Fluorinated ether compounds, lubricants for magnetic recording media, and magnetic recording media

Abstract

The fluorinated ether compound represented by the following formula. R 1 -[B]-[A]-CH2-R 2 -CH2-[C]-[D]-R 3 (R 2 [A] is a perfluoropolyether chain; [B] is formula (2-1); [C] is formula (3-1); [D] is formula (3-2); R 3 For equation (4); R 1 (This is a terminal group.)

Description

Technical Field

[0001] This invention relates to fluorinated ether compounds, lubricants for magnetic recording media, and magnetic recording media.

[0002] This application claims priority based on Japanese Patent Application No. 2020-210570 filed on December 18, 2020, the contents of which are incorporated herein by reference. Background Technology

[0003] In recent years, the amount of information processed via the Internet has increased dramatically. Along with this, the development of recording media for storing information has attracted much attention. In particular, magnetic recording media, as a type of recording medium, is expected to serve as a receiver of increased information capacity due to its ability to store large amounts of information at low cost.

[0004] Generally, to ensure the durability and reliability of magnetic recording media, a protective layer and a lubricating layer are provided on the magnetic layer (magnetic recording layer) of the magnetic recording media. The lubricating layer, which is located on the outermost surface of the magnetic recording media, is required to have various properties such as long-term stability, chemical resistance (to prevent contamination by siloxanes, etc.), abrasion resistance, and heat resistance.

[0005] Previously, as a lubricant for magnetic recording media, substances containing compounds having polar groups such as hydroxyl groups at the ends of fluorinated polymers having repeating structures including CF2 have been proposed (for example, see Patent Documents 1-7).

[0006] Patent Document 1 discloses a compound having multiple hydroxyl groups at both ends of a fluorinated polymer, configured such that the shortest distance between the hydroxyl groups is more than 3 atoms.

[0007] Patent document 2 discloses a fluorinated polyether compound having an aromatic component at one end and a hydroxyl component at the other end of a fluorinated polymer.

[0008] Patent document 3 discloses a compound having a perfluoropolyether backbone and having an aromatic group and a hydroxyl group at the end of the molecule, wherein the aromatic group and the hydroxyl group are respectively bonded to different carbon atoms.

[0009] Patent document 4 discloses a fluorinated ether compound having a perfluoropolyether chain. At one end of the perfluoropolyether chain, a terminal group comprising an organic group having at least one double or triple bond is configured via a divalent linker bonded by an etheric oxygen. At the other end of the perfluoropolyether chain, a terminal group comprising two or three polar groups, each polar group being bonded to a different carbon atom, and the carbon atoms bonded to the aforementioned polar groups being bonded to each other via a linker comprising a carbon atom not bonded to a polar group.

[0010] Patent document 5 discloses a fluorinated ether compound having a perfluoropolyether chain. As the terminal groups at both ends of the fluorinated ether compound, each is provided with an alkyl group that may have a substituent, an organic group having at least one double or triple bond, or a hydrogen atom. Furthermore, a linker group containing a hydroxyl group is disposed between the perfluoropolyether chain and the terminal groups at both ends.

[0011] Patent document 6 discloses a fluorinated ether compound having a perfluoropolyether chain. At one end of the perfluoropolyether chain, an alkyl group, which may have substituents, is configured via a divalent linker. At the other end of the perfluoropolyether chain, a terminal group is configured comprising two or three polar groups, each polar group being bonded to a different carbon atom, and the carbon atoms bonded to the polar groups being bonded to each other via a linker containing a carbon atom not bonded to a polar group.

[0012] Patent Document 7 discloses a fluorinated ether compound having a perfluoropolyether chain. At least one of the terminal groups of the fluorinated ether compound is a group having one or more hydrogen atoms of an organic group having 1 to 8 carbon atoms replaced by a cyano group. Furthermore, a divalent linker having a polar group is disposed between the perfluoropolyether chain and the terminal group.

[0013] Patent Document 8 discloses a method for manufacturing polyol perfluoropolyether compounds useful as lubricants for magnetic media. Patent Document 8 describes the synthesis of activated and protected triols by reacting triols with an activator, followed by nucleophilic substitution reactions between the triols and the hydroxyl groups located at both ends of a functional perfluoropolyether, thereby producing polyol (per)fluoropolyether derivatives.

[0014] Existing technical documents

[0015] Patent documents

[0016] Patent Document 1: Japanese Patent No. 4632144

[0017] Patent Document 2: Japanese Patent No. 5909837

[0018] Patent Document 3: Japanese Patent No. 5465454

[0019] Patent Document 4: International Publication No. 2017 / 154403

[0020] Patent Document 5: International Publication No. 2019 / 054148

[0021] Patent Document 6: International Publication No. 2019 / 049585

[0022] Patent Document 7: International Publication No. 2019 / 039200

[0023] Patent Document 8: Japanese Patent No. 5334064 Summary of the Invention

[0024] The problem that the invention aims to solve

[0025] In recent years, due to the diversification of applications for magnetic recording media, the environmental resistance requirements for these media have become extremely stringent. Consequently, there is a greater need to improve the long-term stability of the lubricating layer, which significantly impacts the reliability and durability of magnetic recording media.

[0026] Pick-up and spin-off characteristics are known indicators of the long-term stability of the lubricating layer. Pick-up refers to the phenomenon where lubricant adheres to the magnetic head as foreign matter (contaminants). Pick-up affects the flight stability of the magnetic head. Spin-off refers to the phenomenon where lubricant is dispersed or evaporated due to the centrifugal force and heat generated by the rotation of the magnetic recording medium. If spin-off occurs, the film thickness of the lubricating layer decreases, thus deteriorating the chemical resistance and wear resistance of the lubricating layer.

[0027] Furthermore, in recent years, the increasing capacity of magnetic recording media has led to further demands for a reduction in magnetic pitch (the distance between the magnetic head and the magnetic layer of the recording medium) and a higher rotational speed of the recording medium. However, if the head's levitation height is low, pickup is easier to occur. Conversely, if the rotational speed of the recording medium is high, spin-off is easier to occur.

[0028] The present invention was made in view of the above circumstances, and its object is to provide a fluorinated ether compound that can form a lubricating layer that is not prone to pickup and spin-off, and is suitable for use as a lubricant for magnetic recording media.

[0029] Furthermore, the object of the present invention is to provide a lubricant for magnetic recording media comprising the fluorinated ether compound of the present invention.

[0030] Furthermore, the object of the present invention is to provide a magnetic recording medium having a lubricating layer comprising the fluorinated ether compound of the present invention.

[0031] Methods for solving problems

[0032] The first aspect of the present invention provides the following fluorinated ether compounds.

[0033] [1] A fluorinated ether compound, characterized by being represented by the following formula (1).

[0034] R 1 -[B]-[A]-CH2-R 2 -CH2-[C]-[D]-R 3 (1)

[0035] (In equation (1), R) 2For perfluoropolyether chains; [A] is represented by the following formula (2-1), where a is an integer from 0 to 3; [B] is represented by the following formula (2-2), where b is an integer from 0 to 3 and c is an integer from 2 to 5; wherein the sum of the values ​​of a and b is 1 to 3; in formula (1), [A] and [B] can be interchanged; [C] is represented by the following formula (3-1), where d is an integer from 0 to 2; [D] is represented by the following formula (3-2), where e is an integer from 0 to 2 and f is an integer from 2 to 5; wherein the sum of the values ​​of d and e is 1 or 2; in formula (1), [C] and [D] can be interchanged; R 3 It is a branched terminal group with 3 to 30 carbon atoms, represented by the following formula (4); L in formula (4) represents an integer from 0 to 6; Y in formula (4) 1 and Y 2 Each is independently a hydrocarbon group containing one primary hydroxyl group and may contain an ether oxygen atom; Y in formula (4) 3 It is a hydrocarbon group containing one primary hydroxyl group and may contain an ether oxygen atom, or a hydrogen atom; R 1 To be able to work with R 3 (The terminal groups can be the same or different.)

[0036]

[0037] The fluorinated ether compound of the first aspect of the present invention preferably has the features described below [2] to

[13] . The features described below [2] to

[13] are also preferably combined in any combination of two or more.

[0038] [2] According to the fluorinated ether compound described in [1], R in the above formula (1) 3 It is any branched end group in the following formulas (5-1) to (5-3).

[0039]

[0040] (In equation (5-1), g represents an integer from 1 to 6; X 1 and X 2 Represented by equation (6); X 1 With X 2 They can be the same or different.

[0041] (In equation (5-2), h represents an integer from 0 to 6; i and j each independently represent an integer from 1 to 6; X 3 and X 4 It can be represented by a hydrogen atom or by formula (6); X 3 With X 4 They can be the same or different.

[0042] (In equation (5-3), k represents an integer from 0 to 6; p, q, and r each independently represent an integer from 1 to 6; X 5 X 6 and X 7 It can be represented by a hydrogen atom or by formula (6); X 5 X 6 and X 7 They can be different from each other, or they can be partially or entirely the same.

[0043] (In equation (6), s represents an integer from 2 to 6, and t represents 1 or 2.)

[0044] [3] According to the fluorinated ether compound described in [1] or [2], R in the above formula (1) 1 It is a branched terminal group with 3 to 30 carbon atoms, represented by the above formula (4).

[0045] [4] According to the fluorinated ether compound described in [2], R in the above formula (1) 1 With R 3 Both are branch-type terminal groups in equations (5-1) to (5-3) above.

[0046] [5] According to any one of [1] to [4], R in the above formula (1) 1 -[B]-[A]-and-[C]-[D]-R 3 same.

[0047] [6] According to the fluorinated ether compound described in [1] or [2], R in the above formula (1) 1 It is represented by the following formula (7).

[0048]

[0049] (In equation (7), u represents an integer from 2 to 6, and v represents 0 or 1; R 4 The alkyl group is a hydrogen atom, may have a substituent without a hydroxyl group, or is an organogroup having at least one double or triple bond; wherein the alkyl group and the organogroup may be straight-chain or branched.

[0050] [7] According to the fluorinated ether compound described in [6], R in the above formula (7) 4 It is an alkyl group having 1 to 6 carbon atoms.

[0051] [8] According to the fluorinated ether compound described in [6], R in the above formula (7) 4 It is an alkyl group having 1 to 6 carbon atoms and a substituent, wherein the substituent is a fluorinated group or a cyano group.

[0052] [9] According to the fluorinated ether compound described in [6], R in the above formula (7) 4 It is any one of the following: an organogroup having 6 to 12 carbon atoms with an aromatic hydrocarbon group, an organogroup having 3 to 10 carbon atoms with an aromatic heterocycle, an alkenyl group having 2 to 8 carbon atoms, and an alkynyl group having 3 to 8 carbon atoms.

[0053]

[10] According to the fluorinated ether compound described in [6], R in the above formula (7) 4 It is one group selected from methyl, ethyl, n-propyl, isopropyl, 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2,2,2,2,2,2-hexafluoroisopropyl, 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl, phenyl, methoxyphenyl, cyanophenyl, phenethyl, thienylethyl, N-methylpyrazolylmethyl, allyl, 3-butenyl, 4-pentenyl, propyne, 3-butynyl, and 4-pentynyl.

[0054]

[11] According to the fluorinated ether compound described in [6], R in the above formula (7) is... 4 It is a hydrogen atom.

[0055]

[12] According to any one of [1] to

[11] , R in the above formula (1) 2 It can be any one of the following formulas (8-1) to (8-4).

[0056] -CF₂O-(CF₂CF₂O) m -(CF2O) n -CF2- (8-1)

[0057] (In equation (8-1), m and n represent the average degree of polymerization, each ranging from 0 to 30; where m or n is 0.1 or higher.)

[0058] -CF(CF3)-(OCF(CF3)CF2) w -OCF(CF3)- (8-2)

[0059] (In equation (8-2), w represents the average degree of polymerization, ranging from 0.1 to 30.)

[0060] -CF2CF2O-(CF2CF2CF2O) x -CF2CF2- (8-3)

[0061] (In equation (8-3), x represents the average degree of polymerization, ranging from 0.1 to 30.)

[0062] -CF2CF2CF2O-(CF2CF2CF2CF2O) y -CF2CF2CF2- (8-4)

[0063] (In equation (8-4), y represents the average degree of polymerization, ranging from 0.1 to 30.)

[0064]

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

[12] has a number average molecular weight in the range of 500 to 10,000.

[0065] A second aspect of the present invention provides a lubricant for magnetic recording media.

[0066]

[14] A lubricant for magnetic recording media, characterized in that it comprises any one of the fluorinated ether compounds described in [1] to

[13] .

[0067] The third aspect of the present invention provides the following magnetic recording medium.

[0068]

[15] A magnetic recording medium, characterized in that it is a magnetic recording medium on a substrate having at least a magnetic layer, a protective layer, and a lubricating layer disposed sequentially.

[0069] The above-mentioned lubricating layer contains any one of the fluorinated ether compounds described in [1] to

[13] .

[0070] The magnetic recording medium of the third aspect of the present invention preferably has the features described in

[16] .

[0071]

[16] According to the magnetic recording medium described in

[15] , the average film thickness of the above-mentioned lubricating layer is 0.5 nm to 2.0 nm.

[0072] The effects of the invention

[0073] The fluorinated ether compound of the present invention is the compound shown in formula (1) above, and is suitable as a material for a lubricant for magnetic recording media.

[0074] The lubricant for magnetic recording media of the present invention comprises the fluorinated ether compound of the present invention. Therefore, a lubricating layer with good adhesion to the protective layer can be formed, which can suppress pick-up and spin-off.

[0075] The magnetic recording medium of the present invention has a lubricating layer that provides good adhesion to the protective layer and can suppress pickup and spin-off. Therefore, it has excellent reliability and durability. Attached Figure Description

[0076] Figure 1 A schematic cross-sectional view showing an example of a preferred embodiment of the magnetic recording medium of the present invention. Detailed Implementation

[0077] In order to solve the above-mentioned problems, the inventors have repeatedly conducted in-depth research on the molecular structure of the fluorinated ether compound contained in the lubricating layer and its relationship with the protective layer, as shown below.

[0078] Conventionally, perfluoropolyether (PFPE) compounds containing hydroxyl groups in their molecules have been used as lubricants to obtain a lubricating layer with good adhesion to the protective layer. However, the lubricating layer formed using conventional lubricants sometimes fails to achieve sufficient adhesion to the protective layer. Furthermore, the inventors have conducted in-depth research and found that if the lubricating layer does not adhere sufficiently to the protective layer, pick-up and spin-off are more likely to occur.

[0079] Therefore, the inventors conducted further and repeated studies to improve the adhesion between the lubricating layer and the protective layer. The results showed that, as a lubricant, a PFPE-based compound with hydroxyl groups was required, and the following results were obtained. <1> and <2> Substances that have certain functions.

[0080] <1> The hydroxyl groups in PFPE compounds effectively participate in the binding of active sites on the protective layer.

[0081] <2> The hydroxyl groups in PFPE compounds participate in the formation of intermolecular hydrogen bonds between PFPE compounds.

[0082] Therefore, the inventors are able to effectively obtain the above-mentioned... <1> and <2> The molecular structures of the functional fluorinated ether compounds have been repeatedly studied.

[0083] The results showed that a fluorinated ether compound could be prepared by configuring specific linkers with secondary hydroxyl groups at both ends of the perfluoropolyether chain via methylene (-CH2-) and branched terminal groups with multiple primary hydroxyl groups at at least one end. Furthermore, it was confirmed that the lubricating layer containing such a fluorinated ether compound exhibited good adhesion to the protective layer and could suppress pick-up and spin-off, leading to the invention.

[0084] The following provides a detailed description of the fluorinated ether compound, the lubricant for magnetic recording media (hereinafter sometimes abbreviated as "lubricant"), and the magnetic recording media of the present invention. Furthermore, the present invention is not limited to the embodiments shown below. For example, the present invention is not limited to the following examples; without departing from the spirit of the present invention, additions, omissions, substitutions, and modifications can be made regarding numbers, quantities, ratios, compositions, types, positions, materials, structures, etc.

[0085] [Fluoroether compounds]

[0086] The fluorinated ether compound in this embodiment is represented by the following formula (1).

[0087] R1 -[B]-[A]-CH2-R 2 -CH2-[C]-[D]-R 3 (1)

[0088] (In equation (1), R) 2 For perfluoropolyether chains; [A] is represented by the following formula (2-1), where a is an integer from 0 to 3; [B] is represented by the following formula (2-2), where b is an integer from 0 to 3 and c is an integer from 2 to 5; wherein the sum of the values ​​of a and b is 1 to 3; in formula (1), [A] and [B] can be interchanged; [C] is represented by the following formula (3-1), where d is an integer from 0 to 2; [D] is represented by the following formula (3-2), where e is an integer from 0 to 2 and f is an integer from 2 to 5; wherein the sum of the values ​​of d and e is 1 or 2; in formula (1), [C] and [D] can be interchanged; R 3 It is a branched terminal group with 3 to 30 carbon atoms, represented by the following formula (4); L in formula (4) represents an integer from 0 to 6; Y in formula (4) 1 and Y 2 Each is independently a hydrocarbon group containing one primary hydroxyl group and may contain an ether oxygen atom; Y in formula (4) 3 It is a hydrocarbon group containing one primary hydroxyl group and may contain an ether oxygen atom, or a hydrogen atom; R 1 To be able to work with R 3 (The terminal groups can be the same or different.)

[0089]

[0090] (R 2 (The PFPE chain shown)

[0091] The fluorinated ether compound of this embodiment is as shown in formula (1), having R 2 The PFPE chains are shown. When a lubricant containing a fluorinated ether compound is applied to the protective layer to form a lubricating layer, the PFPE chains coat the surface of the protective layer and impart lubricity, thereby reducing the friction between the magnetic head and the protective layer. R 2 The PFPE chain shown is not particularly limited and can be appropriately selected according to the performance requirements of the lubricant.

[0092] As R 2 Examples of PFPE chains shown include those formed from polymers of perfluoromethylene oxide, perfluoroethyl oxide, perfluoropropyl oxide, perfluoroisopropyl oxide, perfluorobutyl oxide, and copolymers thereof.

[0093] The PFPE chain can be, for example, a polymer or copolymer derived from perfluoroalkylene oxide, as shown in the following formula (Rf).

[0094] -(CF2) z1 O(CF2O) z2 (CF2CF2O) z3 (CF2CF2CF2O) z4 (CF2CF2CF2CF2O) z5 (CF2) z6 -(Rf)

[0095] (In equation (Rf), z2, z3, z4, and z5 represent the average degree of polymerization, each independently representing 0 to 30; not all of z2, z3, z4, and z5 are simultaneously 0; z1 and z6 represent the average value of the number representing -CF2-, each independently representing 1 to 3; there is no particular restriction on the order of repeating units in equation (Rf).)

[0096] In formula (Rf), z2, z3, z4, and z5 represent the average degree of polymerization, each independently representing 0 to 30, preferably 0 to 20, and more preferably 0 to 15.

[0097] In formula (Rf), z1 and z6 are the average values ​​of the numbers representing -CF2-, each independently representing 1-3. In the polymer shown in formula (Rf), z1 and z6 are determined based on the structure of the repeating units arranged at the ends of the chain structure, etc.

[0098] In equation (Rf), (CF2O), (CF2CF2O), (CF2CF2CF2O), and (CF2CF2CF2CF2O) are repeating units. There are no particular restrictions on the order of the repeating units in equation (Rf). Furthermore, there are no particular restrictions on the number of different types of repeating units in equation (Rf).

[0099] R in equation (1) 2 It is also preferred to use any one of the following formulas (8-1) to (8-5).

[0100] -CF₂O-(CF₂CF₂O) m -(CF2O) n -CF2- (8-1)

[0101] (In equation (8-1), m and n represent the average degree of polymerization, each ranging from 0 to 30; where m or n is 0.1 or higher.)

[0102] In equation (8-1), there is no particular restriction on the order of (CF2-CF2-O) and (CF2-O) as repeating units. In equation (8-1), the number m of (CF2-CF2-O) and the number n of (CF2-O) representing the average degree of polymerization can be the same or different. Equation (8-1) can include any of the following: random copolymers, block copolymers, and alternating copolymers formed from monomer units (CF2-CF2-O) and (CF2-O).

[0103] In formula (8-1), m, representing the average degree of polymerization, is 0–30, preferably 1–20, and more preferably 2–15. In formula (8-1), n, representing the average degree of polymerization, is 0–30, preferably 0–20, and more preferably 0–15. In formula (8.1), when n is 0, m is preferably 1–20. For example, depending on the need, m and n can be 1–3, 3–5, 5–10, 10–25, 20–30, etc.

