Fluorine-containing ether compound, lubricant for magnetic recording medium, and magnetic recording medium

Abstract

This fluorine-containing ether compound is represented by the following formula. R1-O-R2-CH2-R3-CH2-R4-O-R5 (R3 is a perfluoropolyether chain. R2 and R4 are each a divalent linking group having at least one polar group. R1 and R5 are each formula (2), formula (3), or a hydrogen atom. At least one among R1 and R5 is formula (2) or formula (3). In formula (2), X1 is a C1-C30 alkylene group. Y and Z are each a C1-C30 aliphatic group. In formula (3), X2 is a C1-C30 alkylene group. A and B are each a C1-C30 aliphatic group.)

Description

[Technical Field]

[0001] The present invention relates to a fluorine-containing ether compound, a lubricant for a magnetic recording medium, and a magnetic recording medium. This application claims priority based on Japanese Patent Application No. 2023-034983, filed on March 7, 2023, the contents of which are incorporated herein by reference. [Background technology]

[0002] In order to improve the recording density of magnetic recording and reproducing devices, development of magnetic recording media suitable for high recording densities is underway. Conventionally, magnetic recording media have a recording layer formed on a substrate, and a protective layer such as carbon formed on the recording layer. The protective layer protects the information recorded on the recording layer and improves the sliding properties of the magnetic head. However, simply providing a protective layer on the recording layer does not provide sufficient durability for the magnetic recording medium. For this reason, a lubricating layer is generally formed by applying a lubricant to the surface of the protective layer.

[0003] As lubricants used in forming the lubricating layer of magnetic recording media, for example, those containing compounds having polar groups such as hydroxyl groups or amino groups at the end of a fluorine-based polymer having a repeating structure containing -CF2- have been proposed.

[0004] For example, perfluoropolyether compounds having a plurality of hydroxy groups and having terminal substituents such that the shortest distance between the hydroxy groups is three atoms or more are known as lubricants (see, for example, Patent Document 1). Also known is a lubricant containing a fluoropolyether compound having an aromatic group and a hydroxyl group (see, for example, Patent Document 2). Patent Document 2 also describes a compound represented by formula (1) in which an amide group is bonded to the terminal via a phenylene group.

[0005] Patent Document 3 also discloses the use of a fluoropolyether compound as a lubricant, which has a plurality of perfluoropolyether groups, a terminal group having at least one hydroxyl group, and a linking group consisting of a hydrocarbon group having at least one hydroxyl group.

[0006] Patent Document 4 discloses a fluorine-containing ether compound in which divalent linking groups having polar groups are linked to both ends of a perfluoropolyether chain, and at least one of the chains is linked to an end group in which one or more hydrogen atoms of a chain organic group having 1 to 8 carbon atoms have been substituted with a group having an amide bond. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent No. 4632144 (B) [Patent Document 2] Japanese Patent Application Publication No. 2013-163667 (A) [Patent Document 3] Japanese Patent No. 6763980 (B) [Patent Document 4] WO 2019 / 039265(A) Summary of the Invention [Problem to be solved by the invention]

[0008] In magnetic recording and reproducing devices, there is a demand for an even smaller flying height of the magnetic head, which in turn requires a thinner lubricating layer in the magnetic recording medium. However, generally, reducing the thickness of a lubricating layer tends to reduce the chemical resistance and wear resistance of the magnetic recording medium. Furthermore, reducing the thickness of a lubricating layer can result in insufficient corrosion resistance of the magnetic recording medium. For these reasons, there is a demand for a lubricating layer that has excellent chemical resistance and wear resistance and a high corrosion-inhibiting effect on the magnetic recording medium.

[0009] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a fluorine-containing ether compound that has excellent chemical resistance and abrasion resistance, is capable of forming a lubricating layer that has a high corrosion-inhibiting effect on magnetic recording media, and can be suitably used as a material for lubricants for magnetic recording media. Another object of the present invention is to provide a lubricant for magnetic recording media which contains the fluorinated ether compound of the present invention and is capable of forming a lubricating layer having good chemical resistance, wear resistance, and excellent corrosion resistance. Another object of the present invention is to provide a magnetic recording medium having a lubricating layer containing the fluorine-containing ether compound of the present invention, which has good chemical resistance, abrasion resistance, and excellent corrosion resistance. [Means for solving the problem]

[0010] The present invention relates to the following:

[0011] [1] A fluorine-containing ether compound represented by the following formula (1): R 1 -OR 2 -CH2-R 3 -CH2-R 4 -OR 5 (1) (In formula (1), R 3 is a perfluoropolyether chain. 2 and R 4 are divalent linking groups having one or more polar groups, and may be the same or different. 1 and R 5 is a terminal group represented by the following formula (2), a terminal group represented by the following formula (3), or a hydrogen atom, and R 1 and R 5 may be the same or different. 1 and R 5 At least one of the groups is a terminal group represented by the following formula (2) or (3):

[0012] [ka] (In formula (2), X 1 is an alkylene group having 1 to 30 carbon atoms. Y and Z are each independently an aliphatic group having 1 to 30 carbon atoms which may contain a polar group or an ether oxygen atom. Y and Z may be bonded to each other to form a cyclic structure. (In formula (3), X 2 is an alkylene group having 1 to 30 carbon atoms. A and B are each independently an aliphatic group having 1 to 30 carbon atoms which may contain a polar group or an ether oxygen atom. A and B may be bonded to each other to form a cyclic structure.

[0013] [2] R in the formula (1) 1 and R 5 are each independently a terminal group represented by the formula (2) or (3). [3] R in the formula (1) 1 and R 5 The fluorine-containing ether compound according to [2], wherein [4] R in the formula (1) 1 and R 5 The fluorine-containing ether compound according to [2], wherein [5] R in the formula (1) 1 and R 5 The fluorine-containing ether compound according to [1], wherein one of the following is a terminal group represented by the formula (2) or (3), and the other is a hydrogen atom.

[0014] [6] -R in the formula (1) 2 -O- and -R 4 The fluorine-containing ether compound according to any one of [1] to [5], wherein each —O— is independently represented by the following formula (4):

[0015] [ka] (In formula (4), l represents an integer of 1 to 3. l m's each independently represent an integer of 1 to 6. l n's each independently represent an integer of 1 to 6. In one repeating unit, at least one of m and n is 1. E represents a single bond, -CH2CHO- (the leftmost carbon atom is bonded to an oxygen atom in the repeating unit), -CH2CH2CHO- (the leftmost carbon atom is bonded to an oxygen atom in the repeating unit), or -CH2CH2CH2CHO- (the leftmost carbon atom is bonded to an oxygen atom in the repeating unit). In formula (4), the leftmost oxygen atom is R 3 E is bonded to the methylene group bonded to R 1 or R 5 )

[0016] [7] -R in the formula (1) 2 -O- and -R 4 The fluorine-containing ether compound according to any one of [1] to [6], wherein each —O— is independently represented by the following formula (5-1) or (5-2):

[0017] [ka] In formula (5-1), p represents an integer of 0 to 3, q ​​represents an integer of 0 to 2, and r represents an integer of 1 to 3. In formula (5-1), the leftmost oxygen atom is R 3 The rightmost oxygen atom is attached to a methylene group that is attached to R 1 or R 5 ) In formula (5-2), s represents an integer of 0 to 2, and t represents an integer of 0 to 3. In formula (5-2), the leftmost oxygen atom is R 3 The rightmost oxygen atom is attached to a methylene group that is attached to R 1 or R 5 )

[0018] [8] R in the formula (1) 3 is a perfluoropolyether chain represented by the following formula (6): -(CF2) w1 -O-(CF2O) w2 -(CF2CF2O) w3 -(CF2CF2CF2O) w4 -(CF2CF2CF2CF2O) w5 -(CF2) w6 - (6) (In formula (6), w2, w3, w4, and w5 represent average degrees of polymerization and each independently represent 0 to 20. However, w2, w3, w4, and w5 cannot all be 0 at the same time. w1 and w6 represent average values ​​representing the number of CF2 and each independently represent 1 to 3. There are no particular restrictions on the arrangement order of the repeating units (CF2O), (CF2CF2O), (CF2CF2CF2O), and (CF2CF2CF2CF2O) in formula (6).)

[0019] [9] R in the formula (1) 3 is any one selected from perfluoropolyether chains represented by the following formulae (7-1) to (7-4): -CF2-(OCF2CF2) h -(OCF2) i -OCF2- (7-1) (In formula (7-1), h and i represent the average degree of polymerization, h represents 1 to 20, and i represents 0 to 20.) -CF2CF2-(OCF2CF2CF2) j -OCF2CF2- (7-2) (In formula (7-2), j represents the average degree of polymerization and represents 1 to 15.) -CF2CF2CF2-(OCF2CF2CF2CF2) k -OCF2CF2CF2- (7-3) (In formula (7-3), k represents the average degree of polymerization and represents 1 to 10.) -(CF2) w7 -O-(CF2CF2CF2O) w8 -(CF2CF2O) w9 -(CF2) w10 - (7-4) (In formula (7-4), w8 and w9 represent the average degree of polymerization, each independently representing 1 to 20. w7 and w10 are average values ​​representing the number of CF2, each independently representing 1 to 2.)

[0020]

[10] The fluorinated ether compound according to any one of [1] to [9], which has a number average molecular weight in the range of 500 to 10,000.

[11] A lubricant for magnetic recording media, comprising the fluorine-containing ether compound according to any one of [1] to

[10] .

[0021]

[12] A magnetic recording medium having at least a magnetic layer, a protective layer, and a lubricating layer sequentially provided on a substrate, A magnetic recording medium, wherein the lubricating layer contains the fluorine-containing ether compound according to any one of [1] to

[10] .

[13] The magnetic recording medium according to

[12] , wherein the lubricating layer has an average film thickness of 0.5 nm to 2.0 nm. [Effects of the Invention]

[0022] The fluorine-containing ether compound of the present invention is a compound represented by the above formula (1), and is therefore suitable as a material for a lubricant for a magnetic recording medium. The lubricant for magnetic recording media of the present invention contains the fluorine-containing ether compound of the present invention, and therefore can form a lubricating layer that has good chemical resistance and abrasion resistance and is highly effective in inhibiting corrosion of magnetic recording media.

[0023] The magnetic recording medium of the present invention has a lubricating layer containing the fluorine-containing ether compound of the present invention. Therefore, the magnetic recording medium of the present invention has good chemical resistance and abrasion resistance, excellent corrosion resistance, and excellent reliability and durability. Furthermore, the lubricating layer of the magnetic recording medium of the present invention has good chemical resistance and abrasion resistance and has a high corrosion suppression effect on the magnetic recording medium, so the thickness can be made thin. [Brief explanation of the drawings]

[0024] [Figure 1]1 is a schematic cross-sectional view showing an embodiment of a magnetic recording medium of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0025] In order to solve the above problems, the present inventors have conducted extensive research as described below. Conventionally, fluorine-containing ether compounds having polar groups such as hydroxyl groups at the end of a chain structure have been preferably used as materials for lubricants for magnetic recording media (hereinafter sometimes abbreviated as "lubricants") to be applied to the surface of a protective layer. The polar groups in the fluorine-containing ether compounds bond with active sites on the protective layer, improving the adhesion of the lubricating layer to the protective layer. For this reason, fluorine-containing ether compounds having polar groups not only at the end of the chain structure but also within the chain structure have been particularly preferably used as materials for lubricants.

[0026] However, when a thin lubricating layer is formed on a protective layer using a conventional lubricant, it is difficult to achieve a lubricating layer that has good chemical resistance and wear resistance and a high corrosion-inhibiting effect on magnetic recording media, as will be shown below. That is, if the adhesion of the lubricant to the protective layer is insufficient, the lubricant applied to the protective layer will be bulky. As a result, the lubricant layer is likely to be unevenly coated on the protective layer. If the coating state of the lubricant layer is uneven, the chemical resistance and corrosion resistance of the lubricant layer will be insufficient. Therefore, if the adhesion of the lubricant to the protective layer is insufficient, sufficient chemical resistance and corrosion resistance cannot be obtained unless the film thickness is increased to make the coating state of the lubricant layer on the protective layer uniform.

[0027] Furthermore, if the adhesion of the lubricant to the protective layer is poor, polar groups in the fluorine-containing ether compound that are not involved in bonding with the active sites on the protective layer will be generated, attracting environmental substances that generate pollutants and water that can cause corrosion of the magnetic recording medium to the lubricating layer, thereby deteriorating the chemical resistance of the lubricating layer and the corrosion resistance of the magnetic recording medium.

[0028] One possible method for improving the adhesion of a lubricant to a protective layer is to use, as a lubricant material, a fluorine-containing ether compound having multiple polar groups, in which polar groups are bonded to the carbon atoms at the ends of both chain structures and to carbon atoms in the other chain structures. However, in the case of a lubricating layer formed using such a fluorine-containing ether compound, adhesion to the protective layer is too strong, resulting in insufficient fluidity, loss of lubricity, and insufficient wear resistance. Furthermore, in lubricating layers formed using such fluorine-containing ether compounds, the hydrophilicity of the lubricant is too high, allowing water to easily penetrate, and corrosion of the magnetic recording medium has sometimes been observed.

[0029] Therefore, the present inventors have focused on the bond between the polar group contained in the fluorine-containing ether compound and the active site on the protective layer, and have conducted extensive research to realize a fluorine-containing ether compound that can form a lubricating layer that has a uniform coating state on the protective layer, is less likely to produce polar groups that are not involved in bonding with the active site on the protective layer, has moderately good adhesion, and therefore has good chemical resistance and wear resistance and a high corrosion suppression effect on magnetic recording media.

[0030] As a result, they found that a fluorine-containing ether compound having a methylene group (-CH2-), a divalent linking group having one or more polar groups, an oxygen atom, and an end group having an N,N-substituted amide in which a specific aliphatic group is bonded to a nitrogen atom constituting an amide bond and no hydrogen atom is bonded thereto (hereinafter, sometimes simply referred to as "N,N-substituted amide") or a hydrogen atom, bonded in this order to both ends of a perfluoropolyether chain, and having the end group having the N,N-substituted amide located at at least one end.

[0031] Such fluorine-containing ether compounds include those shown below. <1> This makes it difficult for polar groups that are not involved in bonding with the active sites on the protective layer to be generated, and makes it possible to form a lubricating layer with moderately good adhesion, <2> This allows the formation of a lubricating layer that covers the protective layer uniformly, and <3> This allows the formation of a lubricating layer with good fat solubility, and it is presumed that this provides a lubricating layer with good chemical resistance and abrasion resistance, and a high corrosion suppression effect on the magnetic recording medium.

[0032] <1> In the above-mentioned fluorine-containing ether compound, an end group having a specific N,N-substituted amide is bonded to at least one end. The bond of the carbon atom adjacent to the carbonyl carbon atom or nitrogen atom constituting the amide bond of the N,N-substituted amide possessed by this end group is difficult to freely rotate. Therefore, the N,N-substituted amide possessed by the end group arranged at least one end and the polar group possessed by the divalent linking group adjacent to this end group are unlikely to interact with each other.

