ₁₃ )) CH ₂ OCOC (CH
₃ ) ₂ (C ₆ H ₁₃ )

Example 119 The following compounds were used as a lubricant which is liquid at ordinary temperature. (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ C (H) (OCOC (CH ₃ ) ₂ (C ₆ H ₁₃ )) CH ₂ OCOC (CH
₃ ) ₂ (C ₆ H ₁₃ )

Example 120 The following compounds were used as a lubricant which was liquid at ordinary temperature. F (CF ₂ ) ₆ CH ₂ C (H) (OCOC (CH ₃ ) ₂ (C ₆ H ₁₃ )) CH ₂ OCOC (CH ₃ ) ₂ (C ₆ H
₁₃ )

Example 121 The following compounds were used as a lubricant which is liquid at ordinary temperature. F (CF ₂ ) ₈ CH ₂ C (H) (OCOC (CH ₃ ) ₂ (C ₆ H ₁₃ )) CH ₂ OCOC (CH ₃ ) ₂ (C ₆ H
₁₃ )

Example 122 It was confirmed that the compounds of Examples 115 to 121 were soluble in isopropyl alcohol, methyl isobutyl ketone and normal heptane at a concentration of 1.0% by weight at room temperature.

Example 123 A radius of 16.76 mm to 20.73 mm and a height of 30 n
m, a 3.5-inch size amorphous polyolefin (APO) substrate having a dot-shaped texture zone having an apparent area ratio of 0.5% was formed by injection molding.
On this APO substrate, DC magnetron sputtering
0 nm Ti buffer layer, 50 nm CrTi underlayer,
A 15 nm CoCrPt magnetic layer and a 15 nm nitrogen-containing carbon protective film were sequentially formed.

Example 124 A radius of 16.76 mm to 20.73 mm and a height of 30 n
m, a 3.5-inch size amorphous polyolefin (APO) substrate having a dot-shaped texture zone having an apparent area ratio of 0.5% was formed by injection molding.
On this APO substrate, DC magnetron sputtering
0 nm Si buffer layer, 50 nm CrTi underlayer,
A 15 nm CoCrPt magnetic layer and a 15 nm nitrogen-containing carbon protective film were sequentially formed.

Example 125 A radius of 16.76 mm to 20.73 mm and a height of 30 n
m, a 3.5-inch size amorphous polyolefin (APO) substrate having a dot-shaped texture zone having an apparent area ratio of 0.5% was formed by injection molding.
On this APO substrate, DC magnetron sputtering
A 0 nm SiNx buffer layer, a 50 nm CrTi underlayer, a 15 nm CoCrPt magnetic layer, and a 15 nm nitrogen-containing carbon protective film were sequentially formed.

Example 126 A radius of 16.76 mm to 20.73 mm and a height of 30 n
m, a 3.5-inch size amorphous polyolefin (APO) substrate having a dot-shaped texture zone having an apparent area ratio of 0.5% was formed by injection molding.
On this APO substrate, DC magnetron sputtering
A 0 nm TiNx buffer layer, a 50 nm CrTi underlayer, a 15 nm CoCrPt magnetic layer, and a 15 nm nitrogen-containing carbon protective film were sequentially formed.

Example 127 A radius of 16.76 mm to 20.73 mm and a height of 30 n
m, a 3.5-inch size amorphous polyolefin (APO) substrate having a dot-shaped texture zone having an apparent area ratio of 0.5% was formed by injection molding.
On this APO substrate, DC magnetron sputtering
Buffer layer made of 0 nm Si and 50 nm Ti, 5
A CrTi underlayer of 0 nm, a CoCrPt magnetic layer of 15 nm, and a nitrogen-containing carbon protective film of 15 nm were sequentially formed.

Example 128 A radius of 16.76 mm to 20.73 mm and a height of 30 n
m, a 3.5-inch size amorphous polyolefin (APO) substrate having a dot-shaped texture zone having an apparent area ratio of 0.5% was formed by injection molding.
On this APO substrate, DC magnetron sputtering
Buffer layer consisting of 0 nm SiNx and 50 nm Ti, 50 nm CrTi underlayer, 15 nm CoCrP
A t-magnetic layer and a 15 nm nitrogen-containing carbon protective film were sequentially formed.

Example 129 A radius of 16.76 mm to 20.73 mm and a height of 30 n
m, a 3.5-inch size amorphous polyolefin (APO) substrate having a dot-shaped texture zone having an apparent area ratio of 0.5% was formed by injection molding.
On this APO substrate, DC magnetron sputtering
A 0 nm NiPx buffer layer, a 50 nm CrTi underlayer, a 15 nm CoCrPt magnetic layer, and a 15 nm nitrogen-containing carbon protective film were sequentially formed.

Example 130 A radius of 16.76 mm to 20.73 mm and a height of 30 n
m, a 3.5-inch size amorphous polyolefin (APO) substrate having a dot-shaped texture zone having an apparent area ratio of 0.5% was formed by injection molding.
On this APO substrate, DC magnetron sputtering
Buffer layer consisting of 0 nm NiPx and 50 nm Ti, 50 nm CrTi underlayer, 15 nm CoCrP
A t-magnetic layer and a 15 nm nitrogen-containing carbon protective film were sequentially formed.

Example 131 A radius of 16.76 mm to 20.73 mm and a height of 30 n
m, a 3.5-inch size amorphous polyolefin (APO) substrate having a dot-shaped texture zone having an apparent area ratio of 0.5% was formed by injection molding.
On this APO substrate, DC magnetron sputtering
Buffer layer made of 0 nm Mo and 50 nm Ti, 5
A CrTi underlayer of 0 nm, a CoCrPt magnetic layer of 15 nm, and a nitrogen-containing carbon protective film of 15 nm were sequentially formed.

Examples 132 to 140 The conditions described in Examples 123 to 131 were the same as those in Examples 123 to 131 except that a polycarbonate substrate molded by injection molding was used instead of the APO substrate in Examples 123 to 131. Samples were prepared under the same conditions.

Examples 141 to 149 The conditions described in Examples 123 to 131 were used, except that the hydrogen-containing carbon protective film was used instead of the nitrogen-containing carbon protective film in Examples 123 to 131. A sample was prepared under the same conditions as described above.

A lubricant solution was prepared by combining the alkylamine lubricant of Example 3 and the liquid lubricants of Examples 115 to 121 with methyl isobutyl ketone as a solvent, as shown in Table 7 below. Table 7 Example No. Alkylamine-based lubricant concentration (wt.%) Liquid lubricant concentration (wt.%) 150 Example 3 0.05 Example 115 0.05 151 Example 3 0.05 Example 116 0.05 152 Example 3 0.05 Example Example 117 0.05 153 Example 3 0.05 Example 118 0.05 154 Example 3 0.05 Example 119 0.05 155 Example 3 0.05 Example 120 0.05 156 Example 3 0.05 Example 121 0.05

Comparative Examples 20 to 27 The alkylamine-based lubricant of Example 3 alone or the lubricant which is a liquid at room temperature of Examples 115 to 121 was used alone in a methyl isobutyl ketone solvent as shown in Table 8 below.
Was prepared. Table 8 Comparative Example No. Alkylamine-based lubricant concentration (wt.%) Liquid lubricant concentration (wt.%) 20 Example 3 0.05 -----21 ----Example 115 0.05 22- - - example 116 0.05 23 --- - example 117 0.05 24 --- - example 118 0.05 25 --- - example 119 0.05 26 --- - example 120 0.05 27 - --Example 121 0.05

Example 157 The surfaces of the carbon-based protective films of Examples 123 to 149 were irradiated in the atmosphere for 5 minutes with a low-pressure mercury lamp generating an ultraviolet ray having a wavelength of 184.9 nm. Then, Example 150
-The lubricant solution of Example 156 was spin-coated on the surface of the carbon-based protective film subjected to the ultraviolet irradiation treatment. The spin coating was performed under the conditions of a discharge radius of 22.5 mm, a liquid pressure of 4 kg / cm ² , and a substrate rotation speed of 1000 rpm for 3 seconds. Thereafter, an excessive lubricant solution was shaken off at a substrate rotation speed of 3000 rpm for 3 seconds.

Comparative Example 28 Examples 150 to 156 were obtained without irradiating the surface of the carbon-based protective film of Examples 123 to 149 with ultraviolet rays.
Was spin-coated on the surface of the carbon-based protective film. The spin coating conditions were a discharge radius of 22.5 mm and a liquid pressure of 4
kg / cm ^{2 at} a substrate rotation speed of 1000 rpm for 3 seconds, and then excess lubricant solution is discharged at a substrate rotation speed of 3000 rpm.
Shake off at pm for 3 seconds.