[0104] -CF(CF3)-(OCF(CF3)CF2) w -OCF(CF3)- (8-2)

[0105] (In equation (8-2), w represents the average degree of polymerization, ranging from 0.1 to 30.)

[0106] In formula (8-2), w, representing the average degree of polymerization, is 0.1 to 30. When w is 0.1 to 30, the number-average molecular weight of the fluorinated ether compound in this embodiment is readily within a preferred range. w is preferably 1 to 20, more preferably 2 to 15. Depending on the need, w can be 1 to 3, 3 to 5, 5 to 10, 10 to 20, etc.

[0107] -CF2CF2O-(CF2CF2CF2O) x -CF2CF2- (8-3)

[0108] (In equation (8-3), x represents the average degree of polymerization, ranging from 0.1 to 30.)

[0109] In formula (8-3), x, representing the average degree of polymerization, is 0.1 to 30. When x is 0.1 to 30, the number-average molecular weight of the fluorinated ether compound of this embodiment is readily within a preferred range. x is preferably 1 to 20, more preferably 2 to 15. Depending on the need, x can be 1 to 3, 3 to 5, 5 to 10, 10 to 20, etc.

[0110] -CF2CF2CF2O-(CF2CF2CF2CF2O) y -CF2CF2CF2- (8-4)

[0111] (In equation (8-4), y represents the average degree of polymerization, ranging from 0.1 to 30.)

[0112] In formula (8-4), y, representing the average degree of polymerization, is 0.1 to 30. When y is 0.1 to 30, the number-average molecular weight of the fluorinated ether compound of this embodiment is easily within a preferred range. y is preferably 1 to 20, more preferably 2 to 15. Depending on the need, y can be 1 to 3, 3 to 5, 5 to 10, 10 to 20, etc.

[0113] -(CF2) z7 O-(CF2CF2O) z8 -(CF2CF2CF2O) z9 -(CF2) z10 - (8-5)

[0114] (In equation (8-5), z8 and z9 represent the average degree of polymerization, each independently representing 0.1 to 30; z7 and z10 represent the average value of the number of -CF2-, each independently representing 1 to 2.)

[0115] There is no particular restriction on the order of (CF2CF2O) and (CF2CF2CF2O) as repeating units in formula (8-5). Formula (8-5) may include any of the random copolymers, block copolymers, and alternating copolymers composed of monomer units (CF2CF2O) and (CF2CF2CF2O). In formula (8-5), z8 and z9, which represent the average degree of polymerization, are each independently represented as 0.1 to 30, preferably 1 to 20, and more preferably 2 to 15. z7 and z10 in formula (8-5) are the average values ​​of the number representing -CF2-, and are each independently represented as 1 to 2. z7 and z10 in the polymer shown in formula (8-5) are determined according to the structure of the repeating units arranged at the ends of the chain structure, etc.

[0116] In equation (1) R 2 When R is any one of formulas (8-1) to (8-5), it becomes a fluorinated ether compound that can produce a lubricating layer with good lubricity. Furthermore, in formula (1)... 2 When any of formulas (8-1) to (8-5) is used, the ratio of the number of oxygen atoms (the number of ether bonds (-O-)) to the number of carbon atoms in the PFPE chain, and the arrangement of the oxygen atoms in the PFPE chain, become appropriate. Therefore, a fluorinated ether compound with moderate hardness is obtained. Consequently, the fluorinated ether compound coated on the protective layer does not easily aggregate on the protective layer, and a thinner lubricating layer can be formed with sufficient coverage.

[0117] Furthermore, if R in equation (1) 2If the fluorinated ether compound is any of formulas (8-1) to (8-5), then the synthesis of the fluorinated ether compound is easy and preferred. In particular, in R... 2 In the case of formula (8-1) or formula (8-3), the raw materials are readily available, and therefore are preferred.

[0118] (The connecting base shown in -[C]-[D]-)

[0119] In the fluorinated ether compound of this embodiment shown in formula (1), [C] is represented by formula (3-1) above, and [D] is represented by formula (3-2) above. [C] and [D] in formula (1) are divalent linkers. [C] and [D] are interchangeable in formula (1). d in formula (3-1) and e in formula (3-2) are integers from 0 to 2. The sum of the values ​​of d and e is 1 or 2.

[0120] From the viewpoint of ease of obtaining raw materials and synthesis, formulas (3-1) and (3-2) are preferably combinations of d=1 and e=0, or combinations of d=0 and e=1.

[0121] Furthermore, from the viewpoint of adhesion to the protective layer, formulas (3-1) and (3-2) are preferably a combination of d=2 and e=0, or a combination of d=1 and e=1. In particular, in the case of d=2 and e=0, in fluorinated ether compounds, the two hydroxyl groups in formula (3-1) are oriented in the same direction relative to the extension direction of the PFPE chain, and it is observed that the two hydroxyl groups in formula (3-1) tend to readily adsorb onto substances in the protective layer. Furthermore, in the case of d and e=1 and the binding sequence of [C] and [D] from R... 2 When the side is -[D]-[C]-, the hydroxyl groups contained in the -[D]-[C]- structure are further apart. Therefore, the intramolecular hydrogen bonds of the fluorinated ether compound shown in formula (1) can be smaller, resulting in higher affinity for the protective layer.

[0122] In equation (3-2), f is an integer from 2 to 5. When e is an integer from 1 to 2, f is preferably an integer from 2 to 3, and most preferably 2.

[0123] (R 3 (as shown by the branched end group)

[0124] In equation (1), R 3 It is a branched terminal group with 3 to 30 carbon atoms. R 3 The number of carbon atoms is preferably 3 to 20, more preferably 3 to 12. These numbers can be 3 to 5, 5 to 10, 10 to 15, etc. If R 3 If the number of carbon atoms is 3 to 12, then the proportion of fluorine atoms in the fluorinated ether molecule is reduced, which can suppress the increase of the overall surface free energy of the molecule.

[0125] R in equation (1) 3 Represented by formula (4). Formula (4) is a branched terminal group containing 2 or 3 primary hydroxyl groups with carbon atoms as branch points. R 3 The multiple primary hydroxyl groups contained therein participate in the formation of intermolecular hydrogen bonds between fluorinated ether compounds.

[0126] In equation (4), L represents an integer from 0 to 6. In equation (4), Y... 1 and Y 2 Each is independently a hydrocarbon group containing one primary hydroxyl group and may contain an ether oxygen atom. 1 and Y 2 The hydrocarbon group shown can be straight-chain or branched, and preferably does not contain secondary or tertiary hydroxyl groups. 3 Y is a hydrocarbon group containing one primary hydroxyl group and may contain an ether oxygen atom, or a hydrogen atom. 3 The hydrocarbon group shown can be straight-chain or branched, and preferably does not contain secondary or tertiary hydroxyl groups.

[0127] R 3 Preferably, it contains three or more ether bonds (-O-). In this case, due to R 3 It has moderate softness, so the lubricating layer and the protective layer containing the fluorinated ether compound shown in formula (1) have better adhesion.

[0128] In R 3 In the case of multiple ether bonds, adjacent ether bonds are preferably linked together via linking groups with two or more carbon atoms. In this case, the distance between adjacent ether bonds becomes appropriate, resulting in a fluorinated ether compound that is not prone to aggregation.

[0129] R 3 Preferably, it is any one of the branched-chain end groups from formulas (5-1) to (5-3) below. In R 3 When R is any of the branched terminal bases in equations (5-1) to (5-3), 3 The carbon atoms of the primary hydroxyl groups are bonded to each other via linking groups containing methine and / or methylene, and ether bonds. Therefore, R 3 The distance between adjacent primary hydroxyl groups becomes appropriate, becoming R 3 The multiple primary hydroxyl groups present in a configuration where fluorinated ether compounds readily form hydrogen bonds with each other. Furthermore, if R... 3 For any branched terminal base in equations (5-1) to (5-3) below, then R 3 The large molecular weight of fluorinated ethers reduces the proportion of fluorine atoms in the molecule, thus suppressing the increase in the overall surface free energy of the molecule. To suppress this increase, R... 3More preferably, it is formula (5-1) or (5-2).

[0130]

[0131] (In equation (5-1), g represents an integer from 1 to 6; X 1 and X 2 Represented by equation (6); X 1 With X 2 They can be the same or different.

[0132] In equation (5-2), h represents an integer from 0 to 6; i and j each independently represent an integer from 1 to 6; X3 and X 4 It can be represented by a hydrogen atom or by formula (6). X 3 With X 4 They can be the same or different.

[0133] (In equation (5-3), k represents an integer from 0 to 6; p, q, and r each independently represent an integer from 1 to 6; X 5 X 6 and X 7 It can be represented by a hydrogen atom or by formula (6); X 5 X 6 and X 7 They can be different from each other, or they can be partially or entirely the same.

[0134] (In equation (6), s represents an integer from 2 to 6, and t represents 1 or 2.)

[0135] In formula (5-1), g represents an integer from 1 to 6. To easily ensure the proportion of fluorine atoms in the fluorinated ether compound molecule, g is preferably an integer from 1 to 4, and more preferably 1 or 2. 1 and X 2 It is represented by equation (6). X 1 With X 2 They can be the same or different.

[0136] In formula (5-2), h represents an integer from 0 to 6. To easily ensure the proportion of fluorine atoms in the fluorinated ether compound molecule, h is preferably an integer from 0 to 4, and more preferably an integer from 0 to 2. i and j each independently represent an integer from 1 to 6. To easily ensure the proportion of fluorine atoms in the fluorinated ether compound molecule, i and j are each preferably an integer from 1 to 4, and more preferably 1 or 2. i and j can be the same or different. To facilitate the manufacture of the fluorinated ether compound, i and j are preferably the same. X 3 and X 4 It can be represented by a hydrogen atom or by formula (6). X 3 With X 4 They can be the same or different.

[0137] In formula (5-3), k represents an integer from 0 to 6. To easily ensure the proportion of fluorine atoms in the fluorinated ether compound molecule, k is preferably an integer from 0 to 4, and more preferably an integer from 0 to 2. p, q, and r each independently represent an integer from 1 to 6. To easily ensure the proportion of fluorine atoms in the fluorinated ether compound molecule, p, q, and r are each preferably an integer from 1 to 4, and more preferably 1 or 2. p, q, and r can be different, or partially or completely the same. To facilitate the manufacture of the fluorinated ether compound, p, q, and r are preferably all the same. X 5 X 6 and X 7 It can be represented by a hydrogen atom or by formula (6). X 5 X 6 and X 7 They can be different from each other, or they can be partially or completely the same.

[0138] In formula (6), s represents an integer from 2 to 6. To easily ensure the proportion of fluorine atoms in the fluorinated ether compound molecule, s is preferably an integer from 2 to 4, and more preferably 2 or 3. t represents 1 or 2. When t is 2, each [-(CH2)]... s The s in [-O-] can be the same or different. To easily ensure the proportion of fluorine atoms in the fluorinated ether compound molecule, t is preferably 1.

[0139] Specifically, -[C]-[D]-R in equation (1) 3 The preferred structure is as shown in formulas (9-1)-(9-23).

[0140]

[0141]

[0142]

[0143] (The connecting base shown in -[B]-[A]-)

[0144] In the fluorinated ether compound of this embodiment shown in formula (1), [A] is represented by formula (2-1) above, and [B] is represented by formula (2-2) above. [A] and [B] in formula (1) are divalent linkers. [A] and [B] in formula (1) are interchangeable. a in formula (2-1) and b in formula (2-2) are integers from 0 to 3. The sum of the values ​​of a and b is 1 to 3.

[0145] From the viewpoint of ease of obtaining raw materials and synthesis, formulas (2-1) and (2-2) are preferably combinations of a being 1 and b being 0, or combinations of a being 0 and b being 1.

[0146] Furthermore, from the viewpoint of adhesion to the protective layer, formulas (2-1) and (2-2) are preferably combinations where a is 2 and b is 0, or combinations where a is 1 and b is 1. In particular, in the case where a is 2 and b is 0, in fluorinated ether compounds, the two hydroxyl groups in formula (2-1) are arranged in the same direction stereoscopically relative to the extension direction of the PFPE chain, and it is observed that the two hydroxyl groups in formula (2-1) tend to readily adsorb onto the protective layer. Furthermore, when a and b are 1 and the binding sequence of [A] and [B] is from R... 1 When the side orientation is -[A]-[B]-, the hydroxyl groups contained in the -[A]-[B]- structure are further apart than each other. Therefore, the intramolecular hydrogen bonds of the fluorinated ether compound shown in formula (1) can be smaller, resulting in higher affinity for the protective layer.

[0147] In equation (2-2), c is an integer from 2 to 5. When b is an integer from 1 to 3, c is preferably an integer from 2 to 4, and most preferably 2.

[0148] (R 1 (The terminal base shown)

[0149] In (1) R 1 The terminal groups shown can be appropriately selected based on the performance requirements of lubricants containing fluorinated ether compounds. R 1 With R 3 They can be the same or different.

[0150] R 1 The terminal group is a branched chain with 3 to 30 carbon atoms, which can be the terminal group shown in formula (4) above. In this case, R 1 It becomes a branched terminal group containing two or three primary hydroxyl groups and with a carbon atom as the branch point. Therefore, R 1 The multiple primary hydroxyl groups involved participate in the formation of intermolecular hydrogen bonds between fluorinated ether compounds, further enhancing the intermolecular hydrogen bonds between fluorinated ether compounds.

[0151] In R 1 In the case of the terminal base shown in equation (4), R 1 Preferably, any one of the branched-chain end groups in equations (5-1) to (5-3) above is used. In this case, the preferred values ​​of g in equation (5-1), h to j in equation (5-2), k, p to r in equation (5-3), and s and t in equation (6) are related to R. 3 The same applies to any of the branched end groups in equations (5-1) to (5-3).

[0152] In equation (1), in R 1 In the case of the terminal base shown in equation (4), R is further preferred. 1 With R3 Both are any of the branched end groups in equations (5-1) to (5-3) above.

[0153] In equation (1), in R 1 In the case of the terminal base shown in equation (4), R is preferred. 1 With R 3 Similarly, further optimization of R 1 With R 3 Both are any of the branched end groups in equations (5-1) to (5-3) above.

[0154] R in equation (1) is particularly preferred. 1 -[B]-[A]-、and -[C]-[D]-R 3 For the same structure, thus R 2 The PFPE chain shown has a symmetrical structure on both sides. In this case, the manufacturing cost becomes low due to its ease of manufacture.

[0155] Specifically, in equation (1) -[A]-[B]-R 1 The preferred structure is the one shown in formulas (9-1) to (9-23) above.

[0156] In the fluorinated ether compound of this embodiment shown in formula (1), R 1 It can be the terminal base shown in equation (7) below. In this case, through R 1 The large molecular weight of fluorinated ethers reduces the proportion of fluorine atoms in the molecule, thus suppressing the increase of the overall surface free energy of the molecule.

[0157]

[0158] (In equation (7), u represents an integer from 2 to 6, and v represents 0 or 1; R 4 The alkyl group is a hydrogen atom, may have a substituent without a hydroxyl group, or is an organogroup having at least one double or triple bond; wherein the alkyl group and the organogroup may be straight-chain or branched.

[0159] In equation (7), u represents an integer from 2 to 6, and v represents 0 or 1. When v in equation (7) is 0, the proportion of fluorine atoms in the fluorinated ether compound molecule decreases, which can more effectively suppress the increase of the overall surface free energy of the molecule. When v is 1, since the ether bond contained in equation (7) imparts flexibility to the fluorinated ether compound shown in equation (1), it is easier to adsorb onto the protective layer.

[0160] Furthermore, when v is 1 in equation (7), since u is an integer from 2 to 6, therefore R 1The terminal group shown is chemically stable and does not easily decompose. u is preferably an integer from 2 to 4, more preferably 2 or 3. If u is 2 or 3, the proportion of fluorine atoms in the fluorinated ether compound molecule is reduced, which can suppress the increase of the overall surface free energy of the molecule.

[0161] R in equation (7) 4 It is any one of the following: a hydrogen atom, an alkyl group that may have substituents that do not contain a hydroxyl group, or an organogroup having at least one double or triple bond.

[0162] In R 4 In the case of hydrogen atoms, R 4 Together with the oxygen atom in formula (7), it forms a hydroxyl group. When v is 1 in formula (7), the R shown in formula (7) 1 It is an alkoxy group with a hydroxyl group at the end. When v is 0 in formula (7), R shown in formula (7) 1 It is a hydroxyl group.

[0163] In R 4 In the case where the atom is hydrogen and v in equation (7) is 1, R is represented by equation (7). 1 Preferred specific examples include -O-CH2CH2-OH (u = 2 in formula (7)) and -O-CH2CH2CH2-OH (u = 3 in formula (7)).

[0164] In R 4 In the case where it is a hydrogen atom and v in equation (7) is 0 (i.e., in R...), 1 In the case of a hydroxyl group, R 1 It can be combined with [A] shown in equation (2-1) or with [B] shown in equation (2-2). In R 1 When combined with [B], R 1 The distance between the hydroxyl groups shown and their adjacent hydroxyl groups becomes more appropriate and is therefore preferred.

[0165] In R 4 When an alkyl group can have a substituent that does not contain a hydroxyl group, it is preferably an alkyl group with 1 to 6 carbon atoms that does not contain a substituent, or an alkyl group with 1 to 6 carbon atoms that has a substituent. The substituent in the alkyl group with 1 to 6 carbon atoms is preferably a fluorinated or cyano group, and does not contain a hydroxyl group. The alkyl group with 1 to 6 carbon atoms that has a substituent is a group in which one or more hydrogen atoms of the alkyl group are replaced by a substituent, and can be a group in which all hydrogen atoms of the alkyl group are replaced by a substituent.

[0166] The alkyl group having 1 to 6 carbon atoms without substituents and the alkyl group having 1 to 6 carbon atoms with substituents may have a straight chain or a branched chain. Specifically, examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl and their structural isomers, and n-hexyl and their structural isomers.

[0167] Examples of alkyl groups having 1 to 6 carbon atoms in which one or more hydrogen atoms are replaced by fluorine groups include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2,2,2,2,2,2-hexafluoroisopropyl, 2,2,3,3,4,4,4-heptafluorobutyl, 2,2,3,3,4,4,5,5,5-nonafluoropentyl, and 2,2,3,3,4,4,5,5,6,6,6-undecylfluorohexyl.

[0168] The alkyl group having 1 to 6 carbon atoms in which one or more hydrogen atoms are replaced by cyano groups can have one or more cyano groups. If the number of cyano groups is large, the polarity of the fluorinated ether compound will be too high. Therefore, the number of cyano groups is preferably two or less, and most preferably 1a.

[0169] Examples of alkyl groups having 1 to 6 carbon atoms in which one or more hydrogen atoms are replaced by a cyano group include 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl, 5-cyanopentyl, 6-cyanohexyl, 2-cyano-1-methylethyl, and 2,2'-dicyanoisopropyl.

[0170] The organogroup having at least one double or triple bond is preferably any one of the following: an organogroup having 6 to 12 carbon atoms of an aromatic hydrocarbon, an organogroup having 3 to 10 carbon atoms of an aromatic heterocycle, an alkenyl group having 2 to 8 carbon atoms, or an alkynyl group having 3 to 8 carbon atoms. The organogroup having at least one double or triple bond can be straight-chain or branched.

[0171] Examples of organic groups having 6 to 12 carbon atoms in aromatic hydrocarbons include phenyl, methoxyphenyl, dimethoxyphenyl, cyanophenyl, dicyanophenyl, fluorophenyl, naphthyl, methoxynaphthyl, benzyl, methoxybenzyl, phenethyl, methoxyphenethyl, fluorophenethyl, naphthylmethyl, and naphthylethyl. When an aromatic hydrocarbon has substituents, the substituents can be attached at any position.

[0172] Examples of organic groups having 3 to 10 carbon atoms and possessing aromatic heterocycles include pyrrole, pyrazolyl, methylpyrazolylmethyl, imidazolyl, furanyl, furfuryl, and so on. azole group, iso Azolyl, thienyl, thienylmethyl, thienylethyl, thiazolyl, methylthiazolylethyl, isothiazolyl, pyridyl, pyrimidinyl, pyrazinyl, dihydroindolyl, benzofuranyl, benzothienyl, benzimidazolyl, benzo[] Azolyl, benzothiazolyl, benzopyrazole, benzisocyanate Azolyl, benzisothiazolyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, zolinyl.

[0173] Examples of alkenyl groups having 2 to 8 carbon atoms include vinyl, allyl, 1-propenyl, isopropenyl, 3-butenyl and its structural isomers, 4-pentenyl and its structural isomers, 5-hexenyl and its structural isomers, 6-heptenyl and its structural isomers, and 7-octenyl and its structural isomers.