[0033] Furthermore, in the above-mentioned fluorine-containing ether compound, the N,N-substituted amide possessed by the terminal group located at at least one end has a structure in which a specific aliphatic group is bonded to the nitrogen atom constituting the amide bond and no hydrogen atom is bonded to it. Therefore, in the above-mentioned fluorine-containing ether compound, the interaction between the N,N-substituted amide possessed by the terminal group located at at least one end and the polar group possessed by the divalent linking group adjacent to this terminal group is more difficult compared to, for example, a case in which one or two hydrogen atoms are bonded to the nitrogen atom constituting the amide bond.

[0034] Furthermore, in the above-mentioned fluorine-containing ether compound, the N,N-substituted amide in the terminal group located at at least one end and the polar group in the divalent linking group adjacent to this terminal group have extremely little ability to inhibit their mutual interaction with the protective layer. Therefore, in the above-mentioned fluorine-containing ether compound, the N,N-substituted amide in the terminal group located at at least one end and the polar group in the divalent linking group adjacent to this terminal group are each considered to be likely to participate in bonding with active sites on the protective layer.

[0035] Furthermore, the N,N-substituted amide in the terminal group located at at least one end exhibits moderate interaction with the protective layer, and the polar groups in the divalent linking group adjacent to the N,N-substituted amide terminal group each independently exhibit good interaction with the protective layer. As a result, the N,N-substituted amide in the terminal group located at at least one end and the polar groups in the divalent linking group adjacent thereto can each independently bond with the numerous functional groups (active sites) present on the protective layer. Therefore, polar groups that do not bond with the active sites on the protective layer are less likely to be generated, and the number of polar groups that do not participate in bonding with the active sites on the protective layer is reduced. Therefore, the above-mentioned fluorine-containing ether compound can form a lubricating layer with moderately good adhesion to the protective layer, and the polar groups in the compound that do not participate in bonding with the active sites on the protective layer are prevented from attracting environmental substances that generate pollutants and water that causes corrosion of magnetic recording media to the lubricating layer.

[0036] <2> In the above-mentioned fluorine-containing ether compound, the N,N-substituted amide possessed by the terminal group arranged at at least one end has a structure in which a specific aliphatic group is bonded to the nitrogen atom constituting the amide bond, and no hydrogen atom is bonded. Therefore, the above-mentioned fluorine-containing ether compound is less likely to aggregate than, for example, a compound in which one or two hydrogen atoms are bonded to the nitrogen atom constituting the amide bond. This is because the polar group possessed by the divalent linking group contained in the above-mentioned fluorine-containing ether compound and the N,N-substituted amide are less likely to interact (when terminal groups having N,N-substituted amides are arranged at both ends, the polar group possessed by the divalent linking group and the N,N-substituted amide, and the N,N-substituted amides themselves).

[0037] Furthermore, the N,N-substituted amide in the terminal group located at at least one end is unlikely to interfere with the adhesion of the polar group in the divalent linking group to the protective layer.Furthermore, when terminal groups having N,N-substituted amides are located at both ends, the N,N-substituted amides are unlikely to interfere with each other's adhesion to the protective layer. For these reasons, the above-mentioned fluorine-containing ether compound easily wets and spreads on the protective layer, and can form a lubricating layer having a uniform coating state.

[0038] <3> In the end group having N,N-substituted amide contained in the above-mentioned fluorine-containing ether compound, a specific aliphatic group is bonded to the nitrogen atom constituting the amide bond, and no hydrogen atom is bonded.Therefore, the above-mentioned fluorine-containing ether compound has good liposolubility compared with, for example, the case where hydrogen atoms are arranged instead of the end group having N,N-substituted amide (in other words, both ends are hydrogen atoms), and the case where one or two hydrogen atoms are bonded to the nitrogen atom constituting the amide bond.Therefore, the above-mentioned fluorine-containing ether compound can effectively prevent the penetration of water that causes corrosion of magnetic recording medium, and can form a lubricating layer that has high corrosion suppression effect on magnetic recording medium.

[0039] Furthermore, the present inventors have confirmed that by using a lubricant containing the above-mentioned fluorine-containing ether compound to form a lubricating layer on the protective layer of a magnetic recording medium, a lubricating layer having good chemical resistance and wear resistance, as well as excellent corrosion resistance, can be formed, and have thus conceived the present invention.

[0040] The fluorine-containing ether compound, the lubricant for magnetic recording media, and the magnetic recording media of the present invention will be described in detail below. Note that the present invention is not limited to the following embodiments. The present invention allows addition, omission, substitution, and modification of the number, amount, ratio, composition, type, position, material, configuration, etc., within the scope of the present invention.

[0041] [Fluorine-containing ether compounds] A fluorine-containing ether compound represented by the following formula (1): R 1 -OR 2 -CH2-R 3 -CH2-R 4 -OR 5 (1) (In formula (1), R 3is a perfluoropolyether chain. 2 and R 4 are divalent linking groups having one or more polar groups, and may be the same or different. 1 and R 5 is a terminal group represented by the following formula (2), a terminal group represented by the following formula (3), or a hydrogen atom, and R 1 and R 5 may be the same or different. 1 and R 5 At least one of the groups is a terminal group represented by the following formula (2) or (3):

[0042] [ka] (In formula (2), X 1 is an alkylene group having 1 to 30 carbon atoms. Y and Z are each independently an aliphatic group having 1 to 30 carbon atoms which may contain a polar group or an ether oxygen atom. Y and Z may be bonded to each other to form a cyclic structure. (In formula (3), X 2 is an alkylene group having 1 to 30 carbon atoms. A and B are each independently an aliphatic group having 1 to 30 carbon atoms which may contain a polar group or an ether oxygen atom. A and B may be bonded to each other to form a cyclic structure.

[0043] (R 2 and R 4 a divalent linking group represented by In the fluorine-containing ether compound represented by formula (1), R 2 and R 4 R is a divalent linking group having one or more polar groups. 2 and R 4 may be the same or may be different from each other.

[0044] R 2 and R 4Examples of polar groups contained in R include a hydroxyl group (-OH), a cyano group (-CN), an amino group (-NH2), a carboxyl group (-COOH), a formyl group (-(C=O)H), a carbonyl group (-CO-), and a sulfo group (-SO3H). Among these, a hydroxyl group is preferred as the polar group. A hydroxyl group has a strong interaction with a protective layer, especially a protective layer formed from a carbon-based material. Therefore, R 2 and R 4 When the polar group contained in is a hydroxyl group, the lubricating layer containing the fluorine-containing ether compound has even higher adhesion to the protective layer.

[0045] R 2 and R 4 The number of polar groups contained in each of R is preferably 1 to 3. Since the number of polar groups is 1 or more, when a lubricating layer is formed on a protective layer using a lubricant containing the fluorine-containing ether compound of this embodiment, a favorable interaction occurs between the lubricating layer and the protective layer. 2 and R 4 If the number of polar groups contained in is 3 or less, R 2 and R 4 The large number of polar groups contained in the fluorine-containing ether compound increases the hydrophilicity of the fluorine-containing ether compound, and the lubricating layer containing this compound can be prevented from allowing the penetration of water, which causes corrosion of magnetic recording media. Also, R 2 and R 4 The number of polar groups contained in each of the above is preferably 1 or 2, since the number of polar groups contained in the fluorinated ether compound represented by formula (1) is likely to be in the range of 4 to 6.

[0046] R 2 and R 4 R is preferably a linking group having 3 to 15 carbon atoms, and more preferably a linking group having 3 to 10 carbon atoms. 2 and R 4 When R is a linking group having 3 or more carbon atoms, the resulting fluorine-containing ether compound is likely to have sufficient hydrophobicity, and the intrusion of water, which causes corrosion of magnetic recording media, can be effectively inhibited, forming a lubricating layer with a high corrosion-inhibiting effect.2 and R 4 When is a linking group having 15 or less carbon atoms, the hydrophobicity of the fluorine-containing ether compound represented by formula (1) is too high, which weakens the interaction between the lubricating layer and the protective layer and prevents a decrease in the adhesion of the lubricating layer to the protective layer.

[0047] R 2 is R 1 and is bonded via an oxygen atom. Therefore, R 1 is formula (2) or (3), R 2 and R 1 is bonded by an ether bond. 1 is a hydrogen atom, R 2 The oxygen atom bonded to R 1 forms a hydroxyl group. R 2 is R 3 It is preferable that the terminal bonded to the adjacent methylene group is an oxygen atom. R 4 is R 5 and is bonded via an oxygen atom. Therefore, R 5 is formula (2) or (3), R 4 and R 5 is bonded by an ether bond. 5 is a hydrogen atom, R 4 The oxygen atom bonded to R 5 forms a hydroxyl group. R 4 is R 3 It is preferable that the terminal bonded to the adjacent methylene group is an oxygen atom.

[0048] -R in formula (1) 2 -O- and -R 4 Each —O— is preferably independently represented by the following formula (4).

[0049] [ka] (In formula (4), l represents an integer of 1 to 3. l m's each independently represent an integer of 1 to 6. l n's each independently represent an integer of 1 to 6. In one repeating unit, at least one of m and n is 1. E represents a single bond, -CH2CHO- (the leftmost carbon atom is bonded to an oxygen atom in the repeating unit), -CH2CH2CHO- (the leftmost carbon atom is bonded to an oxygen atom in the repeating unit), or -CH2CH2CH2CHO- (the leftmost carbon atom is bonded to an oxygen atom in the repeating unit). In formula (4), the leftmost oxygen atom is R 3 E is bonded to the methylene group bonded to R 1 or R 5 )

[0050] In formula (4), l is an integer of 1 to 3. Therefore, formula (4) is a compound having 1 to 3 repeating units (-(CH2) m -CH(OH)-(CH2) n Each repeating unit in formula (4) has one secondary hydroxyl group that has a strong interaction with the protective layer. 1 or R 5 In addition, in formula (4), R 3 The end of the methylene group bonded to R 3 The hydroxyl groups bond to the methylene groups bonded to the protective layer via an ether bond. Therefore, formula (4) has appropriate flexibility. For these reasons, the one to three secondary hydroxyl groups contained in formula (4) are likely to independently participate in bonding with the numerous active sites present on the protective layer, and the formula has excellent adhesion to the protective layer.

[0051] Since l in formula (4) is 3 or less, it is possible to prevent water, which causes corrosion due to too many hydroxyl groups in formula (4), from being attracted to the lubricating layer containing the fluorine-containing ether compound, and it is possible to form a lubricating layer with a high corrosion-inhibiting effect on magnetic recording media. Since a lubricating layer with a better corrosion-inhibiting effect can be obtained, l in formula (4) is preferably an integer of 1 to 2, and most preferably 1.

[0052] When l in formula (4) is 2 or 3, two or three repeating units (-(CH2) m -CH(OH)-(CH2) n The combinations of m and n in —O—) may be different from one another, or some or all of them may be the same.

[0053] When l in formula (4) is 2 or 3, the two or three hydroxyl groups in formula (4) are each bonded to a different carbon atom. Furthermore, the carbon atoms bonded to the hydroxyl groups are bonded to each other via a linking chain that includes a carbon atom not bonded to a hydroxyl group. Therefore, the two or three hydroxyl groups in formula (4) can be oriented in such a way that they can adhere to the protective layer through the linking chain that includes a carbon atom not bonded to a hydroxyl group in formula (4). Therefore, the two or three hydroxyl groups in formula (4) are all likely to be involved in bonding with the numerous active sites present on the protective layer.

[0054] Furthermore, when l in formula (4) is 2 or 3, the carbon atoms included in the linking chain arranged between the carbon atoms to which the hydroxyl groups are bonded prevent the intramolecular interaction between adjacent hydroxyl groups from occurring in preference to the interaction between the hydroxyl groups and the protective layer, thereby improving the adhesion between the hydroxyl groups in formula (4) and the protective layer.

[0055] Furthermore, when l in formula (4) is 2 or 3, the linking chain between the carbon atoms bonded to hydroxyl groups has a linear structure consisting of three or more atoms, including at least two carbon atoms not bonded to hydroxyl groups. Therefore, even if the linking chain between the carbon atoms bonded to hydroxyl groups contains an oxygen atom forming an ether bond, the fluorine-containing ether compound has good hydrophobicity. Furthermore, because the linking chain has a linear structure consisting of three or more atoms, molecular mobility is appropriate, intramolecular aggregation is unlikely to occur, and the compound has excellent adhesion to the protective layer.

[0056] In formula (4), l m's each independently represent an integer from 1 to 6, and l n's each independently represent an integer from 1 to 6. Since l m's and n's in formula (4) are each 1 or greater, the resulting fluorine-containing ether compound has sufficient hydrophobicity, which can effectively inhibit the intrusion of water that causes corrosion of magnetic recording media, and form a lubricating layer with a high corrosion-inhibiting effect.

[0057] In addition, in one repeating unit in formula (4), at least one of m and n is 1. This is because if the number of carbon atoms in the alkylene group between the carbon atom to which the hydroxyl group is bonded and the ether oxygen atom is too large, the mobility of the hydroxyl group contained in formula (4) is not reduced, and interaction with the protective layer is likely to occur.

[0058] In one repeating unit in formula (4), either m or n other than 1 is 6 or less. Therefore, the rigid alkylene chain between the carbon atom to which the hydroxyl group is bonded and the ether oxygen atom is long, which reduces the flexibility of formula (4), weakening the interaction with the protective layer and preventing this part from lifting up.

[0059] In one repeating unit in formula (4), the number of either m or n other than 1 is preferably 4 or less. This is because formula (4) can be prevented from being too hydrophobic, thereby hindering adhesion to the protective layer. Furthermore, formula (4) can be prevented from becoming too bulky, thereby significantly hindering the movement of hydroxyl groups in the fluorinated ether compound. Furthermore, when either m or n other than 1 is 4 or less, the rigid alkylene chain in the main chain of formula (4) becomes too long, thereby reducing the flexibility of formula (4) and preventing a decrease in interaction with the protective layer. For these reasons, when either m or n other than 1 is 4 or less, the hydroxyl groups in the fluorinated ether compound are likely to be independently involved in bonding with active sites on the protective layer.

[0060] In one repeating unit of formula (4), the number of m or n, whichever is not 1, is preferably 3 or less, more preferably 2 or less, and most preferably both m and n are 1. In one repeating unit in formula (4), the number of m and n, whichever is not 1, is the same as R 1 (R 5 ) and the performance required for the lubricant containing the fluorine-containing ether compound.

[0061] For example, the most terminal side of the molecule (R 1 or R 5 When n of the repeating unit arranged on the side bonding to R in formula (1) is 2 or more, when E is a single bond, the hydroxyl group in formula (4) and R in formula (1) 1 (R 5 ) may be more appropriate. Therefore, when E is a single bond, n in the repeating unit located at the terminal end of the molecule in formula (4) may preferably be 2 to 4, and more preferably 2 or 3.

[0062] E in formula (4) is a single bond, -CH2CH2O-, -CH2CH2CH2O-, or -CH2CH2CH2CH2O-, and R in formula (1) 1 (R 5 ) and the performance required for the lubricant containing the fluorine-containing ether compound. When E is a single bond, in formula (4), the most terminal side of the molecule (R 1 or R 5 Repeating unit (-(CH2) m -CH(OH)-(CH2) n -O-) is directly 1 or R 5 and combine.

