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

Abstract

The fluorine-containing ether compound is a fluorine-containing ether compound represented by the following formula. R < 1 >-CH < 2 >-R < 2 >-(CH < 2 >-OCH < 2 >-CR3R < 4 >-CH < 2 > O-CH < 2 >-R < 2 >) z-CH < 2 >-R < 5 > (z is 1 or 2). And R2 is a perfluoropolyether chain. Each of R1 and R5 represents a terminal group having 1 to 50 carbon atoms and having at least one polar group; r3 and R4 may be the same as or different from each other, each of R3 and R4 is an organic group having 1-5 carbon atoms and bonded to a tetra-substituted carbon atom, and each of R3 and R4 does not include a secondary hydroxyl group and a tertiary hydroxyl group but includes one primary hydroxyl group. The organic group may include an ether oxygen atom between carbon atoms, and the terminal bound to the tetra-substituted carbon atom may be an ether oxygen atom).

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.

[0002] This application claims priority based on Japanese Patent Application No. 2022-197136 filed in Japan on December 9, 2022, the contents of which are incorporated herein by reference. Background Art

[0003] In order to increase the recording density in a magnetic recording and reproducing device, the development of a magnetic recording medium suitable for high recording density has been progressing.

[0004] In the past, as a magnetic recording medium, a recording layer is formed on a substrate, and a protective layer formed by carbon etc. is formed on the recording layer. The protective layer protects the information recorded in the recording layer and improves the sliding property of the magnetic head. In addition, the protective layer covers the recording layer to prevent the metal contained in the recording layer from being corroded by environmental substances.

[0005] However, only by setting a protective layer on the recording layer, the durability of the magnetic recording medium cannot be fully obtained. Therefore, a lubricant is applied to the surface of the protective layer to form a lubricating layer. The lubricating layer improves the durability and protective power of the protective layer and prevents the intrusion of pollutants into the inside of the magnetic recording medium.

[0006] As a lubricant used when forming a lubricating layer of a magnetic recording medium, a substance containing a compound having a polar group such as a hydroxyl group at the terminal of a fluorine-based polymer having a repeating structure containing -CF2- has been proposed.

[0007] For example, Patent Documents 1, 2, and 3 disclose fluorine-containing ether compounds containing two perfluoropolyether chains in the molecule and having a linking group having a secondary hydroxyl group disposed between the two perfluoroether chains.

[0008] Patent Document 4 discloses a fluorine-containing ether compound including two perfluoropolyether chains in the molecule and a linking group having both a primary hydroxyl group and a secondary hydroxyl group disposed between the two perfluoroether chains.

[0009] Patent Documents 5, 6 and 7 disclose fluorinated ether compounds having a backbone in which three perfluoropolyether chains are linked via a linking group having a secondary hydroxyl group, and terminal groups having polar groups are linked to both sides of the backbone via methylene groups (-CH2-).

[0010] Prior art literature

[0011] Patent Literature

[0012] Patent Document 1: International Publication No. 2021 / 251335

[0013] Patent Document 2: U.S. Patent Application Publication No. 2020 / 0002640

[0014] Patent Document 3: International Publication No. 2016 / 084781

[0015] Patent Document 4: International Publication No. 2021 / 019998

[0016] Patent Document 5: U.S. Patent Application Publication No. 2016 / 0260452

[0017] Patent Document 6: International Publication No. 2018 / 116742

[0018] Patent Document 7: International Publication No. 2017 / 145995 Summary of the invention

[0019] Problems to be solved by the invention

[0020] In a magnetic recording and reproducing device, it is required to further reduce the flying height of the magnetic head. Therefore, it is required to further reduce the thickness of the protective layer and / or lubricating layer in the magnetic recording medium.

[0021] However, generally speaking, if the thickness of the lubricating layer is reduced, the chemical resistance of the magnetic recording medium tends to decrease. In addition, if the floating amount of the magnetic head is reduced, the fluorine-containing ether compound in the lubricating layer may sometimes adhere to the magnetic head and pick up.

[0022] 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 which can form a lubricating layer having excellent chemical resistance and capable of suppressing adhesion and can be suitably used as a material for a lubricant for a magnetic recording medium.

[0023] Another object of the present invention is to provide a lubricant for a magnetic recording medium comprising the fluorinated ether compound of the present invention and capable of forming a lubricating layer having excellent chemical resistance and capable of suppressing adhesion.

[0024] Another object of the present invention is to provide a magnetic recording medium having a lubricating layer containing the fluorinated ether compound of the present invention, having excellent resistance to chemical substances and with suppressed adhesion.

[0025] Means for solving problems

[0026] The present inventors have conducted intensive studies to solve the above-mentioned problems.

[0027] As a result, it was found that a fluorine-containing ether compound having two or three perfluoropolyether chains, a specific divalent connecting group comprising a tetrasubstituted carbon atom to which two organic groups having primary hydroxyl groups are bonded is arranged between adjacent perfluoropolyether chains via a methylene group, and a methylene group and a specific terminal group are arranged in sequence at both ends of the skeleton comprising the perfluoropolyether chain, thereby arriving at the present invention.

[0028] That is, the present invention relates to the following matters.

[0029] [1] A fluorine-containing ether compound characterized by being represented by the following formula (1).

[0030] R 1 -CH2-R 2 -(CH2-OCH2-CR 3 R 4 -CH2O-CH2-R 2 ) z -CH2-R 5 (1)

[0031] (In formula (1), z is 1 or 2. R 2 is a perfluoropolyether chain. (z+1) R 2 They may be partially or entirely the same, or they may be different. 1 and R 5 may be the same or different, and are terminal groups having 1 to 50 carbon atoms and having at least one polar group. 3 and R 4 The organic groups may be the same or different and are organic groups having 1 to 5 carbon atoms and containing no secondary or tertiary hydroxyl groups but containing one primary hydroxyl group and bonded to the tetrasubstituted carbon atom. The organic group may contain an ether oxygen atom between carbon atoms, and the terminal bonded to the tetrasubstituted carbon atom may be an ether oxygen atom. When z is 2, the two -CR 3 R 4 - can be the same or different. )

[0032] [2] The fluorinated ether compound according to [1], wherein R in the above formula (1) 3 and R 4 Each independently represents any one of the following formulas (2-1) to (2-3).

[0033]

[0034] (In formula (2-1), a is an integer from 1 to 5.)

[0035] (In formula (2-2), b is an integer from 1 to 5.)

[0036] (In formula (2-3), c and d are each independently an integer of 1 to 4, and c+d≤5.)

[0037] [3] The fluorinated ether compound according to [1] or [2], wherein R in the formula (1) 1 and R 5 The number of polar groups possessed is any one of 1 to 3.

[0038] [4] The fluorinated ether compound according to any one of [1] to [3], wherein R in the formula (1) 1 and R 5 The polar group is at least one selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, a formyl group, a carbonyl group, a sulfone group, a cyano group, and a group having an amide bond.

[0039] [5] The fluorinated ether compound according to any one of [1] to [4], wherein R in the formula (1) 1 and R 5 Each independently has at least one hydroxyl group as a polar group.

[0040] [6] The fluorinated ether compound according to any one of [1] to [5], wherein R in the formula (1) 1 and R 5 Each independently represents any one of the terminal groups represented by the following formula (4-1) to formula (4-3).

[0041]

[0042] (In formula (4-1), y1 is 1 or 2, and y2 is an integer from 0 to 3. 1 is an aromatic hydrocarbon group, an unsaturated heterocyclic group, an alkenyl group, an alkynyl group, or a polar group. 1 is a polar group. 1 When X is an aromatic hydrocarbon group or an unsaturated heterocyclic group, 1 The atoms that make up the ring structure in 1 The adjacent methylene groups are bonded. 1 When X is alkenyl or alkynyl, 1 The carbon atom that forms the unsaturated bond in 1 Adjacent methylene groups are bonded.)

[0043] (In formula (4-2), y3 is an integer from 1 to 3, y4 is 0 or 1, and y5 is an integer from 0 to 3. 1 is an aromatic hydrocarbon group, an unsaturated heterocyclic group, an alkenyl group, an alkynyl group, or a polar group. 1 is a polar group. 1 When X is an aromatic hydrocarbon group or an unsaturated heterocyclic group,1 The atoms that make up the ring structure in 1 The adjacent methylene groups are bonded. 1 When X is alkenyl or alkynyl, 1 The carbon atom that forms the unsaturated bond in 1 Adjacent methylene groups are bonded.)

[0044] (In formula (4-3), y6 is 0 or 1, y7 is an integer from 1 to 3, and y8 is an integer from 1 to 3. 1 is an aromatic hydrocarbon group, an unsaturated heterocyclic group, an alkenyl group, an alkynyl group, or a polar group. 1 is a polar group. 1 When X is an aromatic hydrocarbon group or an unsaturated heterocyclic group, 1 The atoms that make up the ring structure in 1 The adjacent methylene groups are bonded. 1 When X is alkenyl or alkynyl, 1 The carbon atom that forms the unsaturated bond in 1 Adjacent methylene groups are bonded.)

[0045] [7] The fluorinated ether compound according to any one of [1] to [6], wherein the (z+1)th R in the formula (1) 2 Each is independently a perfluoropolyether chain represented by the following formula (3).

[0046] -(CF2) w1 -O-(CF2O) w2 -(CF2CF2O) w3 -(CF2CF2CF2O) w4 -(CF2CF2CF2CF2O) w5 -(CF2) w6 -(3)

[0047] (In formula (3), w2, w3, w4, and w5 represent average polymerization degrees, and each independently represents 0 to 20. However, w2, w3, w4, and w5 are not all 0 at the same time. w1 and w6 represent average values ​​of the number of CF2, and each independently represents 1 to 3. There is no particular limitation on the order of arrangement of (CF2O), (CF2CF2O), (CF2CF2CF2O), and (CF2CF2CF2CF2O) as repeating units in formula (3).)

[0048] [8] The fluorinated ether compound according to any one of [1] to [7], wherein the (z+1)th R in the formula (1) 2 Each independently represents any one selected from the group consisting of perfluoropolyether chains represented by the following formula (3-1) to formula (3-4).

[0049] -CF2-(OCF2CF2) n -(OCF2) o -OCF2-(3-1)

[0050] (In formula (3-1), n ​​and o represent the average degree of polymerization, n represents 1 to 20, and o represents 0 to 20.)

[0051] -CF2CF2-(OCF2CF2CF2) p -OCF2CF2-(3-2)

[0052] (In formula (3-2), p represents the average degree of polymerization and is 1 to 15.)

[0053] -CF2CF2CF2-(OCF2CF2CF2CF2) q -OCF2CF2CF2-(3-3)

[0054] (In formula (3-3), q represents the average degree of polymerization and is 1 to 10.)

[0055] -(CF2) w7 -O-(CF2CF2CF2O) w8 -(CF2CF2O) w9 -(CF2) w10 -(3-4)

[0056] (In formula (3-4), w8 and w9 represent average polymerization degrees, and each independently represents 1 to 20. w7 and w10 represent average values ​​of the number of CF2 groups, and each independently represents 1 to 2.)

[0057] [9] The fluorinated ether compound according to any one of [1] to [8], wherein in the above formula (1), z -CR 3 R 4 -R in 3 and R 4 All the same.

[0058]

[10] The fluorinated ether compound according to any one of [1] to [9], wherein the (z+1)th R in the formula (1) 2 All the same.

[0059]

[11] The fluorinated ether compound according to any one of [1] to

[10] , wherein R in the formula (1) 1 and R 5 same.

[0060]

[12] The fluorinated ether compound according to any one of [1] to

[11] , wherein the number average molecular weight is within the range of 500 to 10,000.

[0061]

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

[12] .

[0062]

[14] A magnetic recording medium, characterized in that at least a magnetic layer, a protective layer, and a lubricating layer are provided in this order on a substrate,

[0063] The lubricating layer contains the fluorine-containing ether compound described in any one of [1] to

[12] .

[0064]

[15] The magnetic recording medium according to

[14] , wherein the average film thickness of the lubricating layer is 0.5 nm to 2.0 nm.

[0065] Effects of the Invention

[0066] The fluorine-containing ether compound of the present invention is a compound represented by the above formula (1), and is suitable as a material for a lubricant for a magnetic recording medium.

[0067] Since the lubricant for a magnetic recording medium of the present invention contains the fluorinated ether compound of the present invention, it is possible to form a lubricating layer having excellent chemical resistance and a high adhesion suppressing effect.

[0068] The magnetic recording medium of the present invention has a lubricating layer comprising a fluorinated ether compound of the present invention. Therefore, the magnetic recording medium of the present invention has good chemical resistance, high adhesion suppression effect, and excellent reliability and durability. In addition, the magnetic recording medium of the present invention has a lubricating layer that has good chemical resistance and can suppress adhesion, so the thickness of the lubricating layer can be made thin, and the floating amount of the magnetic head can be made small. BRIEF DESCRIPTION OF THE DRAWINGS

[0069] Figure 1 This is a schematic cross-sectional view showing one embodiment of the magnetic recording medium of the present invention. DETAILED DESCRIPTION

[0070] The present inventors have conducted intensive studies to solve the above-mentioned problems as described below.

[0071] In the past, as the material of the magnetic recording medium lubricant (hereinafter, sometimes abbreviated as "lubricant") coated on the surface of the protective layer, a fluorine-containing ether compound with polar groups such as hydroxyl groups was preferably used. The polar group contained in the fluorine-containing ether compound combines with the active point on the protective layer to improve the adhesion of the lubricating layer to the protective layer. For the fluorine-containing ether compound in the past, the terminal in the chain structure is configured with a polar group. In addition, when the fluorine-containing ether compound has a plurality of perfluoropolyether chains, a polar group is also configured between adjacent perfluoropolyether chains.

[0072] However, when a thin lubricating layer is formed on a protective layer using a conventional lubricant, it is difficult to realize a lubricating layer having good resistance to chemical substances and a high adhesion suppressing effect.

[0073] The reason for this is that the fluorine-containing ether compound contained in the lubricating layer contains polar groups which are not adsorbed to active sites present in large numbers on the protective layer.

[0074] If the fluorinated ether compound included in the lubricating layer contains polar groups that are not adsorbed to the active points on the protective layer, the lubricant in the lubricating layer becomes bulky, and the coating state of the lubricating layer on the protective layer becomes uneven. In addition, the surface energy of the fluorinated ether compound molecules as a whole becomes high, and chemical substances are easily attached to the lubricating layer containing the fluorinated ether compound. Based on these circumstances, if the fluorinated ether compound included in the lubricating layer contains a large number of polar groups that are not adsorbed to the active points on the protective layer, the chemical substance resistance and adhesion suppression effect of the lubricating layer are likely to become insufficient.

[0075] Therefore, the present inventors have focused on the bonding between the polar groups contained in the fluorinated ether compound and the active sites on the protective layer, and have conducted intensive studies to realize a fluorinated ether compound that is less likely to produce polar groups that are not involved in bonding with the active sites on the protective layer.

[0076] As a result, the present inventors have come to the following understanding: Among the polar groups contained in the fluorinated ether compound, the secondary hydroxyl group contained in the divalent linking group disposed between adjacent perfluoropolyether chains is particularly unlikely to participate in the bonding with the active point on the protective layer. That is, the fluorinated ether compound having a divalent linking group containing a secondary hydroxyl group between adjacent perfluoropolyether chains still has room for improvement from the viewpoint of adsorption to the protective layer. Therefore, the present inventors have further repeatedly conducted research in order to develop a fluorinated ether compound having a divalent linking group between adjacent perfluoropolyether chains that can further improve bonding with the protective layer.

[0077] Specifically, the inventors converted the secondary hydroxyl groups contained in the divalent linking groups disposed between adjacent perfluoropolyether chains contained in the fluorinated ether compound into primary hydroxyl groups with high mobility and adsorption, and in order to fully ensure the bonding points with the protective layer, the number of primary hydroxyl groups contained in the divalent linking groups was set to 2. Furthermore, a lubricating layer was formed using the fluorinated ether compound. As a result, a lubricating layer with good chemical resistance and high adhesion inhibition effect was obtained.

[0078] Furthermore, the inventors have repeatedly conducted in-depth studies and found that as long as a fluorinated ether compound having two or three perfluoropolyether chains is prepared, a specific divalent linking group containing a tetrasubstituted carbon atom bonded to two organic groups having one primary hydroxyl group is arranged between adjacent perfluoropolyether chains via a methylene group (-CH2-), and a methylene group and a specific terminal group having at least one polar group are sequentially arranged at both ends of the skeleton containing the perfluoropolyether chain. The specific divalent linking group in the above-mentioned fluorinated ether compound has two organic side chains branched from the tetrasubstituted carbon atom. The two organic side chains may be the same or different, and are organic groups having 1 to 5 carbon atoms and containing no secondary hydroxyl groups and tertiary hydroxyl groups but containing one primary hydroxyl group. The above-mentioned organic group may contain an ether oxygen atom between carbon atoms, and the terminal bonded to the above-mentioned tetrasubstituted carbon atom may be an ether oxygen atom.

[0079] For such fluorinated ether compounds, polar groups that do not participate in the binding with the active points present on the protective layer are not easily generated due to the reasons shown below <1> to <5>. Therefore, the two ends of the two or three perfluoropolyether chains of the above-mentioned fluorinated ether compounds are respectively in close contact with the protective layer through the two primary hydroxyl groups contained in the divalent linking group (or, the two primary hydroxyl groups contained in the divalent linking group and the polar groups possessed by the terminal groups). Therefore, the state of the fluorinated ether compound of this embodiment applied on the protective layer is not easy to become large in volume, it is easy to wet and spread on the protective layer, and it is easy to obtain a lubricating layer with a uniform coating state. As a result, it has good adhesion to the protective layer, a high coverage rate, and is not easy to introduce pollutants. Therefore, it is presumed that a lubricating layer with excellent chemical resistance and good adhesion inhibition effect can be formed.

[0080] <1> For the above-mentioned fluorinated ether compound, the above-mentioned divalent linking group has two organic side chains branched from a tetrasubstituted carbon atom. The two organic side chains are each an organic group having 1 to 5 carbon atoms and containing one primary hydroxyl group and bonded to the tetrasubstituted carbon atom. Therefore, the distance between each of the two primary hydroxyl groups contained in the above-mentioned divalent linking group and the tetrasubstituted carbon atom in the divalent linking group is appropriate. Therefore, it is not easy for the two primary hydroxyl groups contained in the above-mentioned divalent linking group to be blocked from bonding to the active points on the protective layer by the bulky parts in the fluorinated ether compound such as the nearby perfluoropolyether chain and the tetrasubstituted carbon atom in the divalent linking group.

[0081] <2> The two primary hydroxyl groups contained in the above-mentioned divalent linking group are each arranged in an organic group having 1 to 5 carbon atoms bonded to a tetrasubstituted carbon atom. Therefore, the distance between the two primary hydroxyl groups contained in the divalent linking group is appropriate. Therefore, aggregation of the primary hydroxyl groups caused by the distance between the two primary hydroxyl groups being too close is not easy to occur. In addition, since the distance between the two primary hydroxyl groups is not far, if one of the primary hydroxyl groups contained in the above-mentioned divalent linking group is bonded to the protective layer, the distance between the other primary hydroxyl group and the protective layer also becomes closer. As a result, the other primary hydroxyl group can be oriented to easily induce adsorption to the protective layer. Therefore, the two primary hydroxyl groups contained in the divalent linking group do not hinder each other from bonding to the active points on the protective layer, and the two primary hydroxyl groups are easy to bond to the active points on the protective layer at the same time.

[0082] <3> The above two organic side chains are organic groups with 1 to 5 carbon atoms that do not contain secondary hydroxyl groups and tertiary hydroxyl groups but contain one primary hydroxyl group and are bonded to a tetrasubstituted carbon atom. Therefore, the periphery of the primary hydroxyl group arranged in each organic group is sterically empty. In addition, the primary hydroxyl group generally has a high degree of freedom and can move freely compared to the secondary hydroxyl group. Therefore, the two primary hydroxyl groups contained in the above two-valent linking group can each move spontaneously relative to the active point on the protective layer. Therefore, the two primary hydroxyl groups contained in the above two-valent linking group can easily form a bond with the active point on the protective layer.

[0083] <4> In the case where the above-mentioned fluorinated ether compound has three perfluoropolyether chains, there are two of the above-mentioned divalent linking groups in the molecule. In this case, the perfluoropolyether chain is arranged between two adjacent divalent linking groups. Therefore, the distance between the two primary hydroxyl groups of each of the two adjacent divalent linking groups will not become too close. Therefore, the two primary hydroxyl groups contained in each of the above-mentioned two divalent linking groups are not easily hindered from binding to the active points on the protective layer through the primary hydroxyl groups contained in the adjacent divalent linking groups. In addition, agglomeration with the primary hydroxyl groups contained in the two adjacent divalent linking groups is also not easy to occur.

[0084] <5> For the above-mentioned fluorine-containing ether compound, a perfluoropolyether chain is respectively arranged between the above-mentioned divalent linking group and the two terminal groups. Therefore, the distance between the two primary hydroxyl groups contained in the above-mentioned divalent linking group and the polar group contained in each terminal group will not become too close. As a result, the two primary hydroxyl groups contained in the above-mentioned divalent linking group and the polar group contained in each terminal group are not easily hindered from binding with the active point on the protective layer through the adjacent polar group. In addition, since the distance between the above-mentioned divalent linking group and each terminal group is appropriate, the primary hydroxyl groups contained in the above-mentioned divalent linking group and the polar groups in each terminal group are not easy to agglomerate. Therefore, the two primary hydroxyl groups contained in the above-mentioned divalent linking group and the polar groups contained in each terminal group are easy to bind to the active point on the protective layer.

[0085] Furthermore, the fluorine-containing ether compound has two or three perfluoropolyether chains. The two or three perfluoropolyether chains contained in the lubricating layer cover the surface of the protective layer and have low surface energy, thereby imparting chemical resistance to the lubricating layer.

[0086] Furthermore, the present inventors have confirmed that a lubricating layer having excellent chemical resistance and adhesion suppressing effect can be formed by using a lubricant containing the above-mentioned fluorinated ether compound, and have thus arrived at the present invention.

[0087] The fluorine-containing ether compound, the lubricant for a magnetic recording medium, and the magnetic recording medium of the present invention are described in detail below. It should be noted that the present invention is not limited to the embodiments described below.

[0088] [Fluorinated ether compounds]

[0089] The fluorine-containing ether compound of the present embodiment is represented by the following formula (1).

[0090] R 1 -CH2-R 2 -(CH2-OCH2-CR 3 R 4 -CH2O-CH2-R 2 ) z -CH2-R 5 (1)

[0091] (In formula (1), z is 1 or 2. R 2 is a perfluoropolyether chain. (z+1) R 2 They may be partially or entirely the same, or they may be different. 1 and R 5 may be the same or different, and are terminal groups having 1 to 50 carbon atoms and having at least one polar group. 3 and R 4 The organic groups may be the same or different and are organic groups having 1 to 5 carbon atoms and containing no secondary or tertiary hydroxyl groups but containing one primary hydroxyl group and bonded to the tetrasubstituted carbon atom. The organic group may contain an ether oxygen atom between carbon atoms, and the terminal bonded to the tetrasubstituted carbon atom may be an ether oxygen atom. When z is 2, the two -CR 3 R 4 - can be the same or different. )

[0092] In the fluorinated ether compound represented by formula (1), z is 1 or 2. Since z is 2 or less, the fluorinated ether compound represented by formula (1) does not become too large. Therefore, it becomes a fluorinated ether compound that can move freely on the protective layer, is easy to wet and spread on the protective layer, and is easy to obtain a lubricating layer with a uniform film thickness. In addition, since z is 1 or more, for example, compared with the case where z is 0, it becomes a fluorinated ether compound that can form a lubricating layer with good adhesion to the protective layer.

[0093] (-OCH2-CR 3 R 4 -CH2O- (divalent linking group)

[0094] -OCH2-CR 3 R 4 The divalent linking group represented by -CH2O- has two organic side chains (R 3 and R 4 ). 3 and R 4 Each of the two organic groups shown is an organic group having 1 to 5 carbon atoms and containing no secondary or tertiary hydroxyl groups but containing one primary hydroxyl group and bonded to a tetrasubstituted carbon atom. The organic group may contain an ether oxygen atom between carbon atoms, and the terminal bonded to the tetrasubstituted carbon atom may be an ether oxygen atom.

[0095] In the fluorinated ether compound represented by formula (1), R 3 and R 4 The organic groups shown may be the same or different. 3 and R 4 If the organic groups shown are the same, then the 2 The adsorption and mobility of the two primary hydroxyl groups contained in the divalent linking groups between the perfluoropolyether chains (hereinafter sometimes referred to as "PFPE chains") shown in the figure become equal to each other, and no significant difference occurs in the adsorption process of the two primary hydroxyl groups to the protective layer. Therefore, a lubricating layer with better adhesion to the protective layer can be formed, which is preferred.

[0096] In the formula (1), when z is 2, the two -CR 3 R 4 - Each can be the same or different. 3 R 4 - is the same, it is preferred that the fluorine-containing ether compound is easy to manufacture. When z in formula (1) is 2, it is more preferred that 2 -CR 3 R 4 -R in 3 and R 4 All the same.

[0097] In the lubricating layer containing the fluorine-containing ether compound represented by formula (1), R contained in the fluorine-containing ether compound 2 The PFPE chains shown do not have electrostatic interactions with the protective layer. Therefore, the PFPE chains contained in the fluorinated ether compound in the lubricating layer exist at a distance from the protective layer. On the other hand, R 3 and R 4 The organic groups shown each contain one primary hydroxyl group as a polar group. The polar group contained in the fluorinated ether compound in the lubricating layer can have an electrostatic interaction with the protective layer. However, in order for the polar group contained in the fluorinated ether compound in the lubricating layer to have an electrostatic interaction with the protective layer, it is necessary to bring the polar group and the protective layer close to each other until about.

[0098] Therefore, if the two primary hydroxyl groups contained in the divalent linking group between two or three PFPE chains of the fluorinated ether compound are too close to the PFPE chains, the protective layer may be blocked by the presence of The PFPE chain at the position above 100,0 ...

[0099] Specifically, for example, when the divalent linking group between two or three PFPE chains of the fluorinated ether compound represented by formula (1) contains a secondary hydroxyl group (for example, when replacing -CR in formula (1) 3 R 4 -When -CH(OH)- is configured, or when the divalent linking group is -OCH2-CH(OH)-CH2O-CH2-CR 3 R 4 -CH2-OCH2-CH(OH)-CH2O-), the distance between the hydroxyl group contained in the divalent linking group and the PFPE chain tends to become closer than that of the fluorinated ether compound represented by formula (1). Moreover, since the carbon atom to which the hydroxyl group is bonded has two substituents, the secondary hydroxyl group has a lower degree of freedom of movement in the molecule than the primary hydroxyl group. Therefore, the electrostatic interaction between the secondary hydroxyl group contained in the divalent linking group and the protective layer is easily hindered. As a result, when the fluorinated ether compound in the lubricating layer has a divalent linking group containing a secondary hydroxyl group, the divalent linking group is not easy to fully express its function as an adsorption unit to the protective layer.

[0100] In addition, when a plurality of hydroxyl groups with different stereoelectronic environments coexist in the bivalent linking groups between the PFPE chains of the fluorinated ether compound, the hydroxyl groups with high freedom of movement preferentially bind to the protective layer and occupy the active points on the protective layer. Therefore, the active points to which the hydroxyl groups with low mobility can bind are lost, and hydroxyl groups that are not adsorbed to the protective layer are easily generated.

[0101] Specifically, for example, in the case where a primary hydroxyl group and a secondary hydroxyl group having different stereoelectronic environments coexist in a divalent linking group between two or three PFPE chains of the fluorinated ether compound represented by formula (1) (for example, in the case where R 3 and / or R 4 In the case of -OCH2CH(OH)CH2OH, or in the case of -O-CH2-CH(OH)-CH2-O-CH2-C(CH2OH)2-CH2-O-CH2-CH(OH)-CH2-O-), the primary hydroxyl group having higher mobility and adsorption than the secondary hydroxyl group preferentially binds to the active point on the protective layer. Therefore, the active point on the protective layer to which the secondary hydroxyl group can bind is lost, and the secondary hydroxyl group cannot electrostatically interact with the protective layer, and is easily freed from the protective layer. As a result, the surface energy of the fluorinated ether compound molecule as a whole becomes higher, and the chemical substance is easily attached to the lubricating layer containing the fluorinated ether compound.

[0102] Furthermore, even if the divalent linking group contains a primary hydroxyl group, for example, R 3 and R 4 When one of the organic groups is a hydrogen atom, the function of the divalent linking group between two or three PFPE chains as an adsorption unit to the protective layer cannot be fully obtained.

[0103] In the fluorinated ether compound represented by formula (1), R 3 and R 4 The organic group shown is an organic group having 1 to 5 carbon atoms, preferably an organic group having 1 to 3 carbon atoms. 3 and R 4 Since the number of carbon atoms of the organic group shown is 1 or more, the distance between the tetrasubstituted carbon atom in the divalent linking group and the primary hydroxyl group and the distance between two primary hydroxyl groups included in the divalent linking group are appropriate.

[0104] In addition, due to R 3 and R 4 The carbon number of the organic group shown is 5 or less, so the flexibility of the divalent linking group between the PFPE chains becomes good, and the state of the fluorine-containing ether compound coated on the protective layer is not easy to become bulky, and a lubricating layer with uniform film thickness can be formed. 3 and R 4The carbon number of the organic group shown is 5 or less, so the mobility of the two primary hydroxyl groups contained in the divalent linking group is not too high. Therefore, it is difficult for the two primary hydroxyl groups to be oriented to be freed from the protective layer. As a result, it is possible to prevent the two primary hydroxyl groups from being oriented to be freed from the protective layer, thereby increasing the surface energy of the fluorinated ether compound molecules as a whole, and causing the chemical substance to adhere to the lubricating layer containing the fluorinated ether compound. Furthermore, due to R 3 and R 4 The number of carbon atoms of the organic group shown is 5 or less, so that the two primary hydroxyl groups included in the divalent linking group are unlikely to interact with each other, and the primary hydroxyl groups in the divalent linking group and R are unlikely to interact with each other. 1 and R 5 Therefore, the binding of the two primary hydroxyl groups contained in the divalent linking group to the active sites on the protective layer is not easily inhibited, and the divalent linking group is easy to bind to the active sites on the protective layer.

[0105] R 3 and R 4 The organic group shown may contain an ether oxygen atom between carbon atoms, and the terminal connected to the above-mentioned tetrasubstituted carbon atom may be an ether oxygen atom. 3 and / or R 4 When the organic group shown contains an etheric oxygen atom, R containing the etheric oxygen atom 3 and / or R 4 The flexibility of the R containing ether oxygen atoms becomes good. 3 and / or R 4 The primary hydroxyl group in the cation is preferred because it facilitates adhesion with the protective layer.