[0174] Examples of alkyne groups with 3 to 8 carbon atoms include 1-propynyl, propynyl, 3-butynyl and their structural isomers, 4-pentynyl and their structural isomers, 5-hexynyl and their structural isomers, 6-hepynyl and their structural isomers, and 7-octyynyl and their structural isomers.

[0175] From the perspective of ease of acquisition and / or synthesis, R in equation (7) 4 Preferably, the group is selected from one of the following: hydrogen atom, methyl, ethyl, n-propyl, isopropyl, 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2,2,2,2,2,2-hexafluoroisopropyl, 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl, phenyl, methoxyphenyl, cyanophenyl, phenethyl, thiopheneylethyl, N-methylpyrazolylmethyl, allyl, 3-butenyl, 4-pentenyl, propyneyl, 3-butynyl, and 4-pentynyl. More preferably, the group is selected from one of the following: hydrogen atom, methyl, ethyl, n-propyl, 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, 3-cyanopropyl, 4-cyanobutyl, methoxyphenyl, cyanophenyl, allyl, and 3-butenyl.

[0176] Specifically, the fluorinated ether compound represented by formula (1) is preferably a compound represented by formula (AA1) or (BA1).

[0177] The number of repetitions shown by ma1, na1, pa1, and qa1 in equations (AA1) and (BA1) are not necessarily integers because they all represent the average degree of polymerization.

[0178]

[0179] (In formula (AA1), ma1 and na1 represent the average degree of polymerization, where ma1 is 0.1–30 and na1 is 0.1–30.)

[0180] (In formula (BA1), pa1 and qa1 represent the average degree of polymerization, where pa1 is 0.1–30 and qa1 is 0.1–30.)

[0181] Regarding the compounds represented by formulas (AA1) and (BA1), the -[C]-[D]-R in formula (1) above... 3 All of them have the structure shown in equation (9-1).

[0182] Regarding the compounds represented by formulas (AA1) and (BA1), R 2 All of them have the structure shown in equation (8-1).

[0183] The compound represented by formula (AA1) is a compound where a is 1 in formula (2-1) as [A] in formula (1), and b is 1, c is 2, and R is 1 in formula (2-2) as [B]. 1 The substance obtained by arranging the compounds in the order of -[A]-[B]-. The compound represented by formula (AA1) has R... 1 As expressed by equation (7), where v is 0 and R is... 4 It is 3-butenyl.

[0184] The compound represented by formula (BA1) is a substance in formula (2-1) where a is 2 and b is 0 in formula (2-2) where [A] is [B]. The compound represented by formula (BA1) has R... 1 As expressed by equation (7), where v is 0 and R is... 4 It is allyl.

[0185] The values ​​of ma1, na1, pa1, and qa1 can be 0.1–1, 1–3, 3–5, 5–10, 10–15, 15–20, and 20–30, respectively, as needed.

[0186] If the fluorinated ether compound represented by formula (1) is a compound represented by formula (AA1) or (BA1) above, it can form a lubricating layer with good adhesion to the protective layer and can suppress pick-up and spin-off, which is preferred.

[0187] The fluorinated ether compound represented by formula (1) can be a compound represented by the following formulas (AA2)~(AV1), (BA2)~(BR1), (CA1)~(CT1), (DA1)~(DG1).

[0188] The repetitions shown in equations (AA2) to (AV1) na2 to na4, nm2 to nm4, mb1 to mv1, nb1 to nv1, equations (BA2) to (BR1) qa2 to qa4, pb1 to pr1, qb1 to qr1, equations (CA1) to (CT1) va2 to va3, vb2 to vb3, vg2 to vg3, vh2 to vh3, ua1 to ut1, va1 to vt1, and equations (DA1) to (DG1) xa1 to xg1, ya1 to yg1 are all values ​​representing the average degree of polymerization, and therefore are not necessarily integers.

[0189]

[0190] (In formula (AA2), na2 represents the average degree of polymerization, which ranges from 0.1 to 30.)

[0191] (In formula (AA3), na3 represents the average degree of polymerization, which ranges from 0.1 to 30.)

[0192] (In formula (AA4), na4 represents the average degree of polymerization, which ranges from 0.1 to 30.)

[0193] (In formula (AB1), mb1 and nb1 represent the average degree of polymerization, where mb1 is 0.1–30 and nb1 is 0.1–30.)

[0194]

[0195] (In equation (AC1), mc1 and nc1 represent the average degree of polymerization, where mc1 is 0.1–30 and nc1 is 0.1–30.)

[0196] (In formula (AD1), md1 and nd1 represent the average degree of polymerization, where md1 is 0.1–30 and nd1 is 0.1–30.)

[0197] (In formula (AE1), me1 and ne1 represent the average degree of polymerization, with me1 ranging from 0.1 to 30 and ne1 ranging from 0.1 to 30.)

[0198] (In formula (AF1), mf1 and nf1 represent the average degree of polymerization, where mf1 is 0.1–30 and nf1 is 0.1–30.)

[0199]

[0200] (In formula (AG1), mg1 and ng1 represent the average degree of polymerization, where mg1 is 0.1–30 and ng1 is 0.1–30.)

[0201] (In formula (AH1), mh1 and nh1 represent the average degree of polymerization, where mh1 is 0.1–30 and nh1 is 0.1–30.)

[0202] (In formula (AI1), mi1 and ni1 represent the average degree of polymerization, where mi1 is 0.1 to 30 and ni1 is 0.1 to 30.)

[0203] (In formula (AJ1), mj1 and nj1 represent the average degree of polymerization, where mj1 is 0.1–30 and nj1 is 0.1–30.)

[0204]

[0205] (In formula (AK1), mk1 and nk1 represent the average degree of polymerization, where mk1 is 0.1 to 30 and nk1 is 0.1 to 30.)

[0206] (In formula (AL1), ml1 and nl1 represent the average degree of polymerization, where ml1 is 0.1–30 and nl1 is 0.1–30.)

[0207] (In formula (AM1), mm1 and nm1 represent the average degree of polymerization, with mm1 ranging from 0.1 to 30 and nm1 ranging from 0.1 to 30.)

[0208] (In formula (AM2), nm2 represents the average degree of polymerization, which ranges from 0.1 to 30.)

[0209]

[0210] (In formula (AM3), nm3 represents the average degree of polymerization, which ranges from 0.1 to 30.)

[0211] (In formula (AM4), nm4 represents the average degree of polymerization, which ranges from 0.1 to 30.)

[0212] (In equation (AN1), mn1 and nn1 represent the average degree of polymerization, where mn1 is 0.1–30 and nn1 is 0.1–30.)

[0213] (In formula (AO1), mo1 and no1 represent the average degree of polymerization, where mo1 is 0.1–30 and no1 is 0.1–30.)

[0214]

[0215] (In formula (AP1), mp1 and np1 represent the average degree of polymerization, where mp1 is 0.1–30 and np1 is 0.1–30.)

[0216] (In formula (AQ1), mq1 and nq1 represent the average degree of polymerization, where mq1 is 0.1–30 and nq1 is 0.1–30.)

[0217] (In formula (AR1), mr1 and nr1 represent the average degree of polymerization, where mr1 is 0.1–30 and nr1 is 0.1–30.)

[0218] (In formula (AS1), ms1 and ns1 represent the average degree of polymerization, where ms1 is 0.1–30 and ns1 is 0.1–30.)

[0219]

[0220] (In formula (AT1), mt1 and nt1 represent the average degree of polymerization, where mt1 is 0.1–30 and nt1 is 0.1–30.)

[0221] (In formula (AU1), mu1 and nu1 represent the average degree of polymerization, where mu1 is 0.1 to 30 and nu1 is 0.1 to 30.)

[0222] (In formula (AV1), mv1 and nv1 represent the average degree of polymerization, where mv1 is 0.1 to 30 and nv1 is 0.1 to 30.)

[0223] (In formula (BA2), qa2 represents the average degree of polymerization, which ranges from 0.1 to 30.)

[0224]

[0225] (In formula (BA3), qa3 represents the average degree of polymerization, which ranges from 0.1 to 30.)

[0226] (In formula (BA4), qa4 represents the average degree of polymerization, which ranges from 0.1 to 30.)

[0227] (In formula (BB1), pb1 and qb1 represent the average degree of polymerization, where pb1 is 0.1–30 and qb1 is 0.1–30.)

[0228] (In equation (BC1), pc1 and qc1 represent the average degree of polymerization, where pc1 is 0.1–30 and qc1 is 0.1–30.)

[0229]

[0230] (In equation (BD1), pd1 and qd1 represent the average degree of polymerization, where pd1 is 0.1–30 and qd1 is 0.1–30.)

[0231] (In formula (BE1), pe1 and qe1 represent the average degree of polymerization, where pe1 is 0.1–30 and qe1 is 0.1–30.)

[0232] (In formula (BF1), pf1 and qf1 represent the average degree of polymerization, where pf1 is 0.1–30 and qf1 is 0.1–30.)

[0233] (In formula (BG1), pg1 and qg1 represent the average degree of polymerization, where pg1 is 0.1–30 and qg1 is 0.1–30.)

[0234]

[0235] (In formula (BH1), ph1 and qh1 represent the average degree of polymerization, where ph1 is 0.1–30 and qh1 is 0.1–30.)

[0236] (In formula (BI1), pi1 and qi1 represent the average degree of polymerization, where pi1 is 0.1–30 and qi1 is 0.1–30.)

[0237] (In formula (BJ1), pj1 and qj1 represent the average degree of polymerization, where pj1 is 0.1–30 and qj1 is 0.1–30.)

[0238] (In formula (BK1), pk1 and qk1 represent the average degree of polymerization, where pk1 is 0.1–30 and qk1 is 0.1–30.)

[0239]

[0240] (In equation (BL1), pl1 and ql1 represent the average degree of polymerization, where pl1 is 0.1–30 and ql1 is 0.1–30.)

[0241] (In formula (BM1), pm1 and qm1 represent the average degree of polymerization, where pm1 is 0.1 to 30 and qm1 is 0.1 to 30.)

[0242] (In formula (BN1), pn1 and qn1 represent the average degree of polymerization, where pn1 is 0.1–30 and qn1 is 0.1–30.)

[0243] (In formula (BO1), po1 and qo1 represent the average degree of polymerization, with po1 ranging from 0.1 to 30 and qo1 ranging from 0.1 to 30.)

[0244]

[0245] (In formula (BP1), pp1 and qp1 represent the average degree of polymerization, where pp1 is 0.1–30 and qp1 is 0.1–30.)

[0246] (In formula (BQ1), pq1 and qq1 represent the average degree of polymerization, where pq1 is 0.1–30 and qq1 is 0.1–30.)

[0247] (In formula (BR1), pr1 and qr1 represent the average degree of polymerization, where pr1 is 0.1–30 and qr1 is 0.1–30.)

[0248] (In formula (CA1), ua1 and va1 represent the average degree of polymerization, where ua1 is 0.1–30 and va1 is 0.1–30.)

[0249]

[0250] (In formula (CA2), va2 represents the average degree of polymerization, which ranges from 0.1 to 30.)

[0251] (In formula (CA3), va3 represents the average degree of polymerization, which ranges from 0.1 to 30.)

[0252] (In formula (CB1), ub1 and vb1 represent the average degree of polymerization, with ub1 ranging from 0.1 to 30 and vb1 ranging from 0.1 to 30.)

[0253] (In formula (CB2), vb2 represents the average degree of polymerization, which ranges from 0.1 to 30.)

[0254]

[0255] (In formula (CB3), vb3 represents the average degree of polymerization, which ranges from 0.1 to 30.)

[0256] (In formula (CC1), uc1 and vc1 represent the average degree of polymerization, where uc1 is 0.1–30 and vc1 is 0.1–30.)

[0257] (In equation (CD1), ud1 and vd1 represent the average degree of polymerization, with ud1 ranging from 0.1 to 30 and vd1 ranging from 0.1 to 30.)

[0258] (In formula (CE1), ue1 and ve1 represent the average degree of polymerization, with ue1 ranging from 0.1 to 30 and ve1 ranging from 0.1 to 30.)

[0259]

[0260] (In equation (CF1), uf1 and vf1 represent the average degree of polymerization, where uf1 is 0.1 to 30 and vf1 is 0.1 to 30.)

[0261] (In equation (CG1), ug1 and vg1 represent the average degree of polymerization, with ug1 ranging from 0.1 to 30 and vg1 ranging from 0.1 to 30.)

[0262] (In formula (CG2), vg2 represents the average degree of polymerization, which ranges from 0.1 to 30.)

[0263] (In formula (CG3), vg3 represents the average degree of polymerization, which ranges from 0.1 to 30.)

[0264]

[0265] (In formula (CH1), uh1 and vh1 represent the average degree of polymerization, where uh1 is 0.1–30 and vh1 is 0.1–30.)

[0266] (In formula (CH2), vh2 represents the average degree of polymerization, which ranges from 0.1 to 30.)

[0267] (In formula (CH3), vh3 represents the average degree of polymerization, which ranges from 0.1 to 30.)

[0268] (In equation (C11), ui1 and vi1 represent the average degree of polymerization, with ui1 ranging from 0.1 to 30 and vi1 ranging from 0.1 to 30.)

[0269]

[0270] (In formula (CJ1), uj1 and vj1 represent the average degree of polymerization, where uj1 is 0.1–30 and vj1 is 0.1–30.)

[0271] (In formula (CK1), uk1 and vk1 represent the average degree of polymerization, with uk1 ranging from 0.1 to 30 and vk1 ranging from 0.1 to 30.)

[0272] (In formula (CL1), ul1 and vl1 represent the average degree of polymerization, with ul1 ranging from 0.1 to 30 and vl1 ranging from 0.1 to 30.)

[0273] (In formula (CM1), um1 and vm1 represent the average degree of polymerization, where um1 is 0.1 to 30 and vm1 is 0.1 to 30.)

[0274]

[0275] (In formula (CN1), un1 and vn1 represent the average degree of polymerization, where un1 is 0.1 to 30 and vn1 is 0.1 to 30.)

[0276] (In formula (CO1), uo1 and vo1 represent the average degree of polymerization, where uo1 is 0.1–30 and vo1 is 0.1–30.)

[0277] (In formula (CP1), up1 and vp1 represent the average degree of polymerization, where up1 is 0.1 to 30 and vp1 is 0.1 to 30.)

[0278] (In formula (CQ1), uq1 and vq1 represent the average degree of polymerization, where uq1 is 0.1–30 and vq1 is 0.1–30.)

[0279]

[0280] (In formula (CR1), ur1 and vr1 represent the average degree of polymerization, where ur1 is 0.1–30 and vr1 is 0.1–30.)

[0281] (In equation (CS1), us1 and vs1 represent the average degree of polymerization, where us1 is 0.1–30 and vs1 is 0.1–30.)

[0282] (In equation (CT1), ut1 and vt1 represent the average degree of polymerization, where ut1 is 0.1–30 and vt1 is 0.1–30.)

[0283] (In formula (DA1), xa1 and ya1 represent the average degree of polymerization, where xa1 is 0.1–30 and ya1 is 0.1–30.)

[0284]

[0285] (In formula (DB1), xb1 and yb1 represent the average degree of polymerization, where xb1 ranges from 0.1 to 30 and yb1 ranges from 0.1 to 30.)

[0286] (In equation (DC1), xc1 and yc1 represent the average degree of polymerization, where xc1 ranges from 0.1 to 30 and yc1 ranges from 0.1 to 30.)

[0287] (In equation (DD1), xd1 and yd1 represent the average degree of polymerization, with xd1 ranging from 0.1 to 30 and yd1 ranging from 0.1 to 30.)

[0288]

[0289] (In equation (DE1), xe1 and ye1 represent the average degree of polymerization, with xe1 ranging from 0.1 to 30 and ye1 ranging from 0.1 to 30.)

[0290] (In formula (DF1), xf1 and yf1 represent the average degree of polymerization, where xf1 is 0.1 to 30 and yf1 is 0.1 to 30.)

[0291] (In formula (DG1), xg1 and yg1 represent the average degree of polymerization, where xg1 is 0.1–30 and yg1 is 0.1–30.)

[0292] The compounds represented by formulas (AA2) to (AV1) all have a value of 1 for formula (2-1) which represents [A] in formula (1) above, and b = 1, c = 2, and R = 1 for formula (2-2) which represents [B]. 1 Substances obtained by arranging them in the order of -[A]-[B]-. The compounds shown in formulas (AA2) to (AV1) are all R. 1 As expressed by equation (7), where v is 0 and R is... 4 It is 3-butenyl.

[0293] Regarding the compounds represented by formulas (AA2) to (AF1), (AR1), (AS1), and (AV1), the -R in formula (1) above... 3 All have the structure shown in formula (5-1). Regarding the compounds shown in formulas (AG1) to (AP1), (AT1), and (AU1), the -R in formula (1) above... 3 All have the structure shown in formula (5-2). The compound shown in formula (AQ1) has the -R in formula (1) above. 3 The structure is shown in equation (5-3).

[0294] Regarding the compounds represented by formulas (BA2) to (BR1), the -[C]-[D]-R in formula (1) above... 3 All of them have the structure shown in equation (9-1).

[0295] The compounds represented by formulas (BA2) to (BQ1) are all substances in which a = 2 in formula (2-1) as [A] in formula (1) above, and b = 0 in formula (2-2) as [B]. The compound represented by (BR1) is a substance in which a = 3 in formula (2-1) as [A] in formula (1) above, and b = 0 in formula (2-2) as [B].

[0296] The R of the compounds represented by formulas (BA2) to (BR1) 1 All are represented by equation (7), where v is 0 or 1. Regarding the compounds represented by equations (BA2) to (BI1), (BQ1), and (BR1), R... 4 All are organic groups having at least one double or triple bond. Regarding the compounds represented by formulas (BJ1) to (BP1), R... 4 All of them are alkyl groups that can have substituents that do not contain hydroxyl groups.

[0297] Regarding the compounds represented by formulas (CA1) to (CQ1), the -[C]-[D]-R in formula (1) above... 3All of them have the structure shown in equation (9-1).

[0298] Regarding the compounds represented by formulas (CA1) to (CF1), (CP1), and (CQ1), R 1 All are represented by equation (7), where u is 2 to 6, v is 1, and R is 1. 4 It is a hydrogen atom.

[0299] Regarding the compounds represented by formulas (CG1) to (CO1), R 1 Both are hydroxyl groups (R) 1 As expressed by equation (7), where v is 0 and R is... 4 (For hydrogen atoms).

[0300] The compound represented by formula (CR1) contains -[C]-[D]-R in formula (1) above. 3 The structure is shown in formula (9-10). The compound shown in formula (CS1) has -[C]-[D]-R in formula (1) above. 3 The structure is shown in formula (9-11). The compound shown in formula (CT1) has -[C]-[D]-R in formula (1) above. 3 The structure is shown in equation (9-17).

[0301] Regarding the compounds represented by formulas (CR1) to (CT1), R 1 All are represented by equation (7), where u is 2, v is 1, and R is 1. 4 It is a hydrogen atom.

[0302] Regarding the compounds represented by formulas (DA1) to (DG1), R in formula (1) above... 1 With R 3 Both are branched terminal groups of formula (5-1) or formula (5-2). The compounds represented by formulas (DA1) to (DD1_) are all R in formula (1) above. 1 -[B]-[A]-、and -[C]-[D]-R 3 same.

[0303] If the fluorinated ether compound represented by formula (1) is any of the compounds represented by formulas (AA2)~(AV1), (BA2)~(BR1), (CA1)~(CT1), (DA1)~(DG1) above, it can form a lubricating layer with good adhesion to the protective layer and can suppress pick-up and spin-off, which is preferred.

[0304] If the fluorinated ether compound represented by formula (1) is any of the compounds represented by formulas (AA1)~(AQ1), (BA1)~(BR1), (CA1)~(CT1), (DA1)~(DG1) above, then the adhesion to the protective layer is better, and it is particularly preferred.

[0305] The number-average molecular weight (Mn) of the fluorinated ether compound in this embodiment is preferably in the range of 500 to 10,000, more preferably in the range of 700 to 7,000, and particularly preferably in the range of 800 to 4,000.

[0306] If the number-average molecular weight is 500 or higher, the lubricant containing the fluorinated ether compound of this embodiment is less prone to evaporation. Therefore, if the number-average molecular weight is 500 or higher, a lubricating layer capable of suppressing pick-up and spin-off can be formed. Furthermore, if the number-average molecular weight is 10,000 or lower, the viscosity of the fluorinated ether compound is not too high, becoming a suitable viscosity for use as a lubricant. In order to achieve a workable viscosity when applied as a lubricant, the number-average molecular weight of the fluorinated ether compound is more preferably 4,000 or lower. The above molecular weight can be 500-9,000, 600-7,000, 700-5,000, 800-3,000, 900-2,000, 1,000-1,800, 1,100-1,600, or 1,200-1,400 as needed.