[0063] When E in formula (4) is any of -CH2CH2O-, -CH2CH2CH2O-, or -CH2CH2CH2CH2O-, the fluorine-containing ether compound represented by formula (1) becomes highly hydrophobic, and a lubricating layer with a stronger corrosion-inhibiting effect can be formed. Furthermore, when E in formula (4) is any of -CH2CH2O-, -CH2CH2CH2O-, and -CH2CH2CH2CH2O-, the hydroxyl group in formula (4) and R in formula (1) 1 (R 5 ) may become more suitable. As a result, it may be possible to suppress interactions between hydroxyl groups in the fluorinated ether compound molecule, and each hydroxyl group in the fluorinated ether compound represented by formula (1) may be more likely to adhere to the protective layer.

[0064] E in formula (4) is preferably a single bond, -CH2CHO-, or -CH2CH2CHO-, and more preferably a single bond or -CH2CHO-. This is because the fluorine-containing ether compound represented by formula (1) has such high hydrophobicity that the interaction between the lubricating layer and the protective layer is weakened, thereby preventing a decrease in the adhesion of the lubricating layer to the protective layer.

[0065] l in formula (4), n of the repeating unit located at the most terminal side of the molecule in formula (4), and E are R 1 (R 5 It is preferable to determine the ratio depending on the type of the polymer.

[0066] Specifically, R in formula (1) 1 (R 5 ) is a terminal group represented by formula (2) or a terminal group represented by formula (3), and -R 2 -O-(-R 4 When R is represented by formula (4), l in formula (4) is preferably 1 or 2. In this case, the number of secondary hydroxyl groups in formula (4) is 1 or 2. Therefore, R 1 (R 5) is an end group represented by formula (2) or (3), the hydrophobicity of the fluorine-containing ether compound represented by formula (1) is too high, which weakens the interaction between the lubricating layer and the protective layer, reduces the adhesion of the lubricating layer to the protective layer, and prevents a decrease in wear resistance.

[0067] Furthermore, R in formula (1) 1 (R 5 ) is a hydrogen atom, and -R 2 -O-(-R 4 When R is a hydrogen atom, the oxygen atom located at the most terminal side of the molecule of formula (4) is preferably 1 or 2, and most preferably 1. 1 (R 5 ) form a hydroxyl group, the fluorine-containing ether compound represented by formula (1) has too many hydroxyl groups, which increases hydrophilicity and prevents water, which causes corrosion, from being attracted to the lubricating layer, thereby providing a lubricating layer with good corrosion resistance.

[0068] Furthermore, R in formula (1) 1 (R 5 ) is a terminal group represented by formula (2) or a terminal group represented by formula (3), and -R 2 -O-(-R 4 When the repeating unit (4) is represented by the formula (4), E may be any of a single bond, -CH2CHO-, -CH2CH2CH2O-, or -CH2CH2CH2CH2O-, and each of the n's may be any integer from 1 to 6. Even if E is a single bond and n of the repeating unit located at the most terminal side of the molecule in the formula (4) is 1, there may be a group represented by X in the formula (2) between the hydroxyl group located at the most terminal side of the molecule in the formula (4) and the N,N-substituted amide. 1 Or X in formula (3) 2 This is because an alkylene group represented by the following formula is arranged.

[0069] Therefore, the hydroxyl group in formula (4) is R 1 (R 5) is a terminal group represented by formula (2) or formula (3), it is difficult to aggregate with the N,N-substituted amide. Therefore, the hydroxyl group in formula (4) is 1 (R 5 ) is likely to interact with the protective layer whether it is a terminal group represented by formula (2) or a terminal group represented by formula (3). 1 (R 5 ) is a terminal group represented by formula (2) or formula (3), and -R 2 -O-(-R 4 -O-) is formula (4), for example, R 2 (R 4 ) and the carbon atom to which the hydroxyl group in the divalent linking group represented by R 1 (R 5 ) are bonded via only an oxygen atom, the -R 2 -O-(-R 4 The (-O-) portion is less likely to lift up, and a lubricating layer with good adhesion to the protective layer can be formed.

[0070] On the other hand, R in Eq. (1) 1 (R 5 ) is a hydrogen atom, and -R 2 -O-(-R 4 When R in formula (1) is represented by formula (4), it is preferred that E is any of -CH2CHO-, -CH2CH2CH2O-, or -CH2CH2CH2CH2O-, and / or n in the repeating unit located at the most terminal side of the molecule in formula (4) is 2 to 4. 1 (R 5 ) is placed between the alkylene chain having two or more carbon atoms.

[0071] As a result, the oxygen atom located at the most terminal side of the molecule in formula (4) and the hydrogen atom R 1 (R 5) is less likely to aggregate with the hydroxyl group located at the most terminal end of the molecule in formula (4). In addition, the alkylene chain of E in formula (4) and / or the alkylene chain of the repeating unit located at the most terminal end of the molecule in formula (4) improves hydrophobicity. For this reason, the oxygen atom located at the most terminal end of the molecule in formula (4) and the hydrogen atom R 1 (R 5 ) form a hydroxyl group, if the number of hydroxyl groups in the fluorine-containing ether compound represented by formula (1) is too large, the hydrophilicity becomes high, and water, which causes corrosion, can be prevented from being attracted to the lubricating layer, resulting in a lubricating layer with good corrosion resistance.

[0072] -R in formula (1) 2 -O- and -R 4 It is more preferable that each —O— is independently represented by the following formula (5-1) or (5-2).

[0073] [ka] In formula (5-1), p represents an integer of 0 to 3, q ​​represents an integer of 0 to 2, and r represents an integer of 1 to 3. In formula (5-1), the leftmost oxygen atom is R 3 The rightmost oxygen atom is attached to a methylene group that is attached to R 1 or R 5 ) In formula (5-2), s represents an integer of 0 to 2, and t represents an integer of 0 to 3. In formula (5-2), the leftmost oxygen atom is R 3 The rightmost oxygen atom is attached to a methylene group that is attached to R 1 or R 5 )

[0074] Formula (5-1) is a formula in which l in formula (4) is an integer of 1 to 3, l m is 1, and the most R 3The repeating unit n positioned at the end is 1 to 4, the repeating unit positioned at the most terminal side of the molecule in formula (4) is 1, and E is any one of -CH2CH2O-, -CH2CH2CH2O-, or -CH2CH2CH2CH2O-.

[0075] Formula (5-2) is a formula in which l in formula (4) is an integer of 1 to 3, l m is 1, and the most R 3 The repeating unit located at the end has n of 1, the repeating unit located at the most terminal side of the molecule in formula (4) has n of 1 to 4, and E is a single bond.

[0076] q in formula (5-1) and s in formula (5-2) represent an integer of 0 to 2, which corresponds to a number that is 1 less than the number of repeating units in formula (4). When q in formula (5-1) is 1 or 2, and when s in formula (5-2) is 1 or 2, the two or three hydroxyl groups in formula (5-1) or (5-2), like the two or three hydroxyl groups in formula (4), are likely to be involved in bonding with the numerous active sites present on the protective layer, resulting in strong interaction with the protective layer, less intramolecular aggregation, and excellent adhesion to the protective layer.

[0077] In formula (5-1), p represents an integer of 0 to 3, and the most R 3 p corresponds to the number of repeating units n arranged on the side less than 1. p is preferably 0 or 1, and more preferably 0.

[0078] In formula (5-1), the sum of p and r is 6 or less, so the alkylene chain in the main chain portion of formula (5-1) is not too long. Therefore, the long rigid alkylene chain reduces the flexibility of the portion represented by formula (5-1), weakening the interaction with the protective layer and preventing the portion represented by formula (5-1) from lifting up. r is preferably 1 or 2, and more preferably 1.

[0079] In formula (5-2), t represents an integer of 0 to 3, and corresponds to a number that is 1 less than n of the repeating unit located at the terminal end of the molecule in formula (4). t is preferably 1 or 2, and more preferably 1.

[0080] (R 1 and R 5 (end group indicated by In the fluorine-containing ether compound represented by formula (1), R 1 and R 5 is a terminal group represented by the following formula (2), a terminal group represented by the following formula (3), or a hydrogen atom.

[0081] [ka] (In formula (2), X 1 is an alkylene group having 1 to 30 carbon atoms. Y and Z are each independently an aliphatic group having 1 to 30 carbon atoms which may contain a polar group or an ether oxygen atom. Y and Z may be bonded to each other to form a cyclic structure. (In formula (3), X 2 is an alkylene group having 1 to 30 carbon atoms. A and B are each independently an aliphatic group having 1 to 30 carbon atoms which may contain a polar group or an ether oxygen atom. A and B may be bonded to each other to form a cyclic structure.

[0082] In the fluorine-containing ether compound represented by formula (1), R 1 and R 5 At least one of the groups is a terminal group represented by formula (2) or (3). R 1 and R 5 are terminal groups represented by formula (2) or (3), the effect of containing the N,N-substituted amide of formula (2) or (3) becomes more pronounced in the resulting fluorine-containing ether compound, and a lubricating layer with better wear resistance and corrosion resistance is more likely to be obtained.

[0083] In the fluorine-containing ether compound represented by formula (1), R 1 and R 5 When both of R are terminal groups represented by formula (2) or (3), R 1 and R 5 may be the same or different. 1 and R 5 When the values ​​are the same, the coating state of the lubricating layer containing the fluorine-containing ether compound on the protective layer becomes more uniform, and a lubricating layer having better adhesion can be formed.

[0084] In the fluorine-containing ether compound represented by formula (1), R 1 and R 5 One of the two (e.g., R 1 ) is the terminal group represented by formula (2) or (3), the other (e.g., R 5 ) is a hydrogen atom. In this case, R 1 and R 5 The hydrogen atom located on the side other than the terminal group represented by formula (2) or (3) is R 2 or R 4 This fluorine-containing ether compound forms a hydroxyl group with the oxygen atom bonded to the fluorine-containing ether compound. Therefore, this fluorine-containing ether compound has a hydroxyl group at one end that has a strong interaction with the protective layer, and can form a lubricating layer that has excellent adhesion to the protective layer.

[0085] In the fluorine-containing ether compound represented by formula (1), the bond of the carbon atom adjacent to the carbonyl carbon atom or nitrogen atom constituting the amide bond of the N,N-substituted amide in formulas (2) and (3) is difficult to rotate freely. Therefore, the N,N-substituted amide in formulas (2) and (3) and the R adjacent thereto are 2 and / or R 4 The N,N-substituted amide is unlikely to interact with the polar group of the divalent linking group represented by R 2 and / or R 4Therefore, the fluorine-containing ether compound represented by formula (1) easily wets and spreads on the protective layer, and can form a lubricating layer having a uniform coating state.

[0086] Moreover, the N,N-substituted amides of formulas (2) and (3) exhibit a moderate interaction with the protective layer. Therefore, the N,N-substituted amides of formulas (2) and (3) and the adjacent R 2 and / or R 4 a polar group contained in a divalent linking group represented by the formula: 1 and R 5 When one of the groups is a hydrogen atom, the hydroxyl group formed at the other end is believed to be easily involved in bonding with the active site on the protective layer. As a result, the fluorine-containing ether compound represented by formula (1) can form a lubricating layer with adequately good adhesion to the protective layer.

[0087] Furthermore, the N,N-substituted amides of formulas (2) and (3) have good liposolubility. From these facts, the terminal groups represented by formulas (2) and (3) have the function of forming a lubricating layer having good chemical resistance, wear resistance, and corrosion resistance in a fluorinated ether compound containing them.

[0088] The terminal group represented by formula (2) is X 1 The terminal group represented by formula (3) is a group in which the nitrogen atom constituting the amide bond of the N,N-substituted amide is bonded to the carbon atom of X 2 The carbonyl carbon atom that constitutes the amide bond of the N,N-substituted amide is bonded to the carbon atom of the group represented by the formula (I).

[0089] X in the terminal group represented by formula (2) 1 and X in the terminal group represented by formula (3) 2 are each an alkylene group having 1 to 30 carbon atoms. 1 (X 2 ) may have a linear structure or a branched structure. X1 (X 2 ) is an alkylene group having one or more carbon atoms, the N,N-substituted amides of formulas (2) and (3) and the adjacent R 2 and / or R 4 Therefore, the N,N-substituted amides of formulas (2) and (3) and the adjacent R 2 and / or R 4 The polar groups of the divalent linking group represented by the formula (I) can each participate in bonding with the active sites on the protective layer.

[0090] X in the terminal group represented by formula (2) 1 is preferably an alkylene group having 2 or more carbon atoms. The nitrogen atom constituting the amide bond of the N,N-substituted amide represented by formula (2) and the R adjacent to this terminal group are preferably 2 and / or R 4 and space the polar group of the divalent linking group represented by formula (2) from the N,N-substituted amide represented by formula (3) and the R 2 and / or R 4 This is because the interaction with the polar group of the divalent linking group represented by the formula (I) can be suppressed.

[0091] Also, X 1 (X 2 Since X is an alkylene group having 30 or less carbon atoms, the terminal group represented by formula (2) (formula (3)) in the fluorine-containing ether compound represented by formula (1) does not become a steric hindrance that inhibits interaction with the protective layer. Therefore, the N,N-substituted amide of formula (2) (formula (3)) in the fluorine-containing ether compound has good affinity with the protective layer. 1 (X 2 ) is preferably a linear alkylene group having 6 or less carbon atoms, more preferably -CH2-, -CH2CH2-, or -CH2CH2CH2-, and even more preferably -CH2- or -CH2CH2-. X in the terminal group represented by formula (2) 1 is most preferably -CH2CH2-. In addition, X in the terminal group represented by formula (3)2 is most preferably -CH2-.

[0092] Y and Z in the terminal group represented by formula (2) and A and B in the terminal group represented by formula (3) are each independently a polar group or an aliphatic group having 1 to 30 carbon atoms which may contain an ether oxygen atom. The aliphatic group having 1 to 30 carbon atoms may be a saturated aliphatic group or an unsaturated aliphatic group.

[0093] Y and Z in the terminal group represented by formula (2) may be bonded to each other to form a cyclic structure, and A and B in the terminal group represented by formula (3) may be bonded to each other to form a cyclic structure. When Y and Z in the terminal group represented by formula (2) and A and B in the terminal group represented by formula (3) have a polar group, examples of the polar group include a hydroxyl group, a cyano group, an amino group, a carboxyl group, a formyl group, a carbonyl group, and a sulfo group.

[0094] The nitrogen atom constituting the amide bond of the N,N-substituted amide in formula (2) is bonded to one aliphatic group having 1 to 30 carbon atoms (Y in formula (2)) which may contain a polar group or an ether oxygen atom. Also, the nitrogen atom constituting the amide bond of the N,N-substituted amide in formula (3) is bonded to two aliphatic groups having 1 to 30 carbon atoms (A and B in formula (3)) which may contain a polar group or an ether oxygen atom.

[0095] Therefore, for example, compared with a structure in which a hydrogen atom is bonded in place of Y in formula (2), or a structure in which a hydrogen atom is bonded in place of at least one of A and B in formula (3), the end group represented by formula (2) (formula (3)) has low hydrophilicity and good lipophilicity. Therefore, compared with a fluorine-containing ether compound containing a structure in which a hydrogen atom is bonded in place of Y in formula (2), or a structure in which a hydrogen atom is bonded in place of at least one of A and B in formula (3), the fluorine-containing ether compound represented by formula (1) can suppress the attraction and penetration of water, and can form a lubricating layer that can effectively suppress corrosion of magnetic recording media.

