JPH07216375A - Lubricant - Google Patents

Abstract

PURPOSE:To obtain a lubricant which provides a long-lasting stable lubrication. CONSTITUTION:As a lubricant is used a compd. which comprises carbon atoms, hydrogen atoms, fluorine atoms, and ether oxygen atoms and contains the combination of group A with group C, the combination of group B with group C, or both the above-mentioned two combinations provided group A is a perfluoropolyether chains of the formula A: (CnF2nO)m (wherein (n) is an integer of 1-10; and (m) is an integer of 1 or higher); group B is a perfluoroalkylene chain of the formula B: CnF2n (wherein (n) is an integer of 1-15); and group C is a polyether chain of the formula C: (CnH2nO)m (wherein (n) is an integer of 1-6; and (m) is an integer of 1 or higher).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lubricant, and more particularly to a lubricant having a long-term stable lubricity.

[0002]

2. Description of the Related Art Generally, fluorine-based lubricants are excellent in lubricity even though they are expensive, so that the demand for them is increasing in various fields. The demand is increasing in the field etc.

A magnetic recording medium is a typical example thereof, and in particular, a magnetic coating comprising a magnetic powder, a binder resin, an organic solvent and other necessary components is coated on a non-magnetic support and dried to form a coating. Type magnetic recording media, it is easy to make the magnetic layer high in coercive force and thin, and has excellent high-density recording characteristics, but on the other hand, there is no binder resin with high surface smoothness and toughness. It is an indispensable lubricant in ferromagnetic metal thin film type magnetic recording media, which have a large friction coefficient with and are susceptible to wear and damage.

Therefore, for example, perfluoropolyether
Telluride lubricants, partially fluorinated carboxylic acid ester lubricants, and the like are used, and these lubricants are contained in the magnetic layer or are present on the ferromagnetic metal thin film layer (Japanese Patent Laid-Open No. 62-
236118, JP-A-2-210615) to improve durability and running property.

However, even if these conventional perfluoropolyether type lubricants, partially fluorinated carboxylic acid ester type lubricants and the like are contained in the magnetic layer, the durability cannot be sufficiently improved. Also, when it is present on the ferromagnetic metal thin film layer, it exerts an excellent lubricating effect, but the force retained on the surface of the ferromagnetic metal thin film layer is weak,
It is still not sufficient under the severe conditions such as a still picture in a video tape in which the same portion is continuously slid in contact, that is, a still state, and sufficient reliability cannot be obtained.

Therefore, a polar functional group such as a hydroxyl group or an ester group is introduced at the terminal of the perfluoropolyether molecule so as to strongly chemisorb to the surface of the ferromagnetic metal thin film layer (Japanese Patent Publication No. 60-10368). Is being done,
These perfluoropolyether-based lubricants are economically problematic because they are soluble only in expensive and special fluorine-based solvents such as Freon and perfluoroalkane. Also, during solvent recovery, hydrofluoric acid is generated due to thermal decomposition.
There is also a problem in work safety, and a process using a solvent containing a large amount of halogen is not desirable from the viewpoint of protecting the global environment.

Therefore, in recent years, a fluorine-based lubricant that is soluble in a hydrocarbon-based solvent instead of a special solvent such as a fluorine-based solvent has been developed. A compound bound to the molecular end of perfluoropolyether has been proposed. (JP-A-2-78016, JP-A-2-49128)

[0008]

However, in a compound in which a long-chain hydrocarbon of this kind is bonded to the molecular end of perfluoropolyether via an amide bond, an ester bond, etc., the ester bond or the amide bond is It is easily hydrolyzed on the surface of a metal having high chemical activity, and the acid generated by the hydrolysis corrodes the metal surface or produces an adhesive salt, which rather reduces lubricity.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a lubricant having a lubricity excellent in stability for a long period of time when used in a magnetic recording medium or the like.

[0010]

The present invention provides a perfluoropolyether composed of carbon atoms, hydrogen atoms, fluorine atoms and etheric oxygen atoms and represented by the following general formula (A). The chain, the perfluoroalkyl chain represented by (B), and the polyether chain represented by (C) are a combination of (A) and (C) or a combination of (B) and (C). combination, or (a) and (C) combinations and (B) and (C) a combination of both combination with lubricating agents consisting of compounds contained in the molecule _{(a) - (C n F} 2n O ) m-(where, n is an integer from 1 to 10, m is an integer of 1 or _{more) (B) -C n F 2n} -.. ( where, n is an integer of 1 to 15) ( C) - the _{(C n H 2n O) m-} ( where, n is an integer from 1 to 6, m is an integer of 1 or more). By providing a lubricant having excellent lubricity over a long period of time, for example,
Speaking of magnetic recording media, by using this lubricant for magnetic recording media in which a magnetic layer is provided on one or both sides of a non-magnetic support, it is possible to sufficiently improve the still durability under severe operating conditions. It is intended to obtain a magnetic recording medium that maintains high reliability for a long period of time even under severe use conditions.