Comparative Example 29 The surfaces of the carbon-based protective films of Examples 123 to 149 were irradiated in the atmosphere with a low-pressure mercury lamp generating ultraviolet light having a wavelength of 184.9 nm for 5 minutes. Thereafter, Comparative Examples 20 to
The lubricant solution No. 27 was spin-coated on the surface of the carbon-based protective film which had been subjected to the ultraviolet irradiation treatment. The spin coating conditions were a discharge radius of 22.5 mm, a liquid pressure of 4 kg / cm ² , and a substrate rotation speed of 10
The liquid was discharged at 00 rpm for 3 seconds, and then the excess lubricant solution was shaken off at 3000 rpm for 3 seconds.

Example 158 The excess lubricant on the surface of the carbon-based protective film of Example 157 and Comparative Example 29 was ultrasonically cleaned with acetone for 30 seconds, and then the composition ratio of oxygen and carbon (O / C) on the surface of the carbon-based protective film. ) Was measured at a detection angle of 45 degrees using X-ray photoelectron spectroscopy (XPS). As a result, the composition ratio (O / C) of Example 1
57 and on the surface of the carbon-based protective film of Comparative Example 29,
It was confirmed that it was 0.1 or more.

Comparative Example 30 The excess lubricant on the surface of the carbon-based protective film of Comparative Example 28 was subjected to ultrasonic cleaning with acetone for 30 seconds, and then the composition ratio (O / C) of oxygen and carbon on the surface of the carbon-based protective film was determined by X-rays. The measurement was performed at a detection angle of 45 degrees using photoelectron spectroscopy (XPS). As a result, it was confirmed that the composition ratio (O / C) was less than 0.1.

Example 159 The surfaces of the carbon-based protective films of Examples 123 to 149 were subjected to an oxygen plasma treatment for 10 seconds using a 13.56 MHz high frequency power supply in an atmosphere at an oxygen pressure of 3 mTorr. Thereafter, the lubricant solutions of Examples 150 to 156 were spin-coated on the surface of the carbon-based protective film subjected to the oxygen plasma treatment. The spin coating was performed at a discharge radius of 22.5 mm, a liquid pressure of 4 kg / cm ² , and a substrate rotation speed of 1000 rpm for 3 seconds.
Shake off for 3 seconds at rpm.

Example 160 After the excess lubricant on the surface of the carbon-based protective film of Example 159 was ultrasonically cleaned with acetone for 30 seconds, the composition ratio (O / C) of oxygen and carbon on the surface of the carbon-based protective film was determined by X-rays. The measurement was performed at a detection angle of 45 degrees using photoelectron spectroscopy (XPS). As a result, it was confirmed that the composition ratio (O / C) was 0.1 or more.

Example 161 The samples of Example 157, Comparative Examples 28 to 29 and Example 159 were subjected to a CSS (Contact Start and Stop) test using a thin film head having a TiC.Al ₂ O ₃ composite slider. In the CSS test, under an environment of 30 ° C. and 80% RH, at a head vertical load of 3.5 g and a measurement radius of 19 mm, the disk speed was increased to 5400 rpm in 3 seconds, the relative speed was 12.4 m / s, and the sample was levitated for 10 seconds. The test was performed under a test condition of 30 seconds per cycle consisting of decelerating and stopping in 6 seconds and pausing for 11 seconds. In addition, Example 123-
The plastic substrate used for 149 has a radius of 16.76 m.
A dot-shaped texture zone having a height of 30 nm and an apparent area ratio of 0.5% was found in the range of m to 20.73 mm.

Example 162 The samples of Example 157, Comparative Examples 28 to 29 and Example 159 were subjected to a CSS (Contact Start and Stop) test using a thin film head having a TiC.Al ₂ O ₃ composite slider. In a CSS test, the disk was accelerated to a disk rotation speed of 5400 rpm and a relative speed of 12.4 m / s in 3 seconds at a head vertical load of 3.5 g and a measurement radius of 19 mm in an environment of 55 ° C. and 20% RH and a measurement radius of 19 mm. The test was performed under a test condition of 30 seconds per cycle consisting of decelerating and stopping in 6 seconds and pausing for 11 seconds. Examples 121 to 121
The plastic substrate used for 147 has a radius of 16.76 m.
A dot-shaped texture zone having a height of 30 nm and an apparent area ratio of 0.5% was found in the range of m to 20.73 mm.

Example 163 In the CSS test of Example 161 (30 ° C., 80% RH), the maximum value of stiction and CS at the initial stage of disk rotation were measured.
The S durability results are summarized in Table 9 below. Table 9 Sample of CSS characteristics at 30 ° C. and 80% RH Maximum stiction (gf) CSS durability (Cycles) Example 157 0.9 to 1.5> 20000 Comparative Example 28 1.5 to 2.0 10,000 to 15000 Comparative Example 29 (Lubricity) Agent: Comparative Example 20) 1.5> 20000 Comparative Example 29 (Lubricant: Comparative Example 21) 2.0 10000 Comparative Example 29 (Lubricant: Comparative Example 22) 2.0 10000 Comparative Example 29 (Lubricant: Comparative Example 23) 2.0 10000 Comparative Example 29 (Lubricant: Comparative Example 24) 3.5 2000 Comparative Example 29 (Lubricant: Comparative Example 25) 3.5 2000 Comparative Example 29 (Lubricant: Comparative Example 26) 3.5 2000 Comparative Example 29 (Lubricant: Comparative Example 27) 3.5 2000 Example 159 0.9-1.5> 20000

From the results shown in Table 9 above, even if an alkylamine-based lubricant and a two-component mixed lubricant liquid at room temperature were used, the surface of the carbon-based protective film was not subjected to ultraviolet irradiation treatment or oxygen plasma treatment. Also, even if the surface of the carbon-based protective film is treated with ultraviolet light, there is no alkylamine-based lubricant, and only the lubricant that is liquid at normal temperature has a large stiction and the CSS durability is inferior to those of Examples 157 and 159. You can see that. Further, in the case of the sample in which the surface of the carbon-based protective film was subjected to ultraviolet treatment and only the alkylamine-based lubricant was applied thereon, under the environment of 30 ° C. and 80% RH, CSS characteristics equivalent to those of Examples 157 and 159 were obtained. Show.

Example 164 In Example 162 (55 ° C., 20% RH) in the CSS test, the maximum value of the stiction and CS at the initial stage of disk rotation were measured.
The S durability results are summarized in Table 10 below. Table 10 Sample of CSS characteristics at 55 ° C and 20% RH Maximum stiction (gf) CSS durability (Cycles) Example 157 0.5 to 1.2> 20000 Comparative Example 28 1.0 to 1.5 5000 to 10000 Comparative Example 29 (lubrication Agent: Comparative Example 20) 3.5 7000 Comparative Example 29 (Lubricant: Comparative Example 21) 1.5 5000 Comparative Example 29 (Lubricant: Comparative Example 22) 1.5 5000 Comparative Example 29 (Lubricant: Comparative Example 23) 1.5 5000 Comparative Example 29 (Lubricant: Comparative Example 24) 2.0 200 Comparative Example 29 (Lubricant: Comparative Example 25) 2.0 200 Comparative Example 29 (Lubricant: Comparative Example 26) 2.0 2000 Comparative Example 29 (Lubricant: Comparative Example 27) 2.0 2000 Implementation Example 159 0.5-1.2> 20000

As is clear from the results shown in Table 10, in the samples of Examples 157 and 159, even when the test environment was at a high temperature of 55 ° C., stiction was reduced and CSS durability was low. Is equivalent to 30 ° C.
It is considered that the reason why the stiction decreases at 55 ° C. is that the viscosity of the lubricant that is liquid at normal temperature decreases at high temperature. On the other hand, Comparative Example 29 having only an alkylamine lubricant showing good CSS properties at 30 ° C. (lubricant:
In Comparative Example 20), stiction increases at a high temperature of 55 ° C., and CSS durability also decreases. This is because, as described in detail in the prior art, alkylamine lubricants lose boundary lubrication near their melting points.

Therefore, the carbon-based protective film according to the present invention is subjected to ultraviolet irradiation treatment or plasma treatment in an oxygen-containing environment, and the surface thereof is subjected to two-component lubrication comprising an alkylamine-based lubricant and a lubricant which is liquid at room temperature. It can be understood that the sample having the agent exhibits good CSS characteristics in a wide temperature and humidity range from 30 ° C. and 80% RH to 55 ° C. and 20% RH.