[0096] Furthermore, the aliphatic group bonded to the nitrogen atom constituting the amide bond in formula (2) (Y in formula (2)) and the aliphatic group bonded to the nitrogen atom constituting the amide bond in formula (3) (A and B in formula (3)) are bulky compared to a hydrogen atom. Therefore, the fluorine-containing ether compound represented by formula (1) has a structure in which a hydrogen atom is bonded in place of Y in formula (2) or a structure in which a hydrogen atom is bonded in place of at least one of A and B in formula (3), and the N,N-substituted amides in formulas (2) and (3) and the R adjacent thereto are bulky. 2 and / or R 4 The polar group of the divalent linking group represented by the formula (I) is unlikely to interact with the polar group, and therefore is unlikely to aggregate.

[0097] When Y and Z in formula (2) and A and B in formula (3) are linear aliphatic amides that do not form a cyclic structure with each other, the fluidity of the terminal group represented by formula (2) (formula (3)) is high, resulting in a fluorine-containing ether compound that can form a lubricating layer with high repair ability and superior wear resistance.

[0098] When Y and Z in formula (2) and A and B in formula (3) are linear aliphatic amides that do not mutually form a cyclic structure, the fluidity of the terminal group represented by formula (2) (formula (3)) is higher. Therefore, Y and Z in formula (2) and A and B in formula (3) are each preferably independently an aliphatic group having 1 to 8 carbon atoms that may contain a polar group or an ether oxygen atom, and more preferably an aliphatic group having 1 to 2 carbon atoms that may contain a polar group or an ether oxygen atom.

[0099] When Y and Z in formula (2) and A and B in formula (3) do not form a cyclic structure with each other, specifically, each independently represents a group selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, isopropyl, tertiary butyl, isoamyl, 1-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 1-methoxyethyl, 1-methoxypropyl, 2-methoxypropyl, vinyl, allyl, butenyl, propynyl, propargyl, butynyl, methylbutynyl, pentynyl, methylpentynyl, hexynyl, and cyanoethyl. Among these, when Y and Z in formula (2) and A and B in formula (3) do not form a cyclic structure with each other, each independently represents a group selected from methyl, ethyl, and allyl, and more preferably represents a methyl or ethyl group.

[0100] When Y and Z in formula (2) and A and B in formula (3) are aliphatic amides that form a cyclic structure together, the lubricating layer containing this has low hydrophilicity and better corrosion resistance. Also, when Y and Z in formula (2) and A and B in formula (3) are aliphatic amides that have a cyclic structure that does not contain an ether oxygen atom, the lubricating layer containing this has even lower hydrophilicity and better corrosion resistance.

[0101] When Y and Z in the terminal group represented by formula (2) are aliphatic amides that form a cyclic structure together, -YZ- in formula (2) can be, for example, a combination of groups selected from the group consisting of a methylene group (-CH2-), an ether bond (-O-), and an amine structure (-NH-). When Y and Z in formula (2) form a cyclic structure together, the cyclic structure is preferably a 5- to 7-membered ring containing a carbonyl carbon atom and a nitrogen atom that constitute an amide bond.

[0102] Furthermore, when A and B in the terminal group represented by formula (3) are aliphatic amides that form a cyclic structure together, -AB- in formula (3) can be, for example, a combination of groups selected from the group consisting of a methylene group (-CH2-), an ether bond (-O-), and an amine structure (-NH-). When A and B in formula (3) form a cyclic structure together, the cyclic structure is preferably a 5- to 7-membered ring that contains a nitrogen atom that constitutes an amide bond.

[0103] -YZ- in formula (2) and -AB- in formula (3) may have a polar group. When -YZ- in formula (2) and / or -AB- in formula (3) have a polar group, the polar group may be bonded to any carbon atom constituting the cyclic structure, and a polar group (e.g., -NH-) may be contained between the carbon atoms constituting the cyclic structure.

[0104] Examples of the terminal group represented by formula (2) include any of the organic groups represented by the following formulae (2-1) to (2-5). Examples of the terminal group represented by formula (3) include any of the organic groups represented by the following formulae (3-1) to (3-5). The dotted lines in the following formulae (2-1) to (2-5) and (3-1) to (3-5) represent -R in formula (1). 2 -O- or -R 4 It is the bond attached to the oxygen atom of -O-. The terminal group represented by formula (2) or (3) in the fluorinated ether compound of this embodiment is not limited to the organic groups represented by the following formulae (2-1) to (2-5) and (3-1) to (3-5).

[0105] [ka]

[0106] The organic groups represented by formula (2-1), (2-2), (3-1), and (3-2) are linear aliphatic amides. Therefore, the organic groups represented by formula (2-1), (2-2), (3-1), and (3-2) have higher fluidity than the organic groups represented by formula (2-3) to (2-5) or formula (3-3) to (3-5), which are aliphatic amides having a cyclic structure. For this reason, R 1 and / or R 5 The lubricating layer containing the fluorine-containing ether compound, which is an organic group represented by the formula (2-1), (2-2) or (3-1), (3-2), has a high restoring ability to return to its original position even if a part of the lubricating layer is deformed by wear and the fluorine-containing ether compound in the lubricating layer moves to another location. 1 and / or R 5 A fluorine-containing ether compound in which is an organic group represented by formula (2-1), (2-2) or (3-1), (3-2) can form a lubricating layer having superior wear resistance.

[0107] The organic groups represented by formulas (2-3) to (2-4) or (3-3) to (3-4) are aliphatic amides having a cyclic structure and do not contain ether oxygen atoms. Therefore, the organic groups represented by formulas (2-3) to (2-4) or (3-3) to (3-4) have better hydrophobicity than the organic groups represented by formulas (2-1), (2-2), (2-5) or (3-1), (3-2), (3-5). Therefore, R 1 and / or R 5 A lubricating layer containing a fluorine-containing ether compound in which R is an organic group represented by formula (2-3) to (2-4) or (3-3) to (3-4) has low hydrophilicity and can suppress the generation of water that causes corrosion of magnetic recording media. 1 and / or R 5 A fluorine-containing ether compound in which is an organic group represented by formula (2-3) to (2-4) or (3-3) to (3-4) can form a lubricating layer with an even greater corrosion-inhibiting effect on magnetic recording media.

[0108] The organic group represented by formula (2-5) or (3-5) is an aliphatic amide having a cyclic structure containing an ether oxygen atom. Therefore, the organic group represented by formula (2-5) or (3-5) has higher flexibility than the organic groups represented by formulas (2-1) to (2-4) or (3-1) to (3-4). Therefore, R 1 and / or R 5 A lubricating layer containing a fluorine-containing ether compound in which is an organic group represented by formula (2-5) or (3-5) has appropriate flexibility and has good affinity between the polar group in the fluorine-containing ether compound and the protective layer.

[0109] (R 3 (PFPE chain shown as In the fluorine-containing ether compound represented by formula (1), R 3 is a perfluoropolyether chain. 3 When a lubricating layer is formed by applying a lubricant containing the fluorine-containing ether compound of this embodiment onto a protective layer, the PFPE chain represented by R not only covers the surface of the protective layer but also imparts lubricity to the lubricating layer, thereby reducing the frictional force between the magnetic head and the protective layer. 3 The PFPE chain represented by the formula (I) is appropriately selected depending on the performance required of the lubricant containing the fluorine-containing ether compound.

[0110] R 3 Examples of the PFPE chain represented by the formula (1) include those made of a polymer or copolymer of perfluoroalkylene oxide. Examples of perfluoroalkylene oxide include perfluoromethylene oxide, perfluoroethylene oxide, perfluoro-n-propylene oxide, perfluoroisopropylene oxide, and perfluorobutylene oxide.

[0111] R in Equation (1) 3 is preferably a PFPE chain represented by the following formula (6) derived from a polymer or copolymer of perfluoroalkylene oxide. -(CF2) w1 -O-(CF2O) w2 -(CF2CF2O)w3 -(CF2CF2CF2O) w4 -(CF2CF2CF2CF2O) w5 -(CF2) w6 - (6) (In formula (6), w2, w3, w4, and w5 represent average degrees of polymerization and each independently represent 0 to 20. However, w2, w3, w4, and w5 cannot all be 0 at the same time. w1 and w6 represent average values ​​representing the number of CF2 and each independently represent 1 to 3. There are no particular restrictions on the arrangement order of the repeating units (CF2O), (CF2CF2O), (CF2CF2CF2O), and (CF2CF2CF2CF2O) in formula (6).)

[0112] In formula (6), w2, w3, w4, and w5 represent average degrees of polymerization, each independently representing 0 to 20, preferably 0 to 15, and more preferably 0 to 10. In formula (6), w1 and w6 are average values ​​indicating the number of CF2, and each independently represents 1 to 3. w1 and w6 are determined depending on the structure of the repeating unit arranged at the end of the chain structure in the PFPE chain represented by formula (6), etc.

[0113] In formula (6), (CF2O), (CF2CF2O), (CF2CF2CF2O), and (CF2CF2CF2CF2O) are repeating units. There are no particular limitations on the arrangement order of the repeating units in formula (6). There are also no particular limitations on the number of types of repeating units in formula (6).

[0114] R in Equation (1) 3 is preferably any one selected from the PFPE chains represented by the following formulas (7-1) to (7-4). R 3 When R is any one selected from the PFPE chains represented by formulas (7-1) to (7-4), the resulting fluorine-containing ether compound provides a lubricating layer with good lubricity. 3When R is any one of the PFPE chains represented by formulas (7-1) to (7-4), the ratio of the number of oxygen atoms (the number of ether bonds (-O-)) to the number of carbon atoms in the PFPE chain is appropriate. Therefore, the fluorine-containing ether compound has an appropriate hardness. Therefore, the fluorine-containing ether compound applied to the protective layer is less likely to aggregate on the protective layer, and a thinner lubricating layer can be formed with a sufficient coverage. In addition, R 3 A lubricating layer containing a fluorine-containing ether compound in which R is any one selected from the PFPE chains represented by formulas (7-1) to (7-4) is preferred because it will be denser.

[0115] -CF2-(OCF2CF2) h -(OCF2) i -OCF2- (7-1) (In formula (7-1), h and i represent the average degree of polymerization, h represents 1 to 20, and i represents 0 to 20.) -CF2CF2-(OCF2CF2CF2) j -OCF2CF2- (7-2) (In formula (7-2), j represents the average degree of polymerization and represents 1 to 15.) -CF2CF2CF2-(OCF2CF2CF2CF2) k -OCF2CF2CF2- (7-3) (In formula (7-3), k represents the average degree of polymerization and represents 1 to 10.) -(CF2) w7 -O-(CF2CF2CF2O) w8 -(CF2CF2O) w9 -(CF2) w10 - (7-4) (In formula (7-4), w8 and w9 represent the average degree of polymerization, each independently representing 1 to 20. w7 and w10 are average values ​​representing the number of CF2, each independently representing 1 to 2.)

[0116] In formula (7-1), the arrangement order of the repeating units (OCF2CF2) and (OCF2) is not particularly limited. In formula (7-1), the number h of (OCF2CF2) and the number i of (OCF2) may be the same or different. The PFPE chain represented by formula (7-1) may be a polymer of (OCF2CF2). In addition, the PFPE chain represented by formula (7-1) may be any of a random copolymer, a block copolymer, and an alternating copolymer composed of (OCF2CF2) and (OCF2).

[0117] In formulas (7-1) to (7-3), h, which indicates the average degree of polymerization, is 1 to 20, i, which is 0 to 20, j, which is 1 to 15, and k, which is 1 to 10, and therefore the fluorine-containing ether compound provides a lubricating layer with good lubricity. Furthermore, in formulas (7-1) to (7-3), h and i, which indicate the average degree of polymerization, are 20 or less, j is 15 or less, and k is 10 or less, and therefore the viscosity of the fluorine-containing ether compound does not become too high, and lubricants containing the fluorine-containing ether compound are easily applied, which is preferable. h, i, j, and k, which indicate the average degree of polymerization, are preferably 1 to 10, more preferably 1.5 to 8, and even more preferably 2 to 7, and therefore the fluorine-containing ether compound easily wets and spreads on the protective layer, and a lubricating layer with a uniform thickness is easily obtained.

[0118] In formula (7-4), the arrangement order of the repeating units (CFCFCFO) and (CFCFO) is not particularly limited. In formula (7-4), the number w8 of (CFCFCFO) and the number w9 of (CFCFO), which indicate the average degree of polymerization, may be the same or different. Formula (7-4) may include any of a random copolymer, a block copolymer, and an alternating copolymer composed of the monomer units (CFCFCFO) and (CFCFO).

[0119] In formula (7-4), w8 and w9, which represent the average degree of polymerization, are each independently 1 to 20, preferably 1 to 15, and more preferably 1 to 10. In formula (7-4), w7 and w10 are average values ​​indicating the number of CF2, and each independently represents 1 to 2. w7 and w10 are determined depending on the structure of the repeating unit located at the end of the chain structure in the PFPE chain represented by formula (7-4), etc.

[0120] The fluorine-containing ether compound represented by formula (1) preferably has 4 to 6 polar groups. The polar groups also include N,N-substituted amides in the terminal groups represented by formula (2) or (3).

[0121] When the number of polar groups in the fluorine-containing ether compound represented by formula (1) is 4 or more, the adhesion of the lubricating layer containing this to the protective layer is further improved, and it is easier to obtain a lubricating layer with a good coating state. Also, when the number of polar groups in the fluorine-containing ether compound represented by formula (1) is 6 or less, the hydrophilicity of the fluorine-containing ether compound represented by formula (1) is too high, and the induction of water, which causes corrosion, in the lubricating layer containing this can be suppressed. Therefore, the fluorine-containing ether compound represented by formula (1) having the number of polar groups of 6 or less can form a lubricating layer with even higher corrosion suppression effect on magnetic recording media.

[0122] In the fluorine-containing ether compound represented by formula (1), R 1 -OR 2 -and-R 4 -OR 5 may be the same or different. 1 -OR 2 -and-R 4 -OR 5 are the same, the synthesis of the fluorine-containing ether compound is easy, which is preferable.

[0123] Specifically, the fluorine-containing ether compound represented by formula (1) is preferably any one of the compounds represented by the following formulae (AA) to (AL) and (BA) to (BF). When the compound represented by formula (1) is any of the compounds represented by the following formulae (AA) to (AL) and (BA) to (BF), the raw materials are easily available, and a lubricating layer can be formed that has good chemical resistance and wear resistance even when thin, and that has a high corrosion-inhibiting effect on magnetic recording media.

[0124] In the compounds represented by the following formulae (AA) to (AL) and (BA) to (BF), Rf1, Rf2, and Rf3, which represent PFPE chains, each have the following structure. That is, in the compounds represented by the following formulae (AA) to (AL) and (BA) to (BD), Rf1 is a PFPE chain represented by the above formula (7-1). In the compound represented by the following formula (BE), Rf2 is a PFPE chain represented by the above formula (7-2). In the compound represented by the following formula (BF), Rf3 is a PFPE chain represented by the above formula (7-3). Note that h and i in Rf1, j in Rf2, and k in Rf3, which represent PFPE chains in the formulae (AA) to (AL) and (BA) to (BF), are values ​​that indicate the average degree of polymerization, and are not necessarily integers.