In the lubricant containing the combination of the perfluoropolyether chain and the polyether chain, or the combination of the perfluoroalkyl chain and the polyether chain in the molecule of the present invention, the polyether part serves as the solubilizing agent. Since it works, it is easily dissolved in a commonly used hydrocarbon solvent. Further, since the polyether has an appropriate polarity, it has a good affinity with the magnetic powder, and when used in the ferromagnetic metal thin film layer, an appropriate interaction with the ferromagnetic metal thin film layer occurs. Occurs and is stably retained on the surface. Furthermore, since the molecule contains only an ether bond having excellent chemical stability, it does not decompose even when adsorbed on the surface of the active metal. Further, the perfluoropolyether part and the perfluoroalkyl part have an excellent lubricating effect.

Further, --Cl, --OR ₁ (R
₁ is an alkyl group or fluorinated alkyl group having 1 to 18 carbon _{atoms), - OSi (CH 3)} 2 R 2 (R 2 having 1 to 30 carbon atoms
Of any of the above), and does not have a strongly polar functional group such as a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, or salts thereof, so that it is particularly soluble in a hydrocarbon solvent such as a ketone system. Excellent corrosion resistance and low hydrophilicity, so corrosion resistance is not impaired.

Therefore, when this kind of lubricant is contained in the magnetic layer, uniform dispersion in the magnetic layer is easy, and its excellent lubricating effect is sufficiently exhibited even under severe use conditions.
Still durability is sufficiently improved. Also, when this kind of lubricant is present as a lubricant for the ferromagnetic metal thin film layer, it can withstand strong sliding contact with the magnetic head, and its excellent lubrication effect can be fully exerted even under severe operating conditions. The durability is sufficiently improved, the corrosion resistance is good, and the high reliability can be maintained for a long time.

On the other hand, the conventional perfluoropolyether
The telluride lubricant cannot be used by being contained in the magnetic layer because it does not dissolve in a commonly used organic solvent, and since it has a polar functional group only at the end, it is a ferromagnetic metal thin film layer. It is not stably retained on the surface, and sufficient still durability cannot be obtained under severe usage conditions.

Further, since the conventional perfluoropolyether type lubricants and partially fluorinated carboxylic acid ester type lubricants have polar functional groups such as carboxyl group, sulfonic acid group, phosphoric acid group and ester group, These may react with the metal surface, corrode the metal surface, or produce a sticky salt to reduce lubricity. Further, although a functional group such as a hydroxyl group has little reactivity with the metal surface, it is too strongly adsorbed on the metal surface, and sufficient still durability cannot be obtained under severe usage conditions.

Examples of the lubricant containing such a combination of a perfluoropolyether chain and a polyether chain or a combination of a perfluoroalkyl chain and a polyether chain in the molecule include, for example, perfluoropolyether. Chain or par
At least one molecular end of a fluoroalkyl chain includes one having at least one ether bond including a binding portion, and an alkyl chain not containing a polar functional group is bonded, and the molecular end is, for example, , A general formula —CF ₂ — (CH ₂ ) 1 — (OC _n H _2n ) m—X (where X is Cl, OR ₁ (R ₁ is an alkyl group having 1 to 18 carbon atoms or a fluorinated alkyl group), OSi (CH ₃ ) ₂
R ₂ (R ₂ is an alkyl group having 1 to 30 carbon atoms), and 1, m, and n are all integers of 0 or more. )
What is represented by.

Since this kind of lubricant is a compound similar to a block copolymer, it is important to balance the molecular weights of the fluorocarbon part and the hydrocarbon part, and the perfluoropolyether is contained in the center. In the case of a structure having a polyether and an alkyl containing no fluorine atom at both ends thereof, the molecular weight of the perfluoropolyether portion is 10,000 or less, particularly 300 to 5 from the viewpoints of lubricity, solubility, viscosity and the like.
Those having a molecular weight of 000 are preferably used.