[0196]

According to the present invention, the surface of the carbon protective film according to the present invention is irradiated with ultraviolet rays, and the surface is coated with a two-component lubricant of an alkylamine-based solid lubricant and a liquid lubricant at room temperature. It exhibits good CSS characteristics in a wide temperature and humidity range of from 55 ° C. to 20% RH. In addition, since each of the two-component lubricants is soluble in inexpensive general-purpose solvents, there is no need to use expensive perfluoroalkyl-based solvents as in the case of conventional perfluoropolyether-based lubricants. Media manufacturing costs can be greatly reduced.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a use state of a magnetic recording medium of the present invention, in which (A) is a schematic sectional view showing a use state in a state of about 30 ° C. and about 80% RH, and (B). FIG. 3 is a schematic cross-sectional view showing a use state in a state of about 55 ° C. and about 20% RH.

FIG. 2 is a schematic sectional view showing another embodiment of the magnetic recording medium of the present invention.

FIG. 3 is a schematic sectional view showing another embodiment of the magnetic recording medium of the present invention.

FIG. 4 is a schematic cross-sectional view showing a use state in which the magnetic recording medium of the present invention and the magnetic head of the present invention are combined.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Non-magnetic base 3 Magnetic layer 5 Carbon-based protective film 7 Alkylamine-based solid lubricant 9 Modified perfluoropolyether-based liquid lubricant 11 Magnetic head 13 Inorganic buffer layer 15 Chromium alloy base layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI G11B 5/84 G11B 5/84 B // C01B 31/02 101 C01B 31/02 101Z C10N 40:18 (72) Inventor Takeshi Maro 1-88 Ushitora, Ibaraki-shi, Osaka Hitachi Maxell Co., Ltd. (72) Inventor Kazuyoshi Adachi 1-1-88 Ushitora, Ibaraki-shi, Osaka Pref.Hitachi Maxell, Inc. (72) Inventor Yukie Fujimoto Osaka 1-88 Ushitora, Ibaraki-shi, Hitachi Hitachi Maxell, Ltd. (72) Inventor Tatsuo Araki 1-188 Ushitora, Ibaraki, Osaka, Japan

Claims (138)