[0307] Considering the ease of obtaining raw materials for PFPE chains, the fluorinated ether compound in this embodiment is more preferably in the range of 1000 to 3000 in number average molecular weight. If the number average molecular weight is in the range of 1000 to 3000, the coverage rate does not deteriorate even if the film thickness of the lubricating layer is thin, and chemical resistance and abrasion resistance can be maintained. Furthermore, if the number average molecular weight is in the range of 1000 to 3000, the performance balance is optimal from the viewpoint of suppressing lift and spin-off and thinning the lubricating layer.

[0308] The preferred fluorinated ether compound in this embodiment is R. 2 The number-average molecular weight ratio of the PFPE chains to the total molecular weight (PFPE chain / total molecular weight) shown is 0.45–0.90, more preferably 0.55–0.85. This ratio can also be 0.48–0.80, 0.50–0.75, 0.53–0.70, 0.57–0.65, etc. If R 2 When the ratio of the number-average molecular weight of the PFPE chain to the total molecular weight is 0.45 or higher, the proportion of fluorine atoms in the fluorinated ether molecule decreases, which can suppress the increase in the overall surface free energy of the molecule. Furthermore, if the ratio is 0.90 or lower, then the R atoms disposed at both ends of the PFPE chain, relative to the length of the PFPE chain, can be... 1-[B]-[A]- and -[C]-[D]-R 3 The number of hydroxyl groups becomes appropriate. Therefore, a lubricating layer with better adhesion to the protective layer can be formed.

[0309] Here, the reason why a lubricating layer with good adhesion to the protective layer can be formed on the protective layer of the magnetic recording medium when a lubricating layer is formed on the protective layer using a lubricant containing a fluorinated ether compound of this embodiment can suppress pickup and spin-off will be explained.

[0310] In the fluorinated ether compound of this embodiment shown in formula (1), [A], [B], [C], and [D] are divalent linkers having secondary hydroxyl groups. Furthermore, for the fluorinated ether compound of this embodiment, the -[B]-[A]- structure (hereinafter, sometimes abbreviated as "BA structure") containing 1 to 3 secondary hydroxyl groups and the -[C]-[D]- structure (hereinafter, sometimes abbreviated as "CD structure") containing 1 to 2 secondary hydroxyl groups are respectively well balanced and arranged in R via methylene (-CH2-). 2 The two ends of the (PFPE chain). Moreover, the etheric oxygen atoms of the BA and CD structures impart moderate flexibility to the molecular structure of the fluorinated ether compound shown in formula (1).

[0311] Furthermore, in the case where the BA and / or CD structures contain multiple secondary hydroxyl groups, the carbon atoms bound to the secondary hydroxyl groups are linked to each other via linking groups consisting of methylene (-CH2-) and ether bonds (-O-). Therefore, even when the BA and / or CD structures have multiple secondary hydroxyl groups, the distance between adjacent secondary hydroxyl groups becomes appropriate, resulting in a configuration where each secondary hydroxyl group readily adsorbs onto the protective layer.

[0312] Based on these circumstances, when a lubricating layer containing the fluorinated ether compound of this embodiment is formed on the protective layer, the secondary hydroxyl groups contained in the BA structure and the secondary hydroxyl groups contained in the CD structure effectively participate in the binding with the active sites on the protective layer.

[0313] Furthermore, R in equation (1) 3 These are branched terminal groups containing two or three primary hydroxyl groups. Compared to secondary and tertiary hydroxyl groups, primary hydroxyl groups have less steric hindrance and therefore participate effectively in the formation of intermolecular hydrogen bonds between fluorinated ether compounds.

[0314] Thus, in the fluorinated ether compound of this embodiment shown in formula (1), <1> The secondary hydroxyl groups contained in the BA structure and the CD structure effectively participate in the binding of active sites on the protective layer, and <2> R 3 The multiple primary hydroxyl groups contained therein participate in the formation of intermolecular hydrogen bonds between fluorinated ether compounds.

[0315] That is, regarding the lubricating layer containing the fluorinated ether compound of this embodiment, the excellent adsorption force of the secondary hydroxyl groups disposed at both ends of the PFPE chain on the protective layer and the excellent intermolecular force balance of the primary hydroxyl groups of the branched end groups work well and effectively.

[0316] Therefore, the lubricating layer containing the fluorinated ether compound of this embodiment has excellent adhesion to the protective layer. As a result, the fluorinated ether compound that is not adhered to the protective layer as a foreign object (stain) can be prevented from adhering to the magnetic head, and pickup is suppressed. In addition, due to the centrifugal force and / or heat generated by the high-speed rotation of the magnetic recording medium, the lubricant splashing / evaporation, resulting in a reduction in the film thickness of the lubricating layer, is suppressed.

[0317] "Manufacturing method"

[0318] The method for manufacturing the fluorinated ether compound in this embodiment is not particularly limited, and conventionally known manufacturing methods can be used. For example, the fluorinated ether compound in this embodiment can be manufactured using the manufacturing methods shown below.

[0319] First, prepare R with the same characteristics as in equation (1). 2 The corresponding PFPE chain has fluorinated compounds with hydroxymethyl (-CH2OH) groups at both ends of the molecule.

[0320] Next, the hydroxyl group of the hydroxymethyl group at one end of the above-mentioned fluorinated compound is replaced with R containing formula (1). 1 The -[B]-[A]- group (reaction 1). Then, the hydroxyl group of the hydroxymethyl group configured at the other end is replaced with the -[C]-[D]-R group containing formula (1). 3 The terminal group (reaction 2).

[0321] The first and second reactions can be carried out using conventionally known methods, and can be appropriately determined based on the type of terminal group in formula (1). Furthermore, either the first or the second reaction can be carried out in any order.

[0322] The fluorinated ether compound shown in formula (1) can be obtained by the above method.

[0323] Lubricant for magnetic recording media

[0324] The lubricant for the magnetic recording medium in this embodiment comprises a fluorinated ether compound as shown in formula (1).

[0325] Regarding the lubricant of this embodiment, any known material used as a lubricant may be used as needed, provided that it does not impair the properties of the fluorinated ether compound represented by formula (1).

[0326] Specific examples of known materials include, for instance, FOMBLIN (registered trademark) ZDIAC, FOMBLIN ZDEAL, FOMBLIN AM-2001 (and above, manufactured by Solvay Solexis), Moresco A20H (manufactured by Moresco), etc. The known materials used in combination with the lubricant of this embodiment are preferably substances with a number average molecular weight of 1000 to 10000.

[0327] In the case where the lubricant of this embodiment contains materials other than the fluorinated ether compound shown in formula (1), the content of the fluorinated ether compound shown in formula (1) in the lubricant of this embodiment is preferably 50% by mass or more, more preferably 70% by mass or more. The content of the fluorinated ether compound shown in formula (1) may be 80% by mass or more, or 90% by mass or more.

[0328] The lubricant of this embodiment contains a fluorinated ether compound as shown in formula (1), thus obtaining a lubricating layer with good adhesion to the protective layer and the ability to suppress pick-up and spin-off.

[0329] [Magnetic recording media]

[0330] In this embodiment, the magnetic recording medium has at least a magnetic layer, a protective layer, and a lubricating layer sequentially disposed on the substrate.

[0331] For the magnetic recording medium of this embodiment, one or more base layers may be provided between the substrate and the magnetic layer as needed. Alternatively, an adhesion layer and / or a soft magnetic layer may be provided between the base layer and the substrate.

[0332] Figure 1 A schematic cross-sectional view showing one embodiment of the magnetic recording medium of the present invention.

[0333] In this embodiment, the magnetic recording medium 10 is formed on a substrate 11 with an adhesion layer 12, a soft magnetic layer 13, a first base layer 14, a second base layer 15, a magnetic layer 16, a protective layer 17, and a lubricating layer 18 disposed sequentially.

[0334] "Substrate"

[0335] As substrate 11, for example, a non-magnetic substrate on which a film formed of NiP or NiP alloy is formed on a substrate formed of a metal or alloy material such as Al or Al alloy can be used.

[0336] Furthermore, as substrate 11, a non-magnetic substrate formed of non-metallic materials such as glass, ceramic, silicon, silicon carbide, carbon, and resin can be used, or a non-magnetic substrate on which a film of NiP or NiP alloy is formed on a substrate formed of these non-metallic materials can be used.

[0337] Glass substrates are suitable for high recording densities due to their rigidity and excellent smoothness. Examples of glass substrates include aluminosilicate glass substrates. In particular, chemically strengthened aluminosilicate glass substrates are suitable.

[0338] The surface roughness of the main surface of the substrate 11 is preferably ultra-smooth, with Rmax below 6 nm and Ra below 0.6 nm. The surface roughness Rmax and Ra referred to here are based on the specifications of JIS B0601.

[0339] "Adhesion layer"

[0340] The adhesion layer 12 prevents corrosion of the substrate 11 when it is disposed in contact with the soft magnetic layer 13 disposed on the adhesion layer 12.

[0341] 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, for example, by sputtering.

[0342] "Soft magnetic layer"

[0343] The soft magnetic layer 13 preferably has a structure in which a first soft magnetic film, an intermediate layer containing a Ru film, and a second soft magnetic film are stacked sequentially. That is, the soft magnetic layer 13 preferably has a structure in which the soft magnetic films above and below the intermediate layer are antiferroic coupled (AFC) by sandwiching an intermediate layer containing a Ru film between the two soft magnetic films.

[0344] Examples of materials that can be used for the first and second soft magnetic films include CoZrTa alloys and CoFe alloys.

[0345] Preferably, any one of Zr, Ta, or Nb is added to the CoFe alloy used in the first and second soft magnetic films. This promotes the amorphization of the first and second soft magnetic films, improving the orientation of the first substrate layer (seed layer). Simultaneously, it reduces the amount of magnetic head levitation.

[0346] The soft magnetic layer 13 can be formed, for example, by sputtering.

[0347] "First basal layer"

[0348] The first substrate layer 14 is a layer used to control the orientation and crystal size of the second substrate layer 15 and the magnetic layer 16 disposed thereon.

[0349] Examples of first base layers 14 include Cr layers, Ta layers, Ru layers, or CrMo alloy layers, CoW alloy layers, CrW alloy layers, CrV alloy layers, CrTi alloy layers, etc.

[0350] The first base layer 14 can be formed, for example, by sputtering.

[0351] "Second basal layer"

[0352] The second substrate layer 15 is a layer controlled in such a way that the orientation of the magnetic layer 16 becomes well. The second substrate layer 15 is preferably a layer formed of Ru or a Ru alloy.

[0353] The second base layer 15 can be a single layer or multiple layers. If the second base layer 15 is composed of multiple layers, all layers can be made of the same material, or at least one layer can be made of a different material.

[0354] The second base layer 15 can be formed, for example, by sputtering.

[0355] "Magnetic layer"

[0356] The magnetic layer 16 is made of a magnetic film with its easy magnetization axis facing vertically or horizontally relative to the substrate surface. The magnetic layer 16 is a layer containing Co and Pt, and further, in order to improve the SNR (signal-to-noise ratio) characteristics, it can be a layer containing oxides, Cr, B, Cu, Ta, Zr, etc.

[0357] Examples of oxides contained in magnetic layer 16 include SiO2, SiO, Cr2O3, and C. o O, Ta2O3, TiO2, etc.

[0358] The magnetic layer 16 can consist of a single layer or multiple magnetic layers composed of different materials.

[0359] For example, when the magnetic layer 16 is composed of three layers stacked sequentially from bottom to top: a first magnetic layer, a second magnetic layer, and a third magnetic layer, the first magnetic layer is preferably composed of materials containing Co and C. r The first magnetic layer is a granular structure formed from materials containing oxides, such as Pt. Oxides of, for example, Cr, Si, Ta, Al, Ti, Mg, and Co are preferred as the oxides contained in the first magnetic layer. In particular, TiO2, Cr2O3, and SiO2 are suitable. Furthermore, the first magnetic layer is preferably formed from a composite oxide containing two or more oxides. In particular, Cr2O3-SiO2, Cr2O3-TiO2, and SiO2-TiO2 are suitable.

[0360] In addition to Co, Cr, Pt, and oxides, the first magnetic layer may contain one or more elements selected from B, Ta, Mo, Cu, Nd, W, Nb, Sm, Tb, Ru, and Re.

[0361] The second magnetic layer can be made of the same material as the first magnetic layer. The second magnetic layer is preferably granular.

[0362] The third magnetic layer is preferably a non-granular structure formed of a material containing Co, Cr, and Pt, but without oxides. In addition to Co, Cr, and Pt, the third magnetic layer may also contain one or more elements selected from B, Ta, Mo, Cu, Nd, W, Nb, Sm, Tb, Ru, Re, and Mn.

[0363] When the magnetic layer 16 is formed of multiple magnetic layers, it is preferable to provide a non-magnetic layer between adjacent magnetic layers. When the magnetic layer 16 is composed of three layers: a first magnetic layer, a second magnetic layer, and a third magnetic layer, it is preferable to provide a non-magnetic layer between the first magnetic layer and the second magnetic layer, and between the second magnetic layer and the third magnetic layer.

[0364] The non-magnetic layer disposed between adjacent magnetic layers of magnetic layer 16 can be, 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, B, etc.).

[0365] In the non-magnetic layer disposed between adjacent magnetic layers of magnetic layer 16, an alloy material comprising oxides, metal nitrides, or metal carbides is preferably used. Specifically, as oxides, examples include SiO2, Al2O3, Ta2O5, Cr2O3, MgO, Y2O3, TiO2, etc. As metal nitrides, examples include AlN, Si3N4, TaN, CrN, etc. As metal carbides, examples include TaC, BC, SiC, etc.

[0366] Non-magnetic layers can be formed, for example, by sputtering.

[0367] To achieve higher recording density, the magnetic layer 16 is preferably a magnetic layer for perpendicular magnetic recording with its easy magnetization axis oriented perpendicular to the substrate surface. The magnetic layer 16 can also be a magnetic layer for in-plane magnetic recording.

[0368] The magnetic layer 16 can be formed by any conventionally known method, such as vapor deposition, ion beam sputtering, or magnetron sputtering. The magnetic layer 16 is typically formed by sputtering.

[0369] "Protective layer"

[0370] The protective layer 17 protects the magnetic layer 16. The protective layer 17 can consist of one layer or multiple layers. Examples of materials for the protective layer 17 include carbon, nitrogen-containing carbon, and silicon carbide.

[0371] As the protective layer 17, a carbon-based protective layer is preferred, and an amorphous carbon protective layer is particularly preferred. If the protective layer 17 is a carbon-based protective layer, the interaction with the polar groups (especially hydroxyl groups) contained in the fluorinated ether compound in the lubricating layer 18 is enhanced, and therefore it is preferred.

[0372] 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 nitrided carbon, and by adjusting the hydrogen and / or nitrogen content in the carbon-based protective layer.

[0373] The hydrogen content in the carbon-based protective layer is preferably 3 to 20 atomic percent when measured by hydrogen forward scattering (HFS). Furthermore, the nitrogen content in the carbon-based protective layer is preferably 4 to 15 atomic percent when measured by X-ray photoelectron spectrophotometry (XPS).

[0374] The hydrogen and / or nitrogen contained in the carbon-based protective layer do not need to be uniformly contained throughout the entire carbon-based protective layer. The carbon-based protective layer is, for example, suitable as a tilted layer with nitrogen on the lubrication layer 18 side of the protective layer 17 and hydrogen on the magnetic layer 16 side of the protective layer 17. In this case, the adhesion between the magnetic layer 16 and the lubrication layer 18 and the carbon-based protective layer is further improved. This is because the nitrogen in the protective layer 17 acts as an active site, promoting bonding with the lubrication layer. The hydrogen or nitrogen in the carbon-based protective layer also acts as an active site.

[0375] The thickness of the protective layer 17 can be arbitrarily selected, but 1 nm to 7 nm is preferred. If the thickness of the protective layer 17 is 1 nm or more, the performance of the protective layer 17 can be fully obtained. If the thickness of the protective layer 17 is 7 nm or less, it is preferred from the viewpoint of thinning the protective layer 17.

[0376] The film formation method for the protective layer 17 can be: sputtering using a target containing carbon, CVD (chemical vapor deposition) using hydrocarbon raw materials such as ethylene or toluene, and IBD (ion beam deposition).

[0377] When forming a carbon-based protective layer as protective layer 17, the film can be formed, for example, by DC magnetron sputtering. In particular, when forming a carbon-based protective layer as protective layer 17, it is preferable to form an amorphous carbon protective layer by plasma CVD. The amorphous carbon protective layer formed by plasma CVD has a uniform surface and low roughness.

[0378] "Lubrication layer"

[0379] The lubricating layer 18 prevents contamination of the magnetic recording medium 10. In addition, the lubricating layer 18 reduces the friction of the magnetic head of the magnetic recording and playback device that slides on the magnetic recording medium 10, thereby improving the durability of the magnetic recording medium 10.

[0380] like Figure 1 As shown, the lubricating layer 18 is formed in contact with the protective layer 17. The lubricating layer 18 contains the aforementioned fluorinated ether compound.

[0381] When the protective layer 17 disposed below the lubricating layer 18 is a carbon-based protective layer, the lubricating layer 18 is bonded to the protective layer 17 with a high bonding force. As a result, even if the thickness of the lubricating layer 18 is thin, it is easy to obtain a magnetic recording medium 10 with a high coverage of the surface of the protective layer 17, which can effectively prevent contamination of the surface of the magnetic recording medium 10.

[0382] The average film thickness of the lubricating layer 18 is preferably... More preferably If the average film thickness of the lubricating layer 18 is 0.5 nm or more, the lubricating layer 18 will not form islands or meshes but will be formed with a uniform film thickness. Therefore, the surface of the protective layer 17 can be covered with a high coverage rate through the lubricating layer 18. Furthermore, by making the average film thickness of the lubricating layer 18 2.0 nm or less, the lubricating layer 18 can be sufficiently thinned, and the rise of the magnetic head can be sufficiently small.

[0383] If the surface of the protective layer 17 is not covered by the lubricating layer 18 with a sufficiently high coverage, environmental substances adsorbed on the surface of the magnetic recording medium 10 can penetrate through the gaps in the lubricating layer 18 and infiltrate below the lubricating layer 18. These environmental substances penetrating below the lubricating layer 18 adsorb and combine with the protective layer 17 to generate contaminants. Furthermore, during magnetic recording and playback, these contaminants (agglomerated components) adhere (transfer) to the magnetic head as stains, causing head damage or reducing the magnetic recording and playback characteristics of the magnetic recording and playback device.

[0384] Examples of environmental substances that contribute to the formation of pollutants include, for example, siloxane compounds (cyclic siloxanes, linear siloxanes), ionic impurities, high molecular weight hydrocarbons such as octadecane, and plasticizers such as dioctyl phthalate. Examples of metal ions included as ionic impurities include, for example, sodium ions and potassium ions. Examples of inorganic ions included as ionic impurities include, for example, chloride ions, bromide ions, nitrate ions, sulfate ions, and ammonium ions. Examples of organic ions included as ionic impurities include, for example, oxalate ions and formic acid ions.

[0385] "Methods for forming a lubricating layer"

[0386] As a method for forming the lubricating layer 18, for example, a magnetic recording medium in the manufacturing process in which layers up to the protective layer 17 are formed on the substrate 11 is prepared, a lubricating layer forming solution is applied to the protective layer 17, and then dried.

[0387] The lubricant layer forming solution is obtained, for example, by dispersing and dissolving the lubricant for the magnetic recording medium described in the above embodiment in a solvent as needed, to achieve a viscosity and concentration suitable for the coating method. Examples of solvents used in the lubricant layer forming solution include, for instance, fluorinated solvents such as Burberry XF (trade name, manufactured by Mitsui Deyupon Froroike Mikael Co., Ltd.).

[0388] There are no particular limitations on the application method of the solution for forming the lubricating layer; examples include spin coating, spray coating, paper coating, and impregnation.

[0389] When using the immersion method, for example, the following method can be used. First, a substrate 11, with each layer up to the protective layer 17, is immersed in a lubricant layer forming solution added to the immersion tank of the immersion coating apparatus. Then, the substrate 11 is pulled out of the immersion tank at a predetermined speed. As a result, the lubricant layer forming solution is coated onto the surface of the protective layer 17 on the substrate 11.

[0390] By using the impregnation method, the lubricating layer forming solution can be uniformly coated on 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.