Further, in the case of polyether and alkyl which do not contain a fluorine atom, the total of carbon atoms and oxygen atoms is s.
Then, the value Y obtained by dividing 100 times this s by the average molecular weight of perfluoropolyether is preferably 0.5 ≦ Y ≦ 3.0, and when Y is less than 0.5, the solubility by the polyether is Further, the effect of improving the adsorptivity cannot be obtained, and when it is more than 3.0, it becomes difficult to sufficiently exhibit the excellent lubricating effect due to the fluorine atom.

As described above, the total molecular weight of the lubricant containing the combination of the perfluoropolyether chain and the polyether chain or the combination of the perfluoroalkyl chain and the polyether chain in the molecule is 300 to 10,000. If the molecular weight is too small, it is likely to volatilize, and if it is too large, tackiness occurs and the lubricating performance is hindered.

Such a lubricant is a perfluoropolyether.
The ether chain, e.g., the formula _{- (CF 2 CF 2 -O)} p─ (CF 2 -O) q- - (CF 2 CF 2 CF 2 -O) q- - [CF ₂ (CF ₃₎ CF A perfluoropolyether chain having a basic skeleton represented by -O] q- (wherein p and q are natural numbers of 10 to 500) is preferably used.

Further, as the perfluoroalkyl chain,
A perfluoroalkyl chain having a basic skeleton represented by the general formula —C _n F _2n — (where n is a natural number of 1 to 15) is preferably used.

Furthermore, polyether - as the ether chain, the general formula _{- (C n H 2n O)} m- ( where, n is an integer from 1 to 6, m is 1 or more is an integer.) Expressed in A polyether chain having a basic skeleton is preferably used.

Such a lubricant may be synthesized by any synthesis method, and for example, an industrially effective synthesis method is exemplified by, for example, propylene oxide and perfluoro having a terminal functional group being a hydroxyl group. With a polyether compound,
The ether moiety is synthesized by reacting at atmospheric pressure or in an autoclave. Further, a carbonate compound can be used to synthesize an ether bond.

The alkyl terminal is synthesized, for example, by reacting a hydroxyl group at the molecular terminal with a halogenated alkyl compound in the presence of an alkali.

Such lubricants may be used alone or as a mixture of two or more kinds, and particularly, those having a molecular weight of about 2000 containing perfluoropolyether and a molecular weight containing perfluoroalkyl. When a combination of 600 to 800 is used, a more excellent lubricating effect can be obtained.

Further, in some cases, it may be used in combination with other various lubricants, for example, fatty acid or its metal salt, aliphatic ester, aliphatic amide, aliphatic alcohol.
Resins, monosulfides, paraffins, silicone compounds, aliphatic and fluoride esters, other fine powders of perfluoropolyether, polytetrafluoroethylene, etc., as well as molybdenum and graphite inorganic lubricity Used in combination with fine powder etc. with good compatibility.

In order to use such a lubricant as a lubricant for a magnetic recording medium, a fluorine-based solvent such as Freon, a hydrocarbon-based solvent such as tetrahydrofuran, methyl ethyl ketone or isopropyl alcohol is used. And then spray or dry it on the magnetic layer previously formed on a non-magnetic support such as a polyethylene terephthalate film or a polyimide film, or dry it, or vice versa. The layer is dipped and dried. Alternatively, the lubricant may be introduced into the magnetic layer or the like by transfer.

In addition, a lubricant of this kind is mixed and dispersed with a magnetic powder, a binder resin, an organic solvent and other necessary components to prepare a magnetic paint, and this magnetic paint is added to a polyethylene terephthalate film or the like. It is also used by a method of forming a magnetic layer by coating on the non-magnetic support by any means such as spraying or roll coating and drying.

In this case, when the magnetic layer in which this kind of lubricant is present is a ferromagnetic metal thin film layer, it may be a ferromagnetic metal thin film layer having a trace amount of water adhered to its surface. -Ferromagnetic materials such as those coated with anticorrosive materials such as rutile, thin films made of organic compounds, carbon, silicon oxide, etc. by vacuum deposition, sputtering, CVD, plasma, etc. It may be provided on the metal thin film layer.

When used as a lubricant for a magnetic recording medium, the amount used is in the range of 0.1 to 20 mg / m ² , and preferably in the range of 1 to 5 mg / m ^2. If it is too small, it may not be possible to make it evenly exist, and the still durability may not be sufficiently improved. On the contrary, if the amount is too large, the magnetic layer may stick to the magnetic head or the magnetic head cylinder, which is not preferable.