[Claims] 1. A cobalt-based magnetic layer is provided on a non-magnetic substrate, with or without a non-magnetic inorganic buffer layer, and with or without a non-magnetic chromium alloy underlayer. In a thin-film magnetic recording medium provided with a carbon-based protective film containing at least carbon, the carbon-based protective film has at least a carboxyl group on its surface and has a composition ratio of oxygen to carbon (O / C) on the surface.
Alkylamine having at least an amino group [-NH ₂ ] or an N, N-dimethylamino group [-N (CH ₃ ) ₂ ] at the molecular terminal on the carbon-based protective film. It has a two-component lubricant consisting of a system-based lubricant and a lubricant that is liquid at room temperature as a lubricant layer, and the carboxyl group on the surface of the carbon-based protective film and the amino group of the alkylamine-based solid lubricant are chemically bonded. A magnetic recording medium characterized by being coupled by coupling. 2. The non-magnetic substrate is selected from the group consisting of PET, PEN and aramid, and the cobalt-based layer is Co-C
2. The magnetic recording medium according to claim 1, which is an oO magnetic layer. 3. The non-magnetic substrate is a polymer plastic selected from polycarbonate, amorphous polyolefin, polyetherimide, polyether sulfone, and phenol resin, and a guide groove and a pit or a guide groove or a pit is formed on the polymer plastic. 2. The magnetic recording medium according to claim 1, wherein any one of the above is formed. 4. The nonmagnetic substrate is formed by injection-molding polycarbonate, amorphous polyolefin, polyetherimide, polyethersulfone, or phenol resin, and has a height of 15 to 40 nm and an apparent area ratio of 0. 2. The magnetic recording medium according to claim 1, wherein a dot-like texture zone of 1 to 5.0% is formed. 5. The magnetic recording medium according to claim 1, wherein said alkylamine-based lubricant is solid at normal temperature. 6. The magnetic recording medium according to claim 1, wherein the alkylamine-based lubricant has 10 or more carbon atoms. 7. The alkylamine-based lubricant represented by the following formula: C _a H _{2a + 1} NH ₂ or C _a H _{2a + 1} N (CH ₃ ) ₂ (where a is an integer of 10 or more). 7. A saturated alkylamine represented by the formula:
Magnetic recording medium. 8. The alkylamine-based lubricant represented by the following formula: F (CF ₂ ) _b (CH ₂ ) _c NH ₂ or F (CF ₂ ) _b (CH ₂ ) _c N (CH ₃ ) ₂ (wherein b and c are b ≧ 1, c ≧ 1 and b + c
A partially fluorinated saturated alkylamine represented by the following formula:
Or the magnetic recording medium of 6. 9. A lubricant which is liquid at ordinary temperature binds a saturated or unsaturated hydrocarbon chain having 4 or more carbon atoms to one or both ends of perfluoropolyether via an ether bond, an amide bond or an ester bond. 2. A modified perfluoropolyether according to claim 1.
Magnetic recording medium. 10. A lubricant which is liquid at room temperature is provided with a saturated or unsaturated oxygen-containing hydrocarbon chain having 4 or more carbon atoms at one or both ends of perfluoropolyether via an ether bond, an amide bond or an ester bond. 2. The magnetic recording medium according to claim 1, comprising a modified perfluoropolyether bonded thereto. 11. A modified perfluoropolyether having a lubricant which is liquid at ordinary temperature, having one or both ends of perfluoropolyether bonded to a branched hydrocarbon having 4 or more carbon atoms via an ether bond, an amide bond or an ester bond. 2. The magnetic recording medium according to claim 1, comprising a fluoropolyether. 12. The modified perfluoropolyether which is liquid at room temperature has a main chain of-(CF ₂ CF ₂ CF ₂ O) _d -,-(CF ₂ O) _e- (CF ₂ CF
₂ O) _f- or-(C (CF ₃ ) FCF ₂ O) _g- (where d and g are integers of 10 or more, e and f are 1 or more, and e + f
12. The magnetic recording medium according to claim 9, wherein the magnetic recording medium is an integer satisfying ≧ 10). 13. A lubricant which is liquid at normal temperature has 10 carbon atoms.
2. The magnetic recording medium according to claim 1, wherein the unsaturated hydrocarbon is a compound in which a partially fluorinated saturated alkyl having 6 or more carbon atoms is linked to one or both terminals of the unsaturated hydrocarbon by an ether bond, an ester bond, or an amide bond. . 14. A lubricant which is liquid at normal temperature has 10 carbon atoms.
The above-mentioned partially fluorinated saturated alkyl has carbon atoms at both ends.
2. The magnetic recording medium according to claim 1, wherein said unsaturated hydrocarbon is a compound linked by an ether bond, an ester bond or an amide bond. 15. A lubricant which is liquid at normal temperature has 10 carbon atoms.
2. The magnetic recording medium according to claim 1, wherein said partially fluorinated saturated alkyl is a compound in which a branched hydrocarbon having 10 or more carbon atoms is linked to each terminal or one terminal by an ether bond, an ester bond or an amide bond. . 16. A lubricant which is liquid at normal temperature has 10 carbon atoms.
One or both ends of the above saturated hydrocarbons have 1 carbon atom
2. The magnetic recording medium according to claim 1, wherein the compound is a compound in which zero or more unsaturated hydrocarbons are linked by an ether bond, an ester bond, or an amide bond. 17. A lubricant which is liquid at normal temperature has 10 carbon atoms.
2. The magnetic recording medium according to claim 1, wherein said unsaturated hydrocarbon is a compound in which an unsaturated hydrocarbon having 10 or more carbon atoms is linked to both terminals or one terminal of the unsaturated hydrocarbon by an ether bond, an ester bond or an amide bond. 18. A lubricant which is liquid at normal temperature has 10 carbon atoms.
2. A compound in which a saturated hydrocarbon having 10 or more carbon atoms is linked to both terminals of the unsaturated hydrocarbon by an ether bond, an ester bond or an amide bond.
Magnetic recording medium. 19. A lubricant which is liquid at room temperature has 10 carbon atoms.
2. The magnetic recording medium according to claim 1, wherein said saturated hydrocarbon is a compound in which a branched hydrocarbon having 4 or more carbon atoms is linked to each terminal or one terminal of the saturated hydrocarbon by an ether bond, an ester bond or an amide bond. 20. A lubricant which is liquid at normal temperature has 10 carbon atoms.
The unsaturated hydrocarbon has four carbon atoms at both ends or one end.
2. The magnetic recording medium according to claim 1, wherein the compound is a compound in which the branched hydrocarbon is linked by an ether bond, an ester bond, or an amide bond. 21. A lubricant which is liquid at normal temperature has 10 carbon atoms.
2. The magnetic recording medium according to claim 1, wherein said partially fluorinated saturated alkyl is a compound in which a polyether having a total of 4 or more carbon atoms is linked to each terminal or one terminal by an ether bond, an ester bond or an amide bond. 22. The lubricant which is liquid at normal temperature is dimethylpolysiloxane [-(Si (CH ₃ ) ₂ O) _h- (where h is an integer of 6 or more)]. The magnetic recording medium according to claim 1. 23. A fluorinated dimethylpolysiloxane [-(Si (CF ₃ ) ₂ O] in which a lubricant which is liquid at normal temperature is obtained by partially substituting hydrogen of a methyl group in dimethylpolysiloxane with fluorine or partially fluorinated alkyl. ) _h -,-(Si (CF ₃ ) (CH ₃ ) O) _h-
Or-(Si (C ₂ H ₄ C ₆ F ₁₃ ) ₂ O) _h- (where h is an integer of 6 or more)]. 24. A lubricant which is liquid at normal temperature is represented by the following formula: CH ₃ (Si (CH ₃ ) ₂₀ ) _n -Si (NH ₂ ) ₃ , F (CF ₂ ) _n CH ₂ -Si (NH ₂ ) ₃ or F (CF ₂ ) _n CH ₂ CH ₂ —Si (NH ₂ ) ₃ (where n is an integer of 6 or more), which is a modified dimethylpolysiloxane having a terminal amino group. 2. The magnetic recording medium according to claim 1, wherein: 25. A lubricant which is liquid at room temperature is represented by the following formula: [FC ₆ H ₄ O] _m- (P ₃ N ₃ )-[OC ₆ H ₄ CF ₃ ] _{6 -m} (where m is 0 Is an integer of from 1 to 6).
Magnetic recording medium. 26. A lubricant which is liquid at normal temperature is represented by the following formula: (CF ₃ ) ₂ CF (CF ₂ ) _j CH ₂ CHOCORCH ₂ OCOR (where j is an integer of 2 to 16, and R is -CR ₁ R ₂ R
Indicated by _{3, R 1, R 2,} R 3 are each _{C s H 2s + 1, C} t H
It indicated by _{2t + 1} and _{C u H 2u + 1, s} , t and u are s ≧ 1, t ≧ 1 and u ≧ 1, respectively, and, s + t + u ≧
8 is an integer satisfying 8). 27. A lubricant which is liquid at room temperature is represented by the following formula: F (CF ₂ ) _j CH ₂ CHOCORCH ₂ OCOR (where j is an integer of 2 to 16, and R is —CR ₁ R ₂ R
Indicated by _{3, R 1, R 2,} R 3 are each _{C s H 2s + 1, C} t H
It indicated by _{2t + 1} and _{C u H 2u + 1, s} , t and u are s ≧ 1, t ≧ 1 and u ≧ 1, respectively, and, s + t + u ≧