[0106] R 3 and R 4 The number of ether oxygen atoms that may be contained in the organic group may be one or more, but is preferably only one in order to prevent the fluorine-containing ether compound coated on the protective layer from becoming bulky.

[0107] In R 3 and R 4 When the organic group shown does not contain an ethereal oxygen atom, R 3 and R 4 Preferably, each independently is a group represented by the following formula (2-1). 3 and R 4 When the organic group shown contains an ether oxygen atom, R 3 and R 4 Preferably, each independently is a group represented by the following formula (2-2) or formula (2-3).

[0108] The group represented by formula (2-2) has a linear alkylene chain having 1 to 5 carbon atoms to which a primary hydroxyl group is bonded, and the terminal bonded to the tetrasubstituted carbon atom is an ether oxygen atom. In addition, the group represented by formula (2-3) contains one ether oxygen atom between methylene groups forming the linear alkylene chain having 1 to 5 carbon atoms to which a primary hydroxyl group is bonded.

[0109]

[0110] (In formula (2-1), a is an integer from 1 to 5.)

[0111] (In formula (2-2), b is an integer from 1 to 5.)

[0112] (In formula (2-3), c and d are each independently an integer of 1 to 4, and c+d≤5.)

[0113] In R 3 and R 4 When each is independently any group represented by formula (2-1) to formula (2-3), since a in formula (2-1), b in formula (2-2), c and d in formula (2-3) are each 1 or more, R 3 and R 4 The primary hydroxyl group contained in the organic group shown can form an appropriate distance with the tetrasubstituted carbon atom in the divalent linking group. 3 and R 4 The primary hydroxyl group in is not affected by the bulkiness of the tetrasubstituted carbon atom in the divalent linking group and can move freely. 3 and R 4 The primary hydroxyl groups in the divalent linking group are easy to adhere to the protective layer, and the lubricating layer containing the fluorinated ether compound represented by formula (1) is not easy to float from the protective layer. In addition, since a, b, c and d are greater than 1, the distance between the two primary hydroxyl groups contained in the divalent linking group becomes appropriate, and the primary hydroxyl groups are not easy to agglomerate with each other.

[0114] Since a in Formula (2-1) and b in Formula (2-2) are 5 or less, c and d in Formula (2-3) are each independently 4 or less and c+d is 5 or less, R 3 and R 4 The mobility of the organic radical shown will not become too high, R 3 and R 4 Therefore, the interaction between the two primary hydroxyl groups contained in the divalent linking group and the interaction between the primary hydroxyl group in the divalent linking group and R 1 or R 5 As shown in the interaction of the terminal groups, the two primary hydroxyl groups can effectively bind to the active sites on the protective layer.

[0115] In order to easily obtain these effects, a in formula (2-1) is preferably 1 to 3. b in formula (2-2) is preferably 1 to 3, and more preferably 1 or 2. In addition, c and d in formula (2-3) are preferably each independently an integer of 1 to 3, and c and d are more preferably each 1 or 2. In addition, c+d in formula (2-3) is preferably 2 to 4, and more preferably 2 or 3.

[0116] (R 2 Perfluoropolyether chain shown)

[0117] In the fluorine-containing ether compound represented by formula (1), (z+1) R 2 Each independently represents a PFPE chain. When a lubricant comprising the fluorinated ether compound of this embodiment is applied onto the protective layer to form a lubricating layer, R 2 The PFPE chains shown cover the surface of the protective layer and impart lubricity to the lubricating layer, thereby reducing the friction between the magnetic head and the protective layer. 2 The PFPE chain shown is appropriately selected depending on the performance required of the lubricant containing the fluorine-containing ether compound, etc.

[0118] In the fluorine-containing ether compound represented by formula (1), (z+1) R 2 Some or all of them may be the same, or they may be different. 2 It is preferred that all of them are the same. This is because the coating state of the protective layer with the fluorinated ether compound becomes uniform, and a lubricating layer with better adhesion is obtained. 2 Two or more R 2 The same means (z+1) R 2 Among them, the repeating units containing two or more PFPE chains have the same structure R 2 . In the same R 2 The same repeating unit structure and different average polymerization degrees are also included. 2 .

[0119] As R 2 The PFPE chain shown in the above-mentioned example includes a PFPE chain formed of a polymer or copolymer of a perfluoroalkylene oxide, etc. Examples of the perfluoroalkylene oxide include perfluoroformaldehyde, perfluoroethylene oxide, perfluoropropylene oxide, perfluoroisopropylene oxide, and perfluorobutylene oxide.

[0120] The (z+1) R in formula (1) 2 Preferably, each independently is a PFPE chain represented by the following formula (3) derived from, for example, a polymer or copolymer of a perfluoroalkylene oxide.

[0121] -(CF2) w1 -O-(CF2O) w2-(CF2CF2O) w3 -(CF2CF2CF2O) w4 -(CF2CF2CF2CF2O) w5 -(CF2) w6 -(3)

[0122] (In formula (3), w2, w3, w4, and w5 represent average polymerization degrees, and each independently represents 0 to 20. However, w2, w3, w4, and w5 are not all 0 at the same time. w1 and w6 represent average values ​​of the number of CF2, and each independently represents 1 to 3. There is no particular limitation on the order of arrangement of (CF2O), (CF2CF2O), (CF2CF2CF2O), and (CF2CF2CF2CF2O) as repeating units in formula (3).)

[0123] In formula (3), w2, w3, w4, and w5 represent average polymerization degrees, and are each independently 0 to 20, preferably 0 to 15, and more preferably 0 to 10.

[0124] In formula (3), w1 and w6 are average values ​​representing the number of CF2, and each independently represents 1 to 3. In the PFPE chain represented by formula (3), w1 and w6 are determined by the structure of the repeating unit arranged at the end of the chain structure, etc.

[0125] In formula (3), (CF2O), (CF2CF2CF2O), (CF2CF2CF2O), (CF2CF2CF2CF2O) are repeating units. There is no particular restriction on the arrangement order of the repeating units in formula (3). In addition, there is no particular restriction on the number of types of repeating units in formula (3).

[0126] The (z+1) R in formula (1) 2 Preferably, each independently is any one selected from the group consisting of PFPE chains represented by the following formula (3-1) to formula (3-4).

[0127] If (z+1) R 2 Each independently represents any one of the PFPE chains represented by formula (3-1) to (3-4), and a lubricating layer having good lubricity is obtained. 2When each is independently selected from any one of the PFPE chains represented by formula (3-1) to formula (3-4), the ratio of the number of oxygen atoms (the number of ether bonds (-O-)) in the PFPE chain to the number of carbon atoms is appropriate. Therefore, a fluorinated ether compound having a moderate hardness is obtained. Therefore, the fluorinated ether compound applied to the protective layer is not easily agglomerated on the protective layer, and a thinner lubricating layer can be formed with a sufficient coverage. In addition, the fluorinated ether compound has moderate softness, so that a lubricating layer with better chemical resistance can be formed.

[0128] -CF2-(OCF2CF2) n -(OCF2) o -OCF2-(3-1)

[0129] (In formula (3-1), n ​​and o represent the average degree of polymerization, n represents 1 to 20, and o represents 0 to 20.)

[0130] -CF2CF2-(OCF2CF2CF2) p -OCF2CF2-(3-2)

[0131] (In formula (3-2), p represents the average degree of polymerization and is 1 to 15.)

[0132] -CF2CF2CF2-(OCF2CF2CF2CF2) q -OCF2CF2CF2-(3-3)

[0133] (In formula (3-3), q represents the average degree of polymerization and is 1 to 10.)

[0134] -(CF2) w7 -O-(CF2CF2CF2O) w8 -(CF2CF2O) w9 -(CF2) w10 -(3-4)

[0135] (In formula (3-4), w8 and w9 represent average polymerization degrees, and each independently represents 1 to 20. w7 and w10 represent average values ​​of the number of CF2 groups, and each independently represents 1 to 2.)

[0136] In formula (3-1), there is no particular restriction on the arrangement order of (OCF2CF2) and (OCF2) as repeating units. In formula (3-1), the number n of (OCF2CF2) and the number o of (OCF2) may be the same or different. The PFPE chain shown in formula (3-1) may be a polymer of (OCF2CF2). In addition, the PFPE chain shown in formula (3-1) may be any of a random copolymer, a block copolymer, and an alternating copolymer composed of (OCF2CF2) and (OCF2).

[0137] In formula (3-1) to formula (3-3), since n representing the average degree of polymerization is 1 to 20, o is 0 to 20, p is 1 to 15, and q is 1 to 10, it is a fluorine-containing ether compound that can obtain a lubricating layer with good lubricity. In addition, in formula (3-1) to formula (3-3), since n and o representing the average degree of polymerization are 20 or less, p is 15 or less, and q is 10 or less, the viscosity of the fluorine-containing ether compound does not become too high, and the lubricant containing the fluorine-containing ether compound is easy to apply and is preferred. In order to obtain a fluorine-containing ether compound that is easy to wet and spread on the protective layer and easy to obtain a lubricating layer with a uniform film thickness, n, o, p, and q representing the average degree of polymerization are preferably 1 to 10, more preferably 1.5 to 8, and further preferably 2 to 7.

[0138] In formula (3-4), there is no particular restriction on the arrangement order of (CF2CF2CF2O) and (CF2CF2O) as repeating units. In formula (3-4), the number w8 of (CF2CF2CF2O) and the number w9 of (CF2CF2O) may be the same or different. Formula (3-4) may include any of a random copolymer, a block copolymer, and an alternating copolymer composed of monomer units (CF2CF2CF2O) and (CF2CF2O).

[0139] In formula (3-4), w8 and w9 representing the average degree of polymerization are each independently 1-20, preferably 1-15, and more preferably 1-10.

[0140] w7 and w10 in formula (3-4) are average values ​​representing the number of CF2, and each independently represents 1 to 2. w7 and w10 are determined by the structure of the repeating unit arranged at the end of the chain structure in the perfluoropolyether chain represented by formula (3-4).

[0141] (R 1 and R 5 terminal groups shown)

[0142] In the fluorine-containing ether compound represented by formula (1), R 1 and R 5may be the same or different, and are terminal groups having 1 to 50 carbon atoms and having at least one polar group. 1 and R 5 The terminal groups shown are preferably each independently an organic group having 1 to 20 carbon atoms, more preferably an organic group having 2 to 12 carbon atoms. When the number of carbon atoms is within the above range, the ratio of the number of carbon atoms to the number of polar groups becomes appropriate, resulting in a fluorine-containing ether compound having appropriate molecular polarity.

[0143] R 1 and R 5 The terminal groups shown in the formula (a) are preferably oxygen atoms at the ends of the adjacent methylene groups. 1 and R 5 The fluorine-containing ether compound is bonded to adjacent methylene groups via ether bonds to form a fluorine-containing ether compound having moderate hardness. Therefore, the fluorine-containing ether compound applied on the protective layer is not easily aggregated on the protective layer, and a thinner lubricating layer can be formed with sufficient coverage.

[0144] As R 1 and / or R 5 The polar groups possessed by the terminal groups shown in the figure include, for example, hydroxyl (-OH), amino (-NR 10 R 11 ; R 10 and R 11 Each is independently a hydrogen atom or an organic group. ), carboxyl (-COOH), formyl (-(C=O)H), carbonyl (-CO-), sulfonyl (-SO3H), cyano (-CN), a group having an amide bond (-NR 6 COR 7 or-CONR 8 R 9 ; R 6 , R 7 , R 8 and R 9 Each independently represents a hydrogen atom or an organic group. ) etc. It should be noted that, as shown in the above formula, the "group having an amide bond" includes both a group bonded to the carbon atom constituting the amide bond (e.g., a formamide group (-C(=O)NH2)) and a group bonded to the nitrogen atom constituting the amide bond (e.g., an acetamide group (-NHC(=O)CH3)). In the group having an amide bond, the above R 6 With R 7 can be combined with each other to form a ring, the above R 8 With R 9 The above R in the group having an amide bond may be bonded to each other to form a ring. 6 , R 7 , R 8 and R 9Preferably, they are each independently selected from a hydrogen atom, a methyl group, an ethyl group, a propyl group, and a butyl group.

[0145] In order to further improve the chemical resistance, R 1 and R 5 At least one of the terminal groups shown in the formula preferably has at least one hydroxyl group as a polar group. As a result, a fluorinated ether compound can be formed to obtain a lubricating layer with high adhesion to the protective layer, chemical resistance and adhesion suppression effect. In order to obtain a fluorinated ether compound that can form a lubricating layer with better adhesion to the protective layer, R 1 and R 5 More preferably, each independently has at least one hydroxyl group as a polar group.

[0146] In order to form a fluorinated ether compound capable of forming a lubricating layer having better adhesion to the protective layer, R 1 and R 5 The number of polar groups possessed by the terminal groups represented by is preferably 1 to 3, and more preferably 2 or 3. In order to improve the adhesion with the protective layer and to achieve a thin film of the lubricating layer, R 1 The polar groups contained in R 5 The total number of polar groups included is preferably 3 to 6. If the total number is 3 or more, the adhesion (closeness) of the lubricating layer and the protective layer containing the fluorinated ether compound is higher. In addition, if the total number is 6 or less, in the magnetic recording medium having the lubricating layer containing the fluorinated ether compound, the polarity of the fluorinated ether compound is too high and the adhesion to the magnetic head as a foreign matter (stain) can be prevented.

[0147] R 1 The number of polar groups contained and R 5 The number of polar groups included may be the same or different, but is preferably the same. 1 and R 5 Each contains 2 polar groups, or R 1 and R 5 Each contains three polar groups. In this case, the lubricant containing the fluorine-containing ether compound and the protective layer are well-balanced and closely attached. Therefore, it is easy to obtain a lubricating layer with high coverage, chemical resistance and better adhesion inhibition effect.

[0148] In R 1 and / or R 5 When containing two or more polar groups, R 1 Neutralize and / or R 5 The types of polar groups contained in may be partially the same, entirely the same, or entirely different.

[0149] In R1 and / or R 5 When two or more polar groups are included, the two or more polar groups are preferably bonded to different carbon atoms, and one or more carbon atoms are included between the carbon atoms to which the adjacent polar groups are bonded. In this case, the adjacent polar groups are bonded to form an appropriate interatomic distance compared to the case where the carbon atoms to which the adjacent polar groups are bonded are directly bonded to each other. Therefore, R 1 and / or R 5 The multiple polar groups possessed by the protective layer are oriented so as to be closely attached to the protective layer. 1 and / or R 5 The multiple polar groups possessed are less likely to aggregate and can easily form bonds with active sites on the protective layer.

[0150] R 1 and / or R 5 The terminal group shown may be an organic group having at least one polar group and further having a carbon-carbon unsaturated bond site. 1 and / or R 5 When the terminal group shown has a carbon-carbon unsaturated bond site, the terminal group is preferably an organic group having at least one selected from an aromatic hydrocarbon group, an unsaturated heterocyclic group, an alkenyl group, and an alkynyl group.

[0151] Examples of the aromatic hydrocarbon group include phenyl, methoxyphenyl, fluorophenyl, naphthyl, methoxynaphthyl, etc. The aromatic hydrocarbon group includes a group in which a substituent (such as a methoxy group or a fluoro group) is bonded to an aromatic hydrocarbon as described above.

[0152] Examples of the unsaturated heterocyclic group include pyrrolyl, pyrazolyl, methylpyrazolyl, imidazolyl, furyl, furanyl, Azolyl, iso oxazolyl, thienyl, thiazolyl, isothiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, indolinyl, benzofuranyl, benzothiophenyl, benzimidazolyl, benzo Azolyl, benzothiazolyl, benzopyrazolyl, benzisophthalic acid Examples of the unsaturated heterocyclic group include oxazolyl, benzisothiazolyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, cinnolinyl, etc. The unsaturated heterocyclic group includes the group in which a substituent (such as a methyl group) is bonded to the unsaturated heterocyclic ring as described above.

[0153] Examples of the alkenyl group include vinyl, allyl, butenyl, pentenyl, and hexenyl.

[0154] Examples of the alkynyl group include 1-propynyl, propargyl, butynyl, pentynyl, and hexynyl.

[0155] In R 1 and / or R 5When the terminal group has a carbon-carbon unsaturated bond site, it is preferred because the lubricating layer containing the fluorinated ether compound has excellent adhesion to the protective layer and the thickness can be reduced. The reason is described below.

[0156] Among the active points present in large numbers on the protective layer, there are sites where local charging occurs and sites where the charge distribution is expanded. 3 and R 4 The hydroxyl groups (and R 1 and / or R 5 In the case of having a hydroxyl group), and R 1 and / or R 5 The carbon-carbon unsaturated bond sites included in the terminal groups shown are adsorbed to different sites on the protective layer.

[0157] Specifically, R in formula (1) 3 and R 4 The hydroxyl groups (and R 1 and / or R 5 The hydroxyl group in the case of having a hydroxyl group) interacts with the locally charged site on the protective layer through hydrogen atoms via hydrogen bonds, thereby exhibiting adsorption ability. 1 and / or R 5 Since the carbon-carbon unsaturated bond site included in the terminal group has a non-localized charge, it exhibits adsorption capability by interacting with the site where the charge distribution on the protective layer is expanded.

[0158] Therefore, R in formula (1) 3 and R 4 The hydroxyl groups (and R 1 and / or R 5 In the case of having a hydroxyl group), and R 1 and / or R 5 The carbon-carbon unsaturated bond sites contained in the terminal groups shown can interact independently with the active sites on the protective layer. 1 and / or R 5 The fluorinated ether compound having a carbon-carbon unsaturated bond site at the terminal group has a more excellent adhesion between the lubricating layer and the protective layer, exhibits good chemical resistance even with a thin thickness, and has a high adhesion suppressing effect.

[0159] R 1 and R 5 The terminal groups shown preferably contain 2 or 3 polar groups, at least one of which is a hydroxyl terminal group. 1 and R 5Specifically, the terminal groups shown are preferably each independently any one of the terminal groups shown by the following formula (4-1) to formula (4-3).

[0160]

[0161] (In formula (4-1), y1 is 1 or 2, and y2 is an integer from 0 to 3. 1 is an aromatic hydrocarbon group, an unsaturated heterocyclic group, an alkenyl group, an alkynyl group, or a polar group. 1 is a polar group. 1 When X is an aromatic hydrocarbon group or an unsaturated heterocyclic group, 1 The atoms that make up the ring structure in 1 The adjacent methylene groups are bonded. 1 When X is alkenyl or alkynyl, 1 The carbon atom that forms the unsaturated bond in 1 Adjacent methylene groups are bonded.)

[0162] (In formula (4-2), y3 is an integer from 1 to 3, y4 is 0 or 1, and y5 is an integer from 0 to 3. 1 is an aromatic hydrocarbon group, an unsaturated heterocyclic group, an alkenyl group, an alkynyl group, or a polar group. 1 is a polar group. 1 When X is an aromatic hydrocarbon group or an unsaturated heterocyclic group, 1 The atoms that make up the ring structure in 1 The adjacent methylene groups are bonded. 1 When X is alkenyl or alkynyl, 1 The carbon atom that forms the unsaturated bond in 1 Adjacent methylene groups are bonded.)

[0163] (In formula (4-3), y6 is 0 or 1, y7 is an integer from 1 to 3, and y8 is an integer from 1 to 3. 1 is an aromatic hydrocarbon group, an unsaturated heterocyclic group, an alkenyl group, an alkynyl group, or a polar group. 1 is a polar group. 1 When X is an aromatic hydrocarbon group or an unsaturated heterocyclic group, 1 The atoms that make up the ring structure in 1 The adjacent methylene groups are bonded. 1 When X is alkenyl or alkynyl, 1 The carbon atom that forms the unsaturated bond in 1 Adjacent methylene groups are bonded.)

[0164] In formula (4-1) to formula (4-3), in X 1When X is an aromatic hydrocarbon group, 1 The atoms that make up the ring structure in 1 The adjacent methylene groups are bonded. 1 In the case of an aromatic hydrocarbon group, X 1 , the aromatic hydrocarbon groups exemplified above can be used.

[0165] In formula (4-1) to formula (4-3), in X 1 In the case of an unsaturated heterocyclic group, X 1 The atoms that make up the ring structure in 1 The adjacent methylene groups are bonded. 1 In the case of an unsaturated heterocyclic group, X 1 , the unsaturated heterocyclic groups exemplified above can be used.

[0166] In formula (4-1) to formula (4-3), in X 1 In the case of alkenyl, X 1 The carbon atom that forms the unsaturated bond in 1 The adjacent methylene groups are bonded. 1 In the case of alkenyl, X 1 , for example, -CH=CH2, -CH=CHR 12 (R 12 Is an organic group. ), -CR 13 =CHR 14 (R 13 , R 14 Is an organic group. ), -CR 15 =CR 16 R 17 (R 15 , R 16 , R 17 is an organic group. ) etc. 12 ~R 17 The organic groups shown are preferably hydrocarbon groups having 1 to 3 carbon atoms. In formulas (4-1) to (4-3), X 1 In the case of alkenyl, X 1 -CH=CH2 is preferred. -CH=CH2 has a suitable large volume. Therefore, 1 The lubricating layer of the fluorine-containing ether compound having a terminal group of -CH=CH2 tends to be in a state where the bulkiness of the fluorine-containing ether compound on the protective layer is low, and the adhesive property is good.

[0167] In formula (4-1) to formula (4-3), in X 1 In the case of an alkynyl group, X 1 The carbon atom that forms the unsaturated bond in 1The adjacent methylene groups are bonded. 1 In the case of an alkynyl group, as X 1 , for example, -C≡CH, -C≡CR 18 (R 18 is an organic group. ) etc. 18 The organic group represented by is preferably a hydrocarbon group having 1 to 3 carbon atoms. In formulas (4-1) to (4-3), X 1 In the case of an alkynyl group, in order to form a terminal group with a suitable bulkiness, X is preferably 1 -C≡CH.

[0168] In formula (4-1) to formula (4-3), in X 1 In the case of a polar group, X 1 The polar groups exemplified above can be used. Among these polar groups, X 1 Preferably, it is a hydroxyl group, a group having an amide bond, or a cyano group. 1 If the lubricating layer is formed on the protective layer using a lubricant containing the hydroxyl group, the group having an amide bond, or the cyano group, a more suitable interaction occurs between the lubricating layer and the protective layer.

[0169] In formula (4-1) to formula (4-3), X 1 In the case of a polar group, a lubricating layer containing a fluorine-containing ether compound is preferred because it has better adhesion with the protective layer and can be made thinner. The reason is described below.

[0170] In formula (4-1) to formula (4-3), the secondary hydroxyl group in formula (4-1) to formula (4-3) and X 1 The bond is via a divalent organic group which may contain an ether bond. 1 is a polar group, and the secondary hydroxyl group in formula (4-1) to formula (4-3) and X 1 As a result, the distance between the secondary hydroxyl group and X in formula (4-1) to formula (4-3) is appropriate. 1 The polar groups shown are not easily blocked from binding to the active sites on the protective layer by other polar groups. 1 The polar groups shown do not easily aggregate.

[0171] Therefore, the secondary hydroxyl group and X in formula (4-1) to formula (4-3) 1 The polar groups shown can be adsorbed independently on the active sites on the protective layer. As a result, the X 1The lubricating layer of the fluorinated ether compound having a terminal group as a polar group has better adhesion with the protective layer, exhibits good chemical resistance even with a thin thickness, and has a high adhesion suppressing effect.

[0172] In the above, X in formula (4-1) to formula (4-3) 1 Any of a hydroxyl group, a group having an amide bond, a cyano group, and -CH=CH2 is preferred because it is a fluorine-containing ether compound that can form a lubricating layer having a higher coverage rate, and is more excellent in chemical resistance and adhesion suppression effect.

[0173] In the terminal group represented by formula (4-1), y1 is 1 or 2, and y2 is an integer from 0 to 3. When y1 is 1, X 1 is a polar group, and formula (4-1) has two polar groups. In this case, since formula (4-1) has two polar groups, a lubricating layer with good adhesion to the protective layer can be formed. When y1 is 2, X 1 It may be any one of an aromatic hydrocarbon group, an unsaturated heterocyclic group, an alkenyl group, an alkynyl group, and a polar group. 1 When X is any one of an aromatic hydrocarbon group, an unsaturated heterocyclic group, an alkenyl group, and an alkynyl group, Formula (4-1) also has two polar groups. Therefore, a lubricating layer having good adhesion to the protective layer can be formed. 1 is an aromatic hydrocarbon group, an unsaturated heterocyclic group, an alkenyl group or an alkynyl group. Therefore, when the adhesion of the two hydroxyl groups contained in formula (4-1) to the protective layer is not impaired, X 1 The carbon-carbon unsaturated bond sites interact with the π-π of the protective layer, thereby forming a lubricating layer with excellent chemical resistance and adhesion inhibition effect. 1 When it is a polar group, the formula (4-1) has three polar groups. Therefore, a lubricating layer having better adhesion to the protective layer can be formed.

[0174] In the terminal group represented by formula (4-1), y2 is an integer of 0 to 3. For the terminal group represented by formula (4-1), since X in formula (4-1) 1 is a polar group, X 1 The distance to the secondary hydroxyl group in formula (4-1) is not too close, so the polar group in formula (4-1) is not easy to aggregate. 1 In the case of a polar group, for X 1 The distance from the secondary hydroxyl group in formula (4-1) becomes more appropriate, and y2 is preferably 1 or more. For the terminal group represented by formula (4-1), since y2 is 3 or less, X in formula (4-1) 1The mobility of will not become too high, and each polar group possessed by the terminal group can be sufficiently adhered to the protective layer. y2 is more preferably 2 or less.

[0175] In the terminal group represented by formula (4-2), y3 is an integer of 1 to 3. When y4 is 0, X 1 Since y3 is an integer greater than 1, when y4 is 0, X 1 The distance from the secondary hydroxyl group in formula (4-2) becomes appropriate, even if X 1 It is a polar group, and the polar group in formula (4-2) is not easy to agglomerate. In addition, since y3 is an integer greater than 1, when y4 is 1, the distance between the secondary hydroxyl groups in formula (4-2) will not become too close, and the secondary hydroxyl groups in formula (4-2) are not easy to agglomerate. For the terminal group shown in formula (4-2), since y3 is less than 3, the mobility of the terminal group shown in formula (4-2) will not become too high, and each polar group possessed by the terminal group can be fully fitted with the protective layer. y3 is preferably less than 2.

[0176] In the terminal group represented by formula (4-2), y4 is 0 or 1. When y4 is 0, X 1 is a polar group, and formula (4-2) has two polar groups. In this case, since formula (4-2) has two polar groups, a lubricating layer with good adhesion to the protective layer can be formed. When y4 is 1, X 1 It may be any one of an aromatic hydrocarbon group, an unsaturated heterocyclic group, an alkenyl group, an alkynyl group, and a polar group. 1 When X is any one of an aromatic hydrocarbon group, an unsaturated heterocyclic group, an alkenyl group or an alkynyl group, the formula (4-2) also has two polar groups. Therefore, a lubricating layer having good adhesion to the protective layer can be formed. 1 is an aromatic hydrocarbon group, an unsaturated heterocyclic group, an alkenyl group or an alkynyl group. Therefore, when the adhesion of the two hydroxyl groups contained in formula (4-2) to the protective layer is not impaired, X 1 The carbon-carbon unsaturated bond site interacts with the π-π of the protective layer, thereby forming a lubricating layer with excellent chemical resistance and adhesion inhibition effect. 1 When it is a polar group, the formula (4-2) has three polar groups. Therefore, a lubricating layer having excellent adhesion to the protective layer can be formed.

[0177] In the terminal group represented by formula (4-2), y5 is an integer of 0 to 3. For the terminal group represented by formula (4-2), since even if X in formula (4-2) 1 is a polar group, X 1The distance to the secondary hydroxyl group in formula (4-2) is not too close, so the polar group in formula (4-2) is not easy to aggregate. 1 In the case of a polar group, for X 1 The distance from the secondary hydroxyl group in formula (4-2) becomes more appropriate, and y5 is preferably 1 or more. In addition, when y4 is 0, even if y5 is 0, y3 methylene groups are present to form a polar group X. 1 The distance from the secondary hydroxyl group in formula (4-2) becomes appropriate. When y4 is 0, if y5 is 1 or more, the polar group X is formed by y3+y5 methylene groups. 1 The distance from the secondary hydroxyl group in formula (4-2) is more appropriate and therefore preferred. For the terminal group represented by formula (4-2), since y5 is 3 or less, X in formula (4-2) 1 The mobility of the terminal group will not become too high, and each polar group possessed by the terminal group can be sufficiently adhered to the protective layer. y5 is preferably 2 or less.

[0178] In the terminal group represented by formula (4-3), y6 is 0 or 1. When y6 is 0, X 1 is a polar group, and formula (4-3) has two polar groups. In this case, since formula (4-3) has two polar groups, a lubricating layer with good adhesion to the protective layer can be formed. When y6 is 1, X 1 It may be any one of an aromatic hydrocarbon group, an unsaturated heterocyclic group, an alkenyl group, an alkynyl group, and a polar group. 1 When X is an aromatic hydrocarbon group, an unsaturated heterocyclic group, an alkenyl group or an alkynyl group, the formula (4-3) also has two polar groups. Therefore, a lubricating layer having good adhesion to the protective layer can be formed. 1 is an aromatic hydrocarbon group, an unsaturated heterocyclic group, an alkenyl group or an alkynyl group. Therefore, when the adhesion of the two hydroxyl groups contained in formula (4-3) to the protective layer is not impaired, X 1 The carbon-carbon unsaturated bond site interacts with the π-π of the protective layer, thereby forming a lubricating layer with excellent chemical resistance and adhesion inhibition effect. 1 When it is a polar group, the formula (4-3) has three polar groups. Therefore, a lubricating layer having excellent adhesion to the protective layer can be formed.

[0179] In the terminal group represented by formula (4-3), y7 is an integer of 1 to 3. Since y7 is greater than 1, when y6 is 1, the distance between the secondary hydroxyl groups in formula (4-3) will not become too close. Therefore, the secondary hydroxyl groups in formula (4-3) are not easy to agglomerate. For the terminal group represented by formula (4-3), since y7 is less than 3, the mobility of the terminal group represented by formula (4-3) will not become too high, and each polar group possessed by the terminal group can be fully adhered to the protective layer. y7 is preferably less than 2.

[0180] In the terminal group represented by formula (4-3), y8 is an integer of 1 to 3. In the terminal group represented by formula (4-3), since y8 is 1 or more, even if X in formula (4-3) 1 is a polar group, X 1 The distance to the secondary hydroxyl group in formula (4-3) will not become too close. Therefore, the polar group in formula (4-3) is not easy to aggregate. 1 In the case of a polar group, for X 1 The distance from the secondary hydroxyl group in formula (4-3) becomes more appropriate, and y8 is preferably 2 or more. For the terminal group represented by formula (4-3), since y8 is 3 or less, X in formula (4-3) 1 The mobility of the terminal group will not become too high, and the polar groups possessed by the terminal group can be sufficiently adhered to the protective layer.