When it is contained in the magnetic layer, the desired effect cannot be obtained if it is less than 0.1% by weight with respect to the magnetic powder, and if it is more than 20% by weight, the strength of the magnetic layer is lowered. Since the magnetic head is apt to become dirty, 0.1 to 20
It is preferably within the range of weight%.

In the case of a ferromagnetic metal thin film layer, the magnetic layer is formed by Co, Ni, Fe, Co-Ni, Co-Cr, Co.
-P, Co-Ni-P, Fe-Co-B, Fe-Co-
Ni, Co-Ni-Fe-B, Fe-Ni, Fe-C
o, Co-Pt, Co-Ni-Pt, and those obtained by adding oxygen to these materials, a ferromagnetic material generally used for forming a ferromagnetic metal thin film layer is vacuum-deposited, ion-plated,
It is formed by a method such as sputtering or plating on one or both surfaces of the non-magnetic support. The thickness of the ferromagnetic metal thin film layer thus formed is preferably in the range of 0.03 to 1 μm.

In the present invention, especially Co-
Since excellent effects are exhibited when it is used for a Ni—O ferromagnetic metal thin film layer, it is preferable to use it for a ferromagnetic metal thin film layer containing Co, Ni, and O as the main components. It is more preferable to use it for the ferromagnetic metal thin film layer containing Co, Ni, and O as the main components, which is 97/3 to 60/40.

In addition to the above, the magnetic layer is prepared by mixing and dispersing magnetic powder with a binder resin, an organic solvent and other necessary components to prepare a magnetic coating, and the magnetic coating is prepared by using a non-magnetic support such as polyethylene terephthalate film. It is made by coating on top and drying.

In this case, the magnetic powder used is
γ-Fe ₂ O ₃ powder, Fe ₃ O ₄ powder, γ-Fe ₂ O ₃
Iron oxide powder in an intermediate oxidation state between the powder and Fe ₃ O ₄ powder,
Co-containing γ-Fe ₂ O ₃ powder, Co-containing Fe ₃ O ₄ powder, CrO ₂ powder, Fe powder, Co powder, Fe-N
Various conventionally known magnetic powders such as metal powder such as i-Cr alloy powder and barium ferrite powder are widely used.

As the binder resin, vinyl chloride or a copolymer containing it as a main component, a fibrin resin, a polyurethane resin, a polyester resin, a polyvinyl butyral resin, a polyacrylic resin, Epoxy resins, phenolic resins, acrylic resins, polyisocyanate compounds, polyepoxy compounds and the like, which are usually used as binder resins for magnetic recording media, are preferably used.

Further, as the organic solvent, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone,
Toluene, ethyl acetate, tetrahydrofuran, dioxane, dimethylformamide and the like which are generally used in magnetic recording media are used alone or in combination of two or more.

In the magnetic coating composition, various commonly used additives such as abrasives, antistatic agents and dispersants may be optionally added.

A back coat layer may be provided on the back surface of a non-magnetic support having a magnetic layer formed on the surface thereof. The back coat layer contains non-magnetic powder such as carbon black or calcium carbonate. Vinyl chloride or a copolymer containing it as a main component, a urethane-based copolymer, a binder resin such as a fibrin-based resin and the like, and a dispersion and a back coat
The coating material for the back layer is prepared, and the coating material for the back coating layer is applied and dried on the back surface of the non-magnetic support having the magnetic layer formed on the surface.

As the non-magnetic support, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyvinyl chloride and other plastics, aluminum alloys, titanium alloys and the like are preferably used.
The shape of the non-magnetic support may be any of tape, sheet, disk, card, etc., and projections may be formed on the surface.

The case where the lubricant of the present invention is used for a magnetic recording medium has been described above. However, the use of the lubricant of the present invention is not limited to this, and for example, lubricity of a mechanical sliding portion can be improved. It is effectively used for everything you need.

[0042]

EXAMPLES Next, examples of the present invention will be described.
It should be noted that here, an example of application to a magnetic recording medium will be described as a typical one, but it goes without saying that the use, manufacturing method, substance, etc. are not limited.

Example 1 A polyethylene terephthalate film having a thickness of 10 μm was loaded in a vacuum vapor deposition apparatus, and a Co—Ni alloy was heated and evaporated under a residual gas pressure of 5 × 10 ⁻⁵ torr of oxygen gas. , Oblique incident vapor deposition continuously, and Co-Ni-O (Co: Ni = 80: 2) on the polyethylene terephthalate film.
A 0.2 μm-thick ferromagnetic metal thin film layer of 0) was formed.