8 is an integer satisfying 8). 28. Both the alkylamine-based lubricant and the lubricant which is liquid at normal temperature are alcohols such as ethanol, propanol and isopropyl alcohol which are versatile solvents or acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. 28. The magnetic recording medium according to claim 1, which is soluble in ketones or saturated alkyls such as hexane, pentane and heptane. 29. A cobalt-based magnetic layer is provided on a non-magnetic substrate, with or without a non-magnetic inorganic buffer layer, and with or without a non-magnetic chromium alloy underlayer. In a method of manufacturing a thin film magnetic recording medium comprising providing a carbon-based protective film containing at least carbon thereon, the surface of the carbon-based protective film has a wavelength of 184.9 nm at least in an atmosphere containing oxygen. Irradiation treatment with ultraviolet light, or plasma treatment at least in an atmosphere where oxygen is present, allows the surface to have a composition ratio of oxygen and carbon (O / C ratio) of 0.1 or more. An alkylamine-based lubricant that generates at least a carboxyl group and has at least an amino group [-NH ₂ ] or an N, N-dimethylamino group [-N (CH ₃ ) ₂ ] at a molecular terminal on the carbon-based protective film. A two-component lubricant consisting of a lubricant that is liquid at room temperature and forming a lubricating layer by chemically bonding carboxyl groups on the surface of the carbon-based protective film with amino groups of the alkylamine-based solid lubricant. A method for manufacturing a magnetic recording medium. 30. The non-magnetic substrate is selected from the group consisting of PET, PEN and aramid, and the cobalt-based layer is Co-based.
30. The method of claim 29, wherein the method is a CoO magnetic layer. 31. The nonmagnetic substrate is a polymer plastic selected from polycarbonate, amorphous polyolefin, polyetherimide, polyethersulfone, and phenol resin, and a guide groove and a pit or a guide groove or a pit is formed on the polymer plastic. 30. The method of claim 29, wherein any one of: 32. A non-magnetic substrate obtained by injection-molding polycarbonate, amorphous polyolefin, polyetherimide, polyether sulfone, or phenol resin, and having a height of 15 to 40 nm and an apparent area ratio of 0. 30. The method of claim 29, wherein between 1 and 5.0% of the dot texture zones are formed. 33. The alkylamine-based lubricant is selected from alcohols such as ethanol, propanol and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and saturated alkyls such as hexane, pentane and heptane. A lubricant solution having a concentration in the range of 0.005 wt% to 0.50 wt% is prepared by dissolving the lubricant in at least one kind of general-purpose solvent.
It is dissolved in an alcohol such as propanol and isopropyl alcohol, a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, or a saturated alkyl such as hexane, pentane and heptane in at least one general-purpose solvent to obtain a solution of 0.0
Preparing a lubricant solution having a concentration in the range of 05 wt% to 0.50 wt%, and applying the lubricant solution on the surface of the carbon protective film by a spin coating method, a dip coating method or a spray coating method, or Together with the alkylamine-based lubricant and the lubricant at room temperature, ethanol,
It is dissolved in an alcohol such as propanol and isopropyl alcohol, a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, or a saturated alkyl such as hexane, pentane and heptane in at least one general-purpose solvent to obtain a solution of 0.0
It is characterized in that a lubricant solution having a concentration in the range of 05 wt% to 0.50 wt% is prepared, and this lubricant solution is applied on the surface of the carbon protective film by spin coating, dip coating or spray coating. 30. The method of claim 29. 34. The method according to claim 29, wherein the alkylamine-based lubricant is solid at normal temperature. 35. The method according to claim 29, wherein the alkylamine-based lubricant has 10 or more carbon atoms. 36. The alkylamine-based lubricant represented by the following formula: C _a H _{2a + 1} NH ₂ or C _a H _{2a + 1} N (CH ₃ ) ₂ (where a is an integer of 10 or more) 32. A method according to any of claims 29, 34 or 31, characterized in that it is a saturated alkylamine as shown. 37. The alkylamine-based lubricant represented by the following formula: F (CF ₂ ) _b (CH ₂ ) _c NH ₂ or F (CF ₂ ) _b (CH ₂ ) _c N (CH ₃ ) ₂ (wherein b and c are b ≧ 1, c ≧ 1 and b + c
29. A partially fluorinated saturated alkylamine represented by the formula:
34. The method of any of 34 or 31. 38. A lubricant which is a liquid at ordinary temperature binds a saturated or unsaturated hydrocarbon chain having 4 or more carbon atoms to one end or both ends of perfluoropolyether via an ether bond, an amide bond or an ester bond. 30. The method of claim 29, comprising a modified perfluoropolyether. 39. A lubricant which is liquid at room temperature is provided with a saturated or unsaturated oxygen-containing hydrocarbon chain having 4 or more carbon atoms at one or both ends of perfluoropolyether via an ether bond, an amide bond or an ester bond. 30. The method of claim 29, comprising a modified perfluoropolyether attached. 40. A modified perfluoropolyether in which a lubricant which is liquid at ordinary temperature is bonded to one or both ends of a perfluoropolyether with a branched hydrocarbon having 4 or more carbon atoms via an ether bond, an amide bond or an ester bond. 30. The method of claim 29, comprising a fluoropolyether. 41. The modified perfluoropolyether which is liquid at room temperature has a main chain of-(CF ₂ CF ₂ CF ₂ O) _d -,-(CF ₂ O) _e- (CF ₂ CF
₂ O) _f- or-(C (CF ₃ ) FCF ₂ O) _g- (where d and g are integers of 10 or more, e and f are 1 or more, and e + f
41. The method according to claim 38, wherein the integer is an integer satisfying ≧ 10). 42. A lubricant which is liquid at normal temperature has 10 carbon atoms.
30. The method according to claim 29, wherein the unsaturated hydrocarbon is a compound in which a partially fluorinated saturated alkyl having 6 or more carbon atoms is linked to one or both terminals of the unsaturated hydrocarbon by an ether bond, an ester bond, or an amide bond. 43. A lubricant which is liquid at normal temperature has 10 carbon atoms.
The above-mentioned partially fluorinated saturated alkyl has carbon atoms at both ends.
30. The method according to claim 29, wherein the unsaturated hydrocarbon is a compound linked by an ether bond, an ester bond or an amide bond. 44. A lubricant which is liquid at normal temperature has 10 carbon atoms.
30. The method according to claim 29, wherein the partially fluorinated saturated alkyl is a compound in which a branched hydrocarbon having 10 or more carbon atoms is linked to each terminal or one terminal by an ether bond, an ester bond, or an amide bond. 45. A lubricant which is liquid at normal temperature has 10 carbon atoms.
One or both ends of the above saturated hydrocarbons have 1 carbon atom
30. The method according to claim 29, wherein the compound is a compound in which zero or more unsaturated hydrocarbons are linked by an ether bond, an ester bond, or an amide bond. 46. A lubricant which is liquid at normal temperature has 10 carbon atoms.
30. The method according to claim 29, wherein the compound is a compound in which an unsaturated hydrocarbon having 10 or more carbon atoms is linked to both terminals or one terminal of the unsaturated hydrocarbon by an ether bond, an ester bond, or an amide bond. 47. A lubricant which is liquid at normal temperature has 10 carbon atoms.
3. A compound in which a saturated hydrocarbon having 10 or more carbon atoms is linked to both terminals of the unsaturated hydrocarbon by an ether bond, an ester bond or an amide bond.
Method 9. 48. A lubricant which is liquid at normal temperature has 10 carbon atoms.
The above-mentioned unsaturated hydrocarbon has 1 carbon atom at both terminals or at one terminal.
30. The method according to claim 29, wherein the compound is a compound in which zero or more unsaturated hydrocarbons are linked by an ether bond, an ester bond, or an amide bond. 49. A lubricant which is liquid at normal temperature has 10 carbon atoms.
The unsaturated hydrocarbon has four carbon atoms at both ends or one end.
30. The method according to claim 29, wherein the compound is a compound in which the branched hydrocarbon is linked by an ether bond, an ester bond, or an amide bond. 50. A lubricant which is liquid at normal temperature has 10 carbon atoms.
30. The method according to claim 29, wherein the partially fluorinated saturated alkyl is a compound in which a polyether having a total of 4 or more carbon atoms is linked by ether bond, ester bond or amide bond to both terminals or one terminal. 51. The lubricant which is liquid at ordinary temperature is dimethylpolysiloxane [-(Si (CH ₃ ) ₂ O) _h- (where h is an integer of 6 or more)]. 30. The method of claim 29. 52. A fluorinated dimethylpolysiloxane [-(Si (CF ₃ ) ₂ O] in which a lubricant which is liquid at ordinary temperature is obtained by partially substituting hydrogen of a methyl group in dimethylpolysiloxane with fluorine or partially fluorinated alkyl. ) _h -,-(Si (CF ₃ ) (CH ₃ ) O) _h-
Or _{- (Si (C 2 H 4} C 6 F 13) 2 O) h - ( wherein, h is a is 6 or more integer) The method of claim 29, wherein it is. 53. A lubricant which is liquid at room temperature is represented by the following formula: CH ₃ (Si (CH ₃ ) ₂₀ ) _n -Si (NH ₂ ) ₃ , F (CF ₂ ) _n CH ₂ -Si (NH ₂ ) ₃ or F (CF ₂ ) _n CH ₂ CH ₂ —Si (NH ₂ ) ₃ (where n is an integer of 6 or more), which is a modified dimethylpolysiloxane having a terminal amino group. 30. The method of claim 29, wherein 54. A lubricant which is liquid at room temperature is represented by the following formula: [FC ₆ H ₄ O] _m- (P ₃ N ₃ )-[OC ₆ H ₄ CF ₃ ] _6-m (where m is 0 2 which is an integer of up to 6).
Method 9. 55. A lubricant which is liquid at normal temperature is represented by the following formula: (CF ₃ ) ₂ CF (CF ₂ ) _j CH ₂ CHOCORCH ₂ OCOR (where j is an integer of 2 to 16, and R is -CR ₁ R ₂ R
Indicated by _{3, R 1, R 2,} R 3 are each _{C s H 2s + 1, C} t H
It indicated by _{2t + 1} and _{C u H 2u + 1, s} , t and u are s ≧ 1, t ≧ 1 and u ≧ 1, respectively, and, s + t + u ≧
31. The method of claim 29, wherein the integer is an integer satisfying 8. 56. A lubricant which is liquid at normal temperature is represented by the following formula: F (CF ₂ ) _j CH ₂ CHOCORCH ₂ OCOR (wherein j is an integer of 2 to 16, and R is —CR ₁ R ₂ R