[0125] [ka]

[0126] [ka] (In Rf1 in formula (AA), h and i represent the average degree of polymerization, h represents 1 to 20, and i represents 0 to 20.) (In Rf1 in formula (AB), h and i represent the average degree of polymerization, h represents 1 to 20, and i represents 0 to 20.) (In Rf1 in formula (AC), h and i represent the average degree of polymerization, h represents 1 to 20, and i represents 0 to 20.) (In Rf1 in formula (AD), h and i represent the average degree of polymerization, h represents 1 to 20, and i represents 0 to 20.) (In Rf1 in formula (AE), h and i represent the average degree of polymerization, h represents 1 to 20, and i represents 0 to 20.) (In Rf1 in formula (AF), h and i represent the average degree of polymerization, h represents 1 to 20, and i represents 0 to 20.)

[0127] [ka] (In Rf1 in formula (AG), h and i represent the average degree of polymerization, h represents 1 to 20, and i represents 0 to 20.) (In Rf1 in formula (AH), h and i represent the average degree of polymerization, h represents 1 to 20, and i represents 0 to 20.) (In Rf1 in formula (AI), h and i represent the average degree of polymerization, h represents 1 to 20, and i represents 0 to 20.) (In Rf1 in formula (AJ), h and i represent the average degree of polymerization, h represents 1 to 20, and i represents 0 to 20.) (In Rf1 in formula (AK), h and i represent the average degree of polymerization, h represents 1 to 20, and i represents 0 to 20.) (In Rf1 in formula (AL), h and i represent the average degree of polymerization, h represents 1 to 20, and i represents 0 to 20.)

[0128] [ka] (In Rf1 in formula (BA), h and i represent the average degree of polymerization, h represents 1 to 20, and i represents 0 to 20.) (In Rf1 in formula (BB), h and i represent the average degree of polymerization, h represents 1 to 20, and i represents 0 to 20.) (In Rf1 in formula (BC), h and i represent the average degree of polymerization, h represents 1 to 20, and i represents 0 to 20.) (In Rf1 in formula (BD), h and i represent the average degree of polymerization, h represents 1 to 20, and i represents 0 to 20.) (In Rf2 in formula (BE), j represents the average degree of polymerization and represents 1 to 15.) (In Rf3 in formula (BF), k represents the average degree of polymerization and represents 1 to 10.)

[0129] The fluorine-containing ether compound of this embodiment preferably has a number average molecular weight (Mn) in the range of 500 to 10,000, particularly preferably in the range of 1,000 to 5,000. When the number average molecular weight is 500 or more, a lubricating layer made of a lubricant containing the fluorine-containing ether compound of this embodiment will have excellent heat resistance. The number average molecular weight of the fluorine-containing ether compound is more preferably 1,000 or more. Furthermore, when the number average molecular weight is 10,000 or less, the viscosity of the fluorine-containing ether compound becomes appropriate, and by applying a lubricant containing this, a thin lubricating layer can be easily formed. The number average molecular weight of the fluorine-containing ether compound is preferably 5,000 or less, so that the viscosity becomes easy to handle when applied to a lubricant.

[0130] The number average molecular weight (Mn) of fluorine-containing ether compounds was measured using AVANCEIII400 manufactured by Bruker Biospin. 1 H-NMR and 19 These are values ​​measured by F-NMR. Specifically, 19 The number of repeating units of the PFPE chain is calculated from the integrated value measured by F-NMR to determine the number average molecular weight. For NMR (nuclear magnetic resonance) measurements, the sample is diluted in a hexafluorobenzene / d-acetone (4 / 1 v / v) solvent and measured. 19 The reference for F-NMR chemical shifts is the hexafluorobenzene peak at -164.7 ppm. 1 The reference for H-NMR chemical shifts is the acetone peak at 2.2 ppm.

[0131] The fluorine-containing ether compound of this embodiment is preferably subjected to molecular weight fractionation by an appropriate method to make the molecular weight dispersity (ratio of weight average molecular weight (Mw) / number average molecular weight (Mn)) 1.3 or less. In this embodiment, the method for molecular weight fractionation is not particularly limited, but for example, molecular weight fractionation by silica gel column chromatography, gel permeation chromatography (GPC), or the like, molecular weight fractionation by supercritical extraction, or the like can be used.

[0132] "Manufacturing method" The method for producing the fluorinated ether compound of the present embodiment is not particularly limited, and the compound can be produced by a conventionally known production method. The fluorinated ether compound of the present embodiment can be produced, for example, by the production method shown below.

[0133] (R 1 -OR 2 -and-R 4 -OR 5 (if and are the same) In formula (1), R 1 -OR 2 -and-R 4 -OR 5 To prepare a compound in which R 3 A fluorine-based compound is prepared in which a hydroxymethyl group (-CH2OH) is placed at each end of the perfluoropolyether chain corresponding to the above.

[0134] Next, the hydroxyl group of the hydroxymethyl group located at one end of the fluorine-based compound and R 1 -OR 2 - group (= -R 4 -OR 5 The epoxy group of the epoxy compound having R 3 R is attached to both ends of the perfluoropolyether chain corresponding to 1 -OR 2 - the group corresponding to (=-R 4 -OR 5 A fluorine-containing ether compound of the present embodiment having a group corresponding to

[0135] R in Equation (1) 1 -OR 2 - group (= -R 4 -OR 5 Examples of epoxy compounds having a group represented by the formula (8-1) to (8-14) include compounds represented by the following formulae (8-1) to (8-14): In the formulae (8-11) to (8-14), THP represents a tetrahydropyranyl group.

[0136] [ka]

[0137] When the fluorine-based compound is reacted with the epoxy compound, the hydroxyl group of the epoxy compound may be protected with an appropriate protecting group before the reaction with the fluorine-based compound.

[0138] (R 1 -OR 2 -and-R 4 -OR 5 (if different from In formula (1), R 1 -OR 2 -and-R 4 -OR 5 To produce a compound different from R in formula (1), first 3 A fluorine-based compound is prepared in which a hydroxymethyl group (-CH2OH) is placed at each end of the perfluoropolyether chain corresponding to the above.

[0139] Next, the hydroxyl group of the hydroxymethyl group located at one end of the fluorine-based compound and R 1 -OR 2 - group with the epoxy group of an epoxy compound having a group R 3 R at one end of the perfluoropolyether chain corresponding to 1 -OR 2 An intermediate compound 1 having a group corresponding to - is obtained (first reaction).

[0140] Next, the intermediate compound 1 and -R 4 -OR 5 (second reaction) By carrying out the above steps, R 1 -OR 2 -and-R 4 -OR 5A fluorinated ether compound of the present embodiment different from the above can be obtained.

[0141] [Lubricants for magnetic recording media] The lubricant for a magnetic recording medium of this embodiment contains a fluorine-containing ether compound represented by the above formula (1). The lubricant of the present embodiment can be used by mixing, as needed, known materials used as lubricant materials, as long as the properties resulting from the inclusion of the fluorinated ether compound represented by the above formula (1) are not impaired.

[0142] Specific examples of known materials include FOMBLIN (registered trademark) ZDIAC, FOMBLIN ZDEAL, FOMBLIN AM-2001 (all manufactured by Solvay Solexis), Moresco A20H (manufactured by Moresco), etc. The known material to be mixed with the lubricant of the present embodiment preferably has a number average molecular weight of 1,000 to 10,000.

[0143] When the lubricant of the present embodiment contains a material other than the fluorinated ether compound represented by the above formula (1), the content of the fluorinated ether compound represented by the above formula (1) in the lubricant of the present embodiment is preferably 70 mass% or more, more preferably 90 mass% or more, and even more preferably 95 mass% or more.

[0144] The lubricant of this embodiment contains the fluorine-containing ether compound represented by the above formula (1), and therefore can form a lubricating layer that has good chemical resistance and wear resistance and is highly effective in inhibiting corrosion of magnetic recording media.

[0145] [Magnetic recording media] The magnetic recording medium of this embodiment has at least a magnetic layer, a protective layer, and a lubricating layer provided in this order on a substrate. In the magnetic recording medium of this embodiment, one or more underlayers may be provided between the substrate and the magnetic layer, as needed, and at least one of an adhesive layer and a soft magnetic layer may also be provided between the underlayer and the substrate.

[0146] FIG. 1 is a schematic cross-sectional view showing one embodiment of the magnetic recording medium of the present invention. The magnetic recording medium 10 of this embodiment has a structure in which an adhesive layer 12, a soft magnetic layer 13, a first underlayer 14, a second underlayer 15, a magnetic layer 16, a protective layer 17, and a lubricating layer 18 are sequentially provided on a substrate 11.

[0147] "substrate" The substrate 11 may be, for example, a non-magnetic substrate in which a film made of NiP or a NiP alloy is formed on a base made of a metal or alloy material such as Al or an Al alloy. The substrate 11 may be a non-magnetic substrate made of a non-metallic material such as glass, ceramics, silicon, silicon carbide, carbon, or resin, or may be a non-magnetic substrate having a NiP or NiP alloy film formed on a base made of any of these non-metallic materials.

[0148] "Adhesion layer" The adhesive layer 12 prevents the progress of corrosion of the substrate 11, which occurs when the substrate 11 and the soft magnetic layer 13 provided on the adhesive layer 12 are disposed in contact with each other. The material of the adhesive layer 12 can be appropriately selected from, for example, Cr, a Cr alloy, Ti, a Ti alloy, CrTi, NiAl, an AlRu alloy, etc. The adhesive layer 12 can be formed by, for example, a sputtering method.

[0149] "Soft magnetic layer" The soft magnetic layer 13 preferably has a structure in which a first soft magnetic film, an intermediate layer made of a Ru film, and a second soft magnetic film are laminated in this order. That is, the soft magnetic layer 13 preferably has a structure in which the intermediate layer made of a Ru film is sandwiched between two soft magnetic films, and the soft magnetic films above and below the intermediate layer are antiferro-coupling (AFC).

[0150] The first and second soft magnetic films may be made of a material such as a CoZrTa alloy or a CoFe alloy. It is preferable to add Zr, Ta, or Nb to the CoFe alloy used in the first and second soft magnetic films. This promotes the amorphization of the first and second soft magnetic films. As a result, it is possible to improve the orientation of the first underlayer (seed layer) and reduce the flying height of the magnetic head. The soft magnetic layer 13 can be formed by, for example, a sputtering method.

[0151] "First base layer" The first underlayer 14 is a layer that controls the orientation and crystal size of the second underlayer 15 and magnetic layer 16 that are provided thereon. The first underlayer 14 may be, for example, a Cr layer, a Ta layer, a Ru layer, or a CrMo alloy layer, a CoW alloy layer, a CrW alloy layer, a CrV alloy layer, or a CrTi alloy layer. The first underlayer 14 can be formed by, for example, a sputtering method.

[0152] "Second base layer" The second underlayer 15 is a layer that controls the orientation of the magnetic layer 16. The second underlayer 15 is preferably a layer made of Ru or a Ru alloy. The second underlayer 15 may be a single layer or may be composed of multiple layers. When the second underlayer 15 is composed of multiple layers, all of the layers may be composed of the same material, or at least one layer may be composed of a different material. The second underlayer 15 can be formed by, for example, a sputtering method.

[0153] "Magnetic layer" The magnetic layer 16 is a magnetic film whose easy axis of magnetization is oriented perpendicular or parallel to the substrate surface. The magnetic layer 16 contains Co and Pt. To improve the SNR characteristics, the magnetic layer 16 may contain oxides, Cr, B, Cu, Ta, Zr, or the like. Examples of oxides contained in the magnetic layer 16 include SiO2, SiO, Cr2O3, CoO, Ta2O3, and TiO2.

[0154] The magnetic layer 16 may be composed of a single layer, or may be composed of multiple magnetic layers made of materials with different compositions. For example, when the magnetic layer 16 is composed of three layers, namely, a first magnetic layer, a second magnetic layer, and a third magnetic layer stacked in this order from the bottom, the first magnetic layer preferably has a granular structure made of a material containing Co, Cr, and Pt and further containing an oxide. The oxide contained in the first magnetic layer is preferably, for example, an oxide of Cr, Si, Ta, Al, Ti, Mg, Co, or the like. Among these, TiO2, Cr2O3, SiO2, and the like are particularly suitable. Furthermore, the first magnetic layer is preferably made of a composite oxide containing two or more types of oxides. Among these, Cr2O3-SiO2, Cr2O3-TiO2, SiO2-TiO2, and the like are particularly suitable.

[0155] The first magnetic layer may contain one or more elements selected from B, Ta, Mo, Cu, Nd, W, Nb, Sm, Tb, Ru, and Re in addition to Co, Cr, Pt, and oxides. The second magnetic layer can be made of the same material as the first magnetic layer, and preferably has a granular structure. The third magnetic layer preferably has a non-granular structure made of a material containing Co, Cr, and Pt and not containing oxides, and may contain one or more elements selected from B, Ta, Mo, Cu, Nd, W, Nb, Sm, Tb, Ru, Re, and Mn in addition to Co, Cr, and Pt.

[0156] When magnetic layer 16 is formed of multiple magnetic layers, it is preferable to provide a non-magnetic layer between adjacent magnetic layers. When magnetic layer 16 is formed of three layers, namely, a first magnetic layer, a second magnetic layer, and a third magnetic layer, it is preferable to provide a non-magnetic layer between the first magnetic layer and the second magnetic layer and between the second magnetic layer and the third magnetic layer.

[0157] The non-magnetic layer provided between adjacent magnetic layers of the magnetic layer 16 can suitably be made of, for example, Ru, a Ru alloy, a CoCr alloy, or a CoCrX1 alloy (X1 represents one or more elements selected from Pt, Ta, Zr, Re, Ru, Cu, Nb, Ni, Mn, Ge, Si, O, N, W, Mo, Ti, V, and B).

[0158] The non-magnetic layer provided between adjacent magnetic layers of the magnetic layer 16 preferably uses an alloy material containing an oxide, metal nitride, or metal carbide. Specifically, oxides that can be used include, for example, SiO2, Al2O3, Ta2O5, Cr2O3, MgO, Y2O3, and TiO2. Metal nitrides that can be used include, for example, AlN, Si3N4, TaN, and CrN. Metal carbides that can be used include, for example, TaC, BC, and SiC. The non-magnetic layer can be formed by, for example, a sputtering method.

[0159] To achieve higher recording density, the magnetic layer 16 is preferably a magnetic layer for perpendicular magnetic recording, in which the axis of easy magnetization is oriented perpendicular to the substrate surface, but may also be a magnetic layer for longitudinal magnetic recording. The magnetic layer 16 may be formed by any conventionally known method such as vapor deposition, ion beam sputtering, magnetron sputtering, etc. The magnetic layer 16 is usually formed by sputtering.

[0160] "Protective layer" The protective layer 17 protects the magnetic layer 16. The protective layer 17 may be composed of one layer or multiple layers. A carbon-based protective layer is preferably used as the protective layer 17, and an amorphous carbon protective layer is particularly preferred. If the protective layer 17 is a carbon-based protective layer, the interaction with the polar groups (particularly hydroxyl groups) contained in the fluorine-containing ether compound in the lubricating layer 18 is further enhanced, which is preferable.

[0161] The adhesion between the carbon-based protective layer and the lubricating layer 18 can be controlled by using hydrogenated carbon and / or nitrogenated carbon for the carbon-based protective layer and adjusting the hydrogen and / or nitrogen content in the carbon-based protective layer. The hydrogen content in the carbon-based protective layer is preferably 3 atomic % to 20 atomic % when measured by hydrogen forward scattering (HFS). The nitrogen content in the carbon-based protective layer is preferably 4 atomic % to 15 atomic % when measured by X-ray photoelectron spectroscopy (XPS).