[0181] In the fluorine-containing ether compound represented by formula (1), R 1 With R 5 They can be the same or different. 1 With R 5 If the coating state of the protective layer with the fluorinated ether compound is the same, the coating state of the protective layer with the fluorinated ether compound becomes more uniform, and a lubricating layer with better adhesion can be formed.

[0182] In the fluorine-containing ether compound represented by formula (1), R 1 and R 5 The type of the terminal group shown above can be appropriately selected depending on the performance required of the lubricant containing the fluorine-containing ether compound, etc.

[0183] In the fluorine-containing ether compound represented by formula (1), z is preferably 1, and R 1 With R 5 Same, 2 R 2 The reason is that it is a fluorine-containing ether compound that is easy to synthesize.

[0184] In the fluorine-containing ether compound represented by formula (1), z is preferably 2, and R 1 With R 5 Same, 3 Rs 2The reason is that it is a fluorine-containing ether compound that is easy to synthesize. Further, when z is 2, preferably 2 -CR 3 R 4 -same. The reason is that it is easier to synthesize fluorine-containing ether compounds.

[0185] Specifically, the fluorinated ether compound represented by (1) is preferably any one of the compounds represented by the following formulas (1A) to (1T) and (2A) to (2T). When the compound represented by formula (1) is any one of the compounds represented by the following formulas (1A) to (1T) and (2A) to (2T), the raw material is easy to obtain, and a lubricating layer having excellent adhesion even with a thin thickness, and having better chemical resistance and adhesion suppression effect can be formed.

[0186] The compounds represented by the following formulae (1A) to (1T) and (2A) to (2T) all have R in formula (1): 2 The (z+1) PFPE chains shown are all identical.

[0187] In the compounds represented by the following formulae (1A) to (1T) and (2A) to (2T), Rf1 and Rf2 representing the PFPE chain each have the following structure. That is, in the compounds represented by the following formulae (1A) to (1F), (1J), (1K), (1N), (1P) to (1T), (2A) to (2F), (2J), (2K), (2N), (2P) to (2T), Rf2 is the PFPE chain represented by the above formula (3-2). In the compounds represented by the following formulae (1G) to (1I), (1L), (1M), (1O), (2G) to (2I), (2L), (2M), (2O), Rf1 is the PFPE chain represented by the above formula (3-1). Note that j and k in Rf1 and l in Rf2 representing PFPE chains in Formulae (1A) to (1T) and (2A) to (2T) are values ​​indicating average polymerization degrees and are not necessarily integers.

[0188]

[0189]

[0190] (In the two Rf2 in formula (1A), l represents the average degree of polymerization and is 1 to 15. The l in the two Rf2 may be the same or different.)

[0191] (In the two Rf2 in formula (1B), l represents the average degree of polymerization and is 1 to 15. The l in the two Rf2 may be the same or different.)

[0192] (In the two Rf2 in formula (1C), l represents the average degree of polymerization and is 1 to 15. The l in the two Rf2 may be the same or different.)

[0193] (In the two Rf2 in formula (1D), l represents the average degree of polymerization and is 1 to 15. The l in the two Rf2 may be the same or different.)

[0194] (In the two Rf2 in formula (1E), l represents the average degree of polymerization and is 1 to 15. The l in the two Rf2 may be the same or different.)

[0195]

[0196] (In the two Rf2 in formula (1F), l represents the average degree of polymerization and is 1 to 15. The l in the two Rf2 may be the same or different.)

[0197] (In the two Rf1 in formula (1G), j and k represent the average degree of polymerization, j represents 1 to 20, and k represents 0 to 20. j and k in the two Rf1 may be the same or different.)

[0198] (In the two Rf1 in formula (1H), j and k represent the average degree of polymerization, j represents 1 to 20, and k represents 0 to 20. j and k in the two Rf1 may be the same or different.)

[0199] (In the two Rf1 in formula (1I), j and k represent the average degree of polymerization, j represents 1 to 20, and k represents 0 to 20. j and k in the two Rf1 may be the same or different.)

[0200] (In the two Rf2 in formula (1J), l represents the average degree of polymerization and is 1 to 15. The l in the two Rf2 may be the same or different.)

[0201]

[0202] (In the two Rf2 in formula (1K), l represents the average degree of polymerization and is 1 to 15. The l in the two Rf2 may be the same or different.)

[0203] (In the two Rf1 in formula (1L), j and k represent the average degree of polymerization, j represents 1 to 20, and k represents 0 to 20. j and k in the two Rf1 may be the same or different.)

[0204] (In the two Rf1 in formula (1M), j and k represent the average degree of polymerization, j represents 1 to 20, and k represents 0 to 20. j and k in the two Rf1 may be the same or different.)

[0205] (In the two Rf2 in formula (1N), l represents the average degree of polymerization and is 1 to 15. The l in the two Rf2 may be the same or different.)

[0206] (In the two Rf1 in formula (1O), j and k represent the average degree of polymerization, j represents 1 to 20, and k represents 0 to 20. j and k in the two Rf1 may be the same or different.)

[0207]

[0208] (In the two Rf2 in formula (1P), l represents the average degree of polymerization and is 1 to 15. The l in the two Rf2 may be the same or different.)

[0209] (In the two Rf2 in formula (1Q), l represents the average degree of polymerization and is 1 to 15. The l in the two Rf2 may be the same or different.)

[0210] (In the two Rf2 in the formula (1R), l represents the average degree of polymerization and is 1 to 15. The l in the two Rf2 may be the same or different.)

[0211] (In the two Rf2 in formula (1S), l represents the average degree of polymerization and is 1 to 15. The l in the two Rf2 may be the same or different.)

[0212] (In the two Rf2 in formula (1T), l represents the average degree of polymerization and is 1 to 15. The l in the two Rf2 may be the same or different.)

[0213]

[0214] (In the three Rf2 in formula (2A), l represents the average degree of polymerization and is 1 to 15. The l in the three Rf2 may be different from each other, or may be partially or entirely the same.)

[0215] (In the three Rf2 in formula (2B), l represents the average degree of polymerization and is 1 to 15. The l in the three Rf2 may be different from each other, or may be partially or entirely the same.)

[0216] (In the three Rf2 in formula (2C), l represents the average degree of polymerization and is 1 to 15. The l in the three Rf2 may be different from each other, or may be partially or entirely the same.)

[0217] (In the three Rf2 in formula (2D), l represents the average degree of polymerization and is 1 to 15. The l in the three Rf2 may be different from each other, or may be partially or entirely the same.)

[0218] (In the three Rf2 in formula (2E), l represents the average degree of polymerization and is 1 to 15. The l in the three Rf2 may be different from each other, or may be partially or entirely the same.)

[0219]

[0220] (In the three Rf2 in formula (2F), l represents the average degree of polymerization and is 1 to 15. The l in the three Rf2 may be different from each other, or may be partially or entirely the same.)

[0221] (In the formula (2G), among the three Rf1, j and k represent the average degree of polymerization, j represents 1 to 20, and k represents 0 to 20. The j and k in the three Rf1 may be different from each other, or may be partially or entirely the same.)

[0222] (In the three Rf1 in formula (2H), j and k represent the average degree of polymerization, j represents 1 to 20, and k represents 0 to 20. The j and k in the three Rf1 may be different from each other, or may be partially or entirely the same.)

[0223] (In the three Rf1 in formula (2I), j and k represent the average degree of polymerization, j represents 1 to 20, and k represents 0 to 20. The j and k in the three Rf1 may be different from each other, or may be partially or entirely the same.)

[0224] (In the three Rf2 in formula (2J), l represents the average degree of polymerization and is 1 to 15. The l in the three Rf2 may be different from each other, or may be partially or entirely the same.)

[0225]

[0226] (In the three Rf2 in formula (2K), l represents the average degree of polymerization and is 1 to 15. The l in the three Rf2 may be different from each other, or may be partially or entirely the same.)

[0227] (In the three Rf1 in formula (2L), j and k represent the average degree of polymerization, j represents 1 to 20, and k represents 0 to 20. The j and k in the three Rf1 may be different from each other, or may be partially or entirely the same.)

[0228] (In the three Rf1 in formula (2M), j and k represent the average degree of polymerization, j represents 1 to 20, and k represents 0 to 20. The j and k in the three Rf1 may be different from each other, or may be partially or entirely the same.)

[0229] (In the three Rf2 in formula (2N), l represents the average degree of polymerization and is 1 to 15. The l in the three Rf2 may be different from each other, or may be partially or entirely the same.)

[0230] (In the three Rf1 in formula (2O), j and k represent the average degree of polymerization, j represents 1 to 20, and k represents 0 to 20. The j and k in the three Rf1 may be different from each other, or may be partially or entirely the same.)

[0231]

[0232] (In the three Rf2 in formula (2P), l represents the average degree of polymerization and is 1 to 15. The l in the three Rf2 may be different from each other, or may be partially or entirely the same.)

[0233] (In the three Rf2 in formula (2Q), l represents the average degree of polymerization and is 1 to 15. The l in the three Rf2 may be different from each other, or may be partially or entirely the same.)

[0234] (In the three Rf2 in formula (2R), l represents the average degree of polymerization and is 1 to 15. The l in the three Rf2 may be different from each other, or may be partially or entirely the same.)

[0235] (In the three Rf2 in formula (2S), l represents the average degree of polymerization and is 1 to 15. The l in the three Rf2 may be different from each other, or may be partially or entirely the same.)

[0236] (In the three Rf2 in formula (2T), l represents the average degree of polymerization and is 1 to 15. The l in the three Rf2 may be different from each other, or may be partially or entirely the same.)

[0237] The number average molecular weight (Mn) of the fluorinated ether compound of the present embodiment is preferably in the range of 500 to 10,000, more preferably in the range of 500 to 5,000, and particularly preferably in the range of 1,000 to 3,000. If the number average molecular weight is above 500, the lubricant containing the fluorinated ether compound of the present embodiment is not easy to evaporate, and the lubricant can be prevented from evaporating and being transferred to the magnetic head. In addition, if the number average molecular weight is below 10,000, the viscosity of the fluorinated ether compound is appropriate, and a thin lubricating layer can be easily formed by applying the lubricant containing the fluorinated ether compound. If the number average molecular weight is below 5,000, it becomes a viscosity that is easy to handle when applied to a lubricant, and is therefore more preferred.

[0238] The number average molecular weight (Mn) of the fluorinated ether compound was determined by using AVANCE III 400 manufactured by Bruker Biospin Co., Ltd. 1 H-NMR and 19 Specifically, the value measured by 19The 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. In the measurement of NMR (nuclear magnetic resonance), the sample is diluted in a single or mixed solvent such as hexafluorobenzene, d-acetone, d-tetrahydrofuran, etc. and used for the measurement. 19 The standard of the F-NMR chemical shift was the peak of hexafluorobenzene at -164.7 ppm. 1 The standard of H-NMR chemical shift was set at 2.2 ppm based on the peak of acetone.

[0239] The fluorine-containing ether compound of the present embodiment is preferably subjected to molecular weight fractionation by an appropriate method so that the molecular weight distribution (ratio of weight average molecular weight (Mw) / number average molecular weight (Mn)) is 1.3 or less.

[0240] In the present embodiment, the method for molecular weight fractionation is not particularly limited, and for example, molecular weight fractionation using silica gel column chromatography, gel permeation chromatography (GPC), or the like, molecular weight fractionation using supercritical extraction, or the like can be used.

[0241] "Manufacturing method"

[0242] The method for producing the fluorine-containing ether compound of the present embodiment is not particularly limited, and the fluorine-containing ether compound of the present embodiment can be produced by a conventionally known production method. The fluorine-containing ether compound of the present embodiment can be produced, for example, by the production method described below.

[0243] <First Manufacturing Method>

[0244] In the manufacturing formula (1), z is 1, R 1 With R 5 The same, and R 2 In the case of a fluorinated ether compound having two identical PFPE chains, the production method represented by the following formula (5) can be used.

[0245]

[0246] (In formula (5), PG represents a protecting group. X represents a (pseudo)halogen group. R 3 'With R 4 'Each represents R in formula (1) 3 and R 4 The structure of the hydroxyl group contained is bonded to the protective group, and has a group of carbon atoms bonded to the tetrasubstituted carbon atom. R represents R in formula (1): 1 and R 5 Partial structure of the terminal group shown. )

[0247] (First reaction)

[0248] Prepare R in formula (1) 2The corresponding PFPE chain has a fluorine compound (I) having hydroxymethyl groups (-CH2OH) at both ends. A suitable protecting group (PG) is introduced into the hydroxymethyl group at one end of the fluorine compound (I) to obtain the first intermediate compound (II).

[0249] (Second reaction)

[0250] Next, make both equivalent to -CR 3 R 4 -Partial structure (-CR 3 'R 4 The compound (III) having two (pseudo) halogen groups (X) and a hydroxymethyl group (-CH2OH) not substituted by a protecting group (PG) in the first intermediate compound (II) obtained by the first reaction is reacted. The reaction ratio of the first intermediate compound (II) to the compound (III) is preferably about 2:1 (molar ratio). By reacting the obtained intermediate compound (II) with a hydroxymethyl group (-CH2OH) not substituted by a protecting group (PG) 3 R 4 -Partial structure (-CR 3 'R 4 '-) linker and two perfluoropolyether chains (R 2 ) are subjected to deprotection of the protecting groups (PG) at both ends of the compound (IV) to produce the second intermediate compound (V).

[0251] As the (pseudo)halogen group (X) in the above compound (III), for example, at least one selected from the group consisting of chloro, bromo, iodo, p-toluenesulfonyloxy, methanesulfonyloxy, trifluoromethanesulfonyloxy, perfluoroalkylsulfonyloxy and nitrobenzenesulfonyloxy can be used.

[0252] (Third reaction)

[0253] Then, let R in formula (1) 1 (=R 5 The epoxy compound (VI) having a group (R) of formula (1) reacts with the hydroxyl groups at both ends of the second intermediate compound (V). R in the epoxy compound (VI) has the same 1 or R 5 By performing the third reaction, a structure having a terminal group corresponding to -CR is obtained. 3 R 4 -Partial structure (-CR 3 'R 4 '-) linker and two perfluoropolyether chains (R 2 ) has two ends with R 1 (=R 5 ) is a third intermediate compound (VII) having a corresponding terminal group.

[0254] (Fourth reaction)

[0255] Finally, the protecting group contained in the third intermediate compound (VII) obtained by the third reaction is deprotected by an appropriate method to obtain the fluorine-containing ether compound (VIII).

[0256] By carrying out the above steps, it is possible to produce a compound in which z is 1 and R 1 With R 5 The two terminal groups shown are identical, and R 2 The two PFPE chains shown are identical fluorinated ether compounds.

[0257] When the fluorine-containing ether compound of the present embodiment is produced by the above-mentioned first production method, the compound (III) used in the second reaction includes, for example, compounds represented by the following formulas (A) to (S). The compound (III) can be produced by a known method. The compound (III) can be purchased from a commercial product.

[0258]

[0259] (In formula (A) to formula (S), X is a (pseudo)halogen group, and two Xs in the same molecule may be the same or different. In formula (A) to formula (R), Bn represents a benzyl group.)

[0260] (Method for producing compound (III))

[0261] Compound (III) can be synthesized, for example, using the production method represented by the following formula (6).

[0262]

[0263] (In formula (6), Et represents an ethyl group. X represents a (pseudo)halogen group. R 3 'With R 4 'Each represents R in formula (1) 3 and R 4 The structure of the hydroxyl group contained is combined with a protective group, and has a group of carbon atoms combined with a tetrasubstituted carbon atom. )

[0264] First, use the equivalent of R 3 'Organic (pseudo)halides (XR 3 '), alkylation of the malonate (III-1) is performed to obtain the intermediate compound (III-2). Next, 4 'Organic (pseudo)halides (XR 4') is further reacted with the intermediate compound (III-2). Thus, an intermediate compound (III-3) containing four substituted carbon atoms is obtained. Next, the two ester groups in the intermediate compound (III-3) are reduced to hydroxymethyl groups to obtain an intermediate compound (III-4). Then, the hydroxyl group of the obtained intermediate compound (III-4) is converted into a suitable (pseudo) halogen group. Through the above steps, the compound (III) used in the second reaction is obtained.

[0265] In this embodiment, when the 3 After the organic group of ' is combined with the malonic acid ester (III-1), the equivalent of R 4 ' organic group to construct a tetrasubstituted carbon atom. However, it is also possible to make the equivalent of R 4 After the organic group of ' is combined with the malonic acid ester (III-1), the equivalent of R 3 ' organic group combines to construct a four-substituted carbon atom.

[0266] In the case of using the first manufacturing method to manufacture R in the formula (1) 3 and R 4 In the case of a fluorinated ether compound in which one of the compounds has an oxygen atom bonded to a tetra-substituted carbon atom and the other has a carbon atom bonded to a tetra-substituted carbon atom, as the compound (III) used in the second reaction, for example, a substance synthesized by the production method represented by the following formula (7) can be used.

[0267]

[0268] (In formula (7), Et represents an ethyl group. X represents a (pseudo)halogen group. R 3 'Represented as 3 The included hydroxyl group is combined with the structure of the protective group, and the group other than the oxygen atom combined with the tetrasubstituted carbon atom. 4 'Represented as 4 The structure of the hydroxyl group contained is combined with a protective group, and has a group of carbon atoms combined with a tetrasubstituted carbon atom. )

[0269] First, use the equivalent of R 3 'Organic (pseudo)halides (XR 3 '), alkylation of 2-hydroxymalonic acid ester (III-5) was performed to obtain intermediate compound (III-6). Next, 4 'Organic (pseudo)halides (XR 4') is further reacted with the intermediate compound (III-6). Thus, an intermediate compound (III-7) containing four substituted carbon atoms is obtained. Next, the two ester groups in the intermediate compound (III-7) are reduced to hydroxymethyl groups to obtain an intermediate compound (III-8). Then, the hydroxyl group of the obtained intermediate compound (III-8) is converted into an appropriate (pseudo) halogen group. In the above process, R in formula (1) is prepared 3 and R 4 In the case of a fluorine-containing ether compound in which one of them has an oxygen atom bonded to a tetra-substituted carbon atom and the other has a carbon atom bonded to a tetra-substituted carbon atom, compound (III) used in the second reaction is obtained.

[0270] In this embodiment, when the 3 After the organic group of ' is combined with 2-hydroxymalonic acid ester (III-5), the equivalent of R 4 ' organic group to construct a tetrasubstituted carbon atom. However, it is also possible to make the equivalent of R 4 After the organic group of ' is combined with 2-hydroxymalonic acid ester (III-5), the equivalent of R 3 ' organic group combines to construct a four-substituted carbon atom.

[0271] As the equivalent of R used in the preparation of compound (III) 3 ' and R 4 As the (pseudo)halide of an organic group of ', for example, compounds represented by the following formula (III-9) to (III-13) can be used.

[0272]

[0273] (In formula (III-9) to formula (III-13), Bn represents a benzyl group.)

[0274] When the fluorinated ether compound of the present embodiment is produced by using the first production method, the fluorinated ether compound having R in the formula (1) used in the third reaction 1 (=R 5 ) can be produced, for example, by the method shown in the following formula (8). That is, as shown in the following formula (8), the epoxy compound (VI) having a group (R) of the formula (1) can be used. 1 or R 5 It can be produced by reacting an alcohol having an R group as a partial structure of the terminal group shown in FIG. 1 with a halogen compound having an epoxy group (a bromine compound in the following formula (8)).

[0275]

[0276] (In formula (8), R represents R in formula (1) 1 and R 5 Partial structure of the terminal group shown. )

[0277] The above-mentioned epoxy compound (VI) can also be produced by the method shown below. That is, as shown in the following formula (9), R in the formula (1) is 1 or R 5 The alcohol of the R group of the partial structure of the terminal group shown in the figure is subjected to addition reaction with allyl glycidyl ether. Then, m-chloroperbenzoic acid (mCPBA) is allowed to act to oxidize the unsaturated bond site contained in the compound obtained by the addition reaction. By performing the above steps, the epoxy compound (VI) is obtained.

[0278]

[0279] (In formula (9), R represents R in formula (1) 1 and R 5 Partial structure of the terminal group shown. )

[0280] The above-mentioned epoxy compound (VI) can also be produced by the method shown below. That is, as shown in the following formula (10), R in the formula (1) is 1 or R 5 The alcohol of the R group of the partial structure of the terminal group shown is reacted with a halogen compound having an alkenyl group (a bromine compound in the following formula (10)). Then, m-chloroperbenzoic acid (mCPBA) is allowed to act to oxidize the unsaturated bond site contained in the obtained compound. By performing the above steps, an epoxy compound (VI) is obtained.

[0281]

[0282] (In formula (10), R represents R in formula (1) 1 and R 5 Partial structure of the terminal group shown. )

[0283] As the epoxy compound (VI), a commercial item may be purchased and used.

[0284] When the fluorinated ether compound of the present embodiment is produced by using the first production method, the epoxy compound (VI) may be prepared by replacing R 1 or R 5 The polar group of the R group of the partial structure of the terminal group shown is protected with an appropriate protecting group and then reacted with the second intermediate compound (V) in the third reaction.

[0285] As a first production method, the following method may be used instead of the method represented by the above formula (5).

[0286] (First reaction)

[0287] The above-mentioned epoxy compound (VI) is reacted with the hydroxymethyl group (-CH2OH) at one end of the fluorine-based compound (I) in the formula (5) to obtain a first intermediate compound.

[0288] (Second reaction)

[0289] Next, the compound (III) is reacted with the hydroxymethyl group at one end of the first intermediate compound obtained by the first reaction. The reaction ratio of the first intermediate compound to the compound (III) is preferably about 2:1 (molar ratio). The protecting group contained in the obtained compound is deprotected by an appropriate method.

[0290] By carrying out the above steps, it is possible to produce a compound in which z is 1 and R 1 With R 5 The two terminal groups shown are identical, and R 2 The two PFPE chains shown are identical fluorinated ether compounds.

[0291] <Second manufacturing method>

[0292] In the manufacturing formula (1), z is 1, and R 1 With R 5 The terminal group shown, or R 2 When at least one of the two PFPE chains shown is a different fluorine-containing ether compound, the production method shown below can be used.

[0293] (First reaction)

[0294] First, prepare to 1 Side R 2 The corresponding PFPE chain has hydroxymethyl (-CH2OH) at both ends, which is equivalent to R 1 The epoxy compound of the partial structure of is reacted with one of the terminal hydroxyl groups. Thus, the 1 Side R 2 One end of the corresponding PFPE chain has a 1 The first intermediate compound of the group.

[0295] (Second reaction)

[0296] Next, the first intermediate compound is reacted with the compound (III) in the first production method. The reaction ratio of the first intermediate compound to the compound (III) is preferably about 1:1 (molar ratio).1 Side R 2 One end of the corresponding PFPE chain has 1 The corresponding groups are configured at the other end in sequence with -CR 3 R 4 -partial structure and a (pseudo)halogenated second intermediate compound.

[0297] (Third reaction)

[0298] Next, the same operation as the first intermediate compound was performed to prepare 5 Side R 2 One end of the corresponding PFPE chain has a 5 A third intermediate compound of the group.

[0299] Then, the second intermediate compound is reacted with the third intermediate compound. Thus, a product having a moiety corresponding to -CR between two PFPE chains is obtained. 3 R 4 -The two ends of the chain structure of the linking group of the partial structure have 1 and R 5 A fourth intermediate compound having a corresponding terminal group.

[0300] (Fourth reaction)

[0301] Finally, the protecting group contained in the obtained fourth intermediate compound is deprotected by an appropriate method.

[0302] By sequentially performing the above steps, it is possible to produce a compound wherein z in formula (1) is 1 and R 1 With R 5 The terminal group shown, or R 2 At least one of the two PFPE chains shown is a different fluorinated ether compound.

[0303] <Third Manufacturing Method>

[0304] In the manufacturing formula (1), z is 2, R 2 The three PFPE chains shown are identical, with two linkers containing -CR 3 R 4 - the same groups as shown, R 1 With R 5 In the case of a fluorinated ether compound having the same terminal group as shown, or in the case of a compound having the same terminal group as shown, z in the production formula (1) is 2, R 2 Among the three PFPE chains shown, only the central R 2 Different, the -CR contained in the two linkers 3 R 4 - the same groups as shown, R 1With R 5 In the case of the fluorine-containing ether compounds having the same terminal groups as shown above, the production method shown below can be used.

[0305] (First reaction)

[0306] Prepare R at the center of the molecule in formula (1) 2 The corresponding PFPE chain has a fluorine compound with hydroxymethyl (-CH2OH) at both ends. Next, the hydroxyl groups of the hydroxymethyl groups at both ends of the fluorine compound are reacted with the compound (III) in the first manufacturing method. The reaction ratio of the fluorine compound to the compound (III) is preferably about 1:2 (molar ratio). Thus, R in the center of the molecule in formula (1) is obtained. 2 The two ends of the corresponding perfluoropolyether chain are respectively equipped with -CR 3 R 4 -partial structure and a first intermediate compound of a (pseudo)halogen group.

[0307] (Second reaction)

[0308] Next, the same operation as the first reaction in the first production method is carried out to produce a 1 or R 5 Adjacent R 2 (R not located in the center of the molecule 2 ) A second intermediate compound having an appropriate protecting group introduced into one end of the corresponding PFPE chain.

[0309] (Third reaction)

[0310] Then, the first intermediate compound and the second intermediate compound are mixed and reacted. Then, the obtained product having a structure corresponding to -CR 3 R 4 The protective groups at both ends of the compound having the two linking groups of the partial structure of - and the three PFPE chains are deprotected to produce the third intermediate compound. The reaction ratio of the first intermediate compound to the second intermediate compound is preferably about 1:2 (molar ratio).

[0311] (Fourth reaction)

[0312] Next, the epoxy compound (VI) in the first production method is reacted with the hydroxyl groups at both ends of the third intermediate compound obtained by the third reaction. By performing the fourth reaction, a compound having a structure corresponding to -CR 3 R 4 - The two connecting groups of the partial structure and the two ends of the chain structure of the three PFPE chains have 1 (=R 5) is a fourth intermediate compound having a corresponding terminal group.

[0313] (Fifth Reaction)

[0314] Finally, the protecting group contained in the fourth intermediate compound obtained by the fourth reaction is deprotected by an appropriate method.

[0315] By carrying out the above steps, it is possible to produce a compound in which z in formula (1) is 2 and R 2 The three PFPE chains shown are identical, with two linkers containing -CR 3 R 4 - the same groups as shown, R 1 With R 5 The fluorinated ether compound having the same terminal group as shown, or z in formula (1) is 2, R 2 Among the three PFPE chains shown, only the central R 2 Different, the -CR contained in the two linkers 3 R 4 - the same groups as shown, R 1 With R 5 The fluorine-containing ether compounds shown have the same terminal groups.

[0316] In the third production method described above, the second reaction is performed after the first reaction, but the first reaction may be performed after the second reaction.

[0317] Furthermore, as a third production method, the following method may be used instead of the above-mentioned second reaction to fifth reaction.

[0318] (Second reaction)

[0319] Prepare R in formula (1) 1 or R 5 Adjacent R 2 (R not located in the center of the molecule 2 ) A fluorine-based compound having hydroxymethyl groups (-CH2OH) at both ends of the corresponding PFPE chain. The epoxy compound (VI) in the first production method is reacted with the hydroxymethyl group at one end of the fluorine-based compound to obtain a second intermediate compound.

[0320] (Third reaction)

[0321] Next, the first intermediate compound obtained by the first reaction is reacted with the hydroxymethyl at one end of the second intermediate compound obtained by the second reaction. The reaction ratio of the first intermediate compound and the second intermediate compound is preferably about 1:2 (mol ratio). Thus the protecting group contained in the compound obtained is deprotected by a suitable method. Thus fluorinated ether compounds can be manufactured by carrying out the above operation.

[0322] <Fourth Manufacturing Method>

[0323] In the manufacturing formula (1), z is 2, and the two linking groups contain -CR 3 R 4 - the same groups as shown, R 1 With R 5 In the case of a fluorinated ether compound in which at least one of the terminal groups or three PFPE chains is different, the following production method can be used.

[0324] (First reaction)

[0325] First, in the same manner as the first reaction of the second production method, a 1 Side R 2 One end of the corresponding PFPE chain has a 1 The first intermediate compound of the group.

[0326] (Second reaction)

[0327] The same operation as the first reaction of the fourth production method is carried out to produce 5 Side R 2 One end of the corresponding PFPE chain has a 5 A second intermediate compound of the group.

[0328] (Third reaction)

[0329] The first intermediate compound in the third production method is produced in the same manner as the first reaction in the third production method as a third intermediate compound in the fourth production method.

[0330] (Fourth reaction, fifth reaction)

[0331] A fourth reaction of reacting the first intermediate compound with the third intermediate compound obtained by the third reaction, and a fifth reaction of reacting the second intermediate compound with the fourth intermediate compound obtained by the fourth reaction are sequentially performed. 3 R 4 - The two connecting groups of the partial structure and the two ends of the chain structure of the three PFPE chains have 1 and R 5 A fifth intermediate compound having a corresponding terminal group.

[0332] (Sixth Reaction)

[0333] Finally, the protecting group contained in the fifth intermediate compound obtained by the fifth reaction is deprotected by an appropriate method to produce a fluorine-containing ether compound.

[0334] By carrying out the above steps, it is possible to produce a -CR 3 R 4 - the same groups as shown, R 1 With R 5 The terminal groups shown, and at least one of the three PFPE chains are different fluorinated ether compounds.

[0335] In the fourth production method, the first reaction, the second reaction, and the third reaction are performed in this order, but the order of performing the first reaction to the third reaction is not particularly limited.

[0336] In the fourth production method, the first intermediate compound is used in the fourth reaction and the second intermediate compound is used in the fifth reaction. However, the second intermediate compound may be used in the fourth reaction and the first intermediate compound may be used in the fifth reaction.

[0337] <Fifth Manufacturing Method>

[0338] In the manufacturing formula (1), z is 2, and the two linking groups contain -CR 3 R 4 - The groups shown are different, R 1 With R 5 The terminal groups shown are the same or different, and the three R 2 When the PFPE chains shown are the same or at least one different fluorinated ether compound, the production method shown below can be used.

[0339] (First reaction)

[0340] First, in the same manner as the first reaction of the second production method, a 1 Side R 2 One end of the corresponding PFPE chain has a 1 The first intermediate compound of the group.

[0341] (Second reaction)

[0342] Next, the same operation as the second reaction of the second production method is carried out to produce 1 Side R 2 One end of the corresponding PFPE chain has 1 The corresponding group is configured with the equivalent of R at the other end. 1 Side-CR 3 R 4 -partial structure and a (pseudo)halogenated second intermediate compound.