[0391] In this embodiment, it is preferable to perform heat treatment on the substrate 11 on which the lubricating layer 18 is formed. By performing heat treatment, the adhesion between the lubricating layer 18 and the protective layer 17 is improved, and the bonding force between the lubricating layer 18 and the protective layer 17 is enhanced.

[0392] The heat treatment temperature is preferably 100–180°C. If the heat treatment temperature is above 100°C, the effect of improving the adhesion between the lubricating layer 18 and the protective layer 17 can be sufficiently achieved. Furthermore, by keeping the heat treatment temperature below 180°C, thermal decomposition of the lubricating layer 18 can be prevented. The heat treatment time is preferably 10–120 minutes.

[0393] In this embodiment, in order to further improve the adhesion of the lubricating layer 18 to the protective layer 17, the lubricating layer 18 of the substrate 11 before or after heat treatment can be irradiated with ultraviolet light (UV).

[0394] The magnetic recording medium 10 of this embodiment has at least a magnetic layer 16, a protective layer 17, and a lubricating layer 18 sequentially disposed on a substrate 11. In the magnetic recording medium 10 of this embodiment, a lubricating layer 18 containing the aforementioned fluorinated ether compound is formed in contact with the protective layer 17. Therefore, the magnetic recording medium 10 of this embodiment has a lubricating layer 18 with good adhesion to the protective layer 17, which is not prone to pickup and spin-off, and has excellent reliability and durability.

[0395] The magnetic recording medium 10 of this embodiment, having a lubricating layer 18 that prevents lift-up, allows for a further reduction in magnetic pitch. Furthermore, the lubricating layer 18, which also prevents spin-off, allows for a higher rotational speed. Based on these factors, the magnetic recording medium 10 of this embodiment can contribute to increasing the capacity of the magnetic recording medium. Therefore, the magnetic recording medium 10 of this embodiment is particularly suitable as a disk drive mounted in a LUL (Load Unload) type disk drive device.

[0396] In contrast, in conventional magnetic recording media, the lubricant's adhesion to the protective layer was insufficient. Therefore, reducing the magnetic pitch could easily lead to pickup issues, while increasing the rotational speed of the magnetic recording medium could easily cause spin-off problems. Consequently, in conventional magnetic recording media, it was difficult to maintain reliability and durability while simultaneously reducing the magnetic pitch or increasing the rotational speed of the magnetic recording medium.

[0397] Example

[0398] The present invention will be further described in detail below through examples and comparative examples. However, the present invention is not limited to the following examples.

[0399] [NMR Measurement Methods]

[0400] The structures of the compounds obtained in the following examples were identified using AVANCE III-400 manufactured by Blu-ray Bio-Technica. 1 H-NMR measurements and 19 The determination was performed using F-NMR. In the NMR determination, approximately 10 mg of the sample was weighed and dissolved in approximately 0.5 mL of deuterated acetone (with hexafluorobenzene added as a reference substance). 1 The baseline for the H-NMR chemical shift is set at 2.05 ppm for the acetone peak. 19 The baseline for F-NMR chemical shift is set at -164.7 ppm for the peak of hexafluorobenzene.

[0401] The number-average molecular weight (Mn) of each compound is derived from 19 It is calculated from the results of F-NMR measurements. Specifically, it is derived from the results obtained by...19 The integral intensity of fluorine atoms was measured by 1 / F-NMR, and the number of repeating units in the PFPE chain was calculated. For each compound, the number-average molecular weight of the PFPE chain and the number-average molecular weight of the whole molecule were determined, and their ratio (PFPE ratio = PFPE chain / whole molecule) was calculated. The results are shown in Tables 1 to 5.

[0402] [Example 1]

[0403] The compound (AA1) represented by the above formula (AA1) was obtained by the method shown below (in formula (AA1), ma1, which represents the average degree of polymerization, is 3.4, and na1, which represents the average degree of polymerization, is 3.4).

[0404] First, the compound shown in formula (11-2) was synthesized by the method shown below. Two equivalents of 3-buten-1-ol were reacted with one equivalent of epichlorohydrin to synthesize the compound shown in formula (11-1). The resulting compound of formula (11-1) was reacted with 3,4-dihydro-2H-pyran, and after protecting the hydroxyl group with a tetrahydropyran group, the single-sided double bond was oxidized using m-chloroperoxybenzoic acid to synthesize the compound shown in formula (11-2).

[0405]

[0406] Furthermore, the compound shown in formula (11-4) was synthesized by the method described below. One equivalent of 3-allyloxy-1,2-propanediol was reacted with two equivalents of 2-(2-bromoethoxy)tetrahydro-2H-pyran to synthesize the compound shown in formula (11-3). The double bond of the resulting compound of formula (11-3) was oxidized with m-chloroperoxybenzoic acid to synthesize the compound shown in formula (11-4).

[0407]

[0408] Under a nitrogen atmosphere, add HOCH2CF2O(CF2CF2O) to a 200mL round-bottom flask. m (CF2O) n The following were prepared: 40.0 g of fluoropolyether (number average molecular weight 800, molecular weight distribution 1.1) represented by CF2CH2OH (where m represents the average degree of polymerization and n represents the average degree of polymerization 3.4); 9.01 g of the compound represented by formula (11-2); and 40.0 mL of t-BuOH (tert-butanol). The mixture was stirred at room temperature until homogeneous. Further, 1.68 g of t-BuOK (potassium tert-butoxide) was added to the above-mentioned flask, heated to 70°C, and stirred for 12 hours to allow the reaction to proceed.

[0409] The resulting reaction product was then cooled to 25°C, water was added, and further, Burberry XF (registered trademark) manufactured by Mitsui Deypon Frologie Microcar Co., Ltd. (hereinafter sometimes referred to as "Burberry XF") was added as a solvent to extract the organic layer, which was then washed with water. Anhydrous sodium sulfate was added to the organic layer for dehydration, and after filtration with a drying agent, the filtrate was concentrated. The residue was purified by silica gel column chromatography to obtain the compound (22.0 g) shown in formula (11-5).

[0410]

[0411] (In equation (11-5), m, representing the average degree of polymerization, is 3.4, and n, representing the average degree of polymerization, is 3.4.)

[0412] Under a nitrogen atmosphere, 22.0 g of the compound shown in formula (11-5), 8.90 g of the compound shown in formula (11-4), and 65.0 mL of t-BuOH (tert-butanol) were added to a 200 mL flask and stirred at room temperature until homogeneous. Further, 0.67 g of t-BuOK (potassium tert-butoxide) was added to the above flask, and the mixture was heated to 70 °C and stirred for 16 hours to allow the reaction to proceed.

[0413] The resulting reaction product was then cooled to 25°C, and 104.2 g of 7% hydrogen chloride / methanol reagent was added. The product was then stirred at room temperature for 3 hours to carry out the deprotection reaction.

[0414] The resulting reaction product was neutralized in 250 mL of 7% sodium bicarbonate solution, and the organic layer was extracted by adding chloroform XF and washed with water. Anhydrous sodium sulfate was added to the organic layer for dehydration, and the mixture was filtered off with a drying agent. The filtrate was then concentrated. The residue was purified by silica gel column chromatography to obtain 17.5 g of compound (AA1).

[0415] The resulting compound (AA1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0416] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (2H), 2.34 (2H), 3.40-4.20 (39H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0417] 19F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0418] [Example 2]

[0419] The compound (AA2) shown in the above formula (AA2) was obtained by the method shown below (in formula (AA2), na2, representing the average degree of polymerization, is 5.4).

[0420] Instead of HOCH2CF2O(CF2CF2O) in Example 1 m (CF2O) n The fluorinated polyether (number average molecular weight 800, molecular weight distribution 1.1) represented by CF2CH2OH (where m represents the average degree of polymerization and n represents the average degree of polymerization 3.4) was used instead of HOCH2CF2O (CF2CF2O). z 40.0 g of a fluoropolyether (number average molecular weight 800, molecular weight distribution 1.1) was prepared by the same procedure as in Example 1, except that 17.3 g of compound (AA2) was obtained.

[0421] The resulting compound (AA2) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0422] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (2H), 2.34 (2H), 3.40-4.20 (39H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0423] 19 F-NMR (acetone-d6): δ [ppm] = -78.57 (4F), -88.92 to -89.57 (21.6F)

[0424] [Example 3]

[0425] The compound (AA3) represented by the above formula (AA3) was obtained by the method shown below (in formula (AA3), na3, representing the average degree of polymerization, is 3.1).

[0426] Instead of HOCH2CF2O(CF2CF2O) in Example 1 m (CF2O) nThe fluorinated polyether (number average molecular weight 800, molecular weight distribution 1.1) represented by CF2CH2OH (where m represents the average degree of polymerization and n represents the average degree of polymerization 3.4) was used instead of HOCH2CF2CF2O (CF2CF2CF2O). x The fluoropolyether (number average molecular weight 800, molecular weight distribution 1.1) of CF2CF2CH2OH (where x represents the average degree of polymerization of 3.1) (40.0 g) was obtained by performing the same operation as in Example 1, except that 17.4 g of compound (AA3) was obtained.

[0427] The resulting compound (AA3) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0428] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (2H), 2.34 (2H), 3.40-4.20 (39H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0429] 19 F-NMR (acetone-d6): δ [ppm] = -84.22 (12.4F), -86.40 (4F), -124.30 (4F), -130.08 (6.2F)

[0430] [Example 4]

[0431] The compound (AA4) of the above formula (AA4) was obtained by the method shown below (in formula (AA4), na4, representing the average degree of polymerization, is 2.0).

[0432] Instead of HOCH2CF2O(CF2CF2O) in Example 1 m (CF2O) n The fluorinated polyether (number average molecular weight 800, molecular weight distribution 1.1) represented by CF2CH2OH (where m represents the average degree of polymerization and n represents the average degree of polymerization 3.4) was used instead of HOCH2CF2CF2CF2O (CF2CF2CF2CF2O). y The fluoropolyether (number average molecular weight 800, molecular weight distribution 1.1) of CF2CF2CF2CH2OH (where y represents the average degree of polymerization of 2.0) (40.0 g) was obtained by performing the same operation as in Example 1, except that 17.6 g of compound (AA4) was obtained.

[0433] The resulting compound (AA4) was subjected to...1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0434] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (2H), 2.34 (2H), 3.40-4.20 (39H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0435] 19 F-NMR (acetone-d6): δ [ppm] = -83.70 (12F), -123.32 (4F), -125.85 (8F), -127.63 (4F)

[0436] [Example 5]

[0437] The compound (AB1) represented by the above formula (AB1) was obtained by the method shown below (in formula (AB1), mb1, which represents the average degree of polymerization, is 3.4, and nb1, which represents the average degree of polymerization, is 3.4).

[0438] First, the compound shown in formula (11-6) was synthesized by the method shown below. After reacting 1 equivalent of 3-allyloxy-1,2-propanediol with 2 equivalents of 2-(3-bromopropoxy)tetrahydro-2H-pyran, the double bond of the resulting compound was oxidized with m-chloroperoxybenzoic acid to synthesize the compound shown in formula (11-6).

[0439]

[0440] Instead of the compound represented by formula (11-4) used in Example 1, the compound represented by formula (11-6) (9.21 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 17.9 g of compound (AB1).

[0441] The resulting compound (AB1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0442] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (6H), 2.34 (2H), 3.40-4.20 (39H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0443] 19F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0444] [Example 6]

[0445] The compound (AC1) shown in the above formula (AC1) was obtained by the method shown below (in formula (AC1), mc1, which represents the average degree of polymerization, is 3.4, and nc1, which represents the average degree of polymerization, is 3.4).

[0446] First, the compound shown in formula (11-7) was synthesized by the method shown below. After reacting 1 equivalent of 3-allyloxy-1,2-propanediol with 2 equivalents of 2-(4-bromobutoxy)tetrahydro-2H-pyran, the double bond of the resulting compound was oxidized with m-chloroperoxybenzoic acid to synthesize the compound shown in formula (11-7).

[0447]

[0448] Instead of the compound represented by formula (11-4) used in Example 1, the compound represented by formula (11-7) (9.82 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 18.3 g of compound (AC1).

[0449] The resulting compound (AC1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0450] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (¹⁰H), 2.34 (²H), 3.40-4.20 (³⁹H), 4.98 (¹H), 5.05 (¹H), 5.82 (¹H)

[0451] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0452] [Example 7]

[0453] The compound (AD1) shown in the above formula (AD1) was obtained by the method shown below (in formula (AD1), md1, which represents the average degree of polymerization, is 3.4, and nd1, which represents the average degree of polymerization, is 3.4).

[0454] First, the compound shown in formula (11-8) was synthesized by the method described below. After reacting tetrahydropyranyl glycol with allyl glycidyl ether, 2-(3-bromopropoxy)tetrahydro-2H-pyran was reacted. The double bond of the resulting compound was oxidized with m-chloroperoxybenzoic acid to synthesize the compound shown in formula (11-8).

[0455]

[0456] Instead of the compound represented by formula (11-4) used in Example 1, the compound represented by formula (11-8) (9.70 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 17.9 g of compound (AD1).

[0457] The resulting compound (AD1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0458] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (4H), 2.34 (2H), 3.40-4.20 (39H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0459] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0460] [Example 8]

[0461] The compound (AE1) represented by the above formula (AE1) was obtained by the method shown below (in formula (AE1), me1, which represents the average degree of polymerization, is 3.4, and ne1, which represents the average degree of polymerization, is 3.4).

[0462] First, the compound shown in formula (11-10) was synthesized by the method shown below. The double bond on one side of the di(3-butenyl) ether was oxidized with 1 equivalent of m-chloroperoxybenzoic acid, followed by ring-opening of the epoxy group with concentrated sulfuric acid, thereby synthesizing the compound shown in formula (11-9). 2 equivalents of 2-(2-bromoethoxy)tetrahydro-2H-pyran were reacted with the resulting compound shown in formula (11-9), followed by oxidation with m-chloroperoxybenzoic acid, thereby synthesizing the compound shown in formula (11-10).

[0463]

[0464] Instead of the compound represented by formula (11-4) used in Example 1, the compound represented by formula (11-10) (10.01 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 18.2 g of compound (AE1).

[0465] The resulting compound (AE1) was subjected to 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0466] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (6H), 2.34 (2H), 3.40-4.20 (39H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0467] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0468] [Example 9]

[0469] The compound (AF1) represented by the above formula (AF1) was obtained by the method shown below (in formula (AF1), mf1, which represents the average degree of polymerization, is 3.4, and nf1, which represents the average degree of polymerization, is 3.4).

[0470] First, the compound shown in formula (11-11) was synthesized by the method shown below. After reacting allyl alcohol with the compound shown in formula (11-4) above, the double bond of the resulting compound was oxidized with m-chloroperoxybenzoic acid to synthesize the compound shown in formula (11-11).

[0471]

[0472] Instead of the compound represented by formula (11-4) used in Example 1, the compound represented by formula (11-11) (10.21 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 19.1 g of compound (AF1).

[0473] The resulting compound (AF1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0474] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (2H), 2.34 (2H), 3.40-4.20 (45H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0475] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0476] [Example 10]

[0477] The compound (AG1) represented by the above formula (AG1) was obtained by the method shown below (in formula (AG1), mg1, representing the average degree of polymerization, is 3.4, and ng1, representing the average degree of polymerization, is 3.4).

[0478] First, the compounds shown in formulas (11-13) below were synthesized by the method shown below. 2,2-Dimethyl-1,3-dimethyl ... The carbonyl group of an alkyl-5-one was reduced with lithium aluminum hydride to synthesize the compound shown in formula (11-12). The compound shown in formula (11-13) was synthesized by reacting epibromoethanol with the resulting compound shown in formula (11-12).

[0479]

[0480] Instead of the compound represented by formula (11-4) used in Example 1, the compound represented by formula (11-13) (7.80 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 15.2 g of compound (AG1).

[0481] The resulting compound (AG1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0482] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (2H), 2.34 (2H), 3.40-4.20 (3¹H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0483] 19F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0484] [Example 11]

[0485] The compound (AH1) represented by the above formula (AH1) was obtained by the method shown below (in formula (AH1), mh1, representing the average degree of polymerization, is 3.4, and nh1, representing the average degree of polymerization, is 3.4).

[0486] First, the compounds shown in formulas (11-14) below were synthesized by the method shown below. This was achieved by reacting epibromoethanol with 5-hydroxymethyl-2,2-dimethyl-1,3-didimethyl-2,2-dihydroxy ... The alkane reacts to synthesize the compounds shown in formulas (11-14) below.

[0487]

[0488] Instead of the compound represented by formula (11-4) used in Example 1, the compound represented by formula (11-14) (7.87 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 15.5 g of compound (AH1).

[0489] The resulting compound (AH1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0490] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (2H), 2.10 (1H), 2.34 (2H), 3.40-4.20 (32H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0491] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0492] [Example 12]

[0493] The compound (A11) shown in formula (AI1) was obtained by the method described below (in formula (AI1), mi1, representing the average degree of polymerization, is 3.4, and ni1, representing the average degree of polymerization, is 3.4).

[0494] First, the compounds shown in formulas (11-15) below were synthesized by the method shown below. This was achieved by reacting epibromoethanol with 5-hydroxyethyl-2,2-dimethyl-1,3-dimethyldimethylethanol. The alkane reacts to synthesize the compounds shown in formulas (11-15) below.

[0495]

[0496] Instead of the compound represented by formula (11-4) used in Example 1, the compound represented by formula (11-15) (7.95 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 16.1 g of compound (AI1).

[0497] The resulting compound (AI1) was subjected to 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0498] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (4H), 2.10 (1H), 2.34 (2H), 3.40-4.20 (32H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0499] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0500] [Example 13]

[0501] The compound (AJ1) shown in the above formula (AJ1) was obtained by the method shown below (in formula (AJ1), mj1, which represents the average degree of polymerization, is 3.4, and nj1, which represents the average degree of polymerization, is 3.4).

[0502] First, the compounds shown in formula (11-16) below were synthesized by the method shown below. After reacting 3-butenyl bromide with the compounds shown in formula (11-12) above, oxidation was carried out using m-chloroperoxybenzoic acid to synthesize the compounds shown in formula (11-16) below.

[0503]

[0504] Instead of the compound represented by formula (11-4) used in Example 1, the compound represented by formula (11-16) (7.14 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 14.8 g of compound (AJ1).

[0505] The resulting compound (AJ1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0506] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (4H), 2.34 (2H), 3.40-4.20 (31H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0507] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0508] [Example 14]

[0509] The compound (AK1) represented by the above formula (AK1) was obtained by the method shown below (in formula (AK1), mk1, which represents the average degree of polymerization, is 3.4, and nk1, which represents the average degree of polymerization, is 3.4).

[0510] First, the compounds shown in formula (11-17) below were synthesized by the method shown below. After reacting allyl alcohol with the compounds shown in formula (11-13) above, the double bonds of the resulting compounds were oxidized with m-chloroperoxybenzoic acid to synthesize the compounds shown in formula (11-17) below.

[0511]

[0512] Instead of the compound represented by formula (11-4) used in Example 1, the compound represented by formula (11-17) (8.23 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 16.6 g of compound (AK1).

[0513] The resulting compound (AK1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0514] 1¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (2H), 2.34 (2H), 3.40-4.20 (37H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0515] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0516] [Example 15]

[0517] The compound (AL1) represented by the above formula (AL1) was obtained by the method shown below (in formula (AL1), ml1, which represents the average degree of polymerization, is 3.4, and nl1, which represents the average degree of polymerization, is 3.4).

[0518] First, the compounds shown in formula (11-18) below were synthesized by the method shown below. After reacting 3-buten-1-ol with the compounds shown in formula (11-13) above, the double bonds of the resulting compounds were oxidized with m-chloroperoxybenzoic acid to synthesize the compounds shown in formula (11-18) below.

[0519]

[0520] Instead of the compound represented by formula (11-4) used in Example 1, the compound represented by formula (11-18) (8.31 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 15.6 g of compound (AL1).

[0521] The resulting compound (AL1) was subjected to... i H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0522] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (4H), 2.34 (2H), 3.40-4.20 (37H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0523] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0524] [Example 16]

[0525] The compound (AM1) represented by the above formula (AM1) was obtained by the method shown below (in formula (AM1), mm1, which represents the average degree of polymerization, is 3.4, and nm1, which represents the average degree of polymerization, is 3.4).

[0526] First, the compounds shown in formula (11-20) were synthesized by the method shown below. Two equivalents of tetrahydropyranylethylene glycol were reacted with one equivalent of epichlorohydrin to synthesize the compounds shown in formula (11-19). The resulting compounds of formula (11-19) were then reacted with epibromohydrin to synthesize the compounds shown in formula (11-20).