[0162] The hydrogen and / or nitrogen contained in the carbon-based protective layer does not need to be uniformly contained throughout the carbon-based protective layer. The carbon-based protective layer is preferably a compositionally graded layer, for example, in which nitrogen is contained on the lubricating layer 18 side of protective layer 17 and hydrogen is contained on the magnetic layer 16 side of protective layer 17. In this case, the adhesion between the magnetic layer 16 and lubricating layer 18 and the carbon-based protective layer is further improved.

[0163] The thickness of the protective layer 17 is preferably 1 nm to 7 nm. When the thickness of the protective layer 17 is 1 nm or more, sufficient performance as the protective layer 17 can be obtained. When the thickness of the protective layer 17 is 7 nm or less, it is preferable from the viewpoint of making the protective layer 17 thinner.

[0164] The protective layer 17 can be formed by sputtering using a target material containing carbon, chemical vapor deposition (CVD) using a hydrocarbon raw material such as ethylene or toluene, or ion beam deposition (IBD). When a carbon-based protective layer is formed as protective layer 17, it can be deposited by, for example, DC magnetron sputtering. In particular, when a carbon-based protective layer is formed as protective layer 17, it is preferable to deposit an amorphous carbon protective layer by plasma CVD. The amorphous carbon protective layer deposited by plasma CVD has a uniform surface with little roughness.

[0165] "Lubricant layer" The lubricating layer 18 prevents contamination of the magnetic recording medium 10. The lubricating layer 18 also reduces the frictional force of the magnetic head of the magnetic recording / reproducing device that slides on the magnetic recording medium 10, thereby improving the durability of the magnetic recording medium 10. 1, the lubricating layer 18 is formed on and in contact with the protective layer 17. The lubricating layer 18 is formed by applying the magnetic recording medium lubricant of the above-described embodiment onto the protective layer 17. Therefore, the lubricating layer 18 contains the above-described fluorine-containing ether compound.

[0166] When the protective layer 17 disposed below the lubricating layer 18 is a carbon-based protective layer, the lubricating layer 18 bonds with the protective layer 17 with particularly high bonding strength. As a result, even if the thickness of the lubricating layer 18 is thin, it becomes easier to obtain a magnetic recording medium 10 in which the surface of the protective layer 17 is covered with a high coverage, and contamination of the surface of the magnetic recording medium 10 can be effectively prevented.

[0167] The average thickness of the lubricating layer 18 is preferably 0.5 nm (5 Å) to 2.0 nm (20 Å), and more preferably 0.5 nm (5 Å) to 1.2 nm (12 Å). When the average thickness of the lubricating layer 18 is 0.5 nm or more, the lubricating layer 18 is formed with a uniform thickness without forming an island or mesh-like structure. Therefore, the surface of the protective layer 17 can be covered with the lubricating layer 18 at a high coverage rate. Furthermore, by setting the average thickness of the lubricating layer 18 to 2.0 nm or less, the lubricating layer 18 can be made sufficiently thin, and the flying height of the magnetic head can be made sufficiently small.

[0168] "Method for forming lubricating layer" A method for forming the lubricating layer 18 includes, for example, preparing a magnetic recording medium in the middle of manufacturing in which all layers up to the protective layer 17 are formed on the substrate 11, applying a solution for forming a lubricating layer onto the protective layer 17, and drying the solution.

[0169] The lubricant layer forming solution can be obtained by dispersing and dissolving the lubricant for a magnetic recording medium according to the above embodiment in a solvent as needed, and adjusting the viscosity and concentration to suit the coating method. Examples of solvents used in the lubricating layer-forming solution include fluorine-based solvents such as Vertrel (registered trademark) XF (trade name, manufactured by Mitsui DuPont Fluorochemicals Co., Ltd.) and Asahiklin (registered trademark) AE-3000 (trade name, manufactured by AGC Corporation).

[0170] The method for applying the lubricating layer-forming solution is not particularly limited, but examples thereof include spin coating, spraying, paper coating, and dipping. When using the dipping method, for example, the following method can be used. First, the substrate 11 on which each layer up to the protective layer 17 has been formed is immersed in a lubricant layer-forming solution placed in an immersion tank of a dip coating device. Next, the substrate 11 is lifted from the immersion tank at a predetermined speed. In this way, the lubricant layer-forming solution is applied to the surface of the substrate 11 above the protective layer 17. By using the dipping method, the lubricating layer forming solution can be applied uniformly to the surface of the protective layer 17, and the lubricating layer 18 can be formed on the protective layer 17 with a uniform thickness.

[0171] In this embodiment, it is preferable to perform a heat treatment on the substrate 11 on which the lubricating layer 18 is formed. By performing the heat treatment, the adhesion between the lubricating layer 18 and the protective layer 17 is improved, and the adhesive force between the lubricating layer 18 and the protective layer 17 is also improved. The heat treatment temperature is preferably 100°C to 180°C, and more preferably 100°C to 160°C. When the heat treatment temperature is 100°C or higher, the effect of improving the adhesion between the lubricating layer 18 and the protective layer 17 can be sufficiently obtained. Furthermore, by setting the heat treatment temperature to 180°C or lower, thermal decomposition of the lubricating layer 18 due to the heat treatment can be prevented. The heat treatment time can be adjusted appropriately depending on the heat treatment temperature, and is preferably 10 minutes to 120 minutes.

[0172] In this embodiment, in order to further improve the adhesive strength of the lubricating layer 18 to the protective layer 17, the lubricating layer 18 may be irradiated with ultraviolet (UV) rays before or after the heat treatment.

[0173] The magnetic recording medium 10 of this embodiment has at least a magnetic layer 16, a protective layer 17, and a lubricating layer 18 sequentially formed on a substrate 11. In the magnetic recording medium 10 of this embodiment, a lubricating layer 18 containing the above-mentioned fluorine-containing ether compound is formed on and in contact with the protective layer 17. This lubricating layer 18 has good chemical resistance and wear resistance, and is highly effective in inhibiting corrosion of the magnetic recording medium, even though it is thin. Therefore, the magnetic recording medium 10 of this embodiment has excellent reliability, particularly corrosion resistance, and durability. For this reason, the magnetic recording medium 10 of this embodiment can contribute to reducing magnetic spacing, reduce the magnetic head flying height (for example, 10 nm or less), and operate stably for a long period of time even in harsh environments that accompany diversifying applications. Therefore, the magnetic recording medium 10 of this embodiment is particularly suitable as a magnetic disk to be mounted in a magnetic disk device using the LUL (Load Unload) method. [Example]

[0174] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0175] [Example 1] The compound represented by the above formula (AA) was obtained by the method shown below. Place HOCH2CF2O (CF2CF2O) in a 100 mL recovery flask under a nitrogen gas atmosphere. h (CF2O) i 5 g of a compound (number average molecular weight 1000, molecular weight distribution 1.1) represented by CF2CH2OH (where h, representing the average degree of polymerization, is 4.5, and i, representing the average degree of polymerization, is 4.5), 3.18 g of a compound represented by the above formula (8-1), and 5 mL of t-butanol were charged and stirred at room temperature until homogeneous to form a mixture. 0.30 g of potassium tert-butoxide was added to this mixture, and the mixture was reacted by stirring at 70°C for 16 hours.

[0176] The compound represented by formula (8-1) was synthesized by reacting the hydroxyl group of N,N-dimethylglycolamide with epibromohydrin.

[0177] The reaction mixture was then transferred in small portions to a separatory funnel containing 25 mL of brine and extracted twice with 50 mL of ethyl acetate. The organic layer was washed sequentially with 25 mL of brine, 25 mL of saturated sodium bicarbonate water, and 25 mL of brine, and then dehydrated using anhydrous sodium sulfate. After filtering off the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 4.09 g of compound (AA) (Rf1 in formula (AA) is a PFPE chain represented by formula (7-1) above. In Rf1, h, which indicates the average degree of polymerization, is 4.5, and i, which indicates the average degree of polymerization, is 4.5).

[0178] The obtained compound (AA) 1 H-NMR and 19 F-NMR measurements were carried out and the structure was identified based on the following results. 1 H-NMR (acetone-D6): δ[ppm]=3.25-3.60(8H), 3.65-3.95(4H), 3.75-4.00(2H), 3.85-4.10(4H) 19 F-NMR (acetone-D6): δ[ppm]=-55.5~-51.5(9F), -78.5(2F), -80.5(2F), -91.0~-88.5(18F)

[0179] [Example 2] The compound represented by the above formula (AB) was obtained by the method shown below. The same operation as in Example 1 was performed except that the compound represented by formula (8-2) was used instead of the compound represented by formula (8-1), to obtain 4.15 g of compound (AB) (Rf1 in formula (AB) is a PFPE chain represented by the above formula (7-1). In Rf1, h, which represents the average degree of polymerization, is 4.5, and i, which represents the average degree of polymerization, is 4.5).

[0180] The compound represented by formula (8-2) was synthesized by reacting the hydroxyl group of N,N-diethylglycolamide with epibromohydrin.

[0181] The obtained compound (AB) 1 H-NMR and 19 F-NMR measurements were carried out and the structure was identified based on the following results. 1 H-NMR (acetone-D6): δ[ppm]=1.20-1.30(12H), 3.20-3.60(12H), 3.65-3.95(4H), 3.75-4.00(2H), 3.85-4.10(4H) 19 F-NMR (acetone-D6): δ[ppm]=-55.5~-51.5(9F), -78.5(2F), -80.5(2F), -91.0~-88.5(18F)

[0182] [Example 3] The compound represented by the above formula (AC) was obtained by the method shown below. The same operations as in Example 1 were performed except that the compound represented by formula (8-3) was used instead of the compound represented by formula (8-1), to obtain 4.55 g of compound (AC) (Rf1 in formula (AC) is a PFPE chain represented by the above formula (7-1). In Rf1, h, which indicates the average degree of polymerization, is 4.5, and i, which indicates the average degree of polymerization, is 4.5).

[0183] The compound represented by formula (8-3) was synthesized by reacting the hydroxyl group of glycolylpyrrolidine with epibromohydrin.

[0184] The obtained compound (AC) 1 H-NMR and 19 F-NMR measurements were carried out and the structure was identified based on the following results. 1 H-NMR (acetone-D6): δ[ppm]=1.95-2.15(8H), 3.20-3.60(12H), 3.65-3.95(4H), 3.75-4.00(2H), 3.85-4.10(4H) 19 F-NMR (acetone-D6): δ[ppm]=-55.5~-51.5(9F), -78.5(2F), -80.5(2F), -91.0~-88.5(18F)

[0185] [Example 4] The compound represented by the above formula (AD) was obtained by the method shown below. The same operation as in Example 1 was performed, except that the compound represented by formula (8-4) was used instead of the compound represented by formula (8-1), to obtain 4.60 g of compound (AD) (Rf1 in formula (AD) is a PFPE chain represented by the above formula (7-1). In Rf1, h, which indicates the average degree of polymerization, is 4.5, and i, which indicates the average degree of polymerization, is 4.5).

[0186] The compound represented by formula (8-4) was synthesized by reacting the hydroxyl group of glycolylpiperidine with epibromohydrin.

[0187] The obtained compound (AD) 1 H-NMR and 19 F-NMR measurements were carried out and the structure was identified based on the following results. 1 H-NMR (acetone-D6): δ[ppm]=1.30-1.45(4H), 1.95-2.10(8H), 3.20-3.65(12H), 3.65-3.95(4H), 3.75-4.00(2H), 3.85-4.10(4H) 19 F-NMR (acetone-D6): δ[ppm]=-55.5~-51.5(9F), -78.5(2F), -80.5(2F), -91.0~-88.5(18F)

[0188] [Example 5] The compound represented by the above formula (AE) was obtained by the method shown below. The same operation as in Example 1 was performed, except that the compound represented by formula (8-5) was used instead of the compound represented by formula (8-1), to obtain 4.55 g of compound (AE) (Rf1 in formula (AE) is a PFPE chain represented by the above formula (7-1). In Rf1, h, which represents the average degree of polymerization, is 4.5, and i, which represents the average degree of polymerization, is 4.5).

[0189] The compound represented by formula (8-5) was synthesized by reacting the hydroxyl group of glycolylmorpholine with epibromohydrin.

[0190] The obtained compound (AE) 1 H-NMR and 19 F-NMR measurements were carried out and the structure was identified based on the following results. 1 H-NMR (acetone-D6): δ[ppm]=3.20-3.65(20H), 3.65-3.95(4H), 3.75-4.00(2H), 3.85-4.10(4H) 19 F-NMR (acetone-D6): δ[ppm]=-55.5~-51.5(9F), -78.5(2F), -80.5(2F), -91.0~-88.5(18F)

[0191] [Example 6] The compound represented by the above formula (AF) was obtained by the method shown below. The same operation as in Example 1 was performed except that the compound represented by formula (8-6) was used instead of the compound represented by formula (8-1), to obtain 4.00 g of compound (AF) (Rf1 in formula (AF) is a PFPE chain represented by the above formula (7-1). In Rf1, h, which represents the average degree of polymerization, is 4.5, and i, which represents the average degree of polymerization, is 4.5).

[0192] The compound represented by formula (8-6) was synthesized by reacting the hydroxyl group of N-(2-hydroxyethyl)-N-methylacetamide with epibromohydrin.

[0193] The obtained compound (AF) 1 H-NMR and 19 F-NMR measurements were carried out and the structure was identified based on the following results. 1 H-NMR (acetone-D6): δ[ppm]=2.00(6H), 2.65(6H), 3.20-3.80(12H), 3.85-4.10(4H) 19F-NMR (acetone-D6): δ[ppm]=-55.5~-51.5(9F), -78.5(2F), -80.5(2F), -91.0~-88.5(18F)

[0194] [Example 7] The compound represented by the above formula (AG) was obtained by the method shown below. The same operation as in Example 1 was performed except that the compound represented by formula (8-7) was used instead of the compound represented by formula (8-1), to obtain 4.05 g of compound (AG) (Rf1 in formula (AG) is a PFPE chain represented by the above formula (7-1). In Rf1, h, which indicates the average degree of polymerization, is 4.5, and i, which indicates the average degree of polymerization, is 4.5).

[0195] The compound represented by formula (8-7) was synthesized by reacting the hydroxyl group of N-(2-hydroxyethyl)-N-ethylacetamide with epibromohydrin.

[0196] The obtained compound (AG) 1 H-NMR and 19 F-NMR measurements were carried out and the structure was identified based on the following results. 1 H-NMR (acetone-D6): δ[ppm]=1.65-1.85(6H), 2.00(6H), 3.00(4H), 3.20-3.80(12H), 3.85-4.10(4H) 19 F-NMR (acetone-D6): δ[ppm]=-55.5~-51.5(9F), -78.5(2F), -80.5(2F), -91.0~-88.5(18F)

[0197] [Example 8] The compound represented by the above formula (AH) was obtained by the method shown below. The same operation as in Example 1 was performed, except that a compound represented by formula (8-8) was used instead of the compound represented by formula (8-1), to obtain 4.05 g of compound (AH) (Rf1 in formula (AH) is a PFPE chain represented by the above formula (7-1). In Rf1, h, which represents the average degree of polymerization, is 4.5, and i, which represents the average degree of polymerization, is 4.5).