[0343] (Third reaction)

[0344] The same operation as the first reaction of the fifth production method is carried out to produce 5 Side R 2 One end of the corresponding PFPE chain has a 5 A third intermediate compound of the group.

[0345] (Fourth reaction)

[0346] The same operation as the second reaction of the fifth production method is carried out to produce 5 Side R 2 One end of the corresponding PFPE chain has 5 The corresponding group is configured with the equivalent of R at the other end. 5 Side-CR 3 R 4 -partial structure and a fourth intermediate compound of a (pseudo)halogen group.

[0347] (Fifth reaction, Sixth reaction)

[0348] Prepare R at the center of the molecule in formula (1) 2 The corresponding PFPE chains are provided with fluorochemical compounds having hydroxymethyl groups (-CH2OH) at both ends. Furthermore, a fifth reaction of reacting the second intermediate compound with one terminal hydroxyl group of the above-mentioned fluorochemical compound and a sixth reaction of reacting the fourth intermediate compound with the terminal hydroxyl group of the obtained fifth intermediate compound are sequentially performed. Thus, a fluorochemical compound having three PFPE chains and -CR arranged between adjacent PFPE chains is obtained. 3 R 4 - The two ends of the chain structure of the two linking groups of the partial structure have 1 and R 5 The sixth intermediate compound has the corresponding terminal group.

[0349] (Seventh Reaction)

[0350] Finally, the protecting group contained in the sixth intermediate compound obtained by the sixth reaction is deprotected by an appropriate method to produce a fluorine-containing ether compound.

[0351] By carrying out the above steps, it is possible to produce a -CR 3 R 4 - The groups shown are different, R 1 With R 5 The terminal groups shown are the same or different, and the three R 2 The PFPE chains shown are the same or contain at least 1 different fluorinated ether compound.

[0352] In the fifth production method, the third reaction and the fourth reaction are performed after the first reaction and the second reaction. However, the first reaction and the second reaction may be performed after the third reaction and the fourth reaction.

[0353] In the fifth production method, the second intermediate compound is used in the fifth reaction and the fourth intermediate compound is used in the sixth reaction. However, the fourth intermediate compound may be used in the fifth reaction and the second intermediate compound may be used in the sixth reaction.

[0354] [Lubricant for magnetic recording media]

[0355] The lubricant for a magnetic recording medium according to the present embodiment contains a fluorine-containing ether compound represented by formula (1).

[0356] The lubricant of the present embodiment may be mixed with known materials used as lubricant materials as needed, as long as the properties due to the inclusion of the fluorine-containing ether compound represented by the above formula (1) are not impaired.

[0357] 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 used in combination with the lubricant of the present embodiment preferably has a number average molecular weight of 500 to 10,000.

[0358] When the lubricant of the present embodiment contains a material other than the fluorinated ether compound represented by formula (1), the content of the fluorinated ether compound represented by formula (1) in the lubricant of the present embodiment is preferably 50% by mass or more, more preferably 70% by mass or more. The content of the fluorinated ether compound represented by formula (1) may be 80% by mass or more, or 90% by mass or more.

[0359] Since the lubricant of this embodiment contains the fluorine-containing ether compound represented by the above formula (1), it can form a lubricating layer with excellent adhesion to the protective layer, and can cover the surface of the protective layer with a high coverage rate even if the thickness is thin. Therefore, according to the lubricant of this embodiment, a lubricating layer with high resistance to chemical substances of the magnetic recording medium and excellent adhesion suppression effect can be obtained even if the thickness is thin.

[0360] [Magnetic recording media]

[0361] The magnetic recording medium of this embodiment includes at least a magnetic layer, a protective layer, and a lubricating layer provided in this order on a substrate.

[0362] In the magnetic recording medium of this embodiment, one or more underlayers may be provided between the substrate and the magnetic layer as required. In addition, an adhesion layer and / or a soft magnetic layer may be provided between the underlayer and the substrate.

[0363] Figure 1 This is a schematic cross-sectional view showing one embodiment of the magnetic recording medium of the present invention.

[0364] The magnetic recording medium 10 of the present embodiment has a structure in which an adhesion 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 .

[0365] "Substrate"

[0366] As the substrate 11 , 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 can be used.

[0367] In addition, as the substrate 11, a non-magnetic substrate formed of a non-metallic material such as glass, ceramics, silicon, silicon carbide, carbon, or resin can be used, or a non-magnetic substrate having a film of NiP or NiP alloy formed on a base formed of these non-metallic materials can be used.

[0368] "Attachment Layer"

[0369] The adhesion layer 12 prevents the substrate 11 from being corroded when the substrate 11 and the soft magnetic layer 13 provided on the adhesion layer 12 are arranged in contact with each other.

[0370] The material of the adhesion layer 12 can be appropriately selected from, for example, Cr, Cr alloy, Ti, Ti alloy, CrTi, NiAl, AlRu alloy, etc. The adhesion layer 12 can be formed by, for example, sputtering.

[0371] "Soft magnetic layer"

[0372] The soft magnetic layer 13 preferably has a structure in which a first soft magnetic film, an intermediate layer composed of a Ru film, and a second soft magnetic film are stacked in sequence. That is, the soft magnetic layer 13 preferably has a structure in which the upper and lower soft magnetic films of the intermediate layer are antiferrocoupled (AFC) by sandwiching an intermediate layer composed of a Ru film between two soft magnetic films.

[0373] Examples of the material of the first soft magnetic film and the second soft magnetic film include CoZrTa alloy and CoFe alloy.

[0374] Preferably, any one of Zr, Ta, and Nb is added to the CoFe alloy used for the first soft magnetic film and the second soft magnetic film. This promotes the amorphization of the first soft magnetic film and the second soft magnetic film. As a result, the orientation of the first base layer (seed layer) can be improved, and the floating amount of the magnetic head can be reduced.

[0375] The soft magnetic layer 13 can be formed by, for example, sputtering.

[0376] "1st base layer"

[0377] The first underlayer 14 is a layer for controlling the orientation and crystal size of the second underlayer 15 and the magnetic layer 16 provided thereon.

[0378] Examples of the first base layer 14 include a Cr layer, a Ta layer, a Ru layer, a CrMo alloy layer, a CoW alloy layer, a CrW alloy layer, a CrV alloy layer, a CrTi alloy layer, and the like.

[0379] The first base layer 14 can be formed by, for example, sputtering.

[0380] "Second base layer"

[0381] The second underlayer 15 is a layer controlled so as to improve the orientation of the magnetic layer 16. The second underlayer 15 is preferably a layer formed of Ru or a Ru alloy.

[0382] The second base layer 15 may be composed of a single layer or a plurality of layers. When the second base layer 15 is composed of a plurality of layers, all layers may be composed of the same material, or at least one layer may be composed of a different material.

[0383] The second base layer 15 can be formed by, for example, sputtering.

[0384] "Magnetic layer"

[0385] The magnetic layer 16 is composed of a magnetic film whose easy magnetization axis is oriented in a vertical or horizontal direction relative to the substrate surface. The magnetic layer 16 is a layer containing Co and Pt. In order to improve the SNR characteristics, the magnetic layer 16 may be a layer containing oxide, Cr, B, Cu, Ta, Zr, etc.

[0386] Examples of the oxide contained in the magnetic layer 16 include SiO 2 , SiO, Cr 2 O 3 , CoO, Ta 2 O 3 , and TiO 2 .

[0387] The magnetic layer 16 may be composed of a single layer or a plurality of magnetic layers formed of materials having different compositions.

[0388] For example, when the magnetic layer 16 is composed of three layers, namely, the first magnetic layer, the second magnetic layer, and the third magnetic layer, which are stacked in order from the bottom, the first magnetic layer is preferably a granular structure formed by a material containing Co, Cr, Pt, and further containing an oxide. As the oxide contained in the first magnetic layer, it is preferred to use, for example, oxides of Cr, Si, Ta, Al, Ti, Mg, Co, etc. Among them, in particular, TiO2, Cr2O3, SiO2, etc. can be used appropriately. In addition, the first magnetic layer is preferably formed by a composite oxide to which two or more oxides are added. In particular, Cr2O3-SiO2, Cr2O3-TiO2, SiO2-TiO2, etc. can be used appropriately. In addition to Co, Cr, Pt, and oxides, the first magnetic layer may also contain one or more elements selected from B, Ta, Mo, Cu, Nd, W, Nb, Sm, Tb, Ru, and Re.

[0389] The second magnetic layer can be made of the same material as that of the first magnetic layer. The second magnetic layer preferably has a granular structure.

[0390] The third magnetic layer is preferably a non-granular structure formed of a material containing Co, Cr, and Pt and containing no oxide. In addition to Co, Cr, and Pt, the third magnetic layer may contain one or more elements selected from B, Ta, Mo, Cu, Nd, W, Nb, Sm, Tb, Ru, Re, and Mn.

[0391] When the magnetic layer 16 is formed of a plurality of magnetic layers, a non-magnetic layer is preferably provided between adjacent magnetic layers. When the magnetic layer 16 is composed of three layers, namely, a first magnetic layer, a second magnetic layer, and a third magnetic layer, a non-magnetic layer is preferably provided between the first magnetic layer and the second magnetic layer, and between the second magnetic layer and the third magnetic layer.

[0392] The non-magnetic layer arranged between adjacent magnetic layers of the magnetic layer 16 can be suitably made of, for example, Ru, Ru alloy, CoCr alloy, 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), etc.

[0393] In the non-magnetic layer provided between adjacent magnetic layers of the magnetic layer 16, an alloy material containing oxide, metal nitride, or metal carbide is preferably used. Specifically, as oxides, for example, SiO2, Al2O3, Ta2O5, Cr2O3, MgO, Y2O3, TiO2, etc. can be used. As metal nitrides, for example, AlN, Si3N4, TaN, CrN, etc. can be used. As metal carbides, for example, TaC, BC, SiC, etc. can be used.

[0394] The non-magnetic layer can be formed by, for example, sputtering.

[0395] In order to achieve a higher recording density, the magnetic layer 16 is preferably a perpendicular magnetic recording magnetic layer in which the easy magnetization axis is oriented perpendicularly to the substrate surface. The magnetic layer 16 may be an in-plane magnetic recording magnetic layer.

[0396] The magnetic layer 16 can 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.

[0397] "Protective layer"

[0398] The protective layer 17 protects the magnetic layer 16. The protective layer 17 may be composed of one layer or multiple layers. Examples of the material of the protective layer 17 include carbon, carbon containing nitrogen, silicon carbide, and the like. As the protective layer 17, a carbon-based protective layer can be preferably used, 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 group contained in the fluorine-containing ether compound in the lubricating layer 18 is further improved, so it is preferred.

[0399] The adhesion between the carbon-based protective layer and the lubricating layer 18 can be controlled by making the carbon-based protective layer hydrogenated carbon and / or carbon nitride and adjusting the hydrogen content 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). In addition, the nitrogen content in the carbon-based protective layer is preferably 4 atomic % to 15 atomic % when measured by X-ray photoelectron spectroscopy (XPS).

[0400] The hydrogen and / or nitrogen contained in the carbon-based protective layer does not need to be uniformly contained in the entire carbon-based protective layer. For example, the carbon-based protective layer is a composition gradient layer in which nitrogen is contained on the lubricating layer 18 side of the protective layer 17 and hydrogen is contained on the magnetic layer 16 side of the protective layer 17. In this case, the adhesion between the magnetic layer 16 and the lubricating layer 18 and the carbon-based protective layer is further improved.

[0401] 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 is obtained. When the thickness of the protective layer 17 is 7 nm or less, it is preferred from the viewpoint of reducing the thickness of the protective layer 17.

[0402] As a method for forming the protective layer 17 , a sputtering method using a target containing carbon, a CVD (chemical vapor deposition) method using a hydrocarbon raw material such as ethylene or toluene, an IBD (ion beam deposition) method, or the like can be used.

[0403] When a carbon-based protective layer is formed as the protective layer 17, for example, a film can be formed by a DC magnetron sputtering method. In particular, when a carbon-based protective layer is formed as the protective layer 17, it is preferable to form an amorphous carbon protective layer by a plasma CVD method. The surface of the amorphous carbon protective layer formed by the plasma CVD method is uniform and has little roughness.

[0404] "Lubricating layer"

[0405] The lubricating layer 18 prevents contamination of the magnetic recording medium 10. In addition, the lubricating layer 18 reduces the frictional force of the magnetic head of the magnetic recording and reproducing device sliding on the magnetic recording medium 10, thereby improving the durability of the magnetic recording medium 10.

[0406] Lubricating layer 18 Figure 1 As shown, the lubricating layer 18 is formed in contact with the protective layer 17. The lubricating layer 18 contains the above-mentioned fluorine-containing ether compound.

[0407] When the protective layer 17 disposed under the lubricating layer 18 is a carbon-based protective layer, the lubricating layer 18 is bonded to the protective layer 17 with a particularly high bonding force. As a result, it is easy to obtain a magnetic recording medium 10 in which the surface of the protective layer 17 is coated with a high coverage rate even if the thickness of the lubricating layer 18 is thin, and contamination of the surface of the magnetic recording medium 10 can be effectively prevented.

[0408] The average film thickness of the lubricating layer 18 is preferably More preferably If the average film thickness of the lubricating layer 18 is more than 0.5nm, the lubricating layer 18 is not island-shaped or mesh-shaped but is formed with uniform film thickness. Therefore, the surface of the protective layer 17 can be coated with a high coverage rate by the lubricating layer 18. In addition, by making the average film thickness of the lubricating layer 18 less than 2.0nm, the lubricating layer 18 can be fully filmized, and the floating amount of the magnetic head can be fully reduced.

[0409] When the surface of the protective layer 17 is not covered with a sufficiently high coverage rate by the lubricating layer 18, the environmental substances adsorbed on the surface of the magnetic recording medium 10 penetrate the gaps of the lubricating layer 18 and invade the lower layer of the lubricating layer 18. The environmental substances that invade the lower layer of the lubricating layer 18 are adsorbed and combined with the protective layer 17 to generate pollutants. Furthermore, during magnetic recording and reproducing, the pollutants (agglomerated components) are attached (transferred) to the magnetic head as stains, causing damage to the magnetic head or reducing the magnetic recording and reproducing characteristics of the magnetic recording and reproducing device.

[0410] Environmental substances that cause pollutants to be generated include, for example, siloxane compounds (cyclic siloxane, linear siloxane), ionic impurities, hydrocarbons with high molecular weights such as octacosane, plasticizers such as dioctyl phthalate, etc. Metal ions included in ionic impurities include, for example, sodium ions, potassium ions, etc. Inorganic ions included in ionic impurities include, for example, chloride ions, bromide ions, nitrate ions, sulfate ions, ammonium ions, etc. Organic ions included in ionic impurities include, for example, oxalate ions, formate ions, etc.

[0411] "Method for forming a lubricating layer"

[0412] Examples of a method for forming the lubricating layer 18 include a method of preparing a magnetic recording medium in which each layer up to the protective layer 17 is formed on the substrate 11 , and applying a lubricating layer forming solution on the protective layer 17 and drying the solution.

[0413] The lubricant layer-forming solution is obtained by dispersing and dissolving the lubricant for a magnetic recording medium of the above-described embodiment in a solvent as necessary to obtain a viscosity and a concentration suitable for a coating method.

[0414] Examples of the solvent used in the lubricating layer forming solution include fluorine-based solvents such as Batler (registered trademark) XF (trade name, manufactured by Mitsui Dupont Fluoro Chemical Co., Ltd.) and / or Asahicrine (registered trademark) AE-3000 (trade name, manufactured by AGC Corporation).

[0415] The coating method of the lubricating layer forming solution is not particularly limited, and examples thereof include a spin coating method, a spray method, a paper coating method, and a dipping method.

[0416] When the dipping method is used, for example, the following method can be used. First, the substrate 11 on which each layer up to the protective layer 17 is formed is dipped in the lubricating layer forming solution placed in the dipping tank of the dipping coating device. Next, the substrate 11 is pulled out of the dipping tank at a predetermined speed. Thus, the lubricating layer forming solution is applied to the surface of the substrate 11 on the protective layer 17.

[0417] By using the dipping method, the lubricating layer-forming solution can be uniformly applied to the surface of the protective layer 17 , and the lubricating layer 18 can be formed on the protective layer 17 with a uniform film thickness.

[0418] In the present embodiment, it is preferable to perform 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 adhesion between the lubricating layer 18 and the protective layer 17 is improved.

[0419] The heat treatment temperature is preferably 100 to 180° C. If 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 is sufficiently obtained. In addition, by setting the heat treatment temperature to 180° C. or lower, thermal decomposition of the lubricating layer 18 can be prevented. The heat treatment time is preferably 10 to 120 minutes.

[0420] The magnetic recording medium 10 of the present embodiment has at least a magnetic layer 16, a protective layer 17, and a lubricating layer 18 sequentially arranged on a substrate 11. For the magnetic recording medium 10 of the present embodiment, a lubricating layer 18 containing the above-mentioned fluorine-containing ether compound is formed in contact with the protective layer 17. The lubricating layer 18 has excellent adhesion to the protective layer 17 and has an appropriate surface energy. Even if the thickness is thin, it can cover the surface of the protective layer 17 in a uniform coating state with a high coverage rate, and has good coverage. Therefore, for the magnetic recording medium 10 of the present embodiment, environmental substances that generate pollutants such as ionic impurities are prevented from invading from the gaps in the lubricating layer 18. In addition, the lubricating layer 18 in the magnetic recording medium 10 of the present embodiment is not easy to generate foreign matter (stains), and adhesion can be suppressed. Therefore, the magnetic recording medium 10 of the present embodiment has less pollutants on the surface, has excellent chemical resistance, and has good reliability and durability.

[0421] Example

[0422] The present invention will be described in more detail below by way of examples and comparative examples. It should be noted that the present invention is not limited to the following examples.

[0423] [Example 1]

[0424] The compound represented by the above formula (1A) was obtained by the method shown below.

[0425] (First reaction)

[0426] In a 300 mL eggplant flask under nitrogen atmosphere, add HOCH2CF2CF2O (CF2CF2CF2O) l 20 g of a compound represented by CF2CF2CH2OH (where l in the formula represents the average degree of polymerization and is 3.8) (number average molecular weight 909, molecular weight distribution 1.1), 1.95 g of 3,4-dihydro-2H-pyran, and 44 mL of a mixed solution (volume ratio 1:1) of Asahiklin (registered trademark) AE-3000 (manufactured by AGC Co., Ltd.) and dichloromethane as a fluorine-based solvent were stirred at 0°C until it became uniform to prepare a mixed solution. 0.084 g of p-toluenesulfonic acid monohydrate was added to the mixed solution, and after stirring at 0°C for 30 minutes, it was stirred at room temperature for 2 hours to react.

[0427] The reaction product obtained after the reaction was cooled to 0°C, and 50 mL of saturated sodium bicarbonate water was added to stop the reaction. The resulting reaction solution was transferred to a separatory funnel and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with saline and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 10.8 g of the compound represented by the following formula (11) as an intermediate compound (1A-1).

[0428]

[0429] (In formula (11), THP represents tetrahydropyranyl, and l representing the average degree of polymerization represents 3.8.)

[0430] (Second reaction)

[0431] In a 200 mL eggplant flask under a nitrogen atmosphere, 10.8 g (number average molecular weight 993, 10.9 mmol) of the compound represented by formula (11) as an intermediate compound (1A-1), 3.40 g (molecular weight 624, 5.45 mmol) of the compound represented by the following formula obtained by the following synthesis method, 0.36 g (molecular weight 166, 2.2 mmol) of potassium iodide, and 22 mL of N,N'-dimethylformamide (DMF) were added, and stirred at room temperature to prepare a mixed solution. 10.6 g (molecular weight 325, 32.7 mmol) of cesium carbonate was added to the mixed solution, and the mixture was stirred at 70°C for 5 hours to react.

[0432] The compound represented by formula (A1) is synthesized by reacting benzyl chloromethyl ether with diethyl malonate, reducing the ester using lithium borohydride, and reacting the generated two primary hydroxyl groups with p-toluenesulfonyl chloride.

[0433]

[0434] (In formula (A1), Ts represents a p-toluenesulfonyl group, and Bn represents a benzyl group.)

[0435] The reaction solution obtained after the reaction was returned to room temperature, 28 g of 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 2 hours. The reaction solution was transferred little by little to a separatory funnel added with 100 mL of brine, and extracted 3 times with 200 mL of ethyl acetate. The organic layer was washed with 100 mL of brine, 100 mL of saturated sodium bicarbonate water, and 100 mL of brine in this order, and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated and the residue was refined by silica gel column chromatography. By performing the above steps, 8.0 g of the compound represented by the following formula (12) was obtained as an intermediate compound (1A-2).

[0436]

[0437] (In formula (12), Bn represents a benzyl group, Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 3.8.)

[0438] (Third reaction)

[0439] In a nitrogen atmosphere, 5.0 g (number average molecular weight 2102, 2.4 mmol) of the compound represented by formula (12) as the intermediate compound (1A-2), 1.4 g (molecular weight 202, 7.1 mmol) of the compound (Ep-1) represented by the following formula (13), and 22 mL of tert-butyl alcohol were added to a 200 mL eggplant flask, and stirred at room temperature until the mixture became uniform. 0.053 g (molecular weight 113, 0.48 mmol) of potassium tert-butylate was further added to the uniform liquid, and the mixture was stirred at 70° C. for 16 hours to react.

[0440] The compound (Ep-1) represented by the formula (13) was synthesized by oxidizing a compound in which the hydroxyl group of ethylene glycol monoallyl ether was protected using dihydropyran.

[0441]

[0442] (In formula (13), THP represents tetrahydropyranyl.)

[0443] The reaction product obtained after the reaction was cooled to 25°C, transferred to a separatory funnel to which 100 mL of water was added, and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with water and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 4.5 g of a compound represented by the following formula (14) as an intermediate compound (1A-3).

[0444]

[0445] (In formula (14), THP represents a tetrahydropyranyl group, Bn represents a benzyl group, Rf2 is represented by the above formula, and l in Rf2, which represents an average degree of polymerization, represents 3.8.)

[0446] (Fourth reaction)

[0447] In a nitrogen atmosphere, 4.5 g (number average molecular weight 2506, 1.8 mmol) of the compound represented by formula (14) as the intermediate compound (1A-3), 45 mL of methanol, and 4.5 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until the mixture became homogeneous. 0.45 g of palladium carbon (Pd / C) was further added to the homogeneous liquid, and the mixture was stirred at 70°C for 5 hours to react.

[0448] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 3.6 g (number average molecular weight 2156, 1.7 mmol) of a compound (1A) represented by the following formula (15).

[0449]

[0450] (In formula (15), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 3.8.)

[0451] The obtained compound (1A) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0452] 1 H-NMR (CD3COCD3): δ[ppm]=3.39~4.34(40H)

[0453] 19 F-NMR (CD3COCD3): δ[ppm]=-84.0~-83.0(30.4F), -86.4(8F), -124.3(8F), -130.0~-129.0(15.2F)

[0454] [Example 2]

[0455] (Third reaction)

[0456] In the third reaction of the above-mentioned Example 1, 1.5 g (molecular weight 216, 7.1 mmol) of the compound (Ep-2) represented by the following formula (16) was used instead of the compound (Ep-1) represented by the formula (13). Except for this, the operations up to the third reaction were carried out in the same manner as in Example 1 to obtain 4.6 g of the intermediate compound (1B-3) represented by the formula (17).

[0457] The compound (Ep-2) represented by the formula (16) is synthesized by protecting one hydroxyl group of 1,3-propanediol with a tetrahydropyranyl (THP) group and reacting the other hydroxyl group with epibromohydrin.

[0458]

[0459] (In formula (16), THP represents tetrahydropyranyl.)

[0460]

[0461] (In formula (17), THP represents a tetrahydropyranyl group, Bn represents a benzyl group, Rf2 is represented by the above formula, and l in Rf2, which represents an average degree of polymerization, represents 3.8.)

[0462] (Fourth reaction)

[0463] Under nitrogen atmosphere, 4.5 g of the compound represented by formula (17) as the intermediate compound (1B-3) (number average molecular weight 2534, 1.8 mmol), 45 mL of methanol, and 4.5 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.45 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 5 hours to react.

[0464] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 3.6 g (number average molecular weight 2184, 1.7 mmol) of a compound (1B) represented by the following formula (18).

[0465]

[0466] (In formula (18), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 3.8.)

[0467] The obtained compound (1B) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0468] 1H-NMR (CD3COCD3): δ[ppm]=1.64~1.83(4H), 3.36~4.34(40H)

[0469] 19 F-NMR (CD3COCD3): δ[ppm]=-84.1~-83.0(30.4F), -86.2(8F), -124.4(8F), -130.0~-129.1(15.2F)

[0470] [Example 3]

[0471] (Third reaction)

[0472] In the third reaction of the above-mentioned Example 1, 2.3 g (molecular weight 320, 7.1 mmol) of the compound (Ep-3) represented by the following formula (20) was used instead of the compound (Ep-1) represented by the formula (13). Except for this, the same operations as in Example 1 were carried out until the third reaction to obtain 4.4 g of the intermediate compound (1C-3) represented by the formula (19).

[0473]

[0474] (In formula (19), THP represents a tetrahydropyranyl group, Bn represents a benzyl group, and MOM represents a methoxymethyl group. Rf2 is represented by the above formula, and l in Rf2, which represents an average degree of polymerization, represents 3.8.)

[0475]

[0476] (In formula (20), THP represents tetrahydropyranyl and MOM represents methoxymethyl.)

[0477] The compound (Ep-3) represented by the formula (20) was synthesized by the method shown below.

[0478] A tert-butyldimethylsilyl (TBS) group was introduced as a protecting group into the primary hydroxyl group of 3-allyloxy-1,2-propanediol, and a methoxymethyl (MOM) group was introduced as a protecting group into the secondary hydroxyl group of the obtained compound. The TBS group was removed from the obtained compound, and 2-bromoethoxytetrahydropyran was reacted with the generated primary hydroxyl group. The double bond of the obtained compound was oxidized. Through the above steps, a compound (Ep-3) represented by formula (20) was obtained.

[0479] (Fourth reaction)

[0480] Under nitrogen atmosphere, 4.4 g (number average molecular weight 2743, 1.6 mmol) of the compound represented by formula (19) as the intermediate compound (1C-3), 44 mL of methanol, and 4.4 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.44 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 5 hours to react.

[0481] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 3.4 g (number average molecular weight 2305, 1.5 mmol) of a compound (1C) represented by the following formula (21).

[0482]

[0483] (In formula (21), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 3.8.)

[0484] The obtained compound (1C) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0485] 1 H-NMR (CD3COCD3): δ[ppm]=3.34~4.37(52H)

[0486] 19 F-NMR (CD3COCD3): δ[ppm]=-83.9~-83.1(30.4F), -86.4(8F), -124.2(8F), -130.2~-129.0(15.2F)

[0487] [Example 4]

[0488] (Third reaction)

[0489] In the third reaction of the above-mentioned Example 1, 2.4 g (molecular weight 334, 7.1 mmol) of the compound (Ep-4) represented by the following formula (23) was used instead of the compound (Ep-1) represented by the formula (13). Except for this, the same operations as in Example 1 were carried out until the third reaction to obtain 4.6 g of the intermediate compound (1D-3) represented by the formula (22).

[0490]

[0491] (In formula (22), Bn represents a benzyl group, THP represents a tetrahydropyranyl group, and MOM represents a methoxymethyl group. Rf2 is represented by the above formula, and the l in Rf2 representing the average degree of polymerization is 3.8.)

[0492]

[0493] (In formula (23), THP represents tetrahydropyranyl and MOM represents methoxymethyl.)

[0494] The compound (Ep-4) represented by the formula (23) was synthesized by the method shown below.

[0495] A tert-butyldimethylsilyl (TBS) group was introduced as a protecting group into the primary hydroxyl group of 3-allyloxy-1,2-propanediol, and a methoxymethyl (MOM) group was introduced as a protecting group into the secondary hydroxyl group of the obtained compound. The TBS group was removed from the obtained compound, and 2-(chloropropoxy)tetrahydro-2H-pyran was reacted with the generated primary hydroxyl group. The double bond of the obtained compound was oxidized. Through the above steps, a compound (Ep-4) represented by formula (23) was obtained.

[0496] (Fourth reaction)

[0497] Under nitrogen atmosphere, 4.4 g (number average molecular weight 2771, 1.6 mmol) of the compound represented by formula (22) as the intermediate compound (1D-3), 44 mL of methanol, and 4.4 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.44 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 5 hours to react.

[0498] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 3.1 g of a compound (1D) represented by the following formula (24) (number average molecular weight 2333, 1.3 mmol).

[0499]

[0500] (In formula (24), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 3.8.)

[0501] The obtained compound (1D) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0502] 1H-NMR (CD3COCD3): δ[ppm]=1.63~1.83(4H), 3.37~4.36(52H)

[0503] 19 F-NMR (CD3COCD3): δ[ppm]=-83.9~-83.1(30.4F), -86.4(8F), -124.2(8F), -130.2~-128.9(15.2F)

[0504] [Example 5]

[0505] (Third reaction)

[0506] In the third reaction of the above-mentioned Example 1, 1.5 g (molecular weight 216, 7.1 mmol) of the compound (Ep-5) represented by the following formula (26) was used instead of the compound (Ep-1) represented by the formula (13). Except for this, the same operations as in Example 1 were carried out until the third reaction to obtain 4.4 g of the intermediate compound (1E-3) represented by the formula (25).

[0507]

[0508] (In formula (25), Bn represents a benzyl group, and THP represents a tetrahydropyranyl group. Rf2 is represented by the above formula, and l in Rf2, which represents an average degree of polymerization, represents 3.8.)

[0509]

[0510] (In formula (26), THP represents tetrahydropyranyl.)

[0511] The compound (Ep-5) represented by the formula (26) is synthesized by oxidizing the double bond of a compound obtained by reacting 3-butene-1-ol with 2-bromoethoxytetrahydropyran.

[0512] (Fourth reaction)

[0513] In a nitrogen atmosphere, 4.4 g (number average molecular weight 2534, 1.7 mmol) of the compound represented by formula (25) as the intermediate compound (1E-3), 44 mL of methanol, and 4.4 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.44 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 5 hours to react.

[0514] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 3.3 g of a compound (1E) represented by the following formula (27) (number average molecular weight 2184, 1.6 mmol).

[0515]

[0516] (In formula (27), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 3.8.)