Indicated by _{3, R 1, R 2,} R 3 are each _{C s H 2s + 1, C} t H
It indicated by _{2t + 1} and _{C u H 2u + 1, s} , t and u are s ≧ 1, t ≧ 1 and u ≧ 1, respectively, and, s + t + u ≧
31. The method of claim 29, wherein the integer is an integer satisfying 8. 57. A magnetic head for reading / writing a magnetic recording medium, wherein a sliding surface of the magnetic head has sputtered carbon, plasma CVD carbon, diamond-like carbon, hydrogen-containing carbon, nitrogen-containing carbon or silicon-containing carbon. A carbon-based protective film comprising: a carbon-based protective film having at least a carboxyl group on a surface thereof; and a composition ratio of oxygen to carbon (O / C
Ratio) is 0.1 or more, and at least an amino group [-NH ₂ ] or an N, N-dimethylamino group [-N
(CH ₃ ) ₂ ] having a lubricating layer composed of an alkylamine-based lubricant, wherein a carboxyl group on the surface of the carbon-based protective film and an amino group of the alkylamine-based solid lubricant are bonded by a chemical bond. A magnetic head comprising: 58. The magnetic head according to claim 57, wherein the alkylamine-based lubricant is solid at normal temperature. 59. The magnetic head according to claim 57, wherein the alkylamine-based lubricant has 10 or more carbon atoms. 60. The alkylamine-based lubricant represented by the following formula: C _a H _{2a + 1} NH ₂ or C _a H _{2a + 1} N (CH ₃ ) ₂ (where a is an integer of 10 or more) The magnetic head according to any one of claims 57 to 59, which is a saturated alkylamine represented by the following formula: 61. The alkylamine-based lubricant represented by the following formula: F (CF ₂ ) _b (CH ₂ ) _c NH ₂ or F (CF ₂ ) _b (CH ₂ ) _c N (CH ₃ ) ₂ (wherein b and c are b ≧ 1, c ≧ 1 and b + c
57 is an integer satisfying ≧ 10), and is a partially fluorinated saturated alkylamine represented by the formula:
59. The magnetic head according to any of 59. 62. The magnetic head according to claim 57, wherein the lubricating layer is made of a two-component lubricant further having a lubricant that is liquid at normal temperature, in addition to the alkylamine-based lubricant. 63. A lubricant which is liquid at normal temperature binds a saturated or unsaturated hydrocarbon chain having 4 or more carbon atoms to one or both ends of perfluoropolyether via an ether bond, an amide bond or an ester bond. 63. The magnetic head according to claim 62, comprising a modified perfluoropolyether. 64. A lubricant which is liquid at normal temperature has a saturated or unsaturated oxygen-containing hydrocarbon chain having 4 or more carbon atoms at one or both terminals of perfluoropolyether via an ether bond, an amide bond or an ester bond. 63. The magnetic head of claim 62, wherein the magnetic head is comprised of a bonded modified perfluoropolyether. 65. A modified perfluoropolyether in which a lubricant which is a liquid at room temperature has a branched hydrocarbon having 4 or more carbon atoms bonded to one end or both ends of perfluoropolyether via an ether bond, an amide bond or an ester bond. 63. The magnetic head according to claim 62, comprising a fluoropolyether. 66. A modified perfluoropolyether which is liquid at room temperature, wherein the main chain is-(CF ₂ CF ₂ CF ₂ O) _d -,-(CF ₂ O) _e- (CF ₂ CF
₂ O) _f- or-(C (CF ₃ ) FCF ₂ O) _g- (where d and g are integers of 10 or more, e and f are 1 or more, and e + f
66. The magnetic head according to claim 63, wherein the integer is an integer satisfying ≧ 10). 67. A lubricant which is liquid at normal temperature has 10 carbon atoms.
63. The magnetic head according to claim 62, wherein the unsaturated hydrocarbon is a compound in which a partially fluorinated saturated alkyl having 6 or more carbon atoms is linked to one or both terminals of the unsaturated hydrocarbon by an ether bond, an ester bond, or an amide bond. 68. A lubricant which is liquid at normal temperature has 10 carbon atoms.
The above-mentioned partially fluorinated saturated alkyl has carbon atoms at both ends.
63. The magnetic head according to claim 62, wherein the unsaturated hydrocarbon is a compound linked by an ether bond, an ester bond or an amide bond. 69. A lubricant which is liquid at ordinary temperature has 10 carbon atoms.
63. The magnetic head according to claim 62, wherein said partially fluorinated saturated alkyl is a compound in which a branched hydrocarbon having 10 or more carbon atoms is linked to each terminal or one terminal by an ether bond, an ester bond or an amide bond. 70. A lubricant which is liquid at normal temperature has 10 carbon atoms.
One or both ends of the above saturated hydrocarbons have 1 carbon atom
63. The magnetic head according to claim 62, wherein the compound is a compound in which zero or more unsaturated hydrocarbons are linked by an ether bond, an ester bond, or an amide bond. 71. A lubricant which is liquid at normal temperature has 10 carbon atoms.
63. The magnetic head according to claim 62, wherein said unsaturated hydrocarbon is a compound in which unsaturated hydrocarbons having 10 or more carbon atoms are linked to each terminal or one terminal of the unsaturated hydrocarbon by an ether bond, an ester bond or an amide bond. 72. A lubricant which is liquid at normal temperature has 10 carbon atoms.
7. A compound in which a saturated hydrocarbon having 10 or more carbon atoms is linked to both terminals of the unsaturated hydrocarbon by an ether bond, an ester bond or an amide bond.
2 magnetic head. 73. A lubricant which is liquid at normal temperature has 10 carbon atoms.
The above-mentioned unsaturated hydrocarbon has 1 carbon atom at both terminals or at one terminal.
63. The magnetic head according to claim 62, wherein the compound is a compound in which zero or more unsaturated hydrocarbons are linked by an ether bond, an ester bond, or an amide bond. 74. A lubricant which is liquid at normal temperature has 10 carbon atoms.
The unsaturated hydrocarbon has four carbon atoms at both ends or one end.
63. The magnetic head according to claim 62, wherein the compound is a compound in which the branched hydrocarbon is linked by an ether bond, an ester bond or an amide bond. 75. A lubricant which is liquid at normal temperature has 10 carbon atoms.
63. The magnetic head according to claim 62, wherein the partially fluorinated saturated alkyl is a compound in which a polyether having a total of 4 or more carbon atoms is linked to each terminal or one terminal of the partially fluorinated saturated alkyl by an ether bond, an ester bond or an amide bond. 76. A lubricant which is liquid at normal temperature is dimethylpolysiloxane [-(Si (CH ₃ ) ₂ O) _h- (where h is an integer of 6 or more)]. 63. The magnetic head of claim 62. 77. A fluorinated dimethylpolysiloxane [-(Si (CF ₃ ) ₂ O] in which a lubricant which is liquid at normal temperature is obtained by partially substituting hydrogen of a methyl group in dimethylpolysiloxane with fluorine or partially fluorinated alkyl. ) _h -,-(Si (CF ₃ ) (CH ₃ ) O) _h-
Or _{- (Si (C 2 H 4} C 6 F 13) 2 O) h - magnetic head according to claim 62 (wherein, h is a is 6 or more integer), wherein it is. 78. A lubricant which is liquid at normal temperature is represented by the following formula: CH ₃ (Si (CH ₃ ) ₂₀ ) _n -Si (NH ₂ ) ₃ , F (CF ₂ ) _n CH ₂ -Si (NH ₂ ) ₃ or F (CF ₂ ) _n CH ₂ CH ₂ —Si (NH ₂ ) ₃ (where n is an integer of 6 or more), which is a modified dimethylpolysiloxane having a terminal amino group. 63. The magnetic head of claim 62. 79. A lubricant which is liquid at room temperature is represented by the following formula: [FC ₆ H ₄ O] _m- (P ₃ N ₃ )-[OC ₆ H ₄ CF ₃ ] _6-m (where m is 0 6 which is an integer of up to 6).
2 magnetic head. 80. A lubricant which is liquid at ordinary temperature is represented by the following formula: (CF ₃ ) ₂ CF (CF ₂ ) _j CH ₂ CHOCORCH ₂ OCOR (where j is an integer of 2 to 16, and R is -CR ₁ R ₂ R
Indicated by _{3, R 1, R 2,} R 3 are each _{C s H 2s + 1, C} t H
It indicated by _{2t + 1} and _{C u H 2u + 1, s} , t and u are s ≧ 1, t ≧ 1 and u ≧ 1, respectively, and, s + t + u ≧
63. The magnetic head according to claim 62, which is an integer satisfying 8). 81. A lubricant which is liquid at normal temperature is represented by the following formula: F (CF ₂ ) _j CH ₂ CHOCORCH ₂ OCOR (where j is an integer of 2 to 16, and R is —CR ₁ R ₂ R
Indicated by _{3, R 1, R 2,} R 3 are each _{C s H 2s + 1, C} t H
It indicated by _{2t + 1} and _{C u H 2u + 1, s} , t and u are s ≧ 1, t ≧ 1 and u ≧ 1, respectively, and, s + t + u ≧
63. The magnetic head according to claim 62, which is an integer satisfying 8). 82. Both the alkylamine-based lubricant and the lubricant which is liquid at normal temperature are alcohols such as ethanol, propanol, and isopropyl alcohol which are general-purpose solvents or acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like. The magnetic head according to any one of claims 62 to 78, wherein the magnetic head is soluble in ketones or saturated alkyls such as hexane, pentane and heptane. 83. A method of manufacturing a magnetic head for reading / writing a magnetic recording medium, comprising the steps of:
A carbon-based protective film made of CVD carbon, diamond-like carbon, hydrogen-containing carbon, nitrogen-containing carbon, or silicon-containing carbon is provided. Irradiation treatment with ultraviolet light including the above, or plasma treatment at least in an atmosphere where oxygen is present, such that the composition ratio (O / C ratio) of oxygen and carbon on the surface becomes 0.1 or more. At least a carboxyl group, and at least an amino group at the molecular end on the carbon-based protective film.