[0198] The compound represented by formula (8-8) was synthesized by reacting the hydroxyl group of N-(2-hydroxyethyl)pyrrolidone with epibromohydrin.

[0199] The obtained compound (AH) 1 H-NMR and 19 F-NMR measurements were carried out and the structure was identified based on the following results. 1 H-NMR (acetone-D6): δ[ppm]=2.00-2.65(8H), 3.20-3.80(16H), 3.85-4.10(4H) 19 F-NMR (acetone-D6): δ[ppm]=-55.5~-51.5(9F), -78.5(2F), -80.5(2F), -91.0~-88.5(18F)

[0200] [Example 9] The compound represented by the above formula (AI) was obtained by the method shown below. The same operation as in Example 1 was performed, except that the compound represented by formula (8-9) was used instead of the compound represented by formula (8-1), to obtain 4.15 g of compound (AI) (Rf1 in formula (AI) is a PFPE chain represented by the above formula (7-1). In Rf1, h, which represents the average degree of polymerization, is 4.5, and i, which represents the average degree of polymerization, is 4.5).

[0201] The compound represented by formula (8-9) was synthesized by reacting the hydroxyl group of N-(2-hydroxyethyl)piperidone with epibromohydrin.

[0202] The obtained compound (AI) 1 H-NMR and19 F-NMR measurements were carried out and the structure was identified based on the following results. 1 H-NMR (acetone-D6): δ[ppm]=1.75-1.95(4H), 2.00-2.65(8H), 3.20-3.80(16H), 3.85-4.10(4H) 19 F-NMR (acetone-D6): δ[ppm]=-55.5~-51.5(9F), -78.5(2F), -80.5(2F), -91.0~-88.5(18F)

[0203] [Example 10] The compound represented by the above formula (AJ) was obtained by the method shown below. The same operation as in Example 1 was performed, except that a compound represented by formula (8-10) was used instead of the compound represented by formula (8-1), to obtain 4.00 g of compound (AJ) (Rf1 in formula (AJ) is a PFPE chain represented by the above formula (7-1). In Rf1, h, which represents the average degree of polymerization, is 4.5, and i, which represents the average degree of polymerization, is 4.5).

[0204] The compound represented by formula (8-10) was synthesized by reacting the hydroxyl group of N-(2-hydroxyethyl)morpholinone with epibromohydrin.

[0205] The obtained compound (AJ) 1 H-NMR and 19 F-NMR measurements were carried out and the structure was identified based on the following results. 1 H-NMR (acetone-D6): δ[ppm]=1.75-1.95(4H), 2.00-2.65(8H), 3.20-3.80(16H), 3.85-4.10(4H) 19 F-NMR (acetone-D6): δ[ppm]=-55.5~-51.5(9F), -78.5(2F), -80.5(2F), -91.0~-88.5(18F)

[0206] [Example 11] The compound represented by the above formula (AK) was obtained by the method shown below. Place HOCH2CF2O (CF2CF2O) in a 100 mL recovery flask under a nitrogen gas atmosphere. h (CF2O) i 5 g of a compound (number average molecular weight 1000, molecular weight distribution 1.1) represented by CF2CH2OH (where h, representing the average degree of polymerization, is 4.5, and i, representing the average degree of polymerization, is 4.5), 3.57 g of a compound represented by the above formula (8-11), and 5 mL of t-butanol were charged and stirred at room temperature until homogeneous to form a mixture. 0.30 g of potassium tert-butoxide was added to this mixture, and the mixture was reacted by stirring at 70°C for 16 hours.

[0207] The compound represented by formula (8-11) was synthesized by the following method. Glycolylpiperidine was reacted with allyl glycidyl ether to obtain O-((3-allyloxy-(2-hydroxypropyl))glycolylpiperidine. The hydroxyl group of O-((3-allyloxy-(2-hydroxypropyl))glycolylpiperidine was then protected with dihydropyran, and the double bond was oxidized with m-chloroperbenzoic acid (mCPBA).

[0208] After the reaction, the resulting reaction mixture was returned to room temperature, and 10 g of a 10% hydrogen chloride-methanol solution (hydrogen chloride-methanol reagent (5-10%), manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at room temperature for 4 hours. The reaction mixture was then transferred in small portions to a separatory funnel containing 25 mL of saturated aqueous sodium bicarbonate and extracted twice with 50 mL of ethyl acetate. The organic layer was washed sequentially with 25 mL of brine, 25 mL of saturated aqueous sodium bicarbonate, and 25 mL of brine, and then dehydrated over anhydrous sodium sulfate. After filtering off the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 4.27 g of compound (AK). Rf1 in formula (AK) represents the PFPE chain represented by formula (7-1) above. In Rf1, h, which indicates the average degree of polymerization, is 4.5, and i, which indicates the average degree of polymerization, is 4.5.

[0209] The obtained compound (AK) 1 H-NMR and 19F-NMR measurements were carried out and the structure was identified based on the following results. 1 H-NMR (acetone-D6): δ[ppm]=1.35-1.65(12H), 3.40-3.95(32H), 3.85-4.10(4H) 19 F-NMR (acetone-D6): δ[ppm]=-55.5~-51.5(9F), -78.5(2F), -80.5(2F), -91.0~-88.5(18F)

[0210] [Example 12] The compound represented by the above formula (AL) was obtained by the method shown below. The same operation as in Example 11 was performed except that the compound represented by formula (8-12) was used instead of the compound represented by formula (8-11), to obtain 4.51 g of compound (AL) (Rf1 in formula (AL) is a PFPE chain represented by the above formula (7-1). In Rf1, h, which represents the average degree of polymerization, is 4.5, and i, which represents the average degree of polymerization, is 4.5).

[0211] The compound represented by formula (8-12) was synthesized by the following method. N-methyl-N-(hydroxyethyl)acetamide was reacted with allyl glycidyl ether to obtain N-methyl-N-((3-allyloxy-(2-hydroxy)propan-1-oxy)ethyl)acetamide. The hydroxyl group of N-methyl-N-((3-allyloxy-(2-hydroxy)propan-1-oxy)ethyl)acetamide was then protected with dihydropyran, and the double bond was oxidized with m-chloroperbenzoic acid (mCPBA).

[0212] The obtained compound (AL) 1 H-NMR and 19 F-NMR measurements were carried out and the structure was identified based on the following results. 1 H-NMR (acetone-D6): δ[ppm]=2.00(6H), 2.70(6H), 3.20-3.80(28H), 3.85-4.10(4H) 19F-NMR (acetone-D6): δ[ppm]=-55.5~-51.5(9F), -78.5(2F), -80.5(2F), -91.0~-88.5(18F)

[0213] [Example 13] The compound represented by the above formula (BA) was obtained by the method shown below. (First reaction) Place HOCH2CF2O (CF2CF2O) in a 100 mL recovery flask under a nitrogen gas atmosphere. h (CF2O) i 12.5 g of a compound (number average molecular weight 1000, molecular weight distribution 1.1) represented by CF2CH2OH (where h, representing the average degree of polymerization, is 4.5, and i, representing the average degree of polymerization, is 4.5), 2.40 g of a compound represented by the above formula (8-4), and 12 mL of t-butanol were charged and stirred at room temperature until homogeneous to form a mixture. 1.10 g of potassium tert-butoxide was added to this mixture, and the mixture was reacted by stirring at 70°C for 16 hours.

[0214] The reaction product obtained after the reaction was cooled to 25°C, transferred to a separatory funnel containing 100 mL of water, and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with water and dehydrated over anhydrous sodium sulfate. After filtering off the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 5.62 g of the compound represented by the following formula (9) as intermediate compound 1.

[0215] [ka] (Rf1 in formula (9) is a PFPE chain represented by the above formula (7-1). In Rf1, h representing the average degree of polymerization is 4.5, and i representing the average degree of polymerization is 4.5.)

[0216] (Second reaction) Next, 5.62 g of the compound represented by formula (9), which is the intermediate compound 1 obtained above, 2.70 g of the compound represented by formula (8-13), and 20 mL of t-butanol were placed in a 100 mL recovery flask under a nitrogen gas atmosphere and stirred at room temperature until a homogeneous mixture was obtained. 0.55 g of potassium tert-butoxide was added to this mixture, and the mixture was allowed to react with stirring at 70°C for 16 hours.

[0217] The compound represented by formula (8-13) was synthesized by protecting the hydroxyl group of ethylene glycol monoallyl ether with dihydropyran, followed by oxidation of the double bond with m-chloroperbenzoic acid (mCPBA).

[0218] After the reaction, the resulting reaction mixture was returned to room temperature, and 50 g of a 10% hydrogen chloride-methanol solution (hydrogen chloride-methanol reagent (5-10%), manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at room temperature for 4 hours. The reaction mixture was then transferred in small portions to a separatory funnel containing 100 mL of saturated aqueous sodium bicarbonate and extracted twice with 200 mL of ethyl acetate. The organic layer was washed sequentially with 100 mL of brine, 100 mL of saturated aqueous sodium bicarbonate, and 100 mL of brine, and then dehydrated over anhydrous sodium sulfate. After filtering off the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 3.44 g of compound (BA). (Rf1 in formula (BA) is the PFPE chain represented by formula (7-1) above. In Rf1, h, which indicates the average degree of polymerization, is 4.5, and i, which indicates the average degree of polymerization, is 4.5.)

[0219] The resulting compound (BA) 1 H-NMR and 19 F-NMR measurements were carried out and the structure was identified based on the following results. 1 H-NMR (acetone-D6): δ[ppm]=1.55-1.75(6H), 3.40-3.85(22H), 3.85-4.10(4H) 19 F-NMR (acetone-D6): δ[ppm]=-55.5~-51.5(9F), -78.5(2F), -80.5(2F), -91.0~-88.5(18F)

[0220] [Example 14] The compound represented by the above formula (BB) was obtained by the method shown below. The same operation as in Example 13 was performed except that the compound represented by formula (8-14) was used instead of the compound represented by formula (8-13), to obtain 4.01 g of compound (BB) (Rf1 in formula (BB) is a PFPE chain represented by the above formula (7-1). In Rf1, h, which represents the average degree of polymerization, is 4.5, and i, which represents the average degree of polymerization, is 4.5).

[0221] The compound represented by formula (8-14) was synthesized by the following method. The double bond of ethylene glycol monoallyl ether was oxidized using m-chloroperbenzoic acid (mCPBA), and then reacted with the hydroxyl group of glycidol. After the reaction, the two hydroxyl groups of the resulting compound were protected using dihydropyran.

[0222] The obtained compound (BB) 1 H-NMR and 19 F-NMR measurements were carried out and the structure was identified based on the following results. 1 H-NMR (acetone-D6): δ[ppm]=1.55-1.75(6H), 3.40-3.85(28H), 3.85-4.10(4H) 19 F-NMR (acetone-D6): δ[ppm]=-55.5~-51.5(9F), -78.5(2F), -80.5(2F), -91.0~-88.5(18F)

[0223] [Example 15] The compound represented by the above formula (BC) was obtained by the method shown below. The same operation as in Example 13 was performed except that the compound represented by formula (8-6) was used instead of the compound represented by formula (8-4), to obtain 4.11 g of compound (BC) (Rf1 in formula (BC) is a PFPE chain represented by the above formula (7-1). In Rf1, h, which indicates the average degree of polymerization, is 4.5, and i, which indicates the average degree of polymerization, is 4.5).

[0224] The resulting compound (BC) 1 H-NMR and 19 F-NMR measurements were carried out and the structure was identified based on the following results. 1 H-NMR (acetone-D6): δ[ppm]=2.00(3H), 2.65(3H), 3.20-3.80(12H), 3.85-4.10(4H) 19 F-NMR (acetone-D6): δ[ppm]=-55.5~-51.5(9F), -78.5(2F), -80.5(2F), -91.0~-88.5(18F)

[0225] [Example 16] The compound represented by the above formula (BD) was obtained by the method shown below. The same operation as in Example 13 was performed except that the compound represented by formula (8-6) was used instead of the compound represented by formula (8-13), to obtain 4.31 g of compound (BD) (Rf1 in formula (BD) is a PFPE chain represented by the above formula (7-1). In Rf1, h, which indicates the average degree of polymerization, is 4.5, and i, which indicates the average degree of polymerization, is 4.5).

[0226] The obtained compound (BD) 1 H-NMR and 19 F-NMR measurements were carried out and the structure was identified based on the following results. 1 H-NMR (acetone-D6): δ[ppm]=1.65-1.85(4H), 3.40-3.85(26H), 3.85-4.10(4H) 19 F-NMR (acetone-D6): δ[ppm]=-55.5~-51.5(9F), -78.5(2F), -80.5(2F), -91.0~-88.5(18F)

[0227] [Example 17] The compound represented by the above formula (BE) was obtained by the method shown below. HOCH2CF2O(CF2CF2O) h (CF2O)i Instead of the compound represented by CF2CH2OH, HOCH2CF2CF2O(CF2CF2CF2O) j The same procedure as in Example 4 was performed, except that a compound (number average molecular weight 1000, molecular weight distribution 1.1) represented by CF2CF2CH2OH (where j, representing the average degree of polymerization, is 4.5) was used, to obtain 4.50 g of compound (BE) (Rf2 in formula (BE) is a PFPE chain represented by the above formula (7-2). In Rf2, j, representing the average degree of polymerization, is 4.5).

[0228] The resulting compound (BE) 1 H-NMR and 19 F-NMR measurements were carried out and the structure was identified based on the following results. 1 H-NMR (acetone-D6): δ[ppm]=1.30-1.45(4H), 1.95-2.10(8H), 3.20-3.65(12H), 3.65-3.95(4H), 3.75-4.00(2H), 3.85-4.10(4H) 19 F-NMR (acetone-D6): δ[ppm]=-84.0~-83.0(18F), -86.4(4F), -124.3(4F), -130.0~-129.0(9F)

[0229] [Example 18] The compound represented by the above formula (BF) was obtained by the method shown below. HOCH2CF2O(CF2CF2O) h (CF2O) i Instead of the compound represented by CF2CH2OH, HOCH2CF2CF2CF2O(CF2CF2CF2CF2O) k The same operations as in Example 4 were performed except that a compound (number average molecular weight 1000, molecular weight distribution 1.1) represented by CF2CF2CF2CH2OH (where k, indicating the average degree of polymerization, is 3.0) was used, and 4.44 g of compound (BF) (Rf3 in formula (BF) is a PFPE chain represented by the above formula (7-3). In Rf3, k, indicating the average degree of polymerization, is 3.0) was obtained.

[0230] The resulting compound (BF) 1 H-NMR and 19 F-NMR measurements were carried out and the structure was identified based on the following results. 1 H-NMR (acetone-D6): δ[ppm]=1.30-1.45(4H), 1.95-2.10(8H), 3.20-3.65(12H), 3.65-3.95(4H), 3.75-4.00(2H), 3.85-4.10(4H) 19 F-NMR (acetone-D6): δ[ppm]=-84.0~-83.0(16F), -122.5(4F), -126.0(12F), -129.0~-128.0(4F)

[0231] The compounds (AA) to (AL) and (BA) to (BF) of Examples 1 to 18 thus obtained are each substituted into formula (1) to obtain R 1 , R 2 , R 3 , R 4 , R 5 The structure is shown in Table 1.