[0517] The obtained compound (1E) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0518] 1 H-NMR (CD3COCD3): δ[ppm]=1.65~1.79(4H), 3.41~4.33(40H)

[0519] 19 F-NMR (CD3COCD3): δ[ppm]=-84.0~-83.0(30.4F), -86.4(8F), -124.3(8F), -130.0~-129.0(15.2F)

[0520] [Example 6]

[0521] (Third reaction)

[0522] In the third reaction of the above-mentioned Example 1, 2.4 g (molecular weight 334, 7.1 mmol) of the compound (Ep-6) represented by the following formula (29) was used instead of the compound (Ep-1) represented by the formula (13). Except for this, the same operations as in Example 1 were carried out until the third reaction to obtain 4.6 g of the intermediate compound (1F-3) represented by the formula (28).

[0523]

[0524] (In formula (28), Bn represents a benzyl group, THP represents a tetrahydropyranyl group, and MOM represents a methoxymethyl group. Rf2 is represented by the above formula, and the l in Rf2 representing the average degree of polymerization is 3.8.)

[0525]

[0526] (In formula (29), THP represents tetrahydropyranyl, and MOM represents methoxymethyl.)

[0527] The compound (Ep-6) represented by the formula (29) was synthesized by the method shown below.

[0528] The hydroxyl group of ethylene glycol monoallyl ether was protected with dihydropyran, and the double bond of the obtained compound was oxidized. The epoxy group of the compound obtained by oxidizing the double bond was reacted with the hydroxyl group of 3-butene-1-ol. The secondary hydroxyl group of the obtained compound was protected with a methoxymethyl (MOM) group, and the double bond of the obtained compound was oxidized. Through the above steps, the compound (Ep-6) represented by formula (29) was obtained.

[0529] (Fourth reaction)

[0530] In a nitrogen atmosphere, 4.6 g of the compound represented by formula (28) as the intermediate compound (1F-3) (number average molecular weight 2771, 1.7 mmol), 46 mL of methanol, and 4.6 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.46 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 5 hours to react.

[0531] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 3.6 g of a compound (1F) represented by the following formula (30) (number average molecular weight 2333, 1.6 mmol).

[0532]

[0533] (In formula (30), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 3.8.)

[0534] The obtained compound (1F) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0535] 1 H-NMR (CD3COCD3): δ[ppm]=1.64~1.80(4H), 3.40~4.33(52H)

[0536] 19 F-NMR (CD3COCD3): δ[ppm]=-84.1~-83.0(30.4F), -86.4(8F), -124.4(8F), -130.1~-128.9(15.2F)

[0537] [Example 7]

[0538] The compound represented by the above formula (1G) was obtained by the method shown below.

[0539] (First reaction)

[0540] In a 300 mL eggplant flask under nitrogen atmosphere, add HOCH2CF2O (CF2CF2O) j (CF2O) k 20 g of a compound represented by CF2CH2OH (wherein j representing the average degree of polymerization is 4.0, and k representing the average degree of polymerization is 4.0) (number average molecular weight 906, molecular weight distribution 1.1), 1.95 g of 3,4-dihydro-2H-pyran, and 44 mL of a mixed solution (volume ratio 1:1) of Asahiklin (registered trademark) AE-3000 (manufactured by AGC Co., Ltd.) and dichloromethane as a fluorine-based solvent were stirred at 0°C until it became uniform to prepare a mixed solution. 0.084 g of p-toluenesulfonic acid monohydrate was added to the mixed solution, and after stirring at 0°C for 30 minutes, it was stirred at room temperature for 2 hours to react.

[0541] The reaction product obtained after the reaction was cooled to 0°C, and 50 mL of saturated sodium bicarbonate water was added to stop the reaction. The resulting reaction solution was transferred to a separatory funnel and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with brine and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 10.5 g of the compound represented by the following formula (31) as an intermediate compound (1G-1).

[0542]

[0543] (In formula (31), THP represents a tetrahydropyranyl group, j representing an average degree of polymerization is 4.0, and k representing an average degree of polymerization is 4.0.)

[0544] (Second reaction)

[0545] In a 200 mL eggplant flask under a nitrogen atmosphere, 10.5 g (number average molecular weight 990, 10.6 mmol) of the compound represented by formula (31) as an intermediate compound (1G-1), 3.4 g (molecular weight 624, 5.45 mmol) of the compound represented by the above formula (A1), 0.36 g (molecular weight 166, 2.2 mmol), and 22 mL of N,N'-dimethylformamide (DMF) were added, and stirred at room temperature to prepare a mixed solution. 10.64 g (molecular weight 325, 32.7 mmol) of cesium carbonate was added to the mixed solution, and the mixture was stirred at 70°C for 5 hours to react.

[0546] The reaction solution obtained after the reaction was returned to room temperature, 28 g of 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 2 hours. The reaction solution was transferred little by little to a separatory funnel added with 100 mL of brine, and extracted three times with 200 mL of ethyl acetate. The organic layer was washed with 100 mL of brine, 100 mL of saturated sodium bicarbonate water, and 100 mL of brine in this order, and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated and the residue was refined by silica gel column chromatography. By performing the above steps, 7.9 g of the compound represented by the following formula (32) was obtained as an intermediate compound (1G-2).

[0547]

[0548] (In formula (32), Bn represents a benzyl group, Rf1 is represented by the above formula, j representing the average degree of polymerization in Rf1 is 4.0, and k representing the average degree of polymerization is 4.0.)

[0549] (Third reaction)

[0550] In a 200 mL eggplant flask, 5.0 g (number average molecular weight 2096, 2.4 mmol) of the compound represented by formula (32) as the intermediate compound (1G-2), 1.2 g (molecular weight 172, 7.2 mmol) of the compound (Ep-7) represented by the following formula (33), and 22 mL of tert-butyl alcohol were added under a nitrogen atmosphere, and stirred at room temperature until the mixture became homogeneous. 0.054 g (molecular weight 112, 0.54 mmol) of potassium tert-butylate was further added to the homogeneous liquid, and the mixture was stirred at 70° C. for 16 hours to react.

[0551] The compound (Ep-7) represented by the formula (33) was synthesized by introducing a tetrahydropyranyl (THP) group into the primary hydroxyl group of 3-buten-1-ol and oxidizing the double bond of the resulting compound.

[0552]

[0553] (In formula (33), THP represents tetrahydropyranyl.)

[0554] The reaction product obtained after the reaction was cooled to 25°C, transferred to a separatory funnel to which 100 mL of water was added, and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with water and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 4.1 g of the compound represented by the following formula (34) as an intermediate compound (1G-3).

[0555]

[0556] (In formula (34), THP represents a tetrahydropyranyl group, and Bn represents a benzyl group. Rf1 is represented by the above formula, and j representing the average degree of polymerization in Rf1 is 4.0, and k representing the average degree of polymerization is 4.0.)

[0557] (Fourth reaction)

[0558] In a 200 mL eggplant flask under a nitrogen atmosphere, 4.1 g of the compound represented by formula (34) as an intermediate compound (1G-3) (number average molecular weight 2440, 1.7 mmol), 41 mL of methanol, and 4.1 mL of formic acid were added and stirred at room temperature until the mixture became homogeneous. 0.41 g of palladium carbon (Pd / C) was further added to the homogeneous liquid, and the mixture was stirred at 70°C for 5 hours to react.

[0559] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 3.1 g (number average molecular weight 2091, 1.6 mmol) of a compound (1G) represented by the following formula (35).

[0560]

[0561] (In formula (35), Rf1 is represented by the above formula, j representing the average degree of polymerization in Rf1 is 4.0, and k representing the average degree of polymerization is 4.0.)

[0562] The obtained compound (1G) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0563] 1 H-NMR (CD3COCD3): δ[ppm]=1.66~1.79(4H), 3.42~4.34(32H)

[0564] 19 F-NMR (CD3COCD3): δ[ppm]=-55.6~-50.6(16F), -77.7(4F), -80.3(4F), -91.0~-88.5(32F)

[0565] [Example 8]

[0566] (Third reaction)

[0567] In the third reaction of the above-mentioned Example 7, 1.4 g (molecular weight 200, 7.2 mmol) of the compound (Ep-8) represented by the following formula (37) was used instead of the compound (Ep-7) represented by the formula (33). Except for this, the same operations as in Example 7 were carried out until the third reaction to obtain 4.2 g of the intermediate compound (1H-3) represented by the formula (36).

[0568]

[0569] (In formula (36), THP represents a tetrahydropyranyl group, and Bn represents a benzyl group. Rf1 is represented by the above formula, and j representing the average degree of polymerization in Rf1 is 4.0, and k representing the average degree of polymerization is 4.0.)

[0570]

[0571] (In formula (37), THP represents tetrahydropyranyl.)

[0572] The compound (Ep-8) represented by the formula (37) was produced by the method described below: Specifically, it was synthesized by introducing a tetrahydropyranyl (THP) group into the primary hydroxyl group of 5-hexen-1-ol and oxidizing the double bond of the obtained compound.

[0573] (Fourth reaction)

[0574] In a nitrogen atmosphere, 4.2 g (number average molecular weight 2497, 1.7 mmol) of the compound represented by formula (36) as the intermediate compound (1H-3), 42 mL of methanol, and 4.2 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.42 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 5 hours to react.

[0575] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 3.2 g of the compound (1H) represented by the following formula (38) (number average molecular weight 2147, 1.6 mmol).

[0576]

[0577] (In formula (38), Rf1 is represented by the above formula, j representing the average degree of polymerization in Rf1 is 4.0, and k representing the average degree of polymerization is 4.0.)

[0578] The obtained compound (1H) is 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0579] 1 H-NMR (CD3COCD3): δ[ppm]=1.35~1.83(12H), 3.36~4.32(32H)

[0580] 19 F-NMR (CD3COCD3): δ[ppm]=-55.5~-50.6(16F), -77.6(4F), -80.3(4F), -91.1~-88.4(32F)

[0581] [Example 9]

[0582] The compound represented by the above formula (1I) was obtained by the method shown below.

[0583] (First reaction)

[0584] In a 300 mL eggplant flask under nitrogen atmosphere, add HOCH2CF2O (CF2CF2O) j (CF2O) k 20 g of a compound represented by CF2CH2OH (wherein j representing the average degree of polymerization is 6.3, and k representing the average degree of polymerization is 0) (number average molecular weight 909, molecular weight distribution 1.1), 1.94 g of 3,4-dihydro-2H-pyran, and 44 mL of a mixed solution (volume ratio 1:1) of Asahiklin (registered trademark) AE-3000 (manufactured by AGC Co., Ltd.) and dichloromethane as a fluorine-based solvent were stirred at 0°C until it became uniform to prepare a mixed solution. 0.084 g of p-toluenesulfonic acid monohydrate was added to the mixed solution, and after stirring at 0°C for 30 minutes, it was stirred at room temperature for 2 hours to react.

[0585] The reaction product obtained after the reaction was cooled to 0°C, and 50 mL of saturated sodium bicarbonate water was added to stop the reaction. The resulting reaction solution was transferred to a separatory funnel and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with saline and dehydrated with anhydrous sodium sulfate. After the desiccant was filtered and separated, the filtrate was concentrated, and the residue was refined by silica gel column chromatography to obtain 10.0 g of the compound represented by the following formula (39) as an intermediate compound (1I-1).

[0586]

[0587] (In formula (39), THP represents a tetrahydropyranyl group, j representing an average degree of polymerization is 6.3, and k representing an average degree of polymerization is 0.)

[0588] (Second reaction)

[0589] In a 200 mL eggplant flask, 10.0 g (number average molecular weight 992, 10.1 mmol) of the compound represented by formula (39) as the intermediate compound (II-1), 3.16 g (molecular weight 624, 5.0 mmol) of the compound represented by the above formula (A1), 0.33 g (molecular weight 166, 2.0 mmol), and 20 mL of N,N'-dimethylformamide (DMF) were added under a nitrogen atmosphere, and stirred at room temperature to prepare a mixed solution. 9.83 g (molecular weight 325, 30.2 mmol) of cesium carbonate was added to the mixed solution, and stirred at 70°C for 5 hours to react.

[0590] The reaction solution obtained after the reaction was returned to room temperature, 26 g of 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 2 hours. The reaction solution was transferred little by little to a separatory funnel added with 100 mL of brine, and extracted 3 times with 200 mL of ethyl acetate. The organic layer was washed with 100 mL of brine, 100 mL of saturated sodium bicarbonate water, and 100 mL of brine in this order, and dehydrated with anhydrous sodium sulfate. After the desiccant was filtered and separated, the filtrate was concentrated and the residue was refined by silica gel column chromatography. By performing the above steps, 7.4 g of the compound represented by the following formula (40) was obtained as an intermediate compound (1I-2).

[0591]

[0592] (In formula (40), Bn represents a benzyl group, Rf1 is represented by the above formula, j representing the average degree of polymerization in Rf1 is 6.3, and k representing the average degree of polymerization is 0.)

[0593] (Third reaction)

[0594] In a nitrogen atmosphere, 5.0 g (number average molecular weight 2101, 2.4 mmol) of the compound represented by formula (40) as the intermediate compound (II-2), 2.2 g (molecular weight 304, 7.1 mmol) of the compound (Ep-9) represented by the following formula (41), and 22 mL of tert-butyl alcohol were added to a 200 mL eggplant flask, and stirred at room temperature until the mixture became uniform. 0.053 g (molecular weight 112, 0.48 mmol) of potassium tert-butylate was further added to the uniform liquid, and the mixture was stirred at 70°C for 16 hours to react.

[0595] The compound (Ep-9) represented by the formula (41) was synthesized by the method shown below.

[0596] A tetrahydropyranyl (THP) group was introduced into the primary hydroxyl group of 4-penten-1-ol, and the double bond of the obtained compound was oxidized. The compound obtained by oxidizing the double bond was reacted with allyl alcohol. The secondary hydroxyl group of the obtained compound was protected with a methoxymethyl (MOM) group, and the double bond of the obtained compound was oxidized. The compound (Ep-9) represented by formula (41) was obtained through the above steps.

[0597]

[0598] (In formula (41), THP represents tetrahydropyranyl and MOM represents methoxymethyl.)

[0599] The reaction product obtained after the reaction was cooled to 25°C, transferred to a separatory funnel to which 100 mL of water was added, and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with water and dehydrated with anhydrous sodium sulfate. After the desiccant was filtered and separated, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 4.6 g of the compound represented by the following formula (42) as an intermediate compound (1I-3).

[0600]

[0601] (In formula (42), THP represents a tetrahydropyranyl group, MOM represents a methoxymethyl group, and Bn represents a benzyl group. Rf1 is represented by the above formula, and j representing the average degree of polymerization in Rf1 is 6.3, and k representing the average degree of polymerization is 0.)

[0602] (Fourth reaction)

[0603] Under nitrogen atmosphere, 4.6 g (number average molecular weight 2710, 1.7 mmol) of the compound represented by formula (42) as the intermediate compound (1I-3), 46 mL of methanol, and 4.6 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.46 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 5 hours to react.

[0604] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 3.5 g (number average molecular weight 2272, 1.5 mmol) of compound (1I) represented by the following formula (43).

[0605]

[0606] (In formula (43), Rf1 is represented by the above formula, j representing the average degree of polymerization in Rf1 is 6.3, and k representing the average degree of polymerization is 0.)

[0607] The obtained compound (1I) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0608] 1 H-NMR (CD3COCD3): δ[ppm]=1.34~1.67(8H), 3.39~4.34(44H)

[0609] 19 F-NMR (CD3COCD3): δ [ppm] = -78.6 (4F), -81.3 (4F), -90.0~-88.5 (50.4F)

[0610] [Example 10]

[0611] (First reaction)

[0612] Under nitrogen atmosphere, add HOCH2CF2CF2O (CF2CF2CF2O) into a 200 mL eggplant flask. l 10 g of a compound represented by CF2CF2CH2OH (where l in the formula represents the average degree of polymerization and is 3.8) (number average molecular weight 909, molecular weight distribution 1.1), 2.4 g of a compound represented by the following formula (44) (Ep-10) (molecular weight 272, 8.8 mmol), and 10 mL of tert-butyl alcohol were stirred at room temperature until the mixture became uniform. 0.247 g of potassium tert-butylate (molecular weight 112, 2.2 mmol) was further added to the uniform liquid, and the mixture was stirred at 70°C for 16 hours to react.

[0613] The compound (Ep-10) represented by the formula (44) was synthesized by the method shown below.

[0614] 1,3-Diallyloxy-2-propanol was reacted with 3,4-dihydro-2H-pyran, and one double bond of the obtained compound was oxidized using m-chloroperbenzoic acid. Through the above steps, a compound (Ep-10) represented by formula (44) was obtained.

[0615]

[0616] (In formula (44), THP represents tetrahydropyranyl.)

[0617] The reaction product obtained after the reaction was cooled to 25°C, transferred to a separatory funnel to which 100 mL of water was added, and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with water and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 5.5 g of a compound represented by the following formula (45) as an intermediate compound (1J-1).

[0618]

[0619] (In formula (45), THP represents a tetrahydropyranyl group, Rf2 is represented by the above formula, and l in Rf2, which represents an average degree of polymerization, represents 3.8.)

[0620] (Second reaction)

[0621] In a 200 mL eggplant flask, 5.5 g (number average molecular weight 1181, 4.7 mmol) of the compound represented by formula (45) as the intermediate compound (1J-1), 0.70 g (molecular weight 302, 2.3 mmol) of the compound represented by the following formula (S1), 0.16 g (molecular weight 166, 0.9 mmol), and 7 mL of N,N'-dimethylformamide (DMF) were added under a nitrogen atmosphere, and stirred at room temperature to prepare a mixed solution. 4.5 g (molecular weight 325, 14.0 mmol) of cesium carbonate was added to the mixed solution, and the mixture was stirred at 70°C for 5 hours to react.

[0622]

[0623] The reaction solution obtained after the reaction was returned to room temperature, 24 g of 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 2 hours. The reaction solution was transferred little by little to a separatory funnel added with 100 mL of brine, and extracted three times with 200 mL of ethyl acetate. The organic layer was washed with 100 mL of brine, 100 mL of saturated sodium bicarbonate water, and 100 mL of brine in this order, and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated and the residue was refined by silica gel column chromatography. By performing the above steps, 3.2 g (number average molecular weight 2297, 1.4 mmol) of compound (1J) represented by the following formula (46) was obtained.

[0624]

[0625] (In formula (46), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 3.8.)

[0626] The obtained compound (1J) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0627] 1 H-NMR (CD3COCD3): δ[ppm]=3.39~4.34(46H), 5.14~5.22(2H), 5.26~5.35(2H), 5.87~5.91(2H) 19 F-NMR (CD3COCD3): δ[ppm]=-84.0~-83.0(30.4F), -86.4(8F), -124.3(8F), -130.0~-129.0(15.2F)

[0628] [Example 11]

[0629] (First reaction)

[0630] Under nitrogen atmosphere, add HOCH2CF2CF2O (CF2CF2CF2O) into a 200 mL eggplant flask. l 10 g of a compound represented by CF2CF2CH2OH (where l in the formula represents the average degree of polymerization and is 3.8) (number average molecular weight 909, molecular weight distribution 1.1), 2.6 g of a compound represented by the following formula (47) (Ep-11) (molecular weight 300, 8.8 mmol), and 10 mL of tert-butyl alcohol were stirred at room temperature until the mixture became uniform. 0.247 g of potassium tert-butylate (molecular weight 112, 2.2 mmol) was further added to the uniform liquid, and the mixture was stirred at 70°C for 16 hours to react.

[0631] The compound (Ep-11) represented by the following formula (47) was synthesized by the method shown below.

[0632] Two equivalents of 3-butene-1-ol and one equivalent of epichlorohydrin were reacted. 3,4-dihydro-2H-pyran was reacted with the obtained compound, and the secondary hydroxyl group of the compound was protected with a tetrahydropyranyl (THP) group. The double bond on one side of the obtained compound was oxidized using m-chloroperbenzoic acid. Through the above steps, a compound (Ep-11) represented by formula (47) was obtained.

[0633]

[0634] (In formula (47), THP represents tetrahydropyranyl.)

[0635] The reaction product obtained after the reaction was cooled to 25°C, transferred to a separatory funnel to which 100 mL of water was added, and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with water and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 5.6 g of the compound represented by the following formula (48) as an intermediate compound (1K-1).

[0636]

[0637] (In formula (48), THP represents a tetrahydropyranyl group, Rf2 is represented by the above formula, and l in Rf2, which represents an average degree of polymerization, represents 3.8.)

[0638] (Second reaction)

[0639] In a 200 mL eggplant flask under a nitrogen atmosphere, 5.6 g (number average molecular weight 1209, 4.6 mmol) of the compound represented by formula (48) as the intermediate compound (1K-1), 0.70 g (molecular weight 302, 2.3 mmol) of the compound represented by formula (S1), 0.15 g (molecular weight 166, 0.9 mmol), and 7 mL of N,N'-dimethylformamide (DMF) were added, and stirred at room temperature to prepare a mixed solution. 4.5 g (molecular weight 325, 13.9 mmol) of cesium carbonate was added to the mixed solution, and stirred at 70°C for 5 hours to react.

[0640] The reaction solution obtained after the reaction was returned to room temperature, 24 g of 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 2 hours. The reaction solution was transferred little by little to a separatory funnel added with 100 mL of brine, and extracted three times with 200 mL of ethyl acetate. The organic layer was washed with 100 mL of brine, 100 mL of saturated sodium bicarbonate water, and 100 mL of brine in this order, and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated and the residue was purified by silica gel column chromatography. By performing the above steps, 2.8 g (number average molecular weight 2353, 1.2 mmol) of compound (1K) represented by the following formula (49) was obtained.

[0641]

[0642] (In formula (49), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 3.8.)

[0643] The obtained compound (1K) is subjected to 1 H-NMR and 19The structure was identified based on the following results from F-NMR measurement.

[0644] 1 H-NMR (CD3COCD3): δ[ppm]=1.66~1.81(4H), 2.33~2.43(4H), 3.39~4.34(46H), 5.14~5.22(2H), 5.26~5.35(2H), 5.87~5.91(2H)

[0645] 19 F-NMR (CD3COCD3): δ[ppm]=-84.0~-83.0(30.4F), -86.4(8F), -124.3(8F), -130.0~-129.0(15.2F)

[0646] [Example 12]

[0647] (Third reaction)

[0648] In the third reaction of the above-mentioned Example 9, 2.1 g (molecular weight 299, 7.1 mmol) of the compound (Ep-12) represented by the following formula (50) was used instead of the compound (Ep-9) represented by the formula (41). Except for this, the operations up to the third reaction were carried out in the same manner as in Example 9 to obtain 4.4 g of the intermediate compound (1L-3) represented by the formula (51).

[0649] The compound (Ep-12) represented by the formula (50) was synthesized by the method shown below.

[0650] The reactant obtained by reacting cyanopropanol with epibromohydrin was hydrolyzed. After the primary hydroxyl group of the obtained compound was protected with tert-butyldimethylsilyl, the secondary hydroxyl group was protected with tetrahydropyranyl. The tert-butyldimethylsilyl group was deprotected from the compound having the secondary hydroxyl group protected, and the compound was reacted with epibromohydrin. The above steps gave the compound (Ep-12) represented by formula (50).

[0651]

[0652] (In formula (50), THP represents tetrahydropyranyl.)

[0653]

[0654] (In formula (51), THP represents a tetrahydropyranyl group, and Bn represents a benzyl group. Rf1 is represented by the above formula, and j representing the average degree of polymerization in Rf1 is 6.3, and k representing the average degree of polymerization is 0.)

[0655] (Fourth reaction)

[0656] Under nitrogen atmosphere, 4.4 g (number average molecular weight 2700, 1.6 mmol) of the compound represented by formula (51) as the intermediate compound (1L-3), 44 mL of methanol, and 4.4 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.44 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 5 hours to react.

[0657] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 3.4 g (number average molecular weight 2350, 1.5 mmol) of the compound (1L) represented by the following formula (52).

[0658]

[0659] (In formula (52), Rf1 is represented by the above formula, j representing the average degree of polymerization in Rf1 is 6.3, and k representing the average degree of polymerization is 0.)

[0660] The obtained compound (1L) was subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0661] 1 H-NMR (CD3COCD3): δ[ppm]=1.13~1.25(4H), 2.01~2.12(4H), 3.39~4.36(46H)

[0662] 19 F-NMR (CD3COCD3): δ [ppm] = -78.5 (4F), -81.3 (4F), -90.1~-88.7 (50.4F)

[0663] [Example 13]

[0664] (Third reaction)

[0665] In the third reaction of the above-mentioned Example 7, 2.8 g (molecular weight 389, 7.2 mmol) of the compound (Ep-13) represented by the following formula (54) was used instead of the compound (Ep-7) represented by the formula (33). Except for this, the same operations as in Example 7 were carried out until the third reaction to obtain 4.6 g of the intermediate compound (1M-3) represented by the formula (53).

[0666]

[0667] (In formula (53), THP represents a tetrahydropyranyl group, and Bn represents a benzyl group. Rf1 is represented by the above formula, and j representing the average degree of polymerization in Rf1 is 4.0, and k representing the average degree of polymerization is 4.0.)

[0668] The compound (Ep-13) represented by the formula (54) was synthesized by the following method.

[0669] The hydroxyl group of ethylene glycol monoallyl ether was protected with dihydropyran, and the double bond of the obtained compound was oxidized. The epoxy group of the compound obtained by oxidizing the double bond was reacted with the hydroxyl group of 4-pentene-1-ol. The secondary hydroxyl group of the obtained compound was protected with a THP group, and the double bond of the obtained compound was oxidized. The compound (Ep-13) represented by formula (54) was obtained through the above steps.

[0670]

[0671] (In formula (54), THP represents tetrahydropyranyl.)

[0672] (Fourth reaction)

[0673] Under nitrogen atmosphere, 4.6 g (number average molecular weight 2873, 1.6 mmol) of the compound represented by formula (53) as the intermediate compound (1M-3), 46 mL of methanol, and 4.6 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.46 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 5 hours to react.

[0674] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 3.4 g (number average molecular weight 2355, 1.5 mmol) of a compound (1M) represented by the following formula (55).

[0675]

[0676] (In formula (55), Rf1 is represented by the above formula, j representing the average degree of polymerization in Rf1 is 4.0, and k representing the average degree of polymerization is 4.0.)

[0677] The obtained compound (1M) was subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0678] 1 H-NMR (CD3COCD3): δ[ppm]=1.60~1.83(8H), 3.36~4.35(52H)

[0679] 19 F-NMR (CD3COCD3): δ[ppm]=-55.6~-50.7(16F), -77.7(4F), -80.3(4F), -90.9~-88.6(32F)

[0680] [Example 14]

[0681] (Third reaction)

[0682] In the third reaction of the above-mentioned Example 1, 1.9 g (molecular weight 264, 7.1 mmol) of the compound (Ep-14) represented by the following formula (56) was used instead of the compound (Ep-1) represented by the formula (13). Except for this, the operations up to the third reaction were carried out in the same manner as in Example 1 to obtain 4.4 g of the intermediate compound (1N-3) represented by the formula (57).

[0683]

[0684] (In formula (56), Ph represents a phenyl group.)

[0685]

[0686] (In formula (57), Ph represents a phenyl group, and Bn represents a benzyl group. Rf2 is represented by the above formula, and l in Rf2, which represents an average degree of polymerization, represents 3.8.)

[0687] The compound (Ep-14) represented by the formula (56) was synthesized by the method shown below.

[0688] 1,2,4-butanetriol was reacted with benzaldehyde dimethyl acetal. Thus, a compound in which the hydroxyl groups bonded to the carbon at the 2-position and the carbon at the 4-position of 1,2,4-butanetriol were protected was synthesized. This compound was reacted with 2-bromoethyl oxirane. Through the above steps, a compound (Ep-14) represented by formula (56) was obtained.

[0689] (Fourth reaction)

[0690] Under nitrogen atmosphere, 4.4 g (number average molecular weight 2630, 1.8 mmol) of the compound represented by formula (57) as the intermediate compound (1N-3), 44 mL of methanol, and 4.4 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.44 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 5 hours to react.

[0691] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 3.5 g (number average molecular weight 2273, 1.5 mmol) of the compound (1N) represented by the following formula (58).

[0692]

[0693] (In formula (58), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 3.8.)

[0694] The obtained compound (1N) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0695] 1 H-NMR (CD3COCD3): δ[ppm]=1.63~1.88(8H), 3.29~4.44(44H)

[0696] 19 F-NMR (CD3COCD3): δ[ppm]=-84.0~-83.2(30.4F), -86.3(8F), -124.3(8F), -130.1~-129.0(15.2F)

[0697] [Example 15]

[0698] (Third reaction)

[0699] In the third reaction of the above-mentioned Example 9, 2.3 g (molecular weight 317, 7.1 mmol) of the compound (Ep-15) represented by the following formula (59) was used instead of the compound (Ep-9) represented by the formula (41). Except for this, the operations until the third reaction were carried out in the same manner as in Example 9 to obtain 4.5 g of the intermediate compound (1O-3) represented by the formula (60).

[0700]

[0701] (In formula (59), THP represents tetrahydropyranyl.)

[0702]

[0703] (In formula (60), THP represents a tetrahydropyranyl group, and Bn represents a benzyl group. Rf1 is represented by the above formula, and j representing the average degree of polymerization in Rf1 is 6.3, and k representing the average degree of polymerization is 0.)

[0704] The compound (Ep-15) represented by the formula (59) was synthesized by the method shown below.

[0705] The compound was obtained by reacting 2-acetamideethanol with allyl glycidyl ether. Then, the secondary hydroxyl group of the obtained compound was protected with a tetrahydropyranyl (THP) group. The terminal double bond of the obtained compound was oxidized in dichloromethane using m-chloroperbenzoic acid. Through the above steps, the compound (Ep-15) represented by formula (59) was obtained.

[0706] (Fourth reaction)

[0707] Under nitrogen atmosphere, 4.5 g (number average molecular weight 2736, 1.7 mmol) of the compound represented by formula (60) as the intermediate compound (1O-3), 45 mL of methanol, and 4.5 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.45 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 5 hours to react.

[0708] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 3.6 g (number average molecular weight 2386, 1.5 mmol) of compound (1O) represented by the following formula (61).

[0709]

[0710] (In formula (61), Rf1 is represented by the above formula, j representing the average degree of polymerization in Rf1 is 6.3, and k representing the average degree of polymerization is 0.)

[0711] The obtained compound (1O) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0712] 1 H-NMR (CD3COCD3): δ[ppm]=1.78~1.92(6H), 3.30~4.40(50H), 7.24~7.43(2H)

[0713] 19 F-NMR (CD3COCD3): δ[ppm]=-78.5(4F), -81.3(4F), -90.0~-88.4(50.4F)

[0714] [Example 16]

[0715] (Second reaction)

[0716] In the second reaction of the above-mentioned Example 1, 3.3 g (molecular weight 652, 5.0 mmol) of the compound represented by the following formula (B1) was used instead of the compound represented by formula (A1). Except for this, the operations up to the second reaction were carried out in the same manner as in Example 1 to obtain 7.0 g of the intermediate compound (1P-2) represented by formula (62).