On the other hand, perfluoropolyether whose terminal part is -CF ₂ CH _2- (OCH ₂ CH ₂ ) m-OH (manufactured by Montecatini Co .; Fomblin Z DOL-TX, molecular weight 2200).
O and 220 parts by weight of propylene oxide 35 parts by weight - Tokure - was polymerized in Bed, Pa - Furuoroporie - at both ends of the ether, the following formula _{-CF 2 CH 2 - (OCH 2} CH 2) m- (OC
A compound A having a polyether chain represented by ₃ H ₆ ) n-OH was obtained. This compound A was analyzed by NMR, and it was confirmed that m was 2 and n was 3.

Then, the compound A thus obtained
5.5 parts by weight of thionyl chloride was added to 100 parts by weight, and the mixture was refluxed at 80 ° C. for 2 hours while stirring well, and excess thionyl chloride was distilled off to obtain a compound B having a chlorinated molecular end. The polyether moiety of the compound B is represented by the following chemical formula. _{-CF 2 CH 2 (OCH 2 CH} 2) 2 - (OC 3 H 6)
_3- Cl

The compound B thus obtained was dissolved in tetrahydrofuran to obtain a 0.2% by weight solution of the compound B in tetrahydrofuran, and the Co-N formed on the polyethylene terephthalate film was dissolved in the solution.
The ferromagnetic metal thin film layer made of i-O is dipped, dried,
It was present as a lubricant. Then, it was slit into a width of 8 mm to prepare a video tape.

Example 2 1.9 parts by weight of metallic sodium was dissolved in 2.5 parts by weight of methanol, and 100 parts by weight of the compound B of Example 1 was added thereto.
The reaction was carried out at 80 ° C. for 8 hours while stirring well to obtain a compound C in which the molecular end was methoxylated. Compound C alkyl ether
The structure of the tellurium part is represented by the following chemical formula. _{-CF 2 CH 2 - (OCH 2} CH 2) 2 - (OC
₃ H ₆ ) _3- OCH ₃

Then, in the coating treatment of the compound on the ferromagnetic metal thin film layer in Example 1, the compound C obtained in place of the compound B used in Example 1 was used, and the compound C obtained was used. A video tape was produced by performing a deposition treatment of the compound C obtained in the same manner as in Example 1 on the ferromagnetic metal thin film layer except that a 0.2 wt% tetrahydrofuran solution was used.

Example 3 9 parts by weight of trimethylmethoxysilane was added to 100 parts by weight of the compound A of Example 1 and reacted at 100 ° C. for 8 hours with stirring to remove excess trimethylsilane and methanol as a by-product. Thus, a compound D in which the molecular end was trimethylsilylated was obtained. The structure of the alkyl ether moiety of compound D is represented by the following chemical formula. _{-CF 2 CH 2 - (OCH 2} CH 2) 2 - (OC 3 H 6) 3
-OSi (CH _{3) 3}

Then, in the coating treatment of the compound on the ferromagnetic metal thin film layer in Example 1, the compound D obtained in place of the compound B used in Example 1 was used. Compound D obtained in the same manner as in Example 1 except that a 0.2 wt% tetrahydrofuran solution was used was deposited on the ferromagnetic metal thin film layer to prepare a video tape.

Example 4 After thoroughly replacing the inside of the reaction vessel with nitrogen, Fomblin Z DOL-TX (manufactured by Montecatini Co .; part 100 parts by weight fluoropolyether) n octadecyldimethylchlorosilane 35 〃 chloroform 75 〃 Pyridine (16) was added, and the mixture was reacted at room temperature for 8 hours with vigorous stirring under a nitrogen stream. Thereafter, the pyridine salt was repeatedly extracted and removed with chloroform to obtain a compound E. The structure of the alkyl ether moiety of compound E is represented by the following chemical formula.

Then, in the coating treatment of the compound on the ferromagnetic metal thin film layer in Example 1, 0.2% by weight of the obtained compound E was used instead of the 0.2% by weight tetrahydrofuran solution of the compound B used in Example 1. % Toluene solution was used, and Compound E obtained in the same manner as in Example 1 was applied onto the ferromagnetic metal thin film layer to prepare a video tape.