An alkylamine-based lubricant having [-NH ₂ ] or N, N-dimethylamino group [-N (CH ₃ ) ₂ ] is applied, and the carboxyl group on the surface of the carbon-based protective film and the alkylamine-based solid lubricant are applied. Forming a lubricating layer by chemical bonding with the amino group of (1). 84. The alkylamine-based lubricant is selected from alcohols such as ethanol, propanol and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and saturated alkyls such as hexane, pentane and heptane. A lubricant solution having a concentration in the range of 0.005 wt% to 0.50 wt% is prepared by dissolving the lubricant solution in at least one kind of general-purpose solvent, and the lubricant solution is spin-coated, dip-coated or spray-coated. The method according to claim 83, wherein the method is applied on the surface of the carbon protective film. 85. The method according to claim 83, wherein the alkylamine-based lubricant is solid at normal temperature. 86. The method according to claim 83, wherein the alkylamine-based lubricant has 10 or more carbon atoms. 87. The alkylamine-based lubricant represented by the following formula: C _a H _{2a + 1} NH ₂ or C _a H _{2a + 1} N (CH ₃ ) ₂ (where a is an integer of 10 or more) 89. The method of any of claims 83 to 86, wherein the compound is a saturated alkylamine as shown. 88. The alkylamine-based lubricant represented by the following formula: F (CF ₂ ) _b (CH ₂ ) _c NH ₂ or F (CF ₂ ) _b (CH ₂ ) _c N (CH ₃ ) ₂ (wherein b and c are b ≧ 1, c ≧ 1 and b + c
83. A partially fluorinated saturated alkylamine represented by the following formula:
85. The method of any one of 85. 89. A lubricant layer is formed by applying a two-component lubricant further having a lubricant which is liquid at normal temperature, in addition to the alkylamine-based lubricant.
Method 3. 90. The alkylamine-based lubricant is selected from alcohols such as ethanol, propanol and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and saturated alkyls such as hexane, pentane and heptane. A lubricant solution having a concentration in the range of 0.005 wt% to 0.50 wt% is prepared by dissolving the lubricant in at least one kind of general-purpose solvent.
It is dissolved in an alcohol such as propanol and isopropyl alcohol, a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, or a saturated alkyl such as hexane, pentane and heptane in at least one general-purpose solvent to obtain a solution of 0.0
Preparing a lubricant solution having a concentration in the range of 05 wt% to 0.50 wt%, and applying the lubricant solution on the surface of the carbon protective film by a spin coating method, a dip coating method or a spray coating method, or Together with the alkylamine-based lubricant and the lubricant at room temperature, ethanol,
It is dissolved in an alcohol such as propanol and isopropyl alcohol, a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, or a saturated alkyl such as hexane, pentane and heptane in at least one general-purpose solvent to obtain a solution of 0.0
It is characterized in that a lubricant solution having a concentration in the range of 05 wt% to 0.50 wt% is prepared, and this lubricant solution is applied on the surface of the carbon protective film by spin coating, dip coating or spray coating. 90. The method of claim 89. 91. A lubricant which is liquid at ordinary temperature binds a saturated or unsaturated hydrocarbon chain having 4 or more carbon atoms to one or both ends of perfluoropolyether via an ether bond, an amide bond or an ester bond. 90. The method of claim 89, comprising a modified perfluoropolyether. 92. A lubricant which is liquid at normal temperature has a saturated or unsaturated oxygen-containing hydrocarbon chain having 4 or more carbon atoms at one or both ends of perfluoropolyether via an ether bond, an amide bond or an ester bond. 90. The method of claim 89, comprising a modified perfluoropolyether attached. 93. A modified perfluoropolyether in which a lubricant which is liquid at normal temperature has a branched hydrocarbon having 4 or more carbon atoms bonded to one or both terminals of the perfluoropolyether via an ether bond, an amide bond or an ester bond. 90. The method of claim 89, comprising a fluoropolyether. 94. A modified perfluoropolyether which is liquid at room temperature has a main chain of-(CF ₂ CF ₂ CF ₂ O) _d -,-(CF ₂ O) _e- (CF ₂ CF
₂ O) _f- or-(C (CF ₃ ) FCF ₂ O) _g- (where d and g are integers of 10 or more, e and f are 1 or more, and e + f
The method according to any one of claims 91 to 93, wherein the integer is an integer satisfying ≧ 10). 95. A lubricant which is liquid at normal temperature has 10 carbon atoms.
90. The method according to claim 89, wherein the unsaturated hydrocarbon is a compound in which a partially fluorinated saturated alkyl having 6 or more carbon atoms is linked to one or both terminals of the unsaturated hydrocarbon by an ether bond, an ester bond, or an amide bond. 96. A lubricant which is liquid at normal temperature has 10 carbon atoms.
The above-mentioned partially fluorinated saturated alkyl has carbon atoms at both ends.
90. The method according to claim 89, wherein the unsaturated hydrocarbon is a compound linked by an ether bond, an ester bond or an amide bond. 97. A lubricant which is liquid at normal temperature has 10 carbon atoms.
90. The method according to claim 89, wherein said partially fluorinated saturated alkyl is a compound in which a branched hydrocarbon having 10 or more carbon atoms is linked to each terminal or one terminal by an ether bond, an ester bond or an amide bond. 98. A lubricant which is liquid at normal temperature has 10 carbon atoms.
One or both ends of the above saturated hydrocarbons have 1 carbon atom
90. The method according to claim 89, wherein the compound is a compound in which zero or more unsaturated hydrocarbons are linked by an ether bond, an ester bond, or an amide bond. 99. A lubricant which is liquid at normal temperature has 10 carbon atoms.
90. The method according to claim 89, wherein the compound is a compound in which an unsaturated hydrocarbon having 10 or more carbon atoms is linked to each terminal or one terminal of the unsaturated hydrocarbon by an ether bond, an ester bond, or an amide bond. 100. A lubricant which is liquid at normal temperature has 1 carbon atom.
90. The method according to claim 89, wherein the compound is a compound in which a saturated hydrocarbon having 10 or more carbon atoms is connected to both ends of 0 or more unsaturated hydrocarbons by an ether bond, an ester bond, or an amide bond. 101. A lubricant which is liquid at normal temperature has 1 carbon atoms.
90. The method according to claim 89, wherein the compound is a compound in which an unsaturated hydrocarbon having 10 or more carbon atoms is connected to both ends or one end of 0 or more unsaturated hydrocarbons by an ether bond, an ester bond, or an amide bond. 102. A lubricant which is liquid at normal temperature has 1 carbon atom.
90. The method according to claim 89, wherein the compound is a compound in which a branched hydrocarbon having 4 or more carbon atoms is linked to each terminal or one terminal of 0 or more unsaturated hydrocarbons by an ether bond, an ester bond, or an amide bond. 103. A lubricant which is liquid at normal temperature has 1 carbon atom.
90. The method according to claim 89, wherein the compound is a compound in which a polyether having a total of 4 or more carbon atoms is connected to both ends or one end of at least 0 partially fluorinated saturated alkyl by an ether bond, an ester bond, or an amide bond. 104. The lubricant which is liquid at ordinary temperature is dimethylpolysiloxane [-(Si (CH ₃ ) ₂ O) _h- (where h is an integer of 6 or more)]. 90. The method of claim 89. 105. A fluorinated dimethylpolysiloxane [-(Si (CF ₃ ) ₂ O] in which a lubricant which is liquid at normal temperature is obtained by partially substituting hydrogen of a methyl group in dimethylpolysiloxane with fluorine or partially fluorinated alkyl. ) _h -,-(Si (CF ₃ ) (CH ₃ ) O)
_h - or _{- (Si (C 2 H 4} C 6 F 13) 2 O) h - ( wherein, h is a is 6 or more integer) The method of claim 89, wherein it is. 106. A lubricant which is liquid at room temperature is represented by the following formula: CH ₃ (Si (CH ₃ ) ₂₀ ) _n -Si (NH ₂ ) ₃ , F (CF ₂ ) _n CH ₂ -Si (NH ₂ ) ₃ or F (CF ₂ ) _n CH ₂ CH ₂ —Si (NH ₂ ) ₃ (where n is an integer of 6 or more), which is a modified dimethylpolysiloxane having a terminal amino group. 90. The method of claim 89, wherein 107. A lubricant which is liquid at room temperature is represented by the following formula: [FC ₆ H ₄ O] _m- (P ₃ N ₃ )-[OC ₆ H ₄ CF ₃ ] _6-m (where m is 0 9 is an integer of up to 6).
Method 9. 108. A lubricant which is liquid at normal temperature is represented by the following formula: (CF ₃ ) ₂ CF (CF ₂ ) _j CH ₂ CHOCORCH ₂ OCOR (where j is an integer of 2 to 16, and R is -CR ₁ R ₂ R
Indicated by _{3, R 1, R 2,} R 3 are each _{C s H 2s + 1, C} t H
It indicated by _{2t + 1} and _{C u H 2u + 1, s} , t and u are s ≧ 1, t ≧ 1 and u ≧ 1, respectively, and, s + t + u ≧
90. The method of claim 89, which is an integer satisfying 8. 109. A lubricant which is liquid at ordinary temperature is represented by the following formula: F (CF ₂ ) _j CH ₂ CHOCORCH ₂ OCOR (where j is an integer of 2 to 16, and R is —CR ₁ R ₂ R
Indicated by _{3, R 1, R 2,} R 3 are each _{C s H 2s + 1, C} t H
It indicated by _{2t + 1} and _{C u H 2u + 1, s} , t and u are s ≧ 1, t ≧ 1 and u ≧ 1, respectively, and, s + t + u ≧
90. The method of claim 89, wherein the integer is an integer satisfying 8. 110. A magnetic storage device having at least a magnetic recording medium and a magnetic head, wherein the magnetic recording medium is provided on a non-magnetic substrate with or without a non-magnetic inorganic buffer layer. With or without a chromium alloy underlayer, a cobalt-based magnetic layer with a carbon-based layer consisting of sputtered carbon, plasma CVD carbon, diamond-like carbon, hydrogen-containing carbon, nitrogen-containing carbon or silicon-containing carbon The carbon-based protective film has at least a carboxyl group on its surface, and has a composition ratio of oxygen and carbon (O / C