[0527]

[0528] Instead of the compound represented by formula (11-4) used in Example 1, the compound represented by formula (11-20) (8.90 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 16.3 g of compound (AM1).

[0529] The resulting compound (AM1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0530] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (2H), 2.34 (2H), 3.40-4.20 (39H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0531] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0532] [Example 17]

[0533] The compound (AM2) represented by the above formula (AM2) was obtained by the method shown below (in formula (AM2), nm2, which represents the average degree of polymerization, is 5.4).

[0534] Instead of HOCH2CF2O(CF2CF2O) in Example 16 m (CF2O) nThe fluorinated polyether (number average molecular weight 800, molecular weight distribution 1.1) represented by CF2CH2OH (where m represents the average degree of polymerization and n represents the average degree of polymerization 3.4) was used instead of HOCH2CF2O (CF2CF2O). z 40.0 g of a fluoropolyether (number average molecular weight 800, molecular weight distribution 1.1) was prepared by the same procedure as in Example 16, except that 17.6 g of compound (AM2) was obtained.

[0535] The resulting compound (AM2) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0536] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (2H), 2.34 (2H), 3.40-4.20 (39H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0537] 19 F-NMR (acetone-d6): δ [ppm] = -78.57 (4F), -88.92 to -89.57 (21.6F)

[0538] [Example 18]

[0539] The compound (AM3) represented by the above formula (AM3) was obtained by the method shown below (in formula (AM3), nm3, which represents the average degree of polymerization, is 3.1).

[0540] Instead of HOCH2CF2O(CF2CF2O) in Example 16 m (CF2O) n The fluorinated polyether (number average molecular weight 800, molecular weight distribution 1.1) represented by CF2CH2OH (where m represents the average degree of polymerization and n represents the average degree of polymerization 3.4) was used instead of HOCH2CF2CF2O (CF2CF2CF2O). x The fluoropolyether (number average molecular weight 800, molecular weight distribution 1.1) of CF2CF2CH2OH (where x represents the average degree of polymerization of 3.1) (40.0 g) was obtained by performing the same operation as in Example 16, except that 17.1 g of compound (AM3) was obtained.

[0541] The resulting compound (AM3) was subjected to... 1 H-NMR and 19The structure was identified by F-NMR measurements, and the following results were obtained.

[0542] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (2H), 2.34 (2H), 3.40-4.20 (39H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0543] 19 F-NMR (acetone-d6): δ [ppm] = -84.22 (12.4F), -86.40 (4F), -124.30 (4F), -130.08 (6.2F)

[0544] [Example 19]

[0545] The compound (AM4) represented by the above formula (AM4) was obtained by the method shown below (in formula (AM4), nm4, which represents the average degree of polymerization, is 2.0).

[0546] Instead of HOCH2CF2O(CF2CF2O) in Example 16 m (CF2O) n The fluorinated polyether (number average molecular weight 800, molecular weight distribution 1.1) represented by CF2CH2OH (where m represents the average degree of polymerization and n represents the average degree of polymerization 3.4) was used instead of HOCH2CF2CF2CF2O (CF2CF2CF2CF2O). y The fluoropolyether (number average molecular weight 800, molecular weight distribution 1.1) of CF2CF2CF2CH2OH (where y represents the average degree of polymerization of 2.0) (40.0 g) was obtained by performing the same operation as in Example 16, except that 17.0 g of compound (AM4) was obtained.

[0547] The resulting compound (AM4) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0548] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (2H), 2.34 (2H), 3.40-4.20 (39H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0549] 19 F-NMR (acetone-d6): δ [ppm] = -83.70 (12F), -123.32 (4F), -125.85 (8F), -127.63 (4F)

[0550] [Example 20]

[0551] The compound (AN1) represented by the above formula (AN1) was obtained by the method shown below (in formula (AN1), mn1, which represents the average degree of polymerization, is 3.4, and nn1, which represents the average degree of polymerization, is 3.4).

[0552] First, the compounds shown in formula (11-22) were synthesized by the method shown below. Two equivalents of tetrahydropyranyltrimethylenediol were reacted with one equivalent of epichlorohydrin to synthesize the compounds shown in formula (11-21). The resulting compounds of formula (11-21) were then reacted with epibromohydrin to synthesize the compounds shown in formula (11-22).

[0553]

[0554] Instead of the compound represented by formula (11-4) used in Example 1, the compound represented by formula (11-22) (9.11 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 16.8 g of compound (AN1).

[0555] The resulting compound (AN1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0556] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (6H), 2.34 (2H), 3.40-4.20 (39H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0557] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0558] [Example 21]

[0559] The compound (AO1) represented by the above formula (AO1) was obtained by the method shown below (in formula (AO1), mo1, which represents the average degree of polymerization, is 3.4, and no1, which represents the average degree of polymerization, is 3.4).

[0560] First, the compound shown in formula (11-24) was synthesized by the method shown below. Two equivalents of tetrahydropyranyltetramethylenediol were reacted with one equivalent of epichlorohydrin to synthesize the compound shown in formula (11-23). ​​The compound shown in formula (11-24) was synthesized by reacting the obtained compound shown in formula (11-23) with epibromohydrin.

[0561]

[0562] Instead of the compound represented by formula (11-4) used in Example 1, the compound represented by formula (11-24) (9.31 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 16.4 g of compound (AO1).

[0563] The resulting compound (AO1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0564] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (¹⁰H), 2.34 (²H), 3.40-4.20 (³⁹H), 4.98 (¹H), 5.05 (¹H), 5.82 (¹H)

[0565] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0566] [Example 22]

[0567] The compound (AP1) represented by the above formula (AP1) was obtained by the method shown below (in formula (AP1), mp1, which represents the average degree of polymerization, is 3.4, and np1, which represents the average degree of polymerization, is 3.4).

[0568] First, the compound shown in formula (11-26) was synthesized by the method shown below. Two equivalents of tetrahydropyranyl diethylene glycol were reacted with one equivalent of epichlorohydrin to synthesize the compound shown in formula (11-25). The resulting compound of formula (11-25) was then reacted with epibromohydrin to synthesize the compound shown in formula (11-26).

[0569]

[0570] Instead of the compound represented by formula (11-4) used in Example 1, the compound represented by formula (11-26) (9.10 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 16.9 g of compound (AP1).

[0571] The resulting compound (AP1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0572] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (2H), 2.34 (2H), 3.40-4.20 (47H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0573] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0574] [Example 23]

[0575] The compound (AQ1) represented by the above formula (AQ1) was obtained by the method shown below (in formula (AQ1), mq1, which represents the average degree of polymerization, is 3.4, and nq1, which represents the average degree of polymerization, is 3.4).

[0576] First, the compound shown in formula (11-28) was synthesized by the method shown below. 3,4-dihydro-2H-pyran was reacted with 2-(bromomethyl)-2-(hydroxymethyl)-1,3-propanediol, and the hydroxyl group was protected with a tetrahydropyran group to synthesize the compound shown in formula (11-27). After reacting the obtained compound of formula (11-27) with allyl alcohol, the double bond of the resulting compound was oxidized with m-chloroperoxybenzoic acid to synthesize the compound shown in formula (11-28).

[0577]

[0578] Instead of the compound represented by formula (11-4) used in Example 1, the compound represented by formula (11-28) (7.91 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 15.9 g of compound (AQ1).

[0579] The resulting compound (AQ1) was subjected to... 1 H-NMR and 19The structure was identified by F-NMR measurements, and the following results were obtained.

[0580] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (2H), 2.34 (2H), 3.40-4.20 (35H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0581] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0582] [Example 24]

[0583] The compound (AR1) represented by the above formula (AR1) was obtained by the method shown below (in formula (AR1), mr1, which represents the average degree of polymerization, is 3.4, and nr1, which represents the average degree of polymerization, is 3.4).

[0584] First, the compound shown in formula (11-30) was synthesized by the method shown below. One equivalent of 4-allyloxy-1,2-butanediol was reacted with two equivalents of 2-(6-bromohexyloxy)tetrahydro-2H-pyran to synthesize the compound shown in formula (11-29). The double bond of the resulting compound of formula (11-29) was oxidized with m-chloroperoxybenzoic acid to synthesize the compound shown in formula (11-30).

[0585]

[0586] Instead of the compound represented by formula (11-4) used in Example 1, the compound represented by formula (11-30) (10.61 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 18.1 g of compound (AR1).

[0587] The resulting compound (AR1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0588] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (20H), 2.34 (2H), 3.40-4.20 (39H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0589] 19F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0590] [Example 25]

[0591] The compound (AS1) shown in the above formula (AS1) was obtained by the method shown below (in formula (AS1), ms1, representing the average degree of polymerization, is 3.4, and ns1, representing the average degree of polymerization, is 3.4).

[0592] First, the compound shown in formula (11-32) was synthesized by the method shown below. One equivalent of 8-allyloxy-1,2-octanediol was reacted with two equivalents of 2-(6-bromohexyloxy)tetrahydro-2H-pyran to synthesize the compound shown in formula (11-31). The double bond of the resulting compound of formula (11-31) was oxidized with m-chloroperoxybenzoic acid to synthesize the compound shown in formula (11-32).

[0593]

[0594] Instead of the compound represented by formula (11-4) used in Example 1, the compound represented by formula (11-32) (10.98 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 17.7 g of compound (AS1).

[0595] The resulting compound (AS1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0596] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (28H), 2.34 (2H), 3.40-4.20 (39H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0597] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0598] [Example 26]

[0599] The compound (AT1) represented by the above formula (AT1) was obtained by the method shown below (in formula (AT1), mt1, which represents the average degree of polymerization, is 3.4, and nt1, which represents the average degree of polymerization, is 3.4).

[0600] First, the compounds shown in formula (11-33) below were synthesized by the method shown below. Epibromoethanol was reacted with 5-hydroxyhexyl-2,2-dimethyl-1,3-di ... The alkane reacts to synthesize the compound shown in formula (11-33).

[0601]

[0602] Instead of the compound represented by formula (11-4) used in Example 1, the compound represented by formula (11-33) (7.21 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 15.2 g of compound (AT1).

[0603] The resulting compound (AT1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0604] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (¹²H), 2.10 (¹H), 2.34 (²H), 3.40-4.20 (³²H), 4.98 (¹H), 5.05 (¹H), 5.82 (¹H)

[0605] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0606] [Example 27]

[0607] The compound (AU1) shown in the above formula (AU1) was obtained by the method shown below (in formula (AU1), mu1, which represents the average degree of polymerization, is 3.4, and nu1, which represents the average degree of polymerization, is 3.4).

[0608] First, the compound shown in formula (11-35) was synthesized by the method shown below. Two equivalents of tetrahydropyranylhexamethylenediol were reacted with one equivalent of epichlorohydrin to synthesize the compound shown in formula (11-34). The resulting compound of formula (11-34) was then reacted with epibromohydrin to synthesize the compound shown in formula (11-35).

[0609]

[0610] Instead of the compound represented by formula (11-4) used in Example 1, the compound represented by formula (11-35) (9.41 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 16.2 g of compound (AU1).

[0611] The resulting compound (AU1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0612] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (¹⁸H), 2.34 (²H), 3.40-4.20 (³⁹H), 4.98 (¹H), 5.05 (¹H), 5.82 (¹H)

[0613] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0614] [Example 28]

[0615] The compound (AV1) represented by the above formula (AV1) was obtained by the method shown below (in formula (AV1), mv1, which represents the average degree of polymerization, is 3.4, and nv1, which represents the average degree of polymerization, is 3.4).

[0616] First, the compound shown in formula (11-37) was synthesized by the method shown below. The double bond on one side of the di(6-heptenyl) ether was oxidized with 1 equivalent of m-chloroperoxybenzoic acid, followed by ring-opening of the epoxy group with concentrated sulfuric acid, thereby synthesizing the compound shown in formula (11-36). 2 equivalents of 2-(2-bromoethoxy)tetrahydro-2H-pyran were reacted with the resulting compound of formula (11-36), followed by oxidation with m-chloroperoxybenzoic acid, thereby synthesizing the compound shown in formula (11-37).

[0617]

[0618] Instead of the compound represented by formula (11-4) used in Example 1, the compound represented by formula (11-37) (10.11 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 18.6 g of compound (AV1).

[0619] The resulting compound (AV1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0620] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.58-1.82 (¹⁸H), 2.34 (²H), 3.40-4.20 (³⁹H), 4.98 (¹H), 5.05 (¹H), 5.82 (¹H)

[0621] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0622] [Example 29]

[0623] The compound (BA1) represented by the above formula (BA1) was obtained by the method shown below (in formula (BA1), pa1, which represents the average degree of polymerization, is 3.4, and qa1, which represents the average degree of polymerization, is 3.4).

[0624] First, the compound represented by formula (12-2) was synthesized by the method shown below. 1,3-diallyloxy-2-propanol was reacted with 3,4-dihydro-2H-pyran to synthesize the compound represented by formula (12-1). The double bond on one side of the resulting compound represented by formula (12-1) was oxidized with m-chloroperoxybenzoic acid to synthesize the compound represented by formula (12-2).

[0625]

[0626] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (12-2) (8.17 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 16.7 g of compound (BA1).

[0627] The resulting compound (BA1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0628] 1 ¹H NMR (acetone-d6): δ [ppm] = 3.40-4.20 (39H), 5.10 (1H), 5.25 (1H), 5.91 (1H)

[0629] 19F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0630] [Example 30]

[0631] The compound (BA2) represented by the above formula (BA2) was obtained by the method shown below (in formula (BA2), qa2, which represents the average degree of polymerization, is 5.4).

[0632] Instead of HOCH2CF2O(CF2CF2O) in Example 29 m (CF2O) n The fluorinated polyether (number average molecular weight 800, molecular weight distribution 1.1) represented by CF2CH2OH (where m represents the average degree of polymerization and n represents the average degree of polymerization 3.4) was used instead of HOCH2CF2O (CF2CF2O). z 40.0 g of a fluoropolyether (number average molecular weight 800, molecular weight distribution 1.1) was prepared by the same procedure as in Example 29, except that 17.5 g of compound (BA2) was obtained.

[0633] The resulting compound (BA2) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0634] 1 ¹H NMR (acetone-d6): δ [ppm] = 3.40-4.20 (39H), 5.10 (1H), 5.25 (1H), 5.91 (1H)

[0635] 19 F-NMR (acetone-d6): δ [ppm] = -78.57 (4F), -88.92 to -89.57 (21.6F)

[0636] [Example 31]

[0637] The compound (BA3) represented by the above formula (BA3) was obtained by the method shown below (in formula (BA3), qa3, which represents the average degree of polymerization, is 3.1).

[0638] Instead of HOCH2CF2O(CF2CF2O) in Example 29 m (CF2O) nThe fluorinated polyether (number average molecular weight 800, molecular weight distribution 1.1) represented by CF2CH2OH (where m represents the average degree of polymerization and n represents the average degree of polymerization 3.4) was used instead of HOCH2CF2CF2O (CF2CF2CF2O). x The fluoropolyether (number average molecular weight 800, molecular weight distribution 1.1) of CF2CF2CH2OH (where x represents the average degree of polymerization of 3.1) (40.0 g) was obtained by performing the same operation as in Example 29, except that 16.8 g of compound (BA3) was obtained.

[0639] The resulting compound (BA3) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0640] 1 ¹H NMR (acetone-d6): δ [ppm] = 3.40-4.20 (39H), 5.10 (1H), 5.25 (1H), 5.91 (1H)

[0641] 19 F-NMR (acetone-d6): δ [ppm] = -84.22 (12.4F), -86.40 (4F), -124.30 (4F), -130.08 (6.2F)

[0642] [Example 32]

[0643] The compound (BA4) represented by the above formula (BA4) was obtained by the method shown below (in formula (BA4), qa4, which represents the average degree of polymerization, is 2.0).

[0644] Instead of HOCH2CF2O(CF2CF2O) in Example 29 m (CF2O) n The fluorinated polyether (number average molecular weight 800, molecular weight distribution 1.1) represented by CF2CH2OH (where m represents the average degree of polymerization and n represents the average degree of polymerization 3.4) was used instead of HOCH2CF2CF2CF2O (CF2CF2CF2CF2O). y The fluoropolyether (number average molecular weight 800, molecular weight distribution 1.1) of CF2CF2CF2CH2OH (where y represents the average degree of polymerization of 2.0) (40.0 g) was obtained by performing the same operation as in Example 29, except that 16.5 g of compound (BA4) was obtained.

[0645] The resulting compound (BA4) was subjected to... 1 H-NMR and19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0646] 1 ¹H NMR (acetone-d6): δ [ppm] = 3.40-4.20 (39H), 5.10 (1H), 5.25 (1H), 5.91 (1H)

[0647] 19 F-NMR (acetone-d6): δ [ppm] = -83.70 (12F), -123.32 (4F), -125.85 (8F), -127.63 (4F)

[0648] [Example 33]

[0649] The compound (BB1) represented by the above formula (BB1) was obtained by the method shown below (in formula (BB1), pb1, which represents the average degree of polymerization, is 3.4, and qb1, which represents the average degree of polymerization, is 3.4).

[0650] First, the compound shown in formula (12-4) was synthesized by the method described below. Epibromoethanol was reacted with 3-buten-1-ol, followed by epoxide hydrolysis under acidic conditions to synthesize the compound shown in formula (12-3). After protecting the primary hydroxyl group of the obtained compound (12-3) with tert-butyldimethylsilyl, the secondary hydroxyl group was protected with methoxymethyl, thus removing the tert-butyldimethylsilyl from the resulting compound. Finally, epibromoethanol was reacted with the generated primary hydroxyl group to synthesize the compound shown in formula (12-4).

[0651]

[0652] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (12-4) (8.27 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 15.1 g of compound (BB1).

[0653] The resulting compound (BB1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0654] 1 ¹H-NMR (acetone-d6): δ [ppm] = 2.34 (2H), 3.40-4.20 (39H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0655] 19F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0656] [Example 34]

[0657] The compound (BC1) represented by the above formula (BC1) was obtained by the method shown below (in formula (BC1), pc1, which represents the average degree of polymerization, is 3.4, and qc1, which represents the average degree of polymerization, is 3.4).

[0658] First, the compound shown in formula (12-6) was synthesized by the method described below. Epibromoethanol was reacted with 4-penten-1-ol, followed by epoxide hydrolysis under acidic conditions to synthesize the compound shown in formula (12-5). After protecting the primary hydroxyl group of the obtained compound (12-5) with tert-butyldimethylsilyl, the secondary hydroxyl group was protected with methoxymethyl, thus removing the tert-butyldimethylsilyl from the resulting compound. Finally, epibromoethanol was reacted with the generated primary hydroxyl group to synthesize the compound shown in formula (12-6).

[0659]

[0660] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (12-6) (8.54 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 15.3 g of compound (BC1).

[0661] The resulting compound (BC1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0662] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.67 (2H), 2.15 (2H), 3.40-4.20 (39H), 4.98 (1H), 5.05 (1H), 5.82 (1H)

[0663] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0664] [Example 35]

[0665] The compound (BD1) represented by the above formula (BD1) was obtained by the method shown below (in formula (BD1), pd1, which represents the average degree of polymerization, is 3.4, and qd1, which represents the average degree of polymerization, is 3.4).

[0666] First, the compound shown in formula (12-8) was synthesized by the method described below. After reacting epibromoethanol with propargyl alcohol, the epoxide was hydrolyzed under acidic conditions to synthesize the compound shown in formula (12-7). The primary hydroxyl group of the obtained compound (12-7) was protected with tert-butyldimethylsilyl, and the secondary hydroxyl group was protected with methoxymethyl to remove the tert-butyldimethylsilyl from the resulting compound. Finally, the epibromoethanol was reacted with the generated primary hydroxyl group to synthesize the compound shown in formula (12-8).

[0667]

[0668] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (12-8) (8.21 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 16.5 g of compound (BD1).

[0669] The resulting compound (BD1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0670] 1 ¹H NMR (acetone-d6): δ [ppm] = 2.48 (¹H), 3.40–4.20 (³⁹H)

[0671] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0672] [Example 36]

[0673] The compound (BE1) represented by the above formula (BE1) was obtained by the method shown below (in formula (BE1), pe1, which represents the average degree of polymerization, is 3.4, and qe1, which represents the average degree of polymerization, is 3.4).

[0674] First, the compound shown in formula (12-10) was synthesized by the method shown below. After reacting epibromoethanol with 4-pentyn-1-ol, the epoxide was hydrolyzed under acidic conditions to synthesize the compound shown in formula (12-9). The primary hydroxyl group of the obtained compound (12-9) was protected with tert-butyldimethylsilyl, and the secondary hydroxyl group was protected with methoxymethyl to remove the tert-butyldimethylsilyl from the resulting compound. Finally, the epibromoethanol was reacted with the generated primary hydroxyl group to synthesize the compound shown in formula (12-10).