Example 5 The end portion is —CF ₂ CH ₂ — (OCH ₂ CH ₂ ) m—O.
Perfluoropolyene having H (m is 2 or 3 on average)
Tell (Montecatini Company; Fomblin ZDOL-T
X, molecular weight 2200) 220 parts by weight is heated to 80 ° C. under normal pressure, ethylene oxide is gradually blown into this, and the m of the perfluoropolyether is adjusted to about 5 while monitoring the reaction by increasing the weight. And

Then, this was reacted with a large excess of n-butyl bromide (68.5 parts by weight) in the presence of NaOH according to a conventional method, and the both ends of the perfluoropolyether were reacted with the following chemical formula -CF _{2 CH 2 - (OCH 2 CH 2} ) 5 -O- (C
D is represented by H _{2) 3} -CH ₃ - to give the compound F having an alkyl chain containing ether bond. This compound F was analyzed by NMR and IR, and it was confirmed that m was 5 on average. NMR and I
The R spectrum is shown in FIGS. 1 and 2.

Next, in the treatment for depositing the compound on the ferromagnetic metal thin film layer in Example 1, 0.2% by weight of the obtained compound F was used instead of the 0.2 wt% tetrahydrofuran solution of the compound B used in Example 1. A video tape was produced by performing a deposition treatment of the compound F obtained in the same manner as in Example 1 on the ferromagnetic metal thin film layer except that a wt% tetrahydrofuran solution was used.

Example 6 In the synthesis of compound F in Example 5, instead of perfluoropolyether, perfluoroalkyl alcohol (C ₇ F ₁₅ CH ₂ CH ₂ OH, manufactured by Hoechst Japan Co .; Fluorwet) was used. 600, molecular weight 414) was used, except that 2.0 parts per molecule of ethylene oxide was added in the same manner as in Example 5 except that 88 parts by weight were used, and then etherified with n-butyl bromide to obtain a compound represented by the chemical formula C ₇ F ₁₅ CH 2. ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ O
A compound G represented by C ₄ H ₉ was obtained. This compound G was analyzed by NMR and IR to confirm the chemical structure. Boiling point is 175 ° C
It was /0.1 torr. The NMR and IR spectra are shown in FIGS. 3 and 4.

Next, in the treatment for depositing the compound on the ferromagnetic metal thin film layer in Example 1, 0.2% by weight of the obtained compound G was used instead of the 0.2 wt% tetrahydrofuran solution of the compound B used in Example 1. A video tape was produced by performing a deposition treatment of the compound F obtained in the same manner as in Example 1 on the ferromagnetic metal thin film layer except that a wt% tetrahydrofuran solution was used.

Example 7 In the treatment for depositing the compound on the ferromagnetic metal thin film layer in Example 1, the solution obtained in Example 5 was used instead of the 0.2 wt% tetrahydrofuran solution of the compound B used in Example 1. Compound G and F obtained in the same manner as in Example 1 except that a tetrahydrofuran solution containing 0.1% by weight of each of Compound F and Compound G obtained in Example 6 was used. A dressing process was performed to produce a video tape.

Example 8 Perfluoropolyether was prepared in the same manner as in Example 1 except that 125 parts by weight of 1-dodecane bromide was used in place of n-butyl bromide in the synthesis of compound F in Example 5. at both ends of the ether, the following formula _{-CF 2 CH 2 (OCH 2 CH} 2) m-O─ (CH 2)
A compound H having an alkyl chain containing an ether bond represented by ₁₁ CH ₃ was obtained.

Then, in the coating treatment of the compound on the ferromagnetic metal thin film layer in Example 1, 0.2% by weight of the obtained compound H was used instead of the 0.2% by weight tetrahydrofuran solution of the compound B used in Example 1. % Tetrahydrofuran solution was used to carry out the deposition treatment of the compound H obtained in the same manner as in Example 1 on the ferromagnetic metal thin film layer to prepare a video tape.

Example 9 36.4 parts by weight of a fluoroalkyl alcohol represented by the chemical formula CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ —OH and ethylene oxide were reacted according to a conventional method to give the following chemical formula CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ (OCH ₂ CH ₂ ) m
A compound I having a polyether chain at the end of the fluoroalkyl chain represented by -OH was obtained. During the reaction, the product was analyzed by NMR and reacted until m was about 2.

Compound I thus obtained
Was reacted with 69 parts by weight of a large excess of n-butyl bromide according to a conventional method to give the following chemical formula CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ (OCH ₂ CH ₂ ) m.
A compound J having a fluoroalkyl chain represented by —O (CH ₂ ) ₃ CH ₃ and an alkyl chain containing at least one ether bond including a bonding portion, was obtained at the end of the fluoroalkyl chain.