[0717]

[0718] (In formula (B1), Ts represents a p-toluenesulfonyl group, and Bn represents a benzyl group.)

[0719]

[0720] (In formula (62), Bn represents a benzyl group, Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 3.8.)

[0721] The compound represented by formula (B1) is synthesized by reacting benzyl chloroethyl ether with diethyl malonate, reducing the ester using lithium borohydride, and reacting the generated two primary hydroxyl groups with p-toluenesulfonyl chloride.

[0722] (Third reaction)

[0723] In a 200 mL eggplant flask, 5.0 g (number average molecular weight 2130, 2.4 mmol) of the compound represented by formula (62) as the intermediate compound (1P-2), 1.4 g (molecular weight 202, 7.1 mmol) of the compound (Ep-1) represented by the above formula (13), and 22 mL of tert-butyl alcohol were added under a nitrogen atmosphere, and stirred at room temperature until the mixture became uniform. 0.053 g (molecular weight 112, 0.47 mmol) of potassium tert-butylate was further added to the uniform liquid, and the mixture was stirred at 70° C. for 16 hours to allow the mixture to react.

[0724] The reaction product obtained after the reaction was cooled to 25°C, transferred to a separatory funnel to which 100 mL of water was added, and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with water and dehydrated by anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 4.0 g of a compound represented by the following formula (63) as an intermediate compound (1P-3).

[0725]

[0726] (In formula (63), THP represents a tetrahydropyranyl group, and Bn represents a benzyl group. Rf2 is represented by the above formula, and l in Rf2, which represents an average degree of polymerization, represents 3.8.)

[0727] (Fourth reaction)

[0728] In a nitrogen atmosphere, 4.0 g (number average molecular weight 2534, 1.6 mmol) of the compound represented by formula (63) as the intermediate compound (1P-3), 40 mL of methanol, and 4.0 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.40 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 5 hours to react.

[0729] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 3.1 g of the compound (1P) represented by the following formula (64) (number average molecular weight 2184, 1.4 mmol).

[0730]

[0731] (In formula (64), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 3.8.)

[0732] The obtained compound (1P) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0733] 1 H-NMR (CD3COCD3): δ[ppm]=1.63~1.84(4H), 3.39~4.34(40H)

[0734] 19 F-NMR (CD3COCD3): δ[ppm]=-84.0~-83.0(30.4F), -86.4(8F), -124.3(8F), -130.0~-129.0(15.2F)

[0735] [Example 17]

[0736] (Third reaction)

[0737] In the third reaction of the above-mentioned Example 16, 1.2 g (molecular weight 172, 7.1 mmol) of the compound (Ep-7) represented by the above-mentioned formula (33) was used instead of the compound (Ep-1) represented by the formula (13). Except for this, the operations until the third reaction were carried out in the same manner as in Example 16 to obtain 3.9 g of the intermediate compound (1Q-3) represented by the formula (65).

[0738]

[0739] (In formula (65), THP represents a tetrahydropyranyl group, and Bn represents a benzyl group. Rf2 is represented by the above formula, and l in Rf2, which represents an average degree of polymerization, represents 3.8.)

[0740] (Fourth reaction)

[0741] Under nitrogen atmosphere, 3.9 g (number average molecular weight 2474, 1.6 mmol) of the compound represented by formula (65) as the intermediate compound (1Q-3), 39 mL of methanol, and 3.9 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.39 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 5 hours to react.

[0742] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 3.0 g of the compound (1Q) represented by the following formula (66) (number average molecular weight 2124, 1.4 mmol).

[0743]

[0744] (In formula (66), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 3.8.)

[0745] The obtained compound (1Q) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0746] 1 H-NMR (CD3COCD3): δ[ppm]=1.61~1.85(8H), 3.43~4.32(32H)

[0747] 19 F-NMR (CD3COCD3): δ[ppm]=-55.6~-50.6(16F), -77.8(4F), -80.3(4F), -91.0~-88.4(32F)

[0748] [Example 18]

[0749] (Second reaction)

[0750] In the second reaction of the above-mentioned Example 1, 3.4 g (molecular weight 680, 5.0 mmol) of the compound represented by the following formula (C1) was used instead of the compound represented by formula (A1). Except for this, the operations up to the second reaction were carried out in the same manner as in Example 1 to obtain 7.3 g of the intermediate compound (1R-2) represented by formula (67).

[0751]

[0752] (In formula (C1), Ts represents a p-toluenesulfonyl group, and Bn represents a benzyl group.)

[0753]

[0754] (In formula (67), Bn represents a benzyl group, Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 3.8.)

[0755] The compound represented by formula (C1) is synthesized by reacting benzyl chloropropyl ether with diethyl malonate, reducing the ester using lithium borohydride, and reacting the generated two primary hydroxyl groups with p-toluenesulfonyl chloride.

[0756] (Third reaction)

[0757] In a nitrogen atmosphere, 5.0 g (number average molecular weight 2158, 2.2 mmol) of the compound represented by formula (67) as the intermediate compound (1R-2), 2.1 g (molecular weight 320, 6.5 mmol) of the compound (Ep-3) represented by the above formula (20), and 16 mL of tert-butyl alcohol were added to a 200 mL eggplant flask, and stirred at room temperature until the mixture became uniform. 0.048 g (molecular weight 112, 0.43 mmol) of potassium tert-butylate was further added to the uniform liquid, and the mixture was stirred at 70° C. for 16 hours to react.

[0758] The reaction product obtained after the reaction was cooled to 25°C, transferred to a separatory funnel to which 100 mL of water was added, and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with water and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 4.2 g of the compound represented by the following formula (68) as an intermediate compound (1R-3).

[0759]

[0760] (In formula (68), THP represents tetrahydropyranyl, Bn represents benzyl, and MOM represents methoxymethyl. Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 3.8.)

[0761] (Fourth reaction)

[0762] In a nitrogen atmosphere, 4.2 g of the compound represented by formula (68) as the intermediate compound (1R-3) (number average molecular weight 2799, 2.2 mmol), 42 mL of methanol, and 4.2 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.42 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 5 hours to react.

[0763] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 3.3 g of the compound (1R) represented by the following formula (69) (number average molecular weight 2361, 1.3 mmol).

[0764]

[0765] (In formula (69), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 3.8.)

[0766] The obtained compound (1R) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0767] 1 H-NMR (CD3COCD3): δ[ppm]=1.52~1.81(8H), 3.35~4.38(52H)

[0768] 19 F-NMR (CD3COCD3): δ[ppm]=-84.1~-83.0(30.4F), -86.4(8F), -124.3(8F), -130.2~-129.1(15.2F)

[0769] [Example 19]

[0770] (Second reaction)

[0771] In the second reaction of the above-mentioned Example 1, 3.6 g (molecular weight 712, 5.0 mmol) of the compound represented by the following formula (H1) was used instead of the compound represented by formula (A1). Except for this, the operations up to the second reaction were carried out in the same manner as in Example 1 to obtain 7.5 g of the intermediate compound (1S-2) represented by formula (70).

[0772]

[0773] (In formula (H1), Ts represents a p-toluenesulfonyl group, and Bn represents a benzyl group.)

[0774]

[0775] (In formula (70), Bn represents a benzyl group, Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 3.8.)

[0776] The compound represented by formula (H1) is synthesized by reacting 2-(chloromethoxy)ethoxymethylbenzene with diethyl malonate, reducing the ester using lithium borohydride, and reacting the generated two primary hydroxyl groups with p-toluenesulfonyl chloride.

[0777] (Third reaction)

[0778] In a nitrogen atmosphere, 5.0 g (number average molecular weight 2190, 2.1 mmol) of the compound represented by formula (70) as the intermediate compound (1S-2), 2.1 g (molecular weight 334, 6.4 mmol) of the compound (Ep-6) represented by the above formula (29), and 16 mL of tert-butyl alcohol were added to a 200 mL eggplant flask, and stirred at room temperature until the mixture became uniform. 0.048 g (molecular weight 112, 0.43 mmol) of potassium tert-butylate was further added to the uniform liquid, and the mixture was stirred at 70° C. for 16 hours to react.

[0779] The reaction product obtained after the reaction was cooled to 25°C, transferred to a separatory funnel to which 100 mL of water was added, and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with water and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 4.4 g of the compound represented by the following formula (71) as an intermediate compound (1S-3).

[0780]

[0781] (In formula (71), THP represents tetrahydropyranyl, Bn represents benzyl, and MOM represents methoxymethyl. Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 3.8.)

[0782] (Fourth reaction)

[0783] Under nitrogen atmosphere, 4.4 g (number average molecular weight 2859, 1.4 mmol) of the compound represented by formula (71) as the intermediate compound (1S-3), 42 mL of methanol, and 4.2 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.42 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 5 hours to react.

[0784] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 3.2 g of the compound (1S) represented by the following formula (72) (number average molecular weight 2435, 1.2 mmol).

[0785]

[0786] (In formula (72), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 3.8.)

[0787] The obtained compound (1S) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0788] 1 H-NMR (CD3COCD3): δ[ppm]=1.64~1.80(4H), 3.41~4.32(60H)

[0789] 19 F-NMR (CD3COCD3): δ[ppm]=-55.6~-50.6(16F), -77.7(4F), -80.3(4F), -91.0~-88.5(32F)

[0790] [Example 20]

[0791] (Second reaction)

[0792] In the second reaction of the above-mentioned Example 1, 3.4 g (molecular weight 668, 5.0 mmol) of the compound represented by the following formula (M1) was used instead of the compound represented by formula (A1). Except for this, the operations up to the second reaction were carried out in the same manner as in Example 1 to obtain 7.4 g of the intermediate compound (1T-2) represented by formula (73).

[0793]

[0794] (In formula (M1), Ts represents a p-toluenesulfonyl group, and Bn represents a benzyl group.)

[0795]

[0796] (In formula (73), Bn represents a benzyl group, Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 3.8.)

[0797] The compound represented by formula (M1) is synthesized by reacting 2-(chloromethoxy)ethoxymethylbenzene and benzyl chloromethyl ether with diethyl malonate in sequence, reducing the ester with lithium borohydride, and reacting the generated two primary hydroxyl groups with p-toluenesulfonyl chloride.

[0798] (Third reaction)

[0799] In a nitrogen atmosphere, 5.0 g (number average molecular weight 2146, 2.1 mmol) of the compound represented by formula (73) as the intermediate compound (1T-2), 1.3 g (molecular weight 202, 6.4 mmol) of the compound (Ep-1) represented by the above formula (13), and 16 mL of tert-butyl alcohol were added to a 200 mL eggplant flask, and stirred at room temperature until the mixture became uniform. 0.048 g (molecular weight 112, 0.43 mmol) of potassium tert-butylate was further added to the uniform liquid, and the mixture was stirred at 70° C. for 16 hours to react.

[0800] The reaction product obtained after the reaction was cooled to 25°C, transferred to a separatory funnel to which 100 mL of water was added, and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with water and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 3.9 g of the compound represented by the following formula (74) as an intermediate compound (1T-3).

[0801]

[0802] (In formula (74), THP represents a tetrahydropyranyl group, and Bn represents a benzyl group. Rf2 is represented by the above formula, and l in Rf2, which represents an average degree of polymerization, represents 3.8.)

[0803] (Fourth reaction)

[0804] Under nitrogen atmosphere, 3.9 g (number average molecular weight 2550, 1.4 mmol) of the compound represented by formula (74) as the intermediate compound (1T-3), 39 mL of methanol, and 3.9 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.39 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 5 hours to react.

[0805] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 3.0 g (number average molecular weight 2200, 1.3 mmol) of a compound (1T) represented by the following formula (75).

[0806]

[0807] (In formula (75), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, is 3.8.)

[0808] The obtained compound (1T) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0809] 1 H-NMR (CD3COCD3): δ[ppm]=3.37~4.37(44H)

[0810] 19 F-NMR (CD3COCD3): δ[ppm]=-84.0~-83.0(30.4F), -86.4(8F), -124.3(8F), -130.0~-129.0(15.2F)

[0811] [Example 21]

[0812] (First reaction)

[0813] In a 300 mL eggplant flask under nitrogen atmosphere, add HOCH2CF2CF2O (CF2CF2CF2O) l 10 g of a compound represented by CF2CF2CH2OH (where l in the formula represents the average degree of polymerization and is 2.0) (number average molecular weight 610, molecular weight distribution 1.1), 25.6 g of a compound represented by formula (A1) (molecular weight 624, 41.0 mmol), 1.1 g of potassium iodide (molecular weight 166, 6.6 mmol), and 33 mL of N,N'-dimethylformamide (DMF) were stirred at room temperature to prepare a mixed solution. 21.3 g of cesium carbonate (molecular weight 325, 65.6 mmol) was added to the mixed solution, and the mixture was stirred at 70°C for 10 hours to react.

[0814] The reaction product obtained after the reaction was cooled to 0°C, and 100 mL of water was added to stop the reaction. The resulting reaction solution was transferred to a separatory funnel and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with saline and dehydrated with anhydrous sodium sulfate. After the desiccant was filtered and separated, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 11.0 g of the compound represented by the following formula (76) as an intermediate compound (2A-1).

[0815]

[0816] (In formula (76), Ts represents a p-toluenesulfonyl group, Bn represents a benzyl group, and l representing an average degree of polymerization represents 2.0.)

[0817] (Second reaction)

[0818] In a 300 mL eggplant flask under nitrogen atmosphere, add HOCH2CF2CF2O (CF2CF2CF2O) l 20 g of a compound represented by CF2CF2CH2OH (where l in the formula represents the average degree of polymerization and is 2.0) (number average molecular weight 610, molecular weight distribution 1.1), 2.9 g of 3,4-dihydro-2H-pyran, and 66 mL of a mixed solution (volume ratio 1:1) of Asahiklin (registered trademark) AE-3000 (manufactured by AGC Co., Ltd.) and dichloromethane as a fluorine-based solvent were stirred at 0°C until it became uniform to prepare a mixed solution. 0.13 g of p-toluenesulfonic acid monohydrate was added to the mixed solution, stirred at 0°C for 30 minutes, and then stirred at room temperature for 2 hours to react.

[0819] The reaction product obtained after the reaction was cooled to 0°C, and 50 mL of saturated sodium bicarbonate water was added to stop the reaction. The resulting reaction solution was transferred to a separatory funnel and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with brine and dehydrated with anhydrous sodium sulfate. After the desiccant was filtered and separated, the filtrate was concentrated, and the residue was refined by silica gel column chromatography to obtain 10.0 g of the compound represented by the following formula (77) as an intermediate compound (2A-2).

[0820]

[0821] (In formula (77), THP represents tetrahydropyranyl, and l representing the average degree of polymerization represents 2.0.)

[0822] (Third reaction)

[0823] In a 200 mL eggplant flask under a nitrogen atmosphere, 7.0 g (number average molecular weight 1517, 4.6 mmol) of the compound represented by formula (76) as the intermediate compound (2A-1), 7.0 g (number average molecular weight 694, 10.2 mmol) of the compound represented by formula (77) as the intermediate compound (2A-2), 0.31 g (molecular weight 166, 1.9 mmol), and 10 mL of N,N'-dimethylformamide (DMF) were added, and stirred at room temperature to prepare a mixed solution. 6.0 g (molecular weight 325, 18.5 mmol) of cesium carbonate was added to the mixed solution, and the mixture was stirred at 70°C for 10 hours to react.

[0824] The reaction solution obtained after the reaction was returned to room temperature, 12 g of 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 2 hours. The reaction solution was transferred little by little to a separatory funnel added with 100 mL of brine, and extracted 3 times with 200 mL of ethyl acetate. The organic layer was washed with 100 mL of brine, 100 mL of saturated sodium bicarbonate water, and 100 mL of brine in this order, and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated and the residue was refined by silica gel column chromatography. By performing the above steps, 5.0 g of the compound represented by the following formula (78) was obtained as an intermediate compound (2A-3).

[0825]

[0826] (In formula (78), Bn represents a benzyl group, Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 2.0.)

[0827] (Fourth reaction)

[0828] In a 200 mL eggplant flask, 5.0 g (number average molecular weight 2392, 2.3 mmol) of the compound represented by formula (78) as the intermediate compound (2A-3), 1.0 g (molecular weight 202, 4.9 mmol) of the compound (Ep-1) represented by the above formula (13), and 2.1 mL of tert-butyl alcohol were added under a nitrogen atmosphere, and stirred at room temperature until the mixture became homogeneous. 0.076 g (molecular weight 113, 0.67 mmol) of potassium tert-butylate was further added to the homogeneous liquid, and the mixture was stirred at 70° C. for 16 hours to react.

[0829] The reaction product obtained after the reaction was cooled to 25°C, transferred to a separatory funnel to which 100 mL of water was added, and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with water and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 3.5 g of a compound represented by the following formula (79) as an intermediate compound (2A-4).

[0830]

[0831] (In formula (79), THP represents a tetrahydropyranyl group, and Bn represents a benzyl group. Rf2 is represented by the above formula, and the l in Rf2 representing the average degree of polymerization represents 2.0.)

[0832] (Fifth Reaction)

[0833] Under nitrogen atmosphere, 3.5 g of the compound represented by formula (79) as the intermediate compound (2A-4) (number average molecular weight 2797, 1.3 mmol), 35 mL of methanol, and 3.5 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.35 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 8 hours to react.

[0834] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 2.6 g (number average molecular weight 2271, 1.2 mmol) of a compound (2A) represented by the following formula (80).

[0835]

[0836] (In formula (80), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 2.0.)

[0837] The obtained compound (2A) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0838] 1 H-NMR (CD3COCD3): δ[ppm]=3.37~4.35(54H)

[0839] 19 F-NMR (CD3COCD3): δ[ppm]=-84.2~-83.0(24F), -86.4(12F), -124.3(12F), -130.0~-128.9(12F)

[0840] [Example 22]

[0841] (Fourth reaction)

[0842] In the fourth reaction of the above-mentioned Example 21, 1.4 g (molecular weight 216, 4.9 mmol) of the compound (Ep-2) represented by the above-mentioned formula (16) was used instead of the compound (Ep-1) represented by the formula (13). Except for this, the operations until the fourth reaction were carried out in the same manner as in Example 21 to obtain 3.9 g of the intermediate compound (2B-4) represented by the formula (81).

[0843]

[0844] (In formula (81), THP represents a tetrahydropyranyl group, and Bn represents a benzyl group. Rf2 is represented by the above formula, and the l representing the average degree of polymerization in Rf2 represents 2.0.)

[0845] (Fifth Reaction)

[0846] Under nitrogen atmosphere, 3.9 g (number average molecular weight 2948, 1.4 mmol) of the compound represented by formula (81) as the intermediate compound (2B-4), 39 mL of methanol, and 3.9 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.39 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 8 hours to react.

[0847] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 3.0 g of the compound (2B) represented by the following formula (82) (number average molecular weight 2299, 1.2 mmol).

[0848]

[0849] (In formula (82), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 2.0.)

[0850] The obtained compound (2B) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0851] 1 H-NMR (CD3COCD3): δ[ppm]=1.63~1.82(4H), 3.38~4.38(54H)

[0852] 19 F-NMR (CD3COCD3): δ[ppm]=-84.0~-83.0(24F), -86.4(12F), -124.3(12F), -130.0~-129.0(12F)

[0853] [Example 23]

[0854] (Fourth reaction)

[0855] In the fourth reaction of the above-mentioned Example 21, 1.6 g (molecular weight 320, 4.9 mmol) of the compound (Ep-3) represented by the above-mentioned formula (20) was used instead of the compound (Ep-1) represented by the formula (13). Except for this, the operations until the fourth reaction were carried out in the same manner as in Example 21 to obtain 3.7 g of the intermediate compound (2C-4) represented by the formula (83).

[0856]

[0857] (In formula (83), THP represents a tetrahydropyranyl group, Bn represents a benzyl group, and MOM represents a methoxymethyl group. Rf2 is represented by the above formula, and the l in Rf2 representing the average degree of polymerization represents 2.0.)

[0858] (Fifth Reaction)

[0859] Under nitrogen atmosphere, 3.8 g (number average molecular weight 3032, 1.3 mmol) of the compound represented by formula (83) as the intermediate compound (2C-4), 38 mL of methanol, and 3.8 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.38 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 8 hours to react.

[0860] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 2.6 g (number average molecular weight 2419, 1.2 mmol) of a compound (2C) represented by the following formula (84).

[0861]

[0862] (In formula (84), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 2.0.)

[0863] The obtained compound (2C) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0864] 1 H-NMR (CD3COCD3): δ[ppm]=3.36~4.39(66H)

[0865] 19 F-NMR (CD3COCD3): δ[ppm]=-84.2~-83.0(24F), -86.4(12F), -124.2(12F), -130.2~-129.1(12F)

[0866] [Example 24]

[0867] (Fourth reaction)

[0868] In the fourth reaction of the above-mentioned Example 21, 1.7 g (molecular weight 334, 4.9 mmol) of the compound (Ep-4) represented by the above-mentioned formula (23) was used instead of the compound (Ep-1) represented by the formula (13). Except for this, the operations until the fourth reaction were carried out in the same manner as in Example 21 to obtain 3.8 g of the intermediate compound (2D-4) represented by the formula (85).

[0869]

[0870] (In formula (85), THP represents tetrahydropyranyl, Bn represents benzyl, and MOM represents methoxymethyl. Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 2.0.)

[0871] (Fifth Reaction)

[0872] Under nitrogen atmosphere, 3.7 g (number average molecular weight 3062, 1.3 mmol) of the compound represented by formula (85) as the intermediate compound (2D-4), 37 mL of methanol, and 3.7 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.37 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 8 hours to react.

[0873] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 2.6 g (number average molecular weight 2447, 1.2 mmol) of a compound (2D) represented by the following formula (86).

[0874]

[0875] (In formula (86), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 2.0.)

[0876] The obtained compound (2D) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0877] 1 H-NMR (CD3COCD3): δ[ppm]=1.63~1.85(4H), 3.36~4.35(66H)

[0878] 19F-NMR (CD3COCD3): δ[ppm]=-84.0~-83.0(24F), -86.4(12F), -124.3(12F), -130.0~-129.0(12F)

[0879] [Example 25]

[0880] (Fourth reaction)

[0881] In the fourth reaction of the above-mentioned Example 21, 1.4 g (molecular weight 216, 4.9 mmol) of the compound (Ep-5) represented by the above-mentioned formula (26) was used instead of the compound (Ep-1) represented by the formula (13). Except for this, the operations until the fourth reaction were carried out in the same manner as in Example 21 to obtain 3.8 g of the intermediate compound (2E-4) represented by the formula (87).

[0882]

[0883] (In formula (87), THP represents a tetrahydropyranyl group, and Bn represents a benzyl group. Rf2 is represented by the above formula, and the l representing the average degree of polymerization in Rf2 represents 2.0.)

[0884] (Fifth Reaction)

[0885] Under nitrogen atmosphere, 3.8 g (number average molecular weight 2925, 1.4 mmol) of the compound represented by formula (87) as the intermediate compound (2E-4), 39 mL of methanol, and 3.8 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.38 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 8 hours to react.

[0886] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 2.7 g (number average molecular weight 2299, 1.2 mmol) of a compound (2E) represented by the following formula (88).

[0887]

[0888] (In formula (88), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 2.0.)

[0889] The obtained compound (2E) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0890] 1H-NMR (CD3COCD3): δ[ppm]=1.65~1.79(4H), 3.41~4.33(54H)

[0891] 19 F-NMR (CD3COCD3): δ[ppm]=-84.0~-83.0(24F), -86.4(12F), -124.3(12F), -130.0~-129.0(12F)

[0892] [Example 26]

[0893] (Fourth reaction)

[0894] In the fourth reaction of the above-mentioned Example 21, 1.4 g (molecular weight 334, 4.9 mmol) of the compound (Ep-6) represented by the above-mentioned formula (29) was used instead of the compound (Ep-1) represented by the formula (13). Except for this, the operations until the fourth reaction were carried out in the same manner as in Example 21 to obtain 3.6 g of the intermediate compound (2F-4) represented by the formula (89).

[0895]

[0896] (In formula (89), THP represents a tetrahydropyranyl group, Bn represents a benzyl group, and MOM represents a methoxymethyl group. Rf2 is represented by the above formula, and the l in Rf2 representing the average degree of polymerization represents 2.0.)

[0897] (Fifth Reaction)

[0898] Under nitrogen atmosphere, 3.8 g (number average molecular weight 2925, 1.4 mmol) of the compound represented by formula (89) as the intermediate compound (2F-4), 39 mL of methanol, and 3.8 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.38 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 8 hours to react.

[0899] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 2.7 g (number average molecular weight 2447, 1.2 mmol) of a compound (2F) represented by the following formula (90).

[0900]

[0901] (In formula (90), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 2.0.)

[0902] The obtained compound (2F) is subjected to1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0903] 1 H-NMR (CD3COCD3): δ[ppm]=1.64~1.80(4H), 3.43~4.32(66H)

[0904] 19 F-NMR (CD3COCD3): δ[ppm]=-84.0~-83.0(24F), -86.4(12F), -124.3(12F), -130.0~-129.0(12F)

[0905] [Example 27]

[0906] (First reaction)

[0907] In a 300 mL eggplant flask under nitrogen atmosphere, add HOCH2CF2O (CF2CF2O) j (CF2O) k 10 g of a compound represented by CF2CH2OH (wherein j represents the average degree of polymerization and k represents the average degree of polymerization, 2.4) (number average molecular weight 614, molecular weight distribution 1.1), 25.4 g of a compound represented by formula (A1) (molecular weight 624, 40.7 mmol), 1.1 g of potassium iodide (molecular weight 166, 6.5 mmol), and 33 mL of N,N'-dimethylformamide (DMF) were stirred at room temperature to prepare a mixed solution. 21.2 g of cesium carbonate (molecular weight 325, 65.1 mmol) was added to the mixed solution, and the mixture was stirred at 70°C for 10 hours to react.

[0908] The reaction product obtained after the reaction was cooled to 0°C, and 100 mL of water was added to stop the reaction. The resulting reaction solution was transferred to a separatory funnel and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with saline and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 10.5 g of the compound represented by the following formula (91) as an intermediate compound (2G-1).

[0909]

[0910] (In formula (91), Ts represents a p-toluenesulfonyl group, and Bn represents a benzyl group. Rf1 is represented by the above formula, and j representing the average degree of polymerization in Rf1 is 2.4, and k representing the average degree of polymerization is 2.4.)

[0911] (Second reaction)

[0912] In a 300 mL eggplant flask under nitrogen atmosphere, add HOCH2CF2O (CF2CF2O) j (CF2O) k 20 g of a compound represented by CF2CH2OH (wherein j representing the average degree of polymerization is 2.4, and k representing the average degree of polymerization is 2.4) (number average molecular weight 614, molecular weight distribution 1.1), 2.9 g of 3,4-dihydro-2H-pyran, and 66 mL of a mixed solution (volume ratio 1:1) of Asahiklin (registered trademark) AE-3000 (manufactured by AGC Co., Ltd.) and dichloromethane as a fluorine-based solvent were stirred at 0°C until it became uniform to prepare a mixed solution. 0.12 g of p-toluenesulfonic acid monohydrate was added to the mixed solution, and after stirring at 0°C for 30 minutes, it was stirred at room temperature for 2 hours to react.

[0913] The reaction product obtained after the reaction was cooled to 0°C, and 50 mL of saturated sodium bicarbonate water was added to stop the reaction. The resulting reaction solution was transferred to a separatory funnel and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with brine and dehydrated with anhydrous sodium sulfate. After the desiccant was filtered and separated, the filtrate was concentrated, and the residue was refined by silica gel column chromatography to obtain 10.0 g of the compound represented by the following formula (92) as an intermediate compound (2G-2).

[0914]

[0915] (In formula (92), THP represents a tetrahydropyranyl group, Rf1 is represented by the above formula, j representing the average degree of polymerization in Rf1 is 2.4, and k representing the average degree of polymerization is 2.4.)

[0916] (Third reaction)

[0917] In a 200 mL eggplant flask, 7.0 g (number average molecular weight 1522, 4.6 mmol) of the compound represented by formula (91) as the intermediate compound (2G-1), 7.1 g (number average molecular weight 699, 10.1 mmol) of the compound represented by formula (92) as the intermediate compound (2G-2), 0.31 g (molecular weight 166, 1.9 mmol), and 10 mL of N,N'-dimethylformamide (DMF) were added under a nitrogen atmosphere, and stirred at room temperature to prepare a mixed solution. 6.0 g (molecular weight 325, 18.4 mmol) of cesium carbonate was added to the mixed solution, and the mixture was stirred at 70°C for 10 hours to react.

[0918] The reaction solution obtained after the reaction was returned to room temperature, 12 g of 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 2 hours. The reaction solution was transferred little by little to a separatory funnel added with 100 mL of brine, and extracted three times with 200 mL of ethyl acetate. The organic layer was washed with 100 mL of brine, 100 mL of saturated sodium bicarbonate water, and 100 mL of brine in this order, and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated and the residue was refined by silica gel column chromatography. By performing the above steps, 5.2 g of the compound represented by the following formula (93) was obtained as an intermediate compound (2G-3).

[0919]

[0920] (In formula (93), Bn represents a benzyl group, Rf1 is represented by the above formula, j representing the average degree of polymerization in Rf1 is 2.4, and k representing the average degree of polymerization is 2.4.)

[0921] (Fourth reaction)

[0922] In a 200 mL eggplant flask, 5.0 g (number average molecular weight 2407, 2.2 mmol) of the compound represented by formula (93) as an intermediate compound (2G-3), 0.8 g (molecular weight 172, 4.9 mmol) of the compound (Ep-7) represented by the above formula (33), and 2.1 mL of tert-butyl alcohol were added under a nitrogen atmosphere, and stirred at room temperature until the mixture became homogeneous. 0.076 g (molecular weight 113, 0.67 mmol) of potassium tert-butylate was further added to the homogeneous liquid, and the mixture was stirred at 70° C. for 16 hours to react.

[0923] The reaction product obtained after the reaction was cooled to 25°C, transferred to a separatory funnel to which 100 mL of water was added, and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with water and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 3.6 g of the compound represented by the following formula (94) as an intermediate compound (2G-4).

[0924]

[0925] (In formula (94), THP represents a tetrahydropyranyl group, Bn represents a benzyl group, Rf1 is represented by the above formula, j representing the average degree of polymerization in Rf1 is 2.4, and k representing the average degree of polymerization is 2.4.)

[0926] (Fifth Reaction)

[0927] Under nitrogen atmosphere, 3.6 g of the compound represented by formula (94) as the intermediate compound (2G-4) (number average molecular weight 2752, 1.4 mmol), 36 mL of methanol, and 3.6 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.36 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 8 hours to react.

[0928] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 2.5 g of a compound (2G) represented by the following formula (95) (number average molecular weight 2225, 1.2 mmol).