[0675]

[0676] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (12-10) (8.41 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 16.4 g of compound (BE1).

[0677] The resulting compound (BE1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0678] 1 ¹H NMR (acetone-d6): δ [ppm] = 1.78 (2H), 2.00 (1H), 2.30 (2H), 3.40–4.20 (39H)

[0679] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0680] [Example 37]

[0681] The compound (BF1) represented by the above formula (BF1) was obtained by the method shown below (in formula (BF1), pf1, representing the average degree of polymerization, is 3.4, and qf1, representing the average degree of polymerization, is 3.4).

[0682] First, the compound shown in formula (12-12) was synthesized by the method shown below. After reacting epibromoethanol with 2-thiopheneethanol, the epoxy was hydrolyzed under acidic conditions to synthesize the compound shown in formula (12-11). The primary hydroxyl group of the obtained compound of formula (12-11) was protected with tert-butyldimethylsilyl, and the secondary hydroxyl group was protected with methoxymethyl to remove the tert-butyldimethylsilyl from the obtained compound. Finally, the epibromoethanol was reacted with the generated primary hydroxyl group to synthesize the compound shown in formula (12-12).

[0683]

[0684] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (12-12) (8.21 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 16.9 g of compound (BF1).

[0685] The resulting compound (BF1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0686] 1 ¹H NMR (acetone-d6): δ [ppm] = 3.07 (2H), 3.40–4.20 (39H), 6.90 (2H), 7.23 (1H)

[0687] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0688] [Example 38]

[0689] The compound (BG1) represented by the above formula (BG1) was obtained by the method shown below (in formula (BG1), pg1, representing the average degree of polymerization, is 3.4, and qg1, representing the average degree of polymerization, is 3.4).

[0690] First, compounds of formula (12-14) were synthesized by the method shown below. After reacting epibromoethanol with 1-methylpyrazole-5-methanol, the epoxy was hydrolyzed under acidic conditions to synthesize compounds of formula (12-13). The primary hydroxyl group of the resulting compounds of formula (12-13) was protected with tert-butyldimethylsilyl, and the secondary hydroxyl group was protected with methoxymethyl to remove the tert-butyldimethylsilyl group from the resulting compounds. Finally, epibromoethanol was reacted with the generated primary hydroxyl group to synthesize compounds of formula (12-14).

[0691]

[0692] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (12-14) (8.31 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 16.7 g of compound (BG1).

[0693] The resulting compound (BG1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0694] 1 ¹H NMR (acetone-d6): δ [ppm] = 3.40-4.20 (42H), 6.20 (1H), 7.31 (1H)

[0695] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0696] [Example 39]

[0697] The compound (BH1) represented by the above formula (BH1) was obtained by the method shown below (in formula (BH1), ph1, which represents the average degree of polymerization, is 3.4, and qh1, which represents the average degree of polymerization, is 3.4).

[0698] First, the compounds shown in formulas (12-15) were synthesized by the method shown below. After reacting 4-methoxyphenol with allyl glycidyl ether, the double bond was oxidized using m-chloroperoxybenzoic acid, thereby synthesizing the compounds shown in formulas (12-15).

[0699]

[0700] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (12-15) (8.51 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 16.9 g of compound (BH1).

[0701] The resulting compound (BH1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0702] 1 ¹H NMR (acetone-d6): δ [ppm] = 3.40-4.20 (40H), 6.85 (4H)

[0703] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0704] [Example 40]

[0705] The compound (BI1) represented by the above formula (BI1) was obtained by the method shown below (in formula (BI1), pi1, which represents the average degree of polymerization, is 3.4, and qi1, which represents the average degree of polymerization, is 3.4).

[0706] First, the compounds shown in formulas (12-16) were synthesized by the method shown below. After reacting 3-cyanophenol with allyl glycidyl ether, the double bond was oxidized using m-chloroperoxybenzoic acid, thereby synthesizing the compounds shown in formulas (12-16).

[0707]

[0708] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (12-16) (8.11 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 16.1 g of compound (BI1).

[0709] The resulting compound (BI1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0710] 1 ¹H NMR (acetone-d6): δ [ppm] = 3.40-4.20 (37H), 7.28-7.34 (3H), 7.50 (1H)

[0711] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0712] [Example 41]

[0713] The compound (BJ1) shown in the above formula (BJ1) was obtained by the method shown below (in formula (BJ1), pj1, which represents the average degree of polymerization, is 3.4, and qj1, which represents the average degree of polymerization, is 3.4).

[0714] First, compounds of formula (12-18) were synthesized by the method shown below. After reacting epibromoethanol with 3-cyanopropanol, the epoxy was hydrolyzed under acidic conditions to synthesize compounds of formula (12-17). The primary hydroxyl group of the obtained compounds of formula (12-17) was protected with tert-butyldimethylsilyl, and the secondary hydroxyl group was protected with methoxymethyl to remove the tert-butyldimethylsilyl from the resulting compounds. Finally, epibromoethanol was reacted with the generated primary hydroxyl group to synthesize compounds of formula (12-18).

[0715]

[0716] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (12-18) (8.26 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 16.9 g of compound (BJ1).

[0717] The resulting compound (BJ1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0718] 1 ¹H NMR (acetone-d6): δ [ppm] = 1.88 (2H), 2.54 (2H), 3.40–4.20 (39H)

[0719] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0720] [Example 42]

[0721] The compound (BK1) represented by the above formula (BK1) was obtained by the method shown below (in formula (BK1), pk1, which represents the average degree of polymerization, is 3.4, and qk1, which represents the average degree of polymerization, is 3.4).

[0722] First, compounds of formula (12-20) were synthesized by the method shown below. After reacting epibromoethanol with 4-cyanobutanol, the epoxy was hydrolyzed under acidic conditions to synthesize compounds of formula (12-19). The primary hydroxyl group of the obtained compounds of formula (12-19) was protected with tert-butyldimethylsilyl, and the secondary hydroxyl group was protected with methoxymethyl to remove the tert-butyldimethylsilyl group from the resulting compounds. Finally, epibromoethanol was reacted with the generated primary hydroxyl group to synthesize compounds of formula (12-20).

[0723]

[0724] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (12-20) (8.41 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 17.2 g of compound (BK1).

[0725] The resulting compound (BK1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0726] 1 ¹H NMR (acetone-d6): δ [ppm] = 1.75 (4H), 2.54 (2H), 3.40–4.20 (39H)

[0727] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0728] [Example 43]

[0729] The compound (BL1) represented by the above formula (BL1) was obtained by the method shown below (in formula (BL1), pl1, which represents the average degree of polymerization, is 3.4, and ql1, which represents the average degree of polymerization, is 3.4).

[0730] First, the compounds shown in formula (12-21) were synthesized by the method described below. The primary hydroxyl group of 3-methoxy-1,2-propanediol was protected with tert-butyldimethylsilyl, and the secondary hydroxyl group was protected with methoxymethyl, thus removing the tert-butyldimethylsilyl from the resulting compound. Finally, epibromoethanol was reacted with the generated primary hydroxyl group to synthesize the compounds shown in formula (12-21).

[0731]

[0732] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (12-21) (8.51 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 17.0 g of compound (BL1).

[0733] The resulting compound (BL1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0734] 1 ¹H-NMR (acetone-d6): δ [ppm] = 3.40-4.20 (40H)

[0735] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0736] [Example 44]

[0737] The compound (BM1) represented by the above formula (BM1) was obtained by the method shown below (in formula (BM1), pm1, which represents the average degree of polymerization, is 3.4, and qm1, which represents the average degree of polymerization, is 3.4).

[0738] First, the compounds shown in formulas (12-22) were synthesized by the method described below. The primary hydroxyl group of 3-allyloxy-1,2-propanediol was protected with tert-butyldimethylsilyl, and the secondary hydroxyl group was protected with methoxymethyl. The tert-butyldimethylsilyl group was then removed from the resulting compound. Finally, bromopropane was reacted with the generated primary hydroxyl group, and the double bond was oxidized using m-chloroperoxybenzoic acid to synthesize the compounds shown in formulas (12-22).

[0739]

[0740] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (12-22) (7.80 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 16.9 g of compound (BM1).

[0741] The resulting compound (BM1) was subjected to 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0742] 1 ¹H NMR (acetone-d6): δ [ppm] = 0.84 (3H), 1.55 (2H), 3.40–4.20 (39H)

[0743] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0744] [Example 45]

[0745] The compound (BN1) represented by the above formula (BN1) was obtained by the method shown below (in formula (BN1), pn1, which represents the average degree of polymerization, is 3.4, and qn1, which represents the average degree of polymerization, is 3.4).

[0746] First, the compounds shown in formula (12-23) were synthesized by the method shown below. After reacting 2,2,2-trifluoroethanol with allyl glycidyl ether, the double bond was oxidized using m-chloroperoxybenzoic acid, thereby synthesizing the compounds shown in formula (12-23).

[0747]

[0748] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (12-23) (6.10 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 15.3 g of compound (BN1).

[0749] The resulting compound (BN1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0750] 1 ¹H-NMR (acetone-d6): δ [ppm] = 3.40-4.20 (39H)

[0751] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0752] [Example 46]

[0753] The compound (BO1) represented by the above formula (BO1) was obtained by the method shown below (in formula (BO1), po1, which represents the average degree of polymerization, is 3.4, and qo1, which represents the average degree of polymerization, is 3.4).

[0754] First, the compounds shown in formula (12-24) were synthesized by the method shown below. After reacting 2,2,3,3,3-pentafluoro-1-propanol with allyl glycidyl ether, the double bond was oxidized using m-chloroperoxybenzoic acid, thereby synthesizing the compounds shown in formula (12-24).

[0755]

[0756] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (12-24) (6.46 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 16.1 g of compound (BO1).

[0757] The resulting compound (BO1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0758] 1 ¹H-NMR (acetone-d6): δ [ppm] = 3.40-4.20 (39H)

[0759] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0760] [Example 47]

[0761] The compound (BP1) represented by the above formula (BP1) was obtained by the method shown below (in formula (BP1), pp1, which represents the average degree of polymerization, is 3.4, and qp1, which represents the average degree of polymerization, is 3.4).

[0762] First, the compounds shown in formulas (12-25) were synthesized by the method described below. The primary hydroxyl group of 3-allyloxy-1,2-propanediol was protected with tert-butyldimethylsilyl, and the secondary hydroxyl group was protected with methoxymethyl, thus removing the tert-butyldimethylsilyl from the resulting compound. Finally, after reacting 2-bromoethylmethyl ether with the generated primary hydroxyl group, the double bond was oxidized using m-chloroperoxybenzoic acid to synthesize the compounds shown in formulas (12-25).

[0763]

[0764] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (12-25) (6.98 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 16.4 g of compound (BP1).

[0765] The resulting compound (BP1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0766] 1 ¹H NMR (acetone-d6): δ [ppm] = 3.31 (3H), 3.40-4.20 (41H)

[0767] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0768] [Example 48]

[0769] The compound (BQ1) represented by the above formula (BQ1) was obtained by the method shown below (in formula (BQ1), pq1, which represents the average degree of polymerization, is 3.4, and qq1, which represents the average degree of polymerization, is 3.4).

[0770] First, the compound shown in formula (12-27) was synthesized by the method shown below. After reacting epibromoethanol with ethylene glycol monoallyl ether, the epoxy was hydrolyzed under acidic conditions to synthesize the compound shown in formula (12-26). The primary hydroxyl group of the obtained compound (12-26) was protected with tert-butyldimethylsilyl, and the secondary hydroxyl group was protected with methoxymethyl to remove the tert-butyldimethylsilyl from the obtained compound. Finally, the epibromoethanol was reacted with the generated primary hydroxyl group to synthesize the compound shown in formula (12-27).

[0771]

[0772] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (12-27) (7.12 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 16.5 g of compound (BQ1).

[0773] The resulting compound (BQ1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0774] 1 ¹H NMR (acetone-d6): δ [ppm] = 3.40-4.20 (43H), 5.10 (1H), 5.26 (1H), 5.91 (1H)

[0775] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0776] [Example 49]

[0777] The compound (BR1) represented by the above formula (BR1) was obtained by the method shown below (in formula (BR1), pr1, which represents the average degree of polymerization, is 3.4, and qr1, which represents the average degree of polymerization, is 3.4).

[0778] First, the compound shown in formula (12-28) was synthesized by the method shown below. After reacting allyl alcohol with the compound shown in formula (12-2) above, it was oxidized with m-chloroperoxybenzoic acid to synthesize the compound shown in formula (12-28).

[0779]

[0780] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (12-28) (7.02 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 16.6 g of compound (BR1).

[0781] The resulting compound (BR1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0782] 1¹H NMR (acetone-d6): δ [ppm] = 3.40-4.20 (45H), 5.10 (1H), 5.25 (1H), 5.91 (1H)

[0783] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0784] [Example 50]

[0785] The compound (CA1) shown in the above formula (CA1) was obtained by the method shown below (in formula (CA1), ua1, which represents the average degree of polymerization, is 3.4, and va1, which represents the average degree of polymerization, is 3.4).

[0786] First, after reacting ethylene glycol monoallyl ether with 3,4-dihydro-2H-pyran, it is oxidized with m-chloroperoxybenzoic acid to synthesize the compound shown in formula (13-1).

[0787]

[0788] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (13-1) (6.02 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 16.0 g of compound (CA1).

[0789] The resulting compound (CA1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0790] 1 ¹H-NMR (acetone-d6): δ [ppm] = 3.40-4.20 (36H)

[0791] 19 F-NMR (acetone-d6): δ [ppm] = ~51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), ~89.16 to -91.14 (13.6F)

[0792] [Example 51]

[0793] The compound (CA2) shown in the above formula (CA2) was obtained by the method shown below (in formula (CA2), va2, representing the average degree of polymerization, is 5.4).

[0794] Instead of HOCH2CF2O(CF2CF2O) in Example 50 m (CF2O) n The fluorinated polyether (number average molecular weight 800, molecular weight distribution 1.1) represented by CF2CH2OH (where m represents the average degree of polymerization and n represents the average degree of polymerization 3.4) was used instead of HOCH2CF2O (CF2CF2O). z 40.0 g of a fluoropolyether (number average molecular weight 800, molecular weight distribution 1.1) was prepared by performing the same procedure as in Example 50, except that 15.6 g of compound (CA2) was obtained.

[0795] The resulting compound (CA2) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0796] 1 ¹H-NMR (acetone-d6): δ [ppm] = 3.40-4.20 (36H)

[0797] 19 F-NMR (acetone-d6): δ [ppm] = -78.57 (4F), -88.92 to -89.57 (21.6F)

[0798] [Example 52]

[0799] The compound (CA3) represented by the above formula (CA3) was obtained by the method shown below (in formula (CA3), va3, which represents the average degree of polymerization, is 3.1).

[0800] Instead of HOCH2CF2O(CF2CF2O) in Example 50 m (CF2O) n The fluorinated polyether (number average molecular weight 800, molecular weight distribution 1.1) represented by CF2CH2OH (where m represents the average degree of polymerization and n represents the average degree of polymerization 3.4) was used instead of HOCH2CF2CF2O (CF2CF2CF2O). x The fluoropolyether (number average molecular weight 800, molecular weight distribution 1.1) of CF2CF2CH2OH (where x represents the average degree of polymerization of 3.1) (40.0 g) was obtained by performing the same operation as in Example 50, except that 15.3 g of compound (CA3) was obtained.

[0801] The resulting compound (CA3) was subjected to... 1 H-NMR and 19The structure was identified by F-NMR measurements, and the following results were obtained.

[0802] 1 ¹H-NMR (acetone-d6): δ [ppm] = 3.40-4.20 (36H)

[0803] 19 F-NMR (acetone-d6): δ [ppm] = -84.22 (12.4F), -86.40 (4F), -124.30 (4F), -130.08 (6.2F)

[0804] [Example 53]

[0805] The compound (CB1) represented by the above formula (CB1) was obtained by the method shown below (in formula (CB1), ub1, which represents the average degree of polymerization, is 3.4, and vb1, which represents the average degree of polymerization, is 3.4).

[0806] First, the compound shown in formula (13-3) was synthesized by the method shown below. One equivalent of allyl bromide was reacted with one equivalent of 1,3-propanediol to synthesize the compound shown in formula (13-2). After reacting the resulting compound of formula (13-2) with 3,4-dihydro-2H-pyran, it was oxidized using m-chloroperoxybenzoic acid to synthesize the compound shown in formula (13-3).

[0807]

[0808] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (13-3) (6.22 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 16.2 g of compound (CB1).

[0809] The resulting compound (CB1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0810] 1 ¹H NMR (acetone-d6): δ [ppm] = 1.75 (2H), 3.40–4.20 (36H)

[0811] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0812] [Example 54]

[0813] The compound (CB2) represented by the above formula (CB2) was obtained by the method shown below (in formula (CB2), vb2, representing the average degree of polymerization, is 5.4).

[0814] Instead of HOCH2CF2O(CF2CF2O) in Example 53 m (CF2O) n The fluorinated polyether (number average molecular weight 800, molecular weight distribution 1.1) represented by CF2CH2OH (where m represents the average degree of polymerization and n represents the average degree of polymerization 3.4) was used instead of HOCH2CF2O (CF2CF2O). z 40.0 g of a fluoropolyether (number average molecular weight 800, molecular weight distribution 1.1) was prepared by the same procedure as in Example 53, except that 15.9 g of compound (CB2) was obtained.

[0815] The resulting compound (CB2) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0816] 1 ¹H NMR (acetone-d6): δ [ppm] = 1.75 (2H), 3.40–4.20 (36H)

[0817] 19 F-NMR (acetone-d6): δ [ppm] = -78.57 (4F), -88.92 to -89.57 (21.6F)

[0818] [Example 55]

[0819] The compound (CB3) shown in the above formula (CB3) was obtained by the method shown below (in formula (CB3_), vb3, representing the average degree of polymerization, is 3.1).

[0820] Instead of HOCH2CF2O(CF2CF2O) in Example 53 m (CF a O) n The fluorinated polyether (number average molecular weight 800, molecular weight distribution 1.1) represented by CF2CH2OH (where m represents the average degree of polymerization and n represents the average degree of polymerization 3.4) was used instead of HOCH2CF2CF2O (CF2CF2CF2O). xThe fluoropolyether (number average molecular weight 800, molecular weight distribution 1.1) of CF2CF2CH2OH (where x represents the average degree of polymerization of 3.1) (40.0 g) was obtained by performing the same operation as in Example 53, except that 15.4 g of compound (CB3) was obtained.

[0821] The resulting compound (CB3) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0822] 1 ¹H NMR (acetone-d6): δ [ppm] = 1.75 (2H), 3.40–4.20 (36H)

[0823] 19 F-NMR (acetone-d6): δ [ppm] = -84.22 (12.4F), -86.40 (4F), -124.30 (4F), -130.08 (6.2F)

[0824] [Example 56]

[0825] The compound (CC1) shown in the above formula (CC1) was obtained by the method shown below (in formula (CC1), uc1, which represents the average degree of polymerization, is 3.4, and vc1, which represents the average degree of polymerization, is 3.4).

[0826] First, the compound shown in formula (13-5) was synthesized by the method described below. One equivalent of allyl bromide was reacted with one equivalent of 1,4-butanediol to synthesize the compound shown in formula (13-4). After reacting the resulting compound of formula (13-4) with 3,4-dihydro-2H-pyran, it was oxidized using m-chloroperoxybenzoic acid to synthesize the compound shown in formula (13-5).

[0827]

[0828] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (13-5) (6.56 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 16.4 g of compound (CC1).

[0829] The resulting compound (CC1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0830] 1¹H NMR (acetone-d6): δ [ppm] = 1.75 (4H), 3.40–4.20 (36H)

[0831] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0832] [Example 57]

[0833] The compound (CD1) shown in the above formula (CD1) was obtained by the method shown below (in formula (CD1), ud1, which represents the average degree of polymerization, is 3.4, and vd1, which represents the average degree of polymerization, is 3.4).

[0834] First, 1 equivalent of 3,4-dihydro-2H-pyran is reacted with 1,6-hexanediol. Epibromoethanol is then reacted with the resulting compound to synthesize the compound shown in formula (13-6).

[0835]

[0836] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (13-6) (6.98 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 17.2 g of compound (CD1).

[0837] The resulting compound (CD1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0838] 1 ¹H-NMR (acetone-d6): δ [ppm] = 1.20-1.80 (8H), 3.40-4.20 (36H)

[0839] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0840] [Example 58]

[0841] The compound (CE1) represented by the above formula (CE1) was obtained by the method shown below (in formula (CE1), ue1, which represents the average degree of polymerization, is 3.4, and ve1, which represents the average degree of polymerization, is 3.4).