Compound J thus obtained and perfluoropolyether having hydroxyl groups at both ends (manufactured by Montecatini Co .; Fomblin Z DOL, molecular weight 220)
0) was dissolved in Freon in a weight ratio of 1: 2 to obtain a 0.1% by weight Freon solution of this compound J and perfluoropolyether.

Then, in the treatment of depositing the compound on the ferromagnetic metal thin film layer in Example 1, the obtained solution was used instead of the 0.2 wt% tetrahydrofuran solution of the compound B used in Example 1. Was subjected to a deposition treatment of the compound J obtained in the same manner as in Example 1 and perfluoropolyether on the ferromagnetic metal thin film layer to prepare a video tape.

Example 10 A perfluoropolyether was prepared in the same manner as in Example 9 except that 125 parts by weight of 1-bromide dodecane was used instead of n-butyl bromide in the synthesis of the compound in Example 9. Of the following chemical formula CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ (OCH ₂ CH ₂ ) m
A compound K having a fluoroalkyl chain represented by —O (CH ₂ ) ₁₁ CH ₃ and an alkyl chain containing at least one ether bond including a bonding portion was bonded to the end of the fluoroalkyl chain.

Next, the obtained compound K and perfluoropolyether having hydroxyl groups at both ends (manufactured by Montecatini Co .; Fomblin Z DOL, molecular weight 2200) were dissolved in Freon in a weight ratio of 1: 2. In the coating treatment of the lubricant on the ferromagnetic metal thin film layer in Example 9, the compound J used in Example 9 and the perfluoropolyether were used.
Compound K obtained in the same manner as in Example 9 except that the obtained compound K and a 0.1% by weight freon solution of perfluoropolyether were used instead of the 0.1% by weight freon solution.
And a perfluoropolyether on the ferromagnetic metal thin film layer were deposited to prepare a video tape.

Example 11 α-Fe magnetic powder 100 parts by weight MR-110 (manufactured by Zeon Corporation; vinyl chloride resin) 15 〃 N-2309 (manufactured by Nippon Polyurethane Industry Co., Ltd .; polyurethane 10 〃 resin) Carbon Black 1 〃 α-Al ₂ O ₃ 0.5 〃 Cyclohexanone 150 〃 Toluene 150 〃

After the composition of (1) was mixed and dispersed in a ball mill for 72 hours, it was further added with Coronet L (manufactured by Nippon Polyurethane Industry Co .; trifunctional low molecular weight isocyanate compound).
Was added and mixed for 0.5 hour, and finally 3 parts by weight of the compound B obtained in Example 1 was added to prepare a magnetic coating material. This magnetic paint was applied onto a polyethylene terephthalate film having a thickness of 10 μm so that the thickness after drying would be 3 μm, and dried to form a magnetic layer. After that, 8
A video tape was produced by slitting it into a width of mm.

Example 12 A video tape was produced in the same manner as in Example 8 except that the same amount of the compound F obtained in Example 5 was used in place of the compound B in the composition of the magnetic coating material in Example 8. did.

Example 13 A video tape was produced in the same manner as in Example 8 except that the same amount of the compound K obtained in Example 10 was used in place of the compound B in the composition of the magnetic paint in Example 8. did.

Comparative Example 1 In the coating treatment of the compound on the ferromagnetic metal thin film layer of Example 1, the 0.2 wt% tetrahydrofuran solution of Compound B used in Example 1 was used instead of the compound A of Example 1.
Example 1 except that a 0.2 wt% methanol solution was used
In the same manner as in (1) and (2), the compound A was applied onto the ferromagnetic metal thin film layer to prepare a video tape.

Comparative Example 2 In the treatment of depositing the compound on the ferromagnetic metal thin film layer of Example 1, the methyl ester was added to both ends of the molecule instead of the 0.2 wt% tetrahydrofuran solution of the compound B used in Example 1. Having perfluoropolyether (Montekaty)
D. Fomblin Z DEAL, molecular weight about 2000)
Example 1 except that a 0.2 wt% Freon solution of
In the same manner as above, the perfluoropolyether was applied onto the ferromagnetic metal thin film layer to prepare a video tape.

Comparative Example 3 100 parts by weight of linoleic acid and 150 parts by weight of 1,1 dihydroperfluoro-1-octanol were reacted with stannous oxide as a catalyst to give 1,1-dihydroperfluoro. An octyl linoleate was obtained. The obtained 1,1-dihydroperfluorooctyl linoleate has a boiling point of 170 ° C.
It was /0.1 torr.