[0929]

[0930] (In formula (95), Rf1 is represented by the above formula, j representing the average degree of polymerization in Rf1 is 2.4, and k representing the average degree of polymerization is 2.4.)

[0931] The obtained compound (2G) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0932] 1 H-NMR (CD3COCD3): δ[ppm]=1.64~1.81(4H), 3.44~4.31(46H)

[0933] 19 F-NMR (CD3COCD3): δ[ppm]=-55.6~-50.6(14.4F), -77.7(6F), -80.3(6F), -91.0~-88.5(28.8F)

[0934] [Example 28]

[0935] (Fourth reaction)

[0936] In the fourth reaction of the above-mentioned Example 27, 1.0 g (molecular weight 200, 4.9 mmol) of the compound (Ep-8) represented by the above-mentioned formula (37) was used instead of the compound (Ep-7) represented by the formula (33). Except for this, the operations until the fourth reaction were carried out in the same manner as in Example 27 to obtain 3.7 g of the intermediate compound (2H-4) represented by the formula (96).

[0937]

[0938] (In formula (96), THP represents a tetrahydropyranyl group, and Bn represents a benzyl group. Rf1 is represented by the above formula, and j representing the average degree of polymerization in Rf1 is 2.4, and k representing the average degree of polymerization is 2.4.)

[0939] (Fifth Reaction)

[0940] Under nitrogen atmosphere, 3.7 g (number average molecular weight 2807, 1.4 mmol) of the compound represented by formula (96) as the intermediate compound (2H-4), 37 mL of methanol, and 3.7 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.37 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 8 hours to react.

[0941] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 2.6 g (number average molecular weight 2281, 1.2 mmol) of the compound (2H) represented by the following formula (97).

[0942]

[0943] (In formula (97), Rf1 is represented by the above formula, j representing the average degree of polymerization in Rf1 is 2.4, and k representing the average degree of polymerization is 2.4.)

[0944] The obtained compound (2H) is 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0945] 1 H-NMR (CD3COCD3): δ[ppm]=1.32~1.80(12H), 3.39~4.35(46H)

[0946] 19 F-NMR (CD3COCD3): δ[ppm]=-55.7~-50.5(14.4F), -77.7(6F), -80.3(6F), -91.1~-88.4(28.8F)

[0947] [Example 29]

[0948] (First reaction)

[0949] In a 300 mL eggplant flask under nitrogen atmosphere, add HOCH2CF2O (CF2CF2O) j (CF2O) k10 g of a compound represented by CF2CH2OH (wherein j representing the average degree of polymerization is 3.8, and k representing the average degree of polymerization is 0) (number average molecular weight 618, molecular weight distribution 1.1), 25.2 g of a compound represented by formula (A1) (molecular weight 624, 40.4 mmol), 1.1 g of potassium iodide (molecular weight 166, 6.5 mmol), and 33 mL of N,N'-dimethylformamide (DMF) were stirred at room temperature to prepare a mixed solution. 21.0 g of cesium carbonate (molecular weight 325, 64.6 mmol) was added to the mixed solution, and the mixture was stirred at 70°C for 10 hours to react.

[0950] The reaction product obtained after the reaction was cooled to 0°C, and 100 mL of water was added to stop the reaction. The resulting reaction solution was transferred to a separatory funnel and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with saline and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 10.0 g of the compound represented by the following formula (98) as an intermediate compound (2I-1).

[0951]

[0952] (In formula (98), Ts represents a p-toluenesulfonyl group, and Bn represents a benzyl group. Rf1 is represented by the above formula, and j representing the average degree of polymerization in Rf1 is 3.8, and k representing the average degree of polymerization is 0.)

[0953] (Second reaction)

[0954] In a 300 mL eggplant flask under nitrogen atmosphere, add HOCH2CF2O (CF2CF2O) j (CF2O) k 20 g of a compound represented by CF2CH2OH (wherein j representing the average degree of polymerization is 3.8, and k representing the average degree of polymerization is 0) (number average molecular weight 618, molecular weight distribution 1.1), 2.9 g of 3,4-dihydro-2H-pyran, and 66 mL of a mixed solution (volume ratio 1:1) of Asahiklin (registered trademark) AE-3000 (manufactured by AGC Co., Ltd.) and dichloromethane as a fluorine-based solvent were stirred at 0°C until it became uniform to prepare a mixed solution. 0.12 g of p-toluenesulfonic acid monohydrate was added to the mixed solution, and after stirring at 0°C for 30 minutes, it was stirred at room temperature for 2 hours to react.

[0955] The reaction product obtained after the reaction was cooled to 0°C, and 50 mL of saturated sodium bicarbonate water was added to stop the reaction. The resulting reaction solution was transferred to a separatory funnel and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with brine and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 9.9 g of the compound represented by the following formula (99) as an intermediate compound (2I-2).

[0956]

[0957] (In formula (99), THP represents a tetrahydropyranyl group, Rf1 is represented by the above formula, j representing the average degree of polymerization in Rf1 is 3.8, and k representing the average degree of polymerization is 0.)

[0958] (Third reaction)

[0959] In a 200 mL eggplant flask, 7.0 g (number average molecular weight 1525, 4.6 mmol) of the compound represented by formula (98) as the intermediate compound (2I-1), 7.1 g (number average molecular weight 702, 10.1 mmol) of the compound represented by formula (99) as the intermediate compound (2I-2), 0.31 g (molecular weight 166, 1.8 mmol), and 10 mL of N,N'-dimethylformamide (DMF) were added under a nitrogen atmosphere, and stirred at room temperature to prepare a mixed solution. 6.0 g (molecular weight 325, 18.4 mmol) of cesium carbonate was added to the mixed solution, and the mixture was stirred at 70°C for 10 hours to react.

[0960] The reaction solution obtained after the reaction was returned to room temperature, 12 g of 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 2 hours. The reaction solution was transferred little by little to a separatory funnel added with 100 mL of brine, and extracted 3 times with 200 mL of ethyl acetate. The organic layer was washed with 100 mL of brine, 100 mL of saturated sodium bicarbonate water, and 100 mL of brine in this order, and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated and the residue was refined by silica gel column chromatography. By performing the above steps, 5.0 g of the compound represented by the following formula (100) was obtained as an intermediate compound (2I-3).

[0961]

[0962] (In formula (100), Bn represents a benzyl group, Rf1 is represented by the above formula, j representing the average degree of polymerization in Rf1 is 3.8, and k representing the average degree of polymerization is 0.)

[0963] (Fourth reaction)

[0964] In a nitrogen atmosphere, 5.0 g (number average molecular weight 2418, 2.2 mmol) of the compound represented by formula (100) as the intermediate compound (2I-3), 1.5 g (molecular weight 172, 4.9 mmol) of the compound (Ep-9) represented by the above formula (41), and 2.1 mL of tert-butyl alcohol were added to a 200 mL eggplant flask, and stirred at room temperature until the mixture became homogeneous. 0.076 g (molecular weight 113, 0.67 mmol) of potassium tert-butylate was further added to the homogeneous liquid, and the mixture was stirred at 70° C. for 16 hours to react.

[0965] The reaction product obtained after the reaction was cooled to 25°C, transferred to a separatory funnel to which 100 mL of water was added, and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with water and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 3.5 g of the compound represented by the following formula (101) as an intermediate compound (2I-4).

[0966]

[0967] (In formula (101), THP represents tetrahydropyranyl, Bn represents benzyl, and MOM represents methoxymethyl. Rf1 is represented by the above formula, and j representing the average degree of polymerization in Rf1 is 3.8, and k representing the average degree of polymerization is 0.)

[0968] (Fifth Reaction)

[0969] Under nitrogen atmosphere, 3.5 g (number average molecular weight 3027, 1.2 mmol) of the compound represented by formula (101) as the intermediate compound (2I-4), 35 mL of methanol, and 3.5 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.35 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 8 hours to react.

[0970] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 2.4 g (number average molecular weight 2413, 1.1 mmol) of compound (2I) represented by the following formula (102).

[0971]

[0972] (In formula (102), Rf1 is represented by the above formula, j representing the average degree of polymerization in Rf1 is 3.8, and k representing the average degree of polymerization is 0.)

[0973] The obtained compound (2I) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0974] 1 H-NMR (CD3COCD3): δ[ppm]=1.32~1.70(8H), 3.41~4.30(58H)

[0975] 19 F-NMR (CD3COCD3): δ[ppm]=-78.6(6F), -81.3(6F), -90.0~-88.5(45.6F)

[0976] [Example 30]

[0977] (First reaction)

[0978] In a 300 mL eggplant flask under nitrogen atmosphere, add HOCH2CF2CF2O (CF2CF2CF2O) l 10 g of a compound represented by CF2CF2CH2OH (where l in the formula represents the average degree of polymerization and is 2.0) (number average molecular weight 610, molecular weight distribution 1.1), 12.4 g of a compound represented by formula (S1) (molecular weight 302, 41.0 mmol), 1.1 g of potassium iodide (molecular weight 166, 6.6 mmol), and 33 mL of N,N'-dimethylformamide (DMF) were stirred at room temperature to prepare a mixed solution. 21.3 g of cesium carbonate (molecular weight 325, 65.6 mmol) was added to the mixed solution, and the mixture was stirred at 70°C for 10 hours to react.

[0979] The reaction product obtained after the reaction was cooled to 0°C, and 100 mL of water was added to stop the reaction. The resulting reaction solution was transferred to a separatory funnel and extracted 3 times with 100 mL of ethyl acetate. The organic layer was washed with saline and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 10.0 g of the compound represented by the following formula (103) as an intermediate compound (2J-1).

[0980]

[0981] (In formula (103), l representing the average degree of polymerization is 2.0.)

[0982] (Second reaction)

[0983] Under nitrogen atmosphere, add HOCH2CF2CF2O (CF2CF2CF2O) into a 200 mL eggplant flask. l 20 g of the compound represented by CF2CF2CH2OH (where l in the formula represents the average degree of polymerization and is 2.0) (number average molecular weight 610, molecular weight distribution 1.1), 7.1 g of the compound (Ep-10) represented by the above formula (44) (molecular weight 272, 26.2 mmol), and 31 mL of tert-butyl alcohol were stirred at room temperature until the mixture became uniform. 0.736 g of potassium tert-butylate (molecular weight 113, 6.6 mmol) was further added to the uniform liquid, and the mixture was stirred at 70°C for 16 hours to react.

[0984] The reaction product obtained after the reaction was cooled to 25°C, transferred to a separatory funnel to which 100 mL of water was added, and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with water and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 9.7 g of the compound represented by the following formula (104) as an intermediate compound (2J-2).

[0985]

[0986] (In formula (104), THP represents a tetrahydropyranyl group, Rf2 is represented by the above formula, and l in Rf2, which represents an average degree of polymerization, represents 2.0.)

[0987] (Third reaction)

[0988] In a 200 mL eggplant flask, 5.0 g (number average molecular weight 1052, 4.8 mmol) of the compound represented by formula (103) as the intermediate compound (2J-1), 9.2 g (number average molecular weight 882, 10.5 mmol) of the compound represented by formula (104) as the intermediate compound (2J-2), 0.32 g (molecular weight 166, 1.9 mmol), and 10 mL of N,N'-dimethylformamide (DMF) were added under a nitrogen atmosphere, and stirred at room temperature to prepare a mixed solution. 6.2 g (molecular weight 325, 19.0 mmol) of cesium carbonate was added to the mixed solution, and the mixture was stirred at 70°C for 10 hours to react.

[0989] The reaction solution obtained after the reaction was restored to room temperature, 25 g of 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 2 hours. The reaction solution was transferred little by little to a separatory funnel added with 100 mL of brine, and extracted three times with 200 mL of ethyl acetate. The organic layer was washed with 100 mL of brine, 100 mL of saturated sodium bicarbonate water, and 100 mL of brine in this order, and dehydrated with anhydrous sodium sulfate. After the desiccant was filtered and separated, the filtrate was concentrated and the residue was refined by silica gel column chromatography. By performing the above steps, 3.2 g (number average molecular weight 2411, 1.2 mmol) of compound (2J) represented by the following formula (105) was obtained.

[0990]

[0991] (In formula (105), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 2.0.)

[0992] The obtained compound (2J) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[0993] 1 H-NMR (CD3COCD3): δ[ppm]=3.39~4.34(60H), 5.14~5.22(2H), 5.26~5.35(2H), 5.87~5.91(2H) 19 F-NMR (CD3COCD3): δ[ppm]=-84.0~-83.0(24F), -86.4(12F), -124.3(12F), -130.0~-129.0(12F)

[0994] [Example 31]

[0995] (First reaction)

[0996] The same operation as the first reaction in Example 30 was carried out to obtain an intermediate compound (2J-1) represented by formula (103).

[0997] (Second reaction)

[0998] Under nitrogen atmosphere, add HOCH2CF2CF2O (CF2CF2CF2O) into a 200 mL eggplant flask. l20 g of the compound represented by CF2CF2CH2OH (where l in the formula represents the average degree of polymerization and is 2.0) (number average molecular weight 610, molecular weight distribution 1.1), 7.9 g of the compound (Ep-11) represented by the above formula (47) (molecular weight 300, 26.2 mmol), and 31 mL of tert-butyl alcohol were stirred at room temperature until it became uniform. 0.736 g of potassium tert-butylate (molecular weight 113, 6.6 mmol) was further added to the uniform liquid, and the mixture was stirred at 70°C for 16 hours to react.

[0999] The reaction product obtained after the reaction was cooled to 25°C, transferred to a separatory funnel to which 100 mL of water was added, and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with water and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 9.8 g of the compound represented by the following formula (106) as an intermediate compound (2K-2).

[1000]

[1001] (In formula (106), THP represents a tetrahydropyranyl group, Rf2 is represented by the above formula, and l in Rf2, which represents an average degree of polymerization, represents 2.0.)

[1002] (Third reaction)

[1003] In a 200 mL eggplant flask, 5.0 g (number average molecular weight 1052, 4.8 mmol) of the compound represented by formula (103) as the intermediate compound (2J-1), 9.5 g (number average molecular weight 910, 10.5 mmol) of the compound represented by formula (106) as the intermediate compound (2K-2), 0.32 g (molecular weight 166, 1.9 mmol), and 10 mL of N,N'-dimethylformamide (DMF) were added under a nitrogen atmosphere, and stirred at room temperature to prepare a mixed solution. 6.2 g (molecular weight 325, 19.0 mmol) of cesium carbonate was added to the mixed solution, and the mixture was stirred at 70°C for 10 hours to react.

[1004] The reaction solution obtained after the reaction was returned to room temperature, 25 g of 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 2 hours. The reaction solution was transferred little by little to a separatory funnel added with 100 mL of brine, and extracted three times with 200 mL of ethyl acetate. The organic layer was washed with 100 mL of brine, 100 mL of saturated sodium bicarbonate water, and 100 mL of brine in this order, and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated and the residue was refined by silica gel column chromatography. By performing the above steps, 3.2 g (number average molecular weight 2467, 1.2 mmol) of compound (2K) represented by the following formula (107) was obtained.

[1005]

[1006] (In formula (107), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 2.0.)

[1007] The obtained compound (2K) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[1008] 1 H-NMR (CD3COCD3): δ[ppm]=1.66~1.81(4H), 2.33~2.43(4H), 3.39~4.34(60H), 5.14~5.22(2H), 5.26~5.35(2H), 5.87~5.91(2H)

[1009] 19 F-NMR (CD3COCD3): δ[ppm]=-84.0~-83.0(24F), -86.4(12F), -124.3(12F), -130.0~-129.0(12F)

[1010] [Example 32]

[1011] (Fourth reaction)

[1012] In the fourth reaction of the above-mentioned Example 29, 1.5 g (molecular weight 299, 4.9 mmol) of the compound (Ep-12) represented by the above-mentioned formula (50) was used instead of the compound (Ep-9) represented by the formula (41). Except for this, the operations until the fourth reaction were carried out in the same manner as in Example 29 to obtain 3.6 g of the intermediate compound (2L-4) represented by the formula (108).

[1013]

[1014] (In formula (108), THP represents a tetrahydropyranyl group, and Bn represents a benzyl group. Rf1 is represented by the above formula, and j representing the average degree of polymerization in Rf1 is 3.8, and k representing the average degree of polymerization is 0.)

[1015] (Fifth Reaction)

[1016] Under nitrogen atmosphere, 3.6 g (number average molecular weight 3017, 1.3 mmol) of the compound represented by formula (108) as the intermediate compound (2L-4), 36 mL of methanol, and 3.6 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.36 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 8 hours to react.

[1017] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 2.5 g (number average molecular weight 2491, 1.1 mmol) of a compound (2L) represented by the following formula (109).

[1018]

[1019] (In formula (109), Rf1 is represented by the above formula, j representing the average degree of polymerization in Rf1 is 3.8, and k representing the average degree of polymerization is 0.)

[1020] The obtained compound (2L) was subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[1021] 1 H-NMR (CD3COCD3): δ[ppm]=1.13~1.27(4H), 2.00~2.10(4H), 3.37~4.36(60H)

[1022] 19 F-NMR (CD3COCD3): δ[ppm]=-78.6(6F), -81.3(6F), -90.0~-88.5(45.6F)

[1023] [Example 33]

[1024] (Fourth reaction)

[1025] In the fourth reaction of the above-mentioned Example 27, 1.9 g (molecular weight 388, 4.9 mmol) of the compound (Ep-13) represented by the above-mentioned formula (54) was used instead of the compound (Ep-7) represented by the formula (33). Except for this, the operations until the fourth reaction were carried out in the same manner as in Example 27 to obtain 3.8 g of the intermediate compound (2M-4) represented by the formula (110).

[1026]

[1027] (In formula (110), THP represents a tetrahydropyranyl group, and Bn represents a benzyl group. Rf1 is represented by the above formula, and j representing the average degree of polymerization in Rf1 is 2.4, and k representing the average degree of polymerization is 2.4.)

[1028] (Fifth Reaction)

[1029] Under nitrogen atmosphere, 3.8 g (number average molecular weight 3184, 1.3 mmol) of the compound represented by formula (110) as the intermediate compound (2M-4), 38 mL of methanol, and 3.8 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.38 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 8 hours to react.

[1030] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 2.7 g (number average molecular weight 2490, 1.2 mmol) of a compound (2M) represented by the following formula (111).

[1031]

[1032] (In formula (111), Rf1 is represented by the above formula, j representing the average degree of polymerization in Rf1 is 2.4, and k representing the average degree of polymerization is 2.4.)

[1033] The obtained compound (2M) was subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[1034] 1 H-NMR (CD3COCD3): δ[ppm]=1.64~1.81(8H), 3.37~4.36(62H)

[1035] 19F-NMR (CD3COCD3): δ[ppm]=-55.8~-50.5(14.4F), -77.7(6F), -80.3(6F), -91.0~-88.3(28.8F)

[1036] [Example 34]

[1037] (Fourth reaction)

[1038] In the fourth reaction of the above-mentioned Example 21, 1.3 g (molecular weight 264, 4.9 mmol) of the compound (Ep-14) represented by the above-mentioned formula (56) was used instead of the compound (Ep-1) represented by the formula (13). Except for this, the operations until the fourth reaction were carried out in the same manner as in Example 21 to obtain 3.6 g of the intermediate compound (2N-4) represented by the formula (112).

[1039]

[1040] (In formula (112), Ph represents a phenyl group, and Bn represents a benzyl group. Rf2 is represented by the above formula, and l in Rf2, which represents an average degree of polymerization, represents 2.0.)

[1041] (Fifth Reaction)

[1042] Under nitrogen atmosphere, 3.6 g (number average molecular weight 2921, 1.3 mmol) of the compound represented by formula (112) as the intermediate compound (2N-4), 36 mL of methanol, and 3.6 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.36 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 8 hours to react.

[1043] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 2.6 g (number average molecular weight 2387, 1.2 mmol) of the compound (2N) represented by the following formula (113).

[1044]

[1045] (In formula (113), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 2.0.)

[1046] The obtained compound (2N) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[1047] 1H-NMR (CD3COCD3): δ[ppm]=1.63~1.87(8H), 3.30~4.45(58H)

[1048] 19 F-NMR (CD3COCD3): δ[ppm]=-84.0~-83.0(24F), -86.4(12F), -124.3(12F), -130.0~-129.0(12F)

[1049] [Example 35]

[1050] (Fourth reaction)

[1051] In the fourth reaction of the above-mentioned Example 29, 1.6 g (molecular weight 317, 4.9 mmol) of the compound (Ep-15) represented by the above-mentioned formula (59) was used instead of the compound (Ep-9) represented by the formula (41). Except for this, the operations until the fourth reaction were carried out in the same manner as in Example 29 to obtain 3.7 g of the intermediate compound (2O-4) represented by the formula (114).

[1052]

[1053] (In formula (114), THP represents a tetrahydropyranyl group, Bn represents a benzyl group, Rf1 is represented by the above formula, j representing the average degree of polymerization in Rf1 is 3.8, and k representing the average degree of polymerization is 0.)

[1054] (Fifth Reaction)

[1055] In a nitrogen atmosphere, 3.7 g (number average molecular weight 3053, 1.3 mmol) of the compound represented by formula (114) as the intermediate compound (2O-4), 37 mL of methanol, and 3.7 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.37 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 8 hours to react.

[1056] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 2.6 g (number average molecular weight 2527, 1.1 mmol) of the compound (2O) represented by the following formula (115).

[1057]

[1058] (In formula (115), Rf1 is represented by the above formula, j representing the average degree of polymerization in Rf1 is 3.8, and k representing the average degree of polymerization is 0.)

[1059] The obtained compound (2O) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[1060] 1 H-NMR (CD3COCD3): δ[ppm]=1.75~1.93(6H), 3.30~4.40(64H), 7.25~7.41(2H)

[1061] 19 F-NMR (CD3COCD3): δ[ppm]=-78.6(6F), -81.3(6F), -90.0~-88.5(45.6F)

[1062] [Example 36]

[1063] (First reaction)

[1064] In a 300 mL eggplant flask under nitrogen atmosphere, add HOCH2CF2CF2O (CF2CF2CF2O) l 10 g of a compound represented by CF2CF2CH2OH (where l in the formula represents the average degree of polymerization and is 2.0) (number average molecular weight 610, molecular weight distribution 1.1), 26.8 g of a compound represented by the above formula (B1) (molecular weight 652, 41.0 mmol), 1.1 g of potassium iodide (molecular weight 166, 6.6 mmol), and 33 mL of N,N'-dimethylformamide (DMF) were stirred at room temperature to prepare a mixed solution. 21.3 g of cesium carbonate (molecular weight 325, 65.6 mmol) was added to the mixed solution, and the mixture was stirred at 70°C for 10 hours to react.

[1065] The reaction product obtained after the reaction was cooled to 0°C, and 100 mL of water was added to stop the reaction. The resulting reaction solution was transferred to a separatory funnel and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with saline and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 11.5 g of the compound represented by the following formula (116) as an intermediate compound (2P-1).

[1066]

[1067] (In formula (116), Ts represents a p-toluenesulfonyl group, Bn represents a benzyl group, and l representing an average degree of polymerization represents 2.0.)

[1068] (Second reaction)

[1069] The same operation as the second reaction in Example 21 was carried out to obtain an intermediate compound (2A-2) represented by formula (77).

[1070] (Third reaction)

[1071] In a 200 mL eggplant flask under a nitrogen atmosphere, 7.0 g (number average molecular weight 1571, 4.5 mmol) of the compound represented by formula (116) as the intermediate compound (2P-1), 6.8 g (number average molecular weight 694, 9.8 mmol) of the compound represented by formula (77) as the intermediate compound (2A-2), 0.30 g (molecular weight 166, 1.8 mmol), and 9 mL of N,N'-dimethylformamide (DMF) were added and stirred at room temperature until the mixture became homogeneous. 5.8 g (molecular weight 325, 17.8 mmol) of cesium carbonate was added to the homogeneous liquid, and the mixture was stirred at 70°C for 10 hours to react.

[1072] The reaction solution obtained after the reaction was returned to room temperature, 12 g of 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 2 hours. The reaction solution was transferred little by little to a separatory funnel added with 100 mL of brine, and extracted three times with 200 mL of ethyl acetate. The organic layer was washed with 100 mL of brine, 100 mL of saturated sodium bicarbonate water, and 100 mL of brine in this order, and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated and the residue was refined by silica gel column chromatography. By performing the above steps, 5.0 g of the compound represented by the following formula (117) was obtained as an intermediate compound (2P-3).

[1073]

[1074] (In formula (117), Bn represents a benzyl group, Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 2.0.)

[1075] (Fourth reaction)

[1076] In a 200 mL eggplant flask, 5.0 g (number average molecular weight 2446, 2.2 mmol) of the compound represented by formula (117) as the intermediate compound (2P-3), 0.98 g (molecular weight 202, 4.8 mmol) of the compound (Ep-1) represented by the above formula (13), and 2.1 mL of tert-butyl alcohol were added under a nitrogen atmosphere, and stirred at room temperature until the mixture became homogeneous. 0.074 g (molecular weight 113, 0.66 mmol) of potassium tert-butylate was further added to the homogeneous liquid, and the mixture was stirred at 70° C. for 16 hours to react.

[1077] The reaction product obtained after the reaction was cooled to 25°C, transferred to a separatory funnel to which 100 mL of water was added, and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with water and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 3.6 g of the compound represented by the following formula (118) as an intermediate compound (2P-4).

[1078]

[1079] (In formula (118), THP represents a tetrahydropyranyl group, and Bn represents a benzyl group. Rf2 is represented by the above formula, and l in Rf2, which represents an average degree of polymerization, represents 2.0.)

[1080] (Fifth Reaction)

[1081] Under nitrogen atmosphere, 3.6 g (number average molecular weight 2851, 1.3 mmol) of the compound represented by formula (118) as the intermediate compound (2P-4), 36 mL of methanol, and 3.6 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.36 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 8 hours to react.

[1082] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 2.5 g (number average molecular weight 2327, 1.2 mmol) of the compound (2P) represented by the following formula (119).

[1083]

[1084] (In formula (119), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 2.0.)

[1085] The obtained compound (2P) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[1086] 1 H-NMR (CD3COCD3): δ[ppm]=1.60~1.87(8H), 3.37~4.37(54H)

[1087] 19F-NMR (CD3COCD3): δ[ppm]=-84.0~-83.0(24F), -86.4(12F), -124.3(12F), -130.0~-129.0(12F)

[1088] [Example 37]

[1089] (Fourth reaction)

[1090] In the fourth reaction of the above-mentioned Example 36, 0.8 g (molecular weight 172, 4.8 mmol) of the compound (Ep-7) represented by the above-mentioned formula (33) was used instead of the compound (Ep-1) represented by the formula (13). Except for this, the operations until the fourth reaction were carried out in the same manner as in Example 36 to obtain 3.5 g of the intermediate compound (2Q-4) represented by the formula (120).

[1091]

[1092] (In formula (120), THP represents a tetrahydropyranyl group, Bn represents a benzyl group, Rf2 is represented by the above formula, and l in Rf2, which represents an average degree of polymerization, represents 2.0.)

[1093] (Fifth Reaction)

[1094] Under nitrogen atmosphere, 3.5 g (number average molecular weight 2791, 1.3 mmol) of the compound represented by formula (120) as the intermediate compound (2Q-4), 35 mL of methanol, and 3.5 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.35 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 8 hours to react.

[1095] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 2.5 g (number average molecular weight 2267, 1.2 mmol) of a compound (2Q) represented by the following formula (121).

[1096]

[1097] (In formula (121), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 2.0.)

[1098] The obtained compound (2Q) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[1099] 1H-NMR (CD3COCD3): δ[ppm]=1.60~1.86(12H), 3.37~4.37(46H)

[1100] 19 F-NMR (CD3COCD3): δ[ppm]=-84.0~-83.0(24F), -86.4(12F), -124.3(12F), -130.0~-129.0(12F)

[1101] [Example 38]

[1102] (First reaction)

[1103] In a 300 mL eggplant flask under nitrogen atmosphere, add HOCH2CF2CF2O (CF2CF2CF2O) l 10 g of a compound represented by CF2CF2CH2OH (where l in the formula represents the average degree of polymerization and is 2.0) (number average molecular weight 610, molecular weight distribution 1.1), 27.9 g of a compound represented by the above formula (C1) (molecular weight 680, 41.0 mmol), 1.1 g of potassium iodide (molecular weight 166, 6.6 mmol), and 33 mL of N,N'-dimethylformamide (DMF) were stirred at room temperature to prepare a mixed solution. 21.3 g of cesium carbonate (molecular weight 325, 65.6 mmol) was added to the mixed solution, and the mixture was stirred at 70°C for 10 hours to react.

[1104] The reaction product obtained after the reaction was cooled to 0°C, and 100 mL of water was added to stop the reaction. The resulting reaction solution was transferred to a separatory funnel and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with saline and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was refined by silica gel column chromatography to obtain 11.0 g of the compound represented by the following formula (122) as an intermediate compound (2R-1).

[1105]

[1106] (In formula (122), Ts represents a p-toluenesulfonyl group, Bn represents a benzyl group, and l representing an average degree of polymerization represents 2.0.)

[1107] (Second reaction)

[1108] The same operation as the second reaction in Example 21 was carried out to obtain an intermediate compound (2A-2) represented by formula (77).

[1109] (Third reaction)

[1110] In a 200 mL eggplant flask, 7.0 g (number average molecular weight 1627, 4.3 mmol) of the compound represented by formula (122) as the intermediate compound (2R-1), 6.6 g (number average molecular weight 694, 9.5 mmol) of the compound represented by formula (77) as the intermediate compound (2A-2), 0.29 g (molecular weight 166, 1.7 mmol) of potassium iodide, and 9 mL of N,N'-dimethylformamide (DMF) were added under nitrogen atmosphere, and stirred at room temperature to prepare a mixed solution. 5.6 g (molecular weight 325, 17.2 mmol) of cesium carbonate was added to the mixed solution, and the mixture was stirred at 70°C for 10 hours to react.

[1111] The reaction solution obtained after the reaction was returned to room temperature, 12 g of 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 2 hours. The reaction solution was transferred little by little to a separatory funnel added with 100 mL of brine, and extracted three times with 200 mL of ethyl acetate. The organic layer was washed with 100 mL of brine, 100 mL of saturated sodium bicarbonate water, and 100 mL of brine in this order, and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated and the residue was refined by silica gel column chromatography. By performing the above steps, 5.0 g of the compound represented by the following formula (123) was obtained as an intermediate compound (2R-3).

[1112]

[1113] (In formula (123), Bn represents a benzyl group, Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 2.0.)

[1114] (Fourth reaction)

[1115] In a 200 mL eggplant flask, 5.0 g (number average molecular weight 2502, 2.1 mmol) of the compound represented by formula (123) as an intermediate compound (2R-3), 1.5 g (molecular weight 320, 4.7 mmol) of the compound (Ep-3) represented by the above formula (20), and 2.0 mL of tert-butyl alcohol were added under a nitrogen atmosphere, and stirred at room temperature until the mixture became homogeneous. 0.072 g (molecular weight 113, 0.64 mmol) of potassium tert-butylate was further added to the homogeneous liquid, and the mixture was stirred at 70° C. for 16 hours to react.