Alkylamine having at least an amino group [-NH ₂ ] or an N, N-dimethylamino group [-N (CH ₃ ) ₂ ] at the molecular terminal on the carbon-based protective film. It has a two-component lubricant consisting of a system-based lubricant and a lubricant that is liquid at room temperature as a lubricant layer. The magnetic head is provided with a sputter carbon,
Plasma CVD carbon, diamond-like carbon,
It has a carbon-based protective film made of hydrogen-containing carbon, nitrogen-containing carbon or silicon-containing carbon. The carbon-based protective film has at least a carboxyl group on its surface, and has a composition ratio of oxygen to carbon (O / C
Ratio) is 0.1 or more, and at least an amino group [-NH ₂ ] or an N, N-dimethylamino group [-N
(CH ₃ ) ₂ ] having a lubricating layer composed of an alkylamine-based lubricant, wherein a carboxyl group on the surface of the carbon-based protective film and an amino group of the alkylamine-based solid lubricant are bonded by a chemical bond. A magnetic storage device comprising: 111. The non-magnetic substrate is a polymer plastic selected from polycarbonate, amorphous polyolefin, polyetherimide, polyether sulfone, and phenolic resin, and guide grooves and pits or guide grooves or pits are formed on the polymer plastic. 97. The apparatus of claim 96, wherein any of the following is formed. 112. A nonmagnetic substrate obtained by injection-molding polycarbonate, amorphous polyolefin, polyetherimide, polyethersulfone, or phenol resin, and having a height of 15 to 40 nm and an apparent area ratio of 0. 112. A dot-like texture zone of 1 to 5.0% is formed.
Equipment. 113. The non-magnetic substrate is selected from the group consisting of PET, PEN and aramid, and the Co-based magnetic layer is Co-based.
The device of claim 110, wherein the device is a CoO magnetic layer. 114. The apparatus according to claim 110, wherein the lubricating layer on the carbon-based protective film is made of a two-component lubricant further having a lubricant that is liquid at normal temperature, in addition to the alkylamine-based lubricant. . 115. The apparatus according to claim 110, wherein said alkylamine-based lubricant is solid at room temperature. 116. The method according to claim 110, wherein the alkylamine-based lubricant has 10 or more carbon atoms.
15 devices. 117. The alkylamine-based lubricant represented by the following formula: C _a H _{2a + 1} NH ₂ or C _a H _{2a + 1} N (CH ₃ ) ₂ (where a is an integer of 10 or more) 12. A saturated alkylamine represented by the formula:
5 or 116 device. 118. The alkylamine-based lubricant is represented by the following formula: F (CF ₂ ) _b (CH ₂ ) _c NH ₂ or F (CF ₂ ) _b (CH ₂ ) _c N (CH ₃ ) ₂ (wherein b and c are b ≧ 1, c ≧ 1 and b + c
12. A partially fluorinated saturated alkylamine represented by the following formula:
0, 115 or 116 device. 119. A lubricant which is liquid at normal temperature has 4 carbon atoms at one or both ends of perfluoropolyether via an ether bond, an amide bond or an ester bond.
115. The apparatus according to claim 110 or 114, comprising a modified perfluoropolyether to which said saturated or unsaturated hydrocarbon chain is bonded. 120. A lubricant which is liquid at normal temperature has 4 carbon atoms via one or both ends of perfluoropolyether through an ether bond, an amide bond or an ester bond.
115. The apparatus according to claim 110 or 114, comprising a modified perfluoropolyether to which said saturated or unsaturated oxygen-containing hydrocarbon chain is bonded. 121. A lubricant which is liquid at normal temperature has 4 carbon atoms via an ether bond, an amide bond or an ester bond at one or both ends of perfluoropolyether.
110. A modified perfluoropolyether having the above-mentioned branched hydrocarbon bonded thereto, wherein
14 devices. 122. The main chain of the modified perfluoropolyether which is liquid at room temperature is-(CF ₂ CF ₂ CF ₂ O) _d -,-(CF ₂ O) _e- (CF ₂
CF ₂ O) _f- or-(C (CF ₃ ) FCF ₂ O) _g- (where d and g are 10
E and f are 1 or more, and e +
121. The apparatus according to claim 119, 120 or 121, wherein f is an integer satisfying f≥10. 123. A lubricant which is liquid at normal temperature has 1 carbon atoms.
115. The compound according to claim 110 or 114, wherein the compound is a compound in which a partially fluorinated saturated alkyl having 6 or more carbon atoms is linked to one end or both ends of 0 or more unsaturated hydrocarbons by an ether bond, an ester bond or an amide bond. apparatus. 124. A lubricant which is liquid at normal temperature has 1 carbon atom.
0 or more partially fluorinated saturated alkyl at both ends
115. The device according to claim 110, wherein the compound is a compound in which zero or more unsaturated hydrocarbons are linked by an ether bond, an ester bond, or an amide bond. 125. A lubricant which is liquid at normal temperature has 1 carbon atom.
115. The compound according to claim 110 or 114, wherein the compound is a compound in which a branched hydrocarbon having 10 or more carbon atoms is connected to both terminals or one terminal of zero or more partially fluorinated saturated alkyl by an ether bond, an ester bond, or an amide bond. apparatus. 126. A lubricant which is liquid at normal temperature has 1 carbon atom.
115. The apparatus according to claim 110 or 114, wherein the compound is a compound in which an unsaturated hydrocarbon having 10 or more carbon atoms is linked to one or both ends of zero or more saturated hydrocarbons by an ether bond, an ester bond, or an amide bond. 127. A lubricant which is liquid at normal temperature has 1 carbon atom.
115. The device according to claim 110, wherein the compound is a compound in which an unsaturated hydrocarbon having 10 or more carbon atoms is linked to both ends or one end of 0 or more unsaturated hydrocarbons by an ether bond, an ester bond, or an amide bond. . 128. A lubricant which is liquid at normal temperature has 1 carbon atom.
115. The apparatus according to claim 110 or 114, wherein the compound is a compound in which a saturated hydrocarbon having 10 or more carbon atoms is linked to both ends of 0 or more unsaturated hydrocarbons by an ether bond, an ester bond, or an amide bond. 129. A lubricant which is liquid at normal temperature has 1 carbon atom.
115. The apparatus according to claim 110 or 114, wherein the compound is a compound in which an unsaturated hydrocarbon having 10 or more carbon atoms is linked to each terminal or one end of 0 or more unsaturated hydrocarbons by an ether bond, an ester bond, or an amide bond. . 130. A lubricant which is liquid at normal temperature has 1 carbon atom.
115. The device according to claim 110 or 114, wherein the compound is a compound in which a branched hydrocarbon having 4 or more carbon atoms is linked to both ends or one end of 0 or more unsaturated hydrocarbons by an ether bond, an ester bond, or an amide bond. . 131. A lubricant which is liquid at normal temperature has 1 carbon atom.
115. The apparatus according to claim 110 or 114, wherein the compound is a compound in which a polyether having a total of 4 or more carbon atoms is linked by ether bond, ester bond or amide bond to both terminals or one terminal of partially fluorinated saturated alkyl of 0 or more. . 132. The lubricant which is liquid at ordinary temperature is dimethylpolysiloxane [-(Si (CH ₃ ) ₂ O) _h- (where h is an integer of 6 or more)]. Apparatus according to claim 110 or 114. 133. A fluorinated dimethylpolysiloxane [-(Si (CF ₃ ) ₂ O] in which a lubricant which is liquid at ordinary temperature is obtained by partially substituting hydrogen of a methyl group in dimethylpolysiloxane with fluorine or partially fluorinated alkyl. ) _h -,-(Si (CF ₃ ) (CH ₃ ) O)
_h - or _{- (Si (C 2 H 4} C 6 F 13) 2 O) h - claim 110 or 1 to (wherein, h is a is 6 or more integer), wherein it is]
14 devices. 134. A lubricant which is liquid at ordinary temperature is represented by the following formula: CH ₃ (Si (CH ₃ ) ₂₀ ) _n -Si (NH ₂ ) ₃ , F (CF ₂ ) _n CH ₂ -Si (NH ₂ ) ₃ or F (CF ₂ ) _n CH ₂ CH ₂ —Si (NH ₂ ) ₃ (where n is an integer of 6 or more), which is a modified dimethylpolysiloxane having a terminal amino group. 115. The device of claim 110 or 114. 135. A lubricant which is liquid at room temperature is represented by the following formula: [FC ₆ H ₄ O] _m- (P ₃ N ₃ )-[OC ₆ H ₄ CF ₃ ] _6-m (where m is 0 Is an integer of from 1 to 6).
The device of 10 or 114. 136. A lubricant which is liquid at normal temperature is represented by the following formula: (CF ₃ ) ₂ CF (CF ₂ ) _j CH ₂ CHOCORCH ₂ OCOR (where j is an integer of 2 to 16, and R is -CR ₁ R ₂ R
Indicated by _{3, R 1, R 2,} R 3 are each _{C s H 2s + 1, C} t H
It indicated by _{2t + 1} and _{C u H 2u + 1, s} , t and u are s ≧ 1, t ≧ 1 and u ≧ 1, respectively, and, s + t + u ≧
115. The apparatus of claim 110 or 114, wherein the integer is an integer satisfying 8. 137. A lubricant which is liquid at ordinary temperature is represented by the following formula: F (CF ₂ ) _j CH ₂ CHOCORCH ₂ OCOR (where j is an integer of 2 to 16, and R is -CR ₁ R ₂ R
Indicated by _{3, R 1, R 2,} R 3 are each _{C s H 2s + 1, C} t H
It indicated by _{2t + 1} and _{C u H 2u + 1, s} , t and u are s ≧ 1, t ≧ 1 and u ≧ 1, respectively, and, s + t + u ≧
115. The apparatus of claim 110 or 114, wherein the integer is an integer satisfying 8. 138. Both the alkylamine-based lubricant and the lubricant which is liquid at normal temperature are alcohols such as ethanol, propanol and isopropyl alcohol which are versatile solvents or acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. 115. The compound is soluble in ketones or saturated alkyls such as hexane, pentane and heptane.
137. The apparatus of any of 137.