Then, in the treatment of depositing the compound on the ferromagnetic metal thin film layer in Example 1, the 0.2 wt% tetrahydrofuran solution of the compound B used in Example 1 was replaced with the compound obtained in Comparative Example 3. 1,1-dihydroperfluorooctyl linoleate was obtained in the same manner as in Example 1 except that a 0.2 wt% tetrahydrofuran solution of 1,1-dihydroperfluorooctyl linoleate was used.
A video tape was prepared by applying 1-dihydroperfluorooctyl linoleate onto the ferromagnetic metal thin film layer.

Comparative Example 4 Example 8 was repeated except that in the composition of the magnetic coating material of Example 8, 5 parts by weight of myristic acid and 1 part by weight of butyl stearate were used in place of the compound B used in Example 8. A video tape was produced in the same manner as in.

The magnetic tape obtained in each Example and Comparative Example
With respect to the burs, the still durability, corrosion resistance and storage stability were examined by the following methods.

<Still durability> Still durability is 20
Using a 8 mm VTR (manufactured by Hitachi, Ltd .; VM-H39) under the conditions of 50 ° C. and 50% RH, the still time was measured until the reproduction output decreased by 6 dB compared to the initial stage, and the examination was conducted.

<Contact resistance> Corrosion resistance is 60 ° C., 70% RH
The ratio of deterioration in reproduction output after storage for 1 week was examined.

<Storage Stability> The storage stability was evaluated by the change in friction coefficient immediately after the application treatment and after storage at 60 ° C. and 70% RH for 1 week. The friction coefficient is 6m in diameter with a magnetic tape.
Wrap around 5m SUS cylinder and apply 5g load to 10c
Measurement was performed by sliding back and forth at a speed of m / s, and the measurement value of the 10th pass was used. Table 1 below shows the results.

[0080]

[0081]

As is apparent from Table 1 above, the video tapes obtained in the present invention (Examples 1 to 13) are the same as those in Comparative Example 1.
Compared to the video tapes obtained in Nos. 4 to 4, the still time was long, the corrosion resistance was good, and the friction coefficient was small.
From this, it is understood that the lubricant obtained by the present invention can impart stable lubricity over a long period of time.

[Brief description of drawings]

FIG. 1 MM of a lubricant obtained in Example 5 of the present invention
It is a spectrum figure of R.

FIG. 2 IR of the lubricant obtained in Example 5 of the present invention
FIG.

FIG. 3 MM of the lubricant obtained in Example 6 of the present invention
It is a spectrum figure of R.

FIG. 4 IR of the lubricant obtained in Example 6 of the present invention
FIG.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G11B 5/71 // C10N 20:04 30:06 30:12 40:18 (72) Inventor Isoe Noboru 1-88, Toyora, Ibaraki-shi, Osaka Prefecture Hitachi Maxell Co., Ltd. (72) Inventor, Koji Miyata 1-88, Torora, Ibaraki-shi, Osaka Prefecture Hitachi Maxell, Ltd.

Claims (5)

[Claims] 1. A carbon atom, a hydrogen atom, a fluorine atom and an air atom.
And a perfluoroalkyl chain represented by the following general formula (A), a perfluoroalkyl chain represented by (B), and (C). The polyether chain is a combination of (A) and (C), a combination of (B) and (C), or (A) and (C).
Combinations and (B) and (C) a combination of both combination with lubricating agents consisting of compounds contained in the molecule _{(A) - (C n F} 2n O) m- ( where, n is 1 to 10 is an integer of, m is an integer of 1 or _{more) (B) -C n F 2n} -. ( where, n is an integer of 1~15) (C) -. ( C n H 2n O) m- (However, n is an integer of 1 to 6, and m is an integer of 1 or more.) 2. The lubricant according to claim 1, wherein (A)
And (C) or (B) and (C) bound by an etheric oxygen atom 3. At least one molecular terminus is --OR ₁
(However, R ₁ is an alkyl group having 1 to 18 carbon atoms or a fluorinated alkyl group), -OSi (CH ₃ ) ₂ R ₂ (however, R ₂
Is an alkyl group having 1 to 30 carbon atoms). 4. The lubricant according to claim 1, wherein (A)
And (C) are bound by an ethereal oxygen atom, and at least one molecular end is -Cl 5. The lubricant according to claim 3, which has a molecular weight of 300 to 10,000.