[1116] The reaction product obtained after the reaction was cooled to 25°C, transferred to a separatory funnel to which 100 mL of water was added, and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with water and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 3.7 g of the compound represented by the following formula (124) as an intermediate compound (2R-4).

[1117]

[1118] (In formula (124), THP represents a tetrahydropyranyl group, Bn represents a benzyl group, and MOM represents a methoxymethyl group. Rf2 is represented by the above formula, and the l representing the average degree of polymerization in Rf2 represents 2.0.)

[1119] (Fifth Reaction)

[1120] In a nitrogen atmosphere, 3.7 g (number average molecular weight 3143, 1.2 mmol) of the compound represented by formula (124) as the intermediate compound (2R-4), 37 mL of methanol, and 3.7 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.37 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 8 hours to react.

[1121] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 2.6 g (number average molecular weight 2531, 1.1 mmol) of the compound (2R) represented by the following formula (125).

[1122]

[1123] (In formula (125), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 2.0.)

[1124] The obtained compound (2R) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[1125] 1 H-NMR (CD3COCD3): δ[ppm]=1.60~1.90(16H), 3.35~4.39(66H)

[1126] 19F-NMR (CD3COCD3): δ[ppm]=-84.0~-83.0(24F), -86.4(12F), -124.3(12F), -130.0~-129.0(12F)

[1127] [Example 39]

[1128] (First reaction)

[1129] In a 300 mL eggplant flask under nitrogen atmosphere, add HOCH2CF2CF2O (CF2CF2CF2O) l 10 g of a compound represented by CF2CF2CH2OH (where l in the formula represents the average degree of polymerization and is 2.0) (number average molecular weight 610, molecular weight distribution 1.1), 29.2 g of a compound represented by the above formula (H1) (molecular weight 712, 41.0 mmol), 1.1 g of potassium iodide (molecular weight 166, 6.6 mmol), and 33 mL of N,N'-dimethylformamide (DMF) were stirred at room temperature to prepare a mixed solution. 21.3 g of cesium carbonate (molecular weight 325, 65.6 mmol) was added to the mixed solution, and the mixture was stirred at 70°C for 10 hours to react.

[1130] The reaction product obtained after the reaction was cooled to 0°C, and 100 mL of water was added to stop the reaction. The resulting reaction solution was transferred to a separatory funnel and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with saline and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 12.0 g of the compound represented by the following formula (126) as an intermediate compound (2S-1).

[1131]

[1132] (In formula (126), Ts represents a p-toluenesulfonyl group, Bn represents a benzyl group, and l representing an average degree of polymerization represents 2.0.)

[1133] (Second reaction)

[1134] The same operation as the second reaction in Example 21 was carried out to obtain an intermediate compound (2A-2) represented by formula (77).

[1135] (Third reaction)

[1136] In a 200 mL eggplant flask, 7.0 g (number average molecular weight 1691, 4.1 mmol) of the compound represented by formula (126) as the intermediate compound (2S-1), 6.3 g (number average molecular weight 694, 9.1 mmol) of the compound represented by formula (77) as the intermediate compound (2A-2), 0.28 g (molecular weight 166, 1.7 mmol) of potassium iodide, and 9 mL of N,N'-dimethylformamide (DMF) were added under a nitrogen atmosphere, and stirred at room temperature to prepare a mixed solution. 5.4 g (molecular weight 325, 16.6 mmol) of cesium carbonate was added to the mixed solution, and the mixture was stirred at 70°C for 10 hours to react.

[1137] The reaction solution obtained after the reaction was returned to room temperature, 12 g of 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 2 hours. The reaction solution was transferred little by little to a separatory funnel added with 100 mL of brine, and extracted three times with 200 mL of ethyl acetate. The organic layer was washed with 100 mL of brine, 100 mL of saturated sodium bicarbonate water, and 100 mL of brine in this order, and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated and the residue was refined by silica gel column chromatography. By performing the above steps, 5.2 g of the compound represented by the following formula (127) was obtained as an intermediate compound (2S-3).

[1138]

[1139] (In formula (127), Bn represents a benzyl group, Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 2.0.)

[1140] (Fourth reaction)

[1141] In a 200 mL eggplant flask, 5.0 g (number average molecular weight 2472, 2.1 mmol) of the compound represented by formula (127) as an intermediate compound (2S-3), 1.5 g (molecular weight 320, 4.7 mmol) of the compound (Ep-6) represented by the above formula (29), and 2.0 mL of tert-butyl alcohol were added under a nitrogen atmosphere, and stirred at room temperature until the mixture became uniform. 0.072 g (molecular weight 113, 0.64 mmol) of potassium tert-butylate was further added to the uniform liquid, and the mixture was stirred at 70° C. for 16 hours to react.

[1142] The reaction product obtained after the reaction was cooled to 25°C, transferred to a separatory funnel to which 100 mL of water was added, and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with water and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 3.7 g of the compound represented by the following formula (128) as an intermediate compound (2S-4).

[1143]

[1144] (In formula (128), THP represents a tetrahydropyranyl group, Bn represents a benzyl group, and MOM represents a methoxymethyl group. Rf2 is represented by the above formula, and the l representing the average degree of polymerization in Rf2 represents 2.0.)

[1145] (Fifth Reaction)

[1146] In a nitrogen atmosphere, 3.7 g (number average molecular weight 3067, 1.2 mmol) of the compound represented by formula (128) as the intermediate compound (2S-4), 37 mL of methanol, and 3.7 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.37 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 8 hours to react.

[1147] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 2.5 g (number average molecular weight 2637, 1.0 mmol) of a compound (2S) represented by the following formula (129).

[1148]

[1149] (In formula (129), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 2.0.)

[1150] The obtained compound (2S) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[1151] 1 H-NMR (CD3COCD3): δ[ppm]=1.61~1.83(20H), 3.38~4.40(66H)

[1152] 19F-NMR (CD3COCD3): δ[ppm]=-84.0~-83.0(24F), -86.4(12F), -124.3(12F), -130.0~-129.0(12F)

[1153] [Example 40]

[1154] (First reaction)

[1155] In a 300 mL eggplant flask under nitrogen atmosphere, add HOCH2CF2CF2O (CF2CF2CF2O) l 10 g of a compound represented by CF2CF2CH2OH (where l in the formula represents the average degree of polymerization and is 2.0) (number average molecular weight 610, molecular weight distribution 1.1), 27.4 g of a compound represented by the above formula (M1) (molecular weight 668, 41.0 mmol), 1.1 g of potassium iodide (molecular weight 166, 6.6 mmol), and 33 mL of N,N'-dimethylformamide (DMF) were stirred at room temperature to prepare a mixed solution. 21.3 g of cesium carbonate (molecular weight 325, 65.6 mmol) was added to the mixed solution, and the mixture was stirred at 70°C for 10 hours to react.

[1156] The reaction product obtained after the reaction was cooled to 0°C, and 100 mL of water was added to stop the reaction. The resulting reaction solution was transferred to a separatory funnel and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with saline and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 10.5 g of the compound represented by the following formula (130) as an intermediate compound (2T-1).

[1157]

[1158] (In formula (130), Ts represents a p-toluenesulfonyl group, Bn represents a benzyl group, and l representing an average degree of polymerization represents 2.0.)

[1159] (Second reaction)

[1160] The same operation as the second reaction in Example 21 was carried out to obtain an intermediate compound (2A-2) represented by formula (77).

[1161] (Third reaction)

[1162] In a 200 mL eggplant flask, 7.0 g (number average molecular weight 1603, 4.4 mmol) of the compound represented by formula (130) as the intermediate compound (2T-1), 6.7 g (number average molecular weight 694, 9.6 mmol) of the compound represented by formula (77) as the intermediate compound (2A-2), 0.29 g (molecular weight 166, 1.8 mmol) of potassium iodide, and 9 mL of N,N'-dimethylformamide (DMF) were added under a nitrogen atmosphere, and stirred at room temperature to prepare a mixed solution. 5.7 g (molecular weight 325, 17.5 mmol) of cesium carbonate was added to the mixed solution, and the mixture was stirred at 70°C for 10 hours to react.

[1163] The reaction solution obtained after the reaction was returned to room temperature, 12 g of 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 2 hours. The reaction solution was transferred little by little to a separatory funnel added with 100 mL of brine, and extracted three times with 200 mL of ethyl acetate. The organic layer was washed with 100 mL of brine, 100 mL of saturated sodium bicarbonate water, and 100 mL of brine in this order, and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated and the residue was refined by silica gel column chromatography. By performing the above steps, 5.1 g of the compound represented by the following formula (131) was obtained as an intermediate compound (2T-3).

[1164]

[1165] (In formula (131), Bn represents a benzyl group, Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 2.0.)

[1166] (Fourth reaction)

[1167] In a nitrogen atmosphere, 5.0 g (number average molecular weight 2478, 2.2 mmol) of the compound represented by formula (131) as the intermediate compound (2T-3), 1.0 g (molecular weight 202, 4.8 mmol) of the compound (Ep-1) represented by the above formula (13), and 2.0 mL of tert-butyl alcohol were added to a 200 mL eggplant flask, and stirred at room temperature until the mixture became uniform. 0.073 g (molecular weight 113, 0.65 mmol) of potassium tert-butylate was further added to the uniform liquid, and the mixture was stirred at 70° C. for 16 hours to react.

[1168] The reaction product obtained after the reaction was cooled to 25°C, transferred to a separatory funnel to which 100 mL of water was added, and extracted three times with 100 mL of ethyl acetate. The organic layer was washed with water and dehydrated with anhydrous sodium sulfate. After filtering and separating the desiccant, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 3.6 g of the compound represented by the following formula (132) as an intermediate compound (2T-4).

[1169]

[1170] (In formula (132), THP represents a tetrahydropyranyl group, Bn represents a benzyl group, Rf2 is represented by the above formula, and l in Rf2, which represents an average degree of polymerization, represents 2.0.)

[1171] (Fifth Reaction)

[1172] Under nitrogen atmosphere, 3.6 g (number average molecular weight 2883, 1.3 mmol) of the compound represented by formula (132) as the intermediate compound (2T-4), 36 mL of methanol, and 3.6 mL of formic acid were added to a 200 mL eggplant flask, and stirred at room temperature until it became uniform. 0.36 g of palladium carbon (Pd / C) was further added to the uniform liquid, and the mixture was stirred at 70°C for 8 hours to react.

[1173] The reaction solution obtained after the reaction was filtered to remove Pd / C, and the filtrate was concentrated. After concentration, the residue was purified by silica gel column chromatography to obtain 2.6 g (number average molecular weight 2359, 1.2 mmol) of a compound (2T) represented by the following formula (133).

[1174]

[1175] (In formula (133), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 2.0.)

[1176] The obtained compound (2T) is subjected to 1 H-NMR and 19 The structure was identified based on the following results from F-NMR measurement.

[1177] 1 H-NMR (CD3COCD3): δ[ppm]=3.35~4.40(62H)

[1178] 19 F-NMR (CD3COCD3): δ[ppm]=-84.0~-83.0(24F), -86.4(12F), -124.3(12F), -130.0~-129.0(12F)

[1179] When the compounds (1A) to (1T) and (2A) to (2T) of Examples 1 to 40 obtained in this manner are respectively substituted into the formula (1), the values ​​of z and R 1 , R 2 , R 3 , R 4 , R 5 The structures are shown in Tables 1 to 5.

[1180] [Table 1]

[1181]

[1182] [Table 2]

[1183]

[1184] [Table 3]

[1185]

[1186] [Table 4]

[1187]

[1188] [Table 5]

[1189]

[1190] [Comparative Example 1]

[1191] According to the method described in Patent Document 1, a compound (4A) represented by the following formula (134) was synthesized.

[1192]

[1193] (In formula (134), Rf1 is represented by the above formula, j representing the average degree of polymerization in Rf1 represents 4.0, and k representing the average degree of polymerization represents 4.0.)

[1194] [Comparative Example 2]

[1195] By the method described in Patent Document 4, a compound (4B) represented by the following formula (135) was synthesized.

[1196]

[1197] (In formula (135), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 3.8.)

[1198] [Comparative Example 3]

[1199] By the method described in Patent Document 3, a compound (4C) represented by the following formula (136) was synthesized.

[1200]

[1201] (In formula (136), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 3.8.)

[1202] [Comparative Example 4]

[1203] By the method described in Patent Document 4, a compound (4D) represented by the following formula (137) was synthesized.

[1204]

[1205] (In formula (137), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 3.8.)

[1206] [Comparative Example 5]

[1207] By the method described in Patent Document 4, a compound (4E) represented by the following formula (138) was synthesized.

[1208]

[1209] (In formula (138), Rf2 is represented by the above formula, and l in Rf2, which represents the average degree of polymerization, represents 3.8.)

[1210] [Comparative Example 6]

[1211] By the method described in Patent Document 6, a compound (4F) represented by the following formula (139) was synthesized.

[1212]

[1213] (In formula (139), in the central Rf1, j indicating the average degree of polymerization is 3.8, and k indicating the average degree of polymerization is 0. In the two terminal Rf1s, j indicating the average degree of polymerization is 2.4, and k indicating the average degree of polymerization is 2.4.)

[1214] [Comparative Example 7]

[1215] According to the method described in Patent Document 5, a compound (4G) represented by the following formula (140) was synthesized.

[1216]

[1217] (In formula (140), Rf1 is represented by the above formula, j representing the average degree of polymerization in Rf1 represents 3.8, and k representing the average degree of polymerization represents 0.)

[1218] By the above 1 H-NMR and 19 The number average molecular weight (Mn) of the compounds of Examples 1 to 40 and Comparative Examples 1 to 7 obtained in this way was determined by the results of F-NMR measurement. The results are shown in Tables 6 and 7. It should be noted that the average molecular weight of the synthesized compound is estimated to have a deviation of about 1 to 5 depending on the molecular weight distribution of the fluoropolyether used as a raw material of the compound, the difference in the operation when synthesizing the compound, etc.

[1219] [Table 6]

[1220]

[1221] [Table 7]

[1222]

[1223] Next, a lubricant layer forming solution was prepared by the method described below using the compounds obtained in Examples 1 to 40 and Comparative Examples 1 to 7. Furthermore, the lubricant layer of a magnetic recording medium was formed by the method described below using the obtained lubricant layer forming solution, thereby obtaining magnetic recording media of Examples 1 to 40 and Comparative Examples 1 to 7.

[1224] "Lubricating layer forming solution"

[1225] The fluorinated ether compounds obtained in Examples 1 to 40 and Comparative Examples 1 to 7 were dissolved in a fluorinated solvent, Batorel (registered trademark) XF (trade name, manufactured by Mitsui Dupont Fluoro Chemical Co., Ltd.), respectively, to form a film with a thickness of 1000 Å to 2000 Å on the protective layer. The solution was diluted with Batler XF in a manner of 100% to prepare a lubricating layer forming solution.

[1226] "Magnetic Recording Media"

[1227] A magnetic recording medium was prepared in which an adhesion layer, a soft magnetic layer, a first underlayer, a second underlayer, a magnetic layer, and a protective layer were sequentially provided on a substrate having a diameter of 65 mm. The protective layer was formed of carbon.

[1228] On the protective layer of the magnetic recording medium formed with each layer up to the protective layer, the lubricating layer forming solutions of Examples 1 to 40 and Comparative Examples 1 to 7 were applied by dipping, respectively. It should be noted that the dipping method was carried out under the conditions of dipping speed of 10 mm / sec, dipping time of 30 sec, and pulling speed of 1.2 mm / sec.

[1229] Then, the magnetic recording medium coated with the lubricating layer forming solution was placed in a thermostatic bath at 120° C. and heated for 10 minutes to remove the solvent in the lubricating layer forming solution, thereby forming a lubricating layer on the protective layer to obtain a magnetic recording medium.

[1230] (Film thickness measurement)

[1231] The lubricating layers of the magnetic recording media of Examples 1 to 40 and Comparative Examples 1 to 7 obtained in this manner were measured using FT-IR (trade name: Nicolet iS50, manufactured by Thermo Fisher Scientific) for the peak height in CF vibration expansion and contraction. Next, the film thickness of the lubricating layer was calculated from the measured value of the peak height in CF vibration expansion and contraction of the lubricating layer using a correlation formula obtained by the method described below.

[1232] (Calculation method of correlation formula)

[1233] A magnetic disk was prepared in which an adhesive layer, a soft magnetic layer, a first base layer, a second base layer, a magnetic layer and a protective layer were sequentially arranged on a substrate having a diameter of 65 mm. ( The film thickness of the interval) forms a lubricating layer respectively.

[1234] Then, for each disk with a lubricating layer formed, the film thickness increase from the disk surface without a lubricating layer was measured using an ellipsometer, and the film thickness of the lubricating layer was determined. In addition, for each disk with a lubricating layer formed, the peak height in CF vibration expansion was measured using FT-IR.

[1235] Furthermore, a correlation equation between the peak height obtained by FT-IR and the film thickness of the lubricating layer obtained by using an ellipsometer was determined.

[1236] Next, the magnetic recording media of Examples 1 to 40 and Comparative Examples 1 to 7 were evaluated by an adhesion property test and a chemical substance resistance test by the following methods.

[1237] (Adhesion property test)

[1238] The magnetic recording medium and the magnetic head were installed on the spin stand, and rotated under normal temperature and reduced pressure (about 250 Torr), so that the magnetic head was floated at a fixed point for 10 minutes. Then, the surface of the magnetic head opposite to the magnetic recording medium was analyzed using an ESCA (Electron Spectroscopy for Chemical Analysis) analysis device. The intensity (signal intensity (au)) of the peak derived from fluorine obtained by the analysis using the ESCA analysis device represents the amount of lubricant attached to the magnetic head. Using the obtained signal intensity, the adhesion characteristics were evaluated using the evaluation criteria shown below.

[1239] (Evaluation criteria for adhesion properties)

[1240] A (Excellent): Signal strength 160 or less (very little adhesion)

[1241] B (good): signal strength 161 to 300 (small amount of adhesion)

[1242] C (qualified): signal strength 301-1000 (high adhesion)

[1243] D (failed): signal strength 1001 or more (very high amount of adhesion)

[1244] (Chemical resistance test)

[1245] The contamination degree of the magnetic recording medium caused by the environmental substances that generate the contaminants in a high temperature environment was evaluated by the method shown below. Si ions were used as the environmental substances. The contamination degree of the magnetic recording medium caused by the contaminants generated by the environmental substances was evaluated by measuring the Si adsorption amount as the amount of the contaminants.

[1246] Specifically, the magnetic recording medium as the evaluation object was kept for 240 hours in the presence of siloxane-based Si rubber under a high temperature environment of 85°C and 0% humidity. Next, the Si adsorption amount present on the surface of the magnetic recording medium was analyzed and measured using secondary ion mass spectrometry (SIMS), and the degree of contamination caused by Si ions was evaluated using the Si adsorption amount. The evaluation of the Si adsorption amount was evaluated based on the following evaluation criteria using the numerical value when the result of the Si adsorption amount of Comparative Example 1 was set to 1.00. The results are shown in Tables 6 and 7.

[1247] (Evaluation criteria for chemical resistance)

[1248] A (Excellent): less than 0.70

[1249] B (good): 0.70 or more and less than 0.80

[1250] C (pass): 0.80 or more and less than 1.00

[1251] D (failure): 1.00 or above

[1252] As shown in Table 6, the evaluations of the adhesion property test and the chemical resistance test of the magnetic recording media of Examples 1 to 40 were all A or B, and at least one of them was A. Therefore, it was confirmed that the magnetic recording media of Examples 1 to 40 had a high adhesion suppression effect and high chemical resistance.

[1253] This is presumably because the compounds (1A) to (1T) and (2A) to (2T) forming the lubricating layers of the magnetic recording media of Examples 1 to 40 are less likely to generate polar groups that are not bonded to the functional groups (active sites) present on the protective layer. In other words, this is presumably because the terminal groups R 1 and R 5 The polar group in the linking group and the R bonded to the tetrasubstituted carbon atom 3 and R 4 The primary hydroxyl groups of the lubricating layer are closely attached to the protective layer with a high probability. As a result, the close adhesion of the lubricating layer to the protective layer becomes good, the attachment of the lubricating layer to the magnetic head is suppressed, and the involvement of pollutants caused by polar groups contained in the lubricating layer that are not closely attached to the protective layer is suppressed. Therefore, it is estimated that excellent chemical resistance is obtained and an excellent adhesion inhibition effect is obtained.

[1254] In addition, the magnetic recording media of Examples 1 to 9, 13 to 19, 21 to 29, and 33 to 39 were evaluated as A in the adhesion property test, indicating that the adhesion suppression effect was particularly excellent. This is presumably because the magnetic recording media of the above Examples have the advantages of using R 1 and R 5 is any one of the formulas (4-1) to (4-3), and X 1 is a hydroxyl group or a group having an amide bond, R 3 and R 4 Since the lubricating layer is formed of a compound having the same organic group as shown, the adhesion of the lubricating layer to the protective layer is good and the lubricating layer is not likely to float off the protective layer.

[1255] Furthermore, the evaluation of the chemical substance resistance test of the magnetic recording media of Examples 1, 2, 5, 7, 8, 10 to 12, 16, 17, 20 to 22, 25, 27, 28, 30 to 32, 36, 37, and 40 was A, which was good.

[1256] The magnetic recording media of Examples 10, 11, 30, and 31 are made of R 1 and R 5is formula (4-1) or (4-2), and X 1 Therefore, it is estimated that the magnetic recording media of Examples 10, 11, 30, and 31 have good adhesion to the protective layer due to the π-π interaction between the alkenyl groups in the compound forming the lubricating layer and the protective layer, resulting in good chemical resistance.

[1257] On the other hand, as shown in Table 7, Comparative Examples 1 to 7 having lubricating layers formed using any of Compounds (4A) to (4G) were evaluated as C or D in the adhesion property test and the chemical substance resistance test, which were inferior to Examples 1 to 40.

[1258] This is presumably because, in Comparative Examples 1 to 7, the lubricating layer was formed using a fluorine-containing ether compound that did not satisfy the formula (1).

[1259] Specifically, the magnetic recording media of Comparative Examples 1 and 6 have lubricating layers formed using compounds (4A) and (4F), respectively. The linking group disposed between two or three perfluoropolyether chains of compounds (4A) and (4F) has one secondary hydroxyl group. Therefore, it is estimated that in Comparative Examples 1 and 6, the secondary hydroxyl group in the linking group is not sufficiently adhered to the protective layer, and the adhesion characteristics and chemical resistance are deteriorated.

[1260] The magnetic recording media of Comparative Examples 3 and 7 have lubricating layers formed using compounds (4C) and (4G), respectively. The linking groups disposed between two or three perfluoropolyether chains of compounds (4C) and (4G) have two secondary hydroxyl groups. Therefore, it is estimated that in Comparative Examples 3 and 7, the secondary hydroxyl groups in the linking groups are not sufficiently adhered to the protective layer, and the adhesion characteristics and chemical resistance are deteriorated.

[1261] The magnetic recording media of Comparative Examples 2, 4 and 5 respectively have lubricating layers formed using compounds (4B), (4D) and (4E). The connecting groups disposed between the two perfluoropolyether chains of compounds (4B), (4D) and (4E) have both secondary hydroxyl groups and primary hydroxyl groups. Although the primary hydroxyl groups with high adsorption capacity among the hydroxyl groups contained in the connecting groups can be combined with the protective layer, the secondary hydroxyl groups with low mobility are not sufficiently close to the protective layer due to their low adsorption capacity. As a result, it is presumed that in Comparative Examples 2, 4 and 5, the adhesion properties are poor, and the involvement of pollutants caused by the hydroxyl groups that are not close to the protective layer occurs, resulting in poor resistance to chemical substances.

[1262] Industrial Availability

[1263] By using the lubricant for a magnetic recording medium containing the fluorinated ether compound of the present invention, it is possible to form a lubricating layer which has excellent resistance to chemical substances and excellent adhesion suppressing effect even if the thickness is thin.

[1264] Explanation of symbols

[1265] 10···magnetic recording medium, 11···substrate, 12···adhesion layer, 13···soft magnetic layer, 14···first base layer, 15···second base layer, 16···magnetic layer, 17···protective layer, 18···lubricating layer.

Claims

1. A fluorine-containing ether compound, characterized in that It is represented by the following formula (1): R 1 -CH2-R 2 -(CH2-OCH2-CR 3 R 4 -CH2O-CH2-R 2 ) z -CH2-R 5 (1) In formula (1), z is 1 or 2; R 2 is a perfluoropolyether chain; (z+1) R 2 They may be partially or completely the same, or they may be different; R 1 and R 5 may be the same or different, and are terminal groups having 1 to 50 carbon atoms and at least one polar group; R 3 and R 4 may be the same or different, and are organic groups having 1 to 5 carbon atoms and containing no secondary or tertiary hydroxyl groups but containing one primary hydroxyl group and bonded to the tetrasubstituted carbon atom; the organic group may contain an ether oxygen atom between carbon atoms, and the end bonded to the tetrasubstituted carbon atom may be an ether oxygen atom; when z is 2, the two -CR 3 R 4 -Can be the same or different.

2. The fluorinated ether compound according to claim 1, wherein R in the formula (1) 3 and R 4 Each independently represents any group represented by the following formula (2-1) to formula (2-3), In formula (2-1), a is an integer from 1 to 5; In formula (2-2), b is an integer from 1 to 5; In formula (2-3), c and d are each independently an integer of 1 to 4, and c+d≤5.

3. The fluorinated ether compound according to claim 1 or 2, wherein R in the formula (1) 1 and R 5 The number of polar groups possessed is any one of 1 to 3.

4. The fluorinated ether compound according to claim 1 or 2, wherein R in the formula (1) 1 and R 5 The polar group is at least one selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, a formyl group, a carbonyl group, a sulfone group, a cyano group, and a group having an amide bond.

5. The fluorinated ether compound according to claim 1 or 2, wherein R in the formula (1) 1 and R 5 Each independently has at least one hydroxyl group as a polar group.

6. The fluorinated ether compound according to claim 1 or 2, wherein R in the formula (1) 1 and R 5 Each independently represents any terminal group represented by the following formula (4-1) to formula (4-3), In formula (4-1), y1 is 1 or 2, y2 is an integer from 0 to 3; X 1 is an aromatic hydrocarbon group, an unsaturated heterocyclic group, an alkenyl group, an alkynyl group or a polar group; when y1 is 1, X 1 For polar groups; in X 1 When X is an aromatic hydrocarbon group or an unsaturated heterocyclic group, 1 The atoms that make up the ring structure in 1 The adjacent methylene groups are bonded; 1 When X is alkenyl or alkynyl, 1 The carbon atom that forms the unsaturated bond in 1 The adjacent methylene groups are bonded; In formula (4-2), y3 is an integer from 1 to 3, y4 is 0 or 1, and y5 is an integer from 0 to 3; X 1 is an aromatic hydrocarbon group, an unsaturated heterocyclic group, an alkenyl group, an alkynyl group or a polar group; when y4 is 0, X 1 For polar groups; in X 1 When X is an aromatic hydrocarbon group or an unsaturated heterocyclic group, 1 The atoms that make up the ring structure in 1 The adjacent methylene groups are bonded; 1 When X is alkenyl or alkynyl, 1 The carbon atom that forms the unsaturated bond in 1 The adjacent methylene groups are bonded; In formula (4-3), y6 is 0 or 1, y7 is an integer from 1 to 3, and y8 is an integer from 1 to 3; X 1 is an aromatic hydrocarbon group, an unsaturated heterocyclic group, an alkenyl group, an alkynyl group or a polar group; when y6 is 0, X 1 For polar groups; in X 1 When X is an aromatic hydrocarbon group or an unsaturated heterocyclic group, 1 The atoms that make up the ring structure in 1 The adjacent methylene groups are bonded; 1 When X is alkenyl or alkynyl, 1 The carbon atom that forms the unsaturated bond in 1 Adjacent methylene groups are bonded.

7. The fluorinated ether compound according to claim 1 or 2, wherein the (z+1)th R in the formula (1) 2 Each is independently a perfluoropolyether chain represented by the following formula (3), -(CF2) w1 -O-(CF2O) w2 -(CF2CF2O) w3 -(CF2CF2CF2O) w4 -(CF2CF2CF2CF2O) w5 -(CF2) w6 -(3) In formula (3), w2, w3, w4, and w5 represent average polymerization degrees, and each independently represents 0 to 20; wherein, w2, w3, w4, and w5 are not all 0 at the same time; w1 and w6 are average values ​​of the number of CF2, and each independently represents 1 to 3; there is no particular restriction on the arrangement order of (CF2O), (CF2CF2O), (CF2CF2CF2O), and (CF2CF2CF2CF2O) as repeating units in formula (3).

8. The fluorinated ether compound according to claim 1 or 2, wherein the (z+1)th R in the formula (1) 2 Each independently represents any one selected from the perfluoropolyether chains represented by the following formula (3-1) to (3-4), -CF2-(OCF2CF2) n -(OCF2) o -OCF2-(3-1) In formula (3-1), n ​​and o represent the average degree of polymerization, n represents 1 to 20, and o represents 0 to 20; -CF2CF2-(OCF2CF2CF2) p -OCF2CF2-(3-2) In formula (3-2), p represents the average degree of polymerization and is 1 to 15; -CF2CF2CF2-(OCF2CF2CF2CF2) q -OCF2CF2CF2-(3-3) In formula (3-3), q represents the average degree of polymerization and is 1 to 10; -(CF2) w7 -O-(CF2CF2CF2O) w8 -(CF2CF2O) w9 -(CF2) w10 -(3-4) In formula (3-4), w8 and w9 represent average polymerization degrees, and each independently represents 1 to 20; w7 and w10 represent average values ​​of the number of CF2, and each independently represents 1 to 2.

9. The fluorinated ether compound according to claim 1 or 2, wherein in the formula (1), z -CR 3 R 4 -R in 3 and R 4 All the same.

10. The fluorine-containing ether compound according to claim 1 or 2, wherein the (z+1)th R in the formula (1) 2 All the same.

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

12. The fluorine-containing ether compound according to claim 1 or 2, which has a number average molecular weight in the range of 500 to 10,000.

13. A lubricant for a magnetic recording medium, characterized in that: Contains the fluorine-containing ether compound according to claim 1 or 2.

14. A magnetic recording medium, characterized in that: A magnetic recording medium having at least a magnetic layer, a protective layer and a lubricating layer arranged in sequence on a substrate. The lubricating layer comprises the fluorine-containing ether compound according to claim 1 or 2. 15 . The magnetic recording medium according to claim 14 , wherein the lubricating layer has an average film thickness of 0.5 nm to 2.0 nm.

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