[0232] [Table 1]

[0233] [Table 2]

[0234] [Table 3]

[0235] [Comparative Example 1] The compound represented by the following formula (ZA) was synthesized by the method described in Patent Document 1.

[0236] [ka] (Rf1 in formula (ZA) is a PFPE chain represented by the above formula (7-1). In Rf1, h representing the average degree of polymerization is 4.5, and i representing the average degree of polymerization is 4.5.)

[0237] Comparative Example 2 The compound represented by the following formula (ZB) was synthesized with reference to the method described in Patent Document 2. In Example 1 of Patent Document 2, glycidyl 4-acetaminophenyl ether was used instead of glycidyl phenyl ether.

[0238] [ka] (Rf1 in formula (ZB) is a PFPE chain represented by the above formula (7-1). In Rf1, h representing the average degree of polymerization is 4.5, and i representing the average degree of polymerization is 4.5.)

[0239] Comparative Example 3 A compound represented by the following formula (ZC) was synthesized with reference to the method described in Patent Document 4. In Example 1 of Patent Document 4, 2-hydroxyacetamide was used instead of 3-hydroxypropamide.

[0240] [ka] (Rf1 in formula (ZC) is a PFPE chain represented by the above formula (7-1). In Rf1, h representing the average degree of polymerization is 4.5, and i representing the average degree of polymerization is 4.5.)

[0241] Comparative Example 4 The compound represented by the following formula (ZD) was synthesized by the method described in Patent Document 4.

[0242] [ka] (Rf1 in formula (ZD) is a PFPE chain represented by the above formula (7-1). In Rf1, h representing the average degree of polymerization is 4.5, and i representing the average degree of polymerization is 4.5.)

[0243] Comparative Example 5 The compound represented by the following formula (ZE) was synthesized by the method described in Patent Document 4.

[0244] [ka] (Rf1 in formula (ZE) is a PFPE chain represented by the above formula (7-1). In Rf1, h representing the average degree of polymerization is 4.5, and i representing the average degree of polymerization is 4.5.)

[0245] The number average molecular weights (Mn) of the compounds thus obtained in Examples 1 to 18 and Comparative Examples 1 to 5 were measured by the above-mentioned method. The results are shown in Table 4.

[0246] Next, solutions for forming lubricating layers were prepared by the method described below using the compounds obtained in Examples 1 to 18 and Comparative Examples 1 to 5. Then, using the obtained solutions for forming lubricating layers, lubricating layers for magnetic recording media were formed by the method described below, thereby obtaining the magnetic recording media of Examples 1 to 18 and Comparative Examples 1 to 5.

[0247] "Lubricant layer forming solution" The compounds obtained in Examples 1 to 18 and Comparative Examples 1 to 5 were each dissolved in a fluorine-based solvent, Vertrel (registered trademark) XF (trade name, manufactured by Mitsui DuPont Fluorochemicals Co., Ltd.), and diluted with Vertrel XF so that the film thickness when applied to the protective layer would be 9.0 Å to 9.5 Å, to prepare a solution for forming a lubricating layer.

[0248] "Magnetic recording media" A magnetic recording medium was prepared by sequentially depositing an adhesive layer, a soft magnetic layer, a first underlayer, a second underlayer, a magnetic layer, and a protective layer on a substrate having a diameter of 65 mm. The protective layer was made of carbon. On the protective layer of a magnetic recording medium on which each layer up to the protective layer had been formed, the lubricating layer-forming solutions of Examples 1 to 18 and Comparative Examples 1 to 5 were applied by dipping under the conditions of an immersion speed of 10 mm / sec, an immersion time of 30 seconds, and a pull-up speed of 1.2 mm / sec.

[0249] The magnetic recording medium coated with the lubricating layer-forming solution was then placed in a thermostatic chamber, and a heat treatment was performed at 120°C for 10 minutes to remove the solvent in the lubricating layer-forming solution and improve the adhesion between the protective layer and the lubricating layer, thereby forming a lubricating layer on the protective layer and obtaining a magnetic recording medium.

[0250] (film thickness measurement) The thickness of the lubricating layer of each of the magnetic recording media thus obtained in Examples 1 to 18 and Comparative Examples 1 to 5 was measured using an FT-IR (product name: Nicolet iS50, manufactured by Thermo Fisher Scientific). The results are shown in Table 4.

[0251] Next, the magnetic recording media of Examples 1 to 18 and Comparative Examples 1 to 5 were subjected to the following wear resistance test, chemical resistance test, and corrosion resistance test. (Wear resistance test) Using a pin-on-disk friction and wear tester, a 2 mm diameter alumina ball was slid on the lubricating layer of the magnetic recording medium at a load of 40 gf and a sliding speed of 0.25 m / sec to measure the friction coefficient of the surface of the lubricating layer. The sliding time until the friction coefficient of the surface of the lubricating layer suddenly increased was then measured. The sliding time until the friction coefficient suddenly increased was measured four times for the lubricating layer of each magnetic recording medium, and the average value (time) was used as an index of the wear resistance of the lubricant coating.

[0252] The results for the magnetic recording media using the compounds of Examples 1 to 18 and the compounds of Comparative Examples 1 to 5 are shown in Table 4. The evaluation criteria for wear resistance based on the sliding time until the coefficient of friction suddenly increases were as follows:

[0253] "Evaluation Criteria" A:650sec or more B: 550 seconds or more, less than 650 seconds C: 450 seconds or more, less than 550 seconds D: Less than 450 seconds

[0254] The time until the coefficient of friction increases sharply can be used as an indicator of the wear resistance of the lubricating layer for the following reason: The lubricating layer of a magnetic recording medium wears out as the magnetic recording medium is used, and when the lubricating layer is worn away, the contact and protective layer come into direct contact, causing a sharp increase in the coefficient of friction. The time until the coefficient of friction increases sharply is thought to be correlated with friction testing.

[0255] (Chemical resistance test) The contamination of magnetic recording media by environmental substances that generate contaminants in high-temperature environments was investigated using the following method: Si ions were used as the environmental substances, and the amount of Si adsorption was measured as the amount of contaminants that contaminate the magnetic recording media generated by the environmental substances.

[0256] Specifically, the magnetic recording medium to be evaluated was stored in a high-temperature environment of 85°C and 0% humidity in the presence of siloxane-based Si rubber for 240 hours. The amount of Si adsorption present on the surface of the magnetic recording medium was then analyzed and measured using secondary ion mass spectrometry (SIMS), and the degree of contamination by Si ions was evaluated as the amount of Si adsorption. The amount of Si adsorption was evaluated based on the following criteria, with the result of Comparative Example 1 set at 1.00. The results are shown in Table 4.

[0257] "Evaluation Criteria" A: Si adsorption amount is less than 0.70 B: Si adsorption amount is 0.70 or more and less than 0.90 C:Si adsorption amount is 0.90 or more and less than 1.10 D: Si adsorption amount is 1.10 or more

[0258] (Corrosion resistance test) The magnetic recording media were exposed to conditions of 85°C and 90% relative humidity for 48 hours. After that, the number of corrosion spots with a diameter of 5 microns or more that appeared on the surface of the magnetic recording media was counted using an optical surface analyzer (Candela 7140, manufactured by KLA-Tencor Corporation) and evaluated based on the following criteria. The results are shown in Table 4.

[0259] "Evaluation Criteria" A: Less than 150 locations B: 150 or more, less than 250 C: 250 or more locations, but less than 1,000 locations D: Over 1,000 locations

[0260] [Table 4]

[0261] As shown in Table 4, the magnetic recording media of Examples 1 to 18 were evaluated in all evaluation items as either A or B. This confirms that the lubricating layers of the magnetic recording media of Examples 1 to 18 have good wear resistance and chemical resistance, and are highly effective in inhibiting corrosion of the magnetic recording media.

[0262] In contrast, Comparative Example 1 uses a compound (ZA) that has -CH2CH2OH at both ends and does not contain an N,N-substituted amide terminal group. For this reason, it is believed that Comparative Example 1 exhibits excessive adhesion of the lubricating layer to the protective layer, resulting in insufficient wear resistance, and that the lubricating layer's insufficient lipophilicity attracts environmental pollutants and water, which can corrode magnetic recording media, to the lubricating layer, resulting in insufficient corrosion resistance and chemical resistance. As a result, the magnetic recording medium of Comparative Example 1, which used compound (ZA), received a rating of C in all evaluation items.

[0263] In Comparative Example 2, a compound (ZB) was used that had an amide group (-NHC(=O)CH3) at one end, in which one hydrogen atom was bonded to the nitrogen atom constituting the amide bond via a phenylene group. Because the compound (ZB) used in Comparative Example 2 did not contain a terminal group having an N,N-substituted amide, the lipophilicity of the terminal group was insufficient, and it is presumed that the evaluations of abrasion resistance and chemical resistance were good, but the evaluation of corrosion resistance was C.

[0264] In addition, both Comparative Examples 3 and 4 used compounds (compounds (ZC) and (ZD)) in which the amide groups located at both ends were groups in which two hydrogen atoms were bonded to the nitrogen atom constituting the amide bond, and which did not contain terminal groups having N,N-substituted amide. For this reason, it is presumed that the lipophilicity of compounds (ZC) and (ZD) was insufficient in Comparative Examples 3 and 4. It is also presumed that in Comparative Examples 3 and 4, the amide groups located at both ends of the compounds interacted with the hydroxyl groups in the compounds, causing aggregation or the generation of hydroxyl groups that were not involved in bonding with the active sites on the protective layer, which attracted environmental substances that generate pollutants and water that causes corrosion of magnetic recording media to the lubricating layer. For these reasons, it is presumed that Comparative Example 3, which used compound (ZC), and Comparative Example 4, which used compound (ZD), received a grade of C in all evaluation items.

[0265] Furthermore, Comparative Example 5 uses a compound (ZE) in which the amide groups located at both ends are groups in which one hydrogen atom is bonded to the nitrogen atom constituting the amide bond. Therefore, Comparative Example 5 has better wear resistance and chemical resistance than Comparative Examples 3 and 4, which use compounds in which two hydrogen atoms are bonded to the nitrogen atom constituting the amide bond. However, it is presumed that the corrosion resistance of Comparative Example 5 was evaluated as C because the liposolubility of Compound (ZE) is insufficient. [Industrial Applicability]

[0266] By using a lubricant for magnetic recording media containing the fluorine-containing ether compound of the present invention, it is possible to form a lubricating layer that has excellent adhesion, good chemical resistance and wear resistance, and a high corrosion-inhibiting effect on magnetic recording media, even if it is thin. [Explanation of symbols]

[0267] 10 Magnetic recording media 11 Circuit Board 12 Adhesion layer 13 Soft magnetic layer 14 1st base layer 15 Second base layer 16 Magnetic Layers 17 Protective Layer 18 Lubricating layer

Claims

1. A fluorine-containing ether compound represented by the following formula (1): R １ -O-R ２ -CH ２ -R ３ -CH ２ -R ４ -O-R ５ (1) (In formula (1), R ３ is a perfluoropolyether chain. —R 2 —O— and —R 4 —O— are each independently a divalent linking group represented by the following formula (4), and may be the same or different. R １ and R ５ is a terminal group represented by the following formulas (2-1) to (2-5), a terminal group represented by the following formulas (3-1) to (3-5), or a hydrogen atom, and R １ and R ５ may be the same or different from each other. １ and R ５ At least one of the groups is a terminal group represented by the following formulas (2-1) to (2-5) or (3-1) to (3-5). 【Chemistry 1】 【Chemistry 2】 (In formula (4), l represents an integer of 1 to 3. l's m's each independently represent an integer of 1 to 6. l's n's each independently represent an integer of 1 to 6. In one repeating unit, at least one of m and n is 1. E represents a single bond, -CH 2 CH 2 O- (the leftmost carbon atom is bonded to an oxygen atom in the repeating unit), -CH 2 CH 2 CH 2 O- (the leftmost carbon atom is bonded to an oxygen atom in the repeating unit), or -CH 2 CH 2 CH 2 CH 2 O- (the leftmost carbon atom is bonded to an oxygen atom in the repeating unit). In formula (4), the leftmost oxygen atom is bonded to the methylene group bonded to R 3 , and E is bonded to R 1 or R 5 .)

2. R in the formula (1) １ and R ５ are each independently a terminal group represented by any one of formulas (2-1) to (2-5) or (3-1) to (3-5).

3. R in the formula (1) １ and R ５ The fluorine-containing ether compound according to claim 2, wherein

4. R in the formula (1) １ and R ５ The fluorine-containing ether compound according to claim 2 , wherein

5. R in the formula (1) １ and R ５ 2. The fluorine-containing ether compound according to claim 1, wherein one of the following is a terminal group represented by any one of the formulas (2-1) to (2-5) or (3-1) to (3-5), and the other is a hydrogen atom.

6. R in the formula (1) ３ is a perfluoropolyether chain represented by the following formula (6): -(CF ２ ) ｗ１ -O-(CF ２ O) ｗ２ -(CF ２ CF ２ O) ｗ３ -(CF ２ CF ２ CF ２ O) ｗ４ -(CF ２ CF ２ CF ２ CF ２ O) ｗ５ -(CF ２ ) ｗ６ - (6) (In formula (6), w2, w3, w4, and w5 represent the average degree of polymerization, and each independently represents 0 to 20. However, w2, w3, w4, and w5 cannot all be 0 at the same time. w1 and w6 are CF ２ The repeating units in formula (6) are (CF ２ O), (CF ２ CF ２ O), (CF ２ CF ２ CF ２ O), (CF ２ CF ２ CF ２ CF ２ There are no particular restrictions on the arrangement order of O).

7. R in the formula (1) ３ is any one selected from perfluoropolyether chains represented by the following formulas (7-1) to (7-4): -CF ２ -(OCF ２ CF ２ ) ｈ -(OCF ２ ) ｉ -OCF ２ - (7-1) (In formula (7-1), h and i represent the average degree of polymerization, h represents 1 to 20, and i represents 0 to 20.) -CF ２ CF ２ -(OCF ２ CF ２ CF ２ ) ｊ -OCF ２ CF ２ - (7-2) (In formula (7-2), j represents the average degree of polymerization and represents 1 to 15.) -CF ２ CF ２ CF ２ -(OCF ２ CF ２ CF ２ CF ２ ) ｋ -OCF ２ CF ２ CF ２ - (7-3) (In formula (7-3), k represents the average degree of polymerization and represents 1 to 10.) -(CF ２ ) ｗ７ -O-(CF ２ CF ２ CF ２ O) ｗ８ -(CF ２ CF ２ O) ｗ９ -(CF ２ ) ｗ１０ - (7-4) (In formula (7-4), w8 and w9 represent the average degree of polymerization, each independently representing 1 to 20. w7 and w10 represent CF ２ is an average value representing the number of

8. 6. The fluorine-containing ether compound according to claim 1, which has a number average molecular weight in the range of 500 to 10,000.

9. A lubricant for magnetic recording media, comprising the fluorine-containing ether compound according to any one of claims 1 to 5.

10. A magnetic recording medium having at least a magnetic layer, a protective layer, and a lubricating layer sequentially provided on a substrate, 6. A magnetic recording medium, wherein the lubricating layer comprises the fluorine-containing ether compound according to claim 1.

11. 11. The magnetic recording medium according to claim 10, wherein the lubricating layer has an average film thickness of 0.5 nm to 2.0 nm.

Images