[0842] First, the compound shown in formula (13-8) was synthesized by the method shown below. The primary hydroxyl group of 3-allyloxy-1,2-propanediol was protected with tert-butyldimethylsilyl. Then, the secondary hydroxyl group was protected with methoxymethyl, and the tert-butyldimethylsilyl was removed from the resulting compound to synthesize the compound shown in formula (13-7). After reacting 2-(2-chloroethoxy)tetrahydropyran with the compound shown in formula (13-7), the double bond was oxidized with m-chloroperoxybenzoic acid to synthesize the compound shown in formula (13-8).

[0843]

[0844]

[0845] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (13-8) (7.45 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 17.9 g of compound (CE1).

[0846] The resulting compound (CE1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0847] 1 ¹H-NMR (acetone-d6): δ [ppm] = 3.40-4.20 (42H)

[0848] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0849] [Example 59]

[0850] The compound (CF1) shown in the above formula (CF1) was obtained by the method shown below (in formula (CF1), uf1, which represents the average degree of polymerization, is 3.4, and vf1, which represents the average degree of polymerization, is 3.4).

[0851] First, the compound shown in formula (13-10) was synthesized by the method shown below. The primary hydroxyl group of 3-allyloxy-1,2-propanediol was protected with tert-butyldimethylsilyl. Then, the secondary hydroxyl group was protected with methoxymethyl, and the tert-butyldimethylsilyl was removed from the resulting compound to synthesize the compound shown in formula (13-9). After reacting 2-(3-chloropropoxy)tetrahydropyran with the resulting compound shown in formula (13-9), the double bond was oxidized with m-chloroperoxybenzoic acid to synthesize the compound shown in formula (13-10).

[0852]

[0853] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (13-10) (7.21 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 17.7 g of compound (CF1).

[0854] The resulting compound (CF1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0855] 1 ¹H NMR (acetone-d6): δ [ppm] = 1.75 (2H), 3.40–4.20 (42H)

[0856] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0857] [Example 60]

[0858] The compound (CG1) shown in the above formula (CG1) was obtained by the method shown below (in formula (CG1), ug1, which represents the average degree of polymerization, is 3.4, and vg1, which represents the average degree of polymerization, is 3.4).

[0859] First, the double bond was oxidized with m-chloroperoxybenzoic acid relative to 2-allyloxytetrahydro-2H-pyran to synthesize the compound shown in formula (13-11) below.

[0860]

[0861] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (13-11) (5.21 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 13.8 g of compound (CG1).

[0862] The resulting compound (CG1) was subjected to 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0863] 1 ¹H-NMR (acetone-d6): δ [ppm] = 3.40-4.20 (32H)

[0864] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0865] [Example 61]

[0866] The compound (CG2) represented by the above formula (CG2) was obtained by the method shown below (in formula (CG2), vg2, which represents the average degree of polymerization, is 5.4).

[0867] Instead of HOCH2CF2O(CF2CF2O) in Example 60 m (CF2O) n The fluorinated polyether (number average molecular weight 800, molecular weight distribution 1.1) represented by CF2CH2OH (where m represents the average degree of polymerization and n represents the average degree of polymerization 3.4) was used instead of HOCH2CF2O (CF2CF2O). z 40.0 g of a fluoropolyether (number average molecular weight 800, molecular weight distribution 1.1) represented by CF2CH2OH (where z represents the average degree of polymerization of 5.4) was obtained, except that the same operation as in Example 60 was performed to obtain 15.4 g of compound (CG2).

[0868] The resulting compound (CG2) was subjected to 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0869] 1 ¹H-NMR (acetone-d6): δ [ppm] = 3.40-4.20 (32H)

[0870] 19F-NMR (acetone-d6): δ [ppm] = -78.57 (4F), -88.92 to -89.57 (21.6F)

[0871] [Example 62]

[0872] The compound (CG3) represented by the above formula (CG3) was obtained by the method shown below (in formula (CG3), vg3, which represents the average degree of polymerization, is 3.1).

[0873] Instead of HOCH2CF2O(CF2CF2O) in Example 60 m (CF2O) n The fluorinated polyether (number average molecular weight 800, molecular weight distribution 1.1) represented by CF2CH2OH (where m represents the average degree of polymerization and n represents the average degree of polymerization 3.4) was used instead of HOCH2CF2CF2O (CF2CF2CF2O). x The fluoropolyether (number average molecular weight 800, molecular weight distribution 1.1) of CF2CF2CH2OH (where x represents the average degree of polymerization of 3.1) (40.0 g) was obtained by performing the same operation as in Example 60, except that 15.3 g of compound (CG3) was obtained.

[0874] The resulting compound (CG3) was subjected to 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0875] 1 ¹H-NMR (acetone-d6): δ [ppm] = 3.40-4.20 (32H)

[0876] 19 F-NMR (acetone-d6): δ [ppm] = -84.22 (12.4F), -86.40 (4F), -124.30 (4F), -130.08 (6.2F)

[0877] [Example 63]

[0878] The compound (CH1) shown in the above formula (CH1) was obtained by the method shown below (in formula (CH1), uh1, representing the average degree of polymerization, is 3.4, and vh1, representing the average degree of polymerization, is 3.4).

[0879] First, 3,4-dihydro-2H-pyran was reacted with 3-buten-1-ol to protect the hydroxyl group with a tetrahydropyranyl group, and then oxidized with m-chloroperoxybenzoic acid to synthesize the compounds shown in formulas (13-12) below.

[0880]

[0881] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (13-12) (5.98 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 14.1 g of compound (CH1).

[0882] The resulting compound (CH1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0883] 1 ¹H NMR (acetone-d6): δ [ppm] = 1.40 (2H), 3.40-4.20 (32H)

[0884] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0885] [Example 64]

[0886] The compound (CH2) represented by the above formula (CH2) was obtained by the method shown below (in formula (CH2), vh2, representing the average degree of polymerization, is 5.4).

[0887] Instead of HOCH2CF2O(CF2CF2O) in Example 63 m (CF2O) n The fluorinated polyether (number average molecular weight 800, molecular weight distribution 1.1) represented by CF2CH2OH (where m represents the average degree of polymerization and n represents the average degree of polymerization 3.4) was used instead of HOCH2CF2O (CF2CF2O). z 40.0 g of a fluoropolyether (number average molecular weight 800, molecular weight distribution 1.1) was prepared by performing the same procedure as in Example 63, except that 14.9 g of compound (CH2) was obtained.

[0888] The resulting compound (CH2) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0889] 1¹H NMR (acetone-d6): δ [ppm] = 1.40 (2H), 3.40-4.20 (32H)

[0890] 19 F-NMR (acetone-d6): δ [ppm] = -78.57 (4F), -88.92 to -89.57 (21.6F)

[0891] [Example 65]

[0892] The compound (CH3) of the above formula (CH3) was obtained by the method shown below (in formula (CH3), vh3, representing the average degree of polymerization, is 3.1).

[0893] Instead of HOCH2CF2O(CF2CF2O) in Example 63 m (CF2O) n The fluorinated polyether (number average molecular weight 800, molecular weight distribution 1.1) represented by CF2CH2OH (where m represents the average degree of polymerization and n represents the average degree of polymerization 3.4) was used instead of HOCH2CF2CF2O (CF2CF2CF2O). x The fluoropolyether (number average molecular weight 800, molecular weight distribution 1.1) of CF2CF2CH2OH (where x represents the average degree of polymerization of 3.1) (40.0 g) was obtained by performing the same operation as in Example 63, except that 15.1 g of compound (CH3) was obtained.

[0894] The resulting compound (CH3) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0895] 1 ¹H NMR (acetone-d6): δ [ppm] = 1.40 (2H), 3.40-4.20 (32H)

[0896] 19 F-NMR (acetone-d6): δ [ppm] = -84.22 (12.4F), -86.40 (4F), -124.30 (4F), -130.08 (6.2F)

[0897] [Example 66]

[0898] The compound (CI1) shown in the above formula (CI1) was obtained by the method shown below (in formula (CI1), ui1, which represents the average degree of polymerization, is 3.4, and vi1, which represents the average degree of polymerization, is 3.4).

[0899] First, 3,4-dihydro-2H-pyran is reacted with 4-penten-1-ol to protect the hydroxyl group with a tetrahydropyranyl group, and then oxidized with m-chloroperoxybenzoic acid to synthesize the compound shown in formula (13-13).

[0900]

[0901] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (13-13) (6.01 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 14.3 g of compound (CI1).

[0902] The resulting compound (CI1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0903] 1 ¹H NMR (acetone-d6): δ [ppm] = 1.40-1.60 (4H), 3.40-4.20 (32H)

[0904] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0905] [Example 67]

[0906] The compound (CJ1) shown in the above formula (CJ1) was obtained by the method shown below (in formula (CJ1), uj1, which represents the average degree of polymerization, is 3.4, and vj1, which represents the average degree of polymerization, is 3.4).

[0907] First, 3,4-dihydro-2H-pyran was reacted with 5-hexen-1-ol to protect the hydroxyl group with a tetrahydropyranyl group, and then oxidized with m-chloroperoxybenzoic acid to synthesize the compound shown in formula (13-14) below.

[0908]

[0909] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (13-14) (6.11 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 15.3 g of compound (CJ1).

[0910] The resulting compound (CJ1) was subjected to... 1 H-NMR and 19The structure was identified by F-NMR measurements, and the following results were obtained.

[0911] 1 ¹H NMR (acetone-d6): δ [ppm] = 1.40-1.60 (6H), 3.40-4.20 (32H)

[0912] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0913] [Example 68]

[0914] The compound (CK1) represented by the above formula (CK1) was obtained by the method shown below (in formula (CK1), uk1, which represents the average degree of polymerization, is 3.4, and vk1, which represents the average degree of polymerization, is 3.4).

[0915] First, 3,4-dihydro-2H-pyran was reacted with 6-hepten-1-ol to protect the hydroxyl group with a tetrahydropyranyl group, and then oxidized with m-chloroperoxybenzoic acid to synthesize the compounds shown in formulas (13-15) below.

[0916]

[0917] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (13-15) (6.45 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 15.9 g of compound (CK1).

[0918] The resulting compound (CK1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0919] 1 ¹H NMR (acetone-d6): δ [ppm] = 1.40-1.60 (8H), 3.40-4.20 (32H)

[0920] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0921] [Example 69]

[0922] The compound (CL1) represented by the above formula (CL1) was obtained by the method shown below (in formula (CL1), ul1, which represents the average degree of polymerization, is 3.4, and vl1, which represents the average degree of polymerization, is 3.4).

[0923] First, the compounds shown in formulas (13-16) were synthesized by the method shown below. Relative to 1 equivalent of 3-allyloxy-1,2-propanediol, 2 equivalents of 3,4-dihydro-2H-pyran were reacted, the hydroxyl group was protected with a tetrahydropyran group, and then oxidized with m-chloroperoxybenzoic acid to synthesize the compounds shown in formulas (13-16).

[0924]

[0925] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (13-16) (6.51 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 15.5 g of compound (CL1).

[0926] The resulting compound (CL1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0927] 1 ¹H-NMR (acetone-d6): δ [ppm] = 3.40-4.20 (38H)

[0928] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0929] [Example 70]

[0930] The compound (CM1) shown in the above formula (CM1) was obtained by the method shown below (in formula (CM1), um1, which represents the average degree of polymerization, is 3.4, and vm1, which represents the average degree of polymerization, is 3.4).

[0931] First, the compounds shown in formulas (13-17) were synthesized by the method described below. After reacting allyl alcohol with the compound shown in formula (13-12) above, the secondary hydroxyl group was protected with a tetrahydropyran group by reacting it with 3,4-dihydro-2H-pyran. Then, the double bond was oxidized using m-chloroperoxybenzoic acid to synthesize the compounds shown in formulas (13-17).

[0932]

[0933] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (13-17) (7.21 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 15.3 g of compound (CM1).

[0934] The resulting compound (CM1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0935] 1 ¹H NMR (acetone-d6): δ [ppm] = 1.40 (2H), 3.40-4.20 (38H)

[0936] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0937] [Example 71]

[0938] The compound (CN1) shown in the above formula (CN1) was obtained by the method described below (in formula (CN1), un1, representing the average degree of polymerization, is 3.4, and vn1, representing the average degree of polymerization, is 3.4).

[0939] First, compounds of formula (13-18) were synthesized by the method shown below. After reacting allyl alcohol with the compound of formula (13-13), the secondary hydroxyl group was protected with a tetrahydropyranyl group by reacting it with 3,4-dihydro-2H-pyran. Then, the double bond was oxidized using m-chloroperoxybenzoic acid to synthesize compounds of formula (13-18).

[0940]

[0941] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (13-18) (7.26 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 15.5 g of compound (CN1).

[0942] The resulting compound (CN1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0943] 1¹H NMR (acetone-d6): δ [ppm] = 1.40-1.60 (4H), 3.40-4.20 (38H)

[0944] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0945] [Example 72]

[0946] The compound (CO1) represented by the above formula (CO1) was obtained by the method shown below (in formula (CO1), uo1, which represents the average degree of polymerization, is 3.4, and vo1, which represents the average degree of polymerization, is 3.4).

[0947] First, the compounds shown in formulas (13-19) were synthesized by the method described below. After reacting allyl alcohol with the compounds shown in formula (13-14) above, the secondary hydroxyl group was protected with a tetrahydropyran group by reacting it with 3,4-dihydro-2H-pyran. Then, the double bond was oxidized using m-chloroperoxybenzoic acid to synthesize the compounds shown in formulas (13-19).

[0948]

[0949] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (13-19) (7.56 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 15.3 g of compound (CO1).

[0950] The resulting compound (CO1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0951] 1 ¹H NMR (acetone-d6): δ [ppm] = 1.40-1.60 (6H), 3.40-4.20 (38H)

[0952] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0953] [Example 73]

[0954] The compound (CP1) represented by the above formula (CP1) was obtained by the method shown below (in formula (CP1), up1, which represents the average degree of polymerization, is 3.4, and vp1, which represents the average degree of polymerization, is 3.4).

[0955] First, the compounds shown in formula (13-20) were synthesized by the method shown below. After reacting 2-(2-bromoethoxy)tetrahydro-2H-pyran with 3-buten-1-ol, the mixture was oxidized with m-chloroperoxybenzoic acid to synthesize the compounds shown in formula (13-20).

[0956]

[0957] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (13-20) (5.98 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 14.1 g of compound (CP1).

[0958] The resulting compound (CP1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0959] 1 ¹H NMR (acetone-d6): δ [ppm] = 1.58-1.82 (2H), 3.40-4.20 (36H)

[0960] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0961] [Example 74]

[0962] The compound (CQ1) represented by the above formula (CQ1) was obtained by the method shown below (in formula (CQ1), uq1, which represents the average degree of polymerization, is 3.4, and vq1, which represents the average degree of polymerization, is 3.4).

[0963] First, the compound shown in formula (13-21) was synthesized by the method described below. After reacting 3-buten-1-ol with the compound shown in formula (13-1), it was reacted with 3,4-dihydro-2H-pyran to protect the secondary hydroxyl group with a tetrahydropyranyl group. Then, the double bond was oxidized using m-chloroperoxybenzoic acid to synthesize the compound shown in formula (13-21).

[0964]

[0965] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (13-21) (6.24 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 16.1 g of compound (CQ1).

[0966] The resulting compound (CQ1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0967] 1 ¹H NMR (acetone-d6): δ [ppm] = 1.58-1.82 (2H), 3.40-4.20 (42H)

[0968] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0969] [Example 75]

[0970] The compound (CR1) shown in the above formula (CR1) was obtained by the method shown below (in formula (CR1), ur1, which represents the average degree of polymerization, is 3.4, and vr1, which represents the average degree of polymerization, is 3.4).

[0971] Instead of the compound represented by formula (11-4) used in Example 50, the compound represented by formula (11-13) above (6.80 g) was used, and otherwise the same operation as in Example 50 was performed to obtain 14.2 g of compound (CR1).

[0972] The resulting compound (CR1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0973] 1 ¹H-NMR (acetone-d6): δ [ppm] = 3.40-4.20 (28H)

[0974] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0975] [Example 76]

[0976] The compound (CS1) shown in the above formula (CS1) was obtained by the method shown below (in formula (CS1), us1, which represents the average degree of polymerization, is 3.4, and vs1, which represents the average degree of polymerization, is 3.4).

[0977] Instead of the compound represented by formula (11-4) used in Example 50, the compound represented by formula (11-14) above (6.10 g) was used, and otherwise the same operation as in Example 50 was performed to obtain 14.8 g of compound (CS1).

[0978] The resulting compound (CS1) was subjected to 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0979] 1 ¹H NMR (acetone-d6): δ [ppm] = 2.10 (¹H), 3.40–4.20 (²⁹H)

[0980] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0981] [Example 77]

[0982] The compound (CT1) shown in the above formula (CT1) was obtained by the method shown below (in formula (CT1), ut1, which represents the average degree of polymerization, is 3.4, and vt1, which represents the average degree of polymerization, is 3.4).

[0983] Instead of the compound represented by formula (11-4) used in Example 50, the compound represented by formula (11-20) above (6.80 g) was used, and otherwise the same operation as in Example 50 was performed to obtain 16.1 g of compound (CT1).

[0984] The resulting compound (CT1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0985] 1 ¹H-NMR (acetone-d6): δ [ppm] = 3.40-4.20 (36H)

[0986] 19F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0987] [Example 78]

[0988] The compound (DA1) represented by the above formula (DA1) was obtained by the method shown below (in formula (DA1), xa1, which represents the average degree of polymerization, is 3.4, and ya1, which represents the average degree of polymerization, is 3.4).

[0989] Under a nitrogen atmosphere, add HOCH2CF2O(CF2CF2O) to a 200mL round-bottom flask. m (CF2O) n 10.0 g of a fluorinated polyether (number average molecular weight 800, molecular weight distribution 1.1) represented by CF2CH2OH (where m represents the average degree of polymerization and n represents the average degree of polymerization 3.4) was stirred at room temperature until homogeneous. Further, 0.84 g of t-BuOK (potassium tert-butoxide) was added to the above-mentioned flask, heated to 70°C, and stirred for 16 hours to allow the reaction to proceed.

[0990] The resulting reaction product was then cooled to 25°C, and 45.6 g of 7% hydrogen chloride / methanol reagent was added. The mixture was stirred at room temperature for 3 hours to carry out the deprotection reaction.

[0991] After neutralization with 150 mL of 7% sodium bicarbonate solution, the organic layer was extracted with ethyl acetate and washed with water. Anhydrous sodium sulfate was added to the organic layer for dehydration, and the mixture was filtered through a drying agent. The filtrate was then concentrated. The residue was purified by silica gel column chromatography to obtain 10.5 g of compound (DA1).

[0992] The resulting compound (DA1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0993] 1 ¹H-NMR (acetone-d6): δ [ppm] = 3.40-4.20 (46H)

[0994] 19F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[0995] [Example 79]

[0996] The compound (DB1) shown in the above formula (DB1) was obtained by the method shown below (in formula (DB1), xb1, representing the average degree of polymerization, is 3.4, and yb1, representing the average degree of polymerization, is 3.4).

[0997] Instead of the compound represented by formula (11-4) used in Example 78, the compound represented by formula (11-13) above (4.71 g) was used, and otherwise the same operation as in Example 78 was performed to obtain 8.65 g of compound (DB1).

[0998] The resulting compound (DB1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[0999] 1 ¹H-NMR (acetone-d6): δ [ppm] = 3.40-4.20 (30H)

[1000] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[1001] [Example 80]

[1002] The compound (DC1) shown in the above formula (DC1) was obtained by the method shown below (in formula (DC1), xc1, which represents the average degree of polymerization, is 3.4, and yc1, which represents the average degree of polymerization, is 3.4).

[1003] Instead of the compound represented by formula (11-4) used in Example 78, the compound represented by formula (11-14) above (5.06 g) was used, and otherwise the same operation as in Example 78 was performed to obtain 8.77 g of compound (DC1).

[1004] The resulting compound (DC1) was subjected to 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[1005] 1 ¹H NMR (acetone-d6): δ [ppm] = 2.10 (2H), 3.40-4.20 (32H)

[1006] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[1007] [Example 81]

[1008] The compound (DD1) represented by the above formula (DD1) was obtained by the method shown below (in formula (DD1), xd1, which represents the average degree of polymerization, is 3.4, and yd1, which represents the average degree of polymerization, is 3.4).

[1009] Instead of the compound represented by formula (11-4) used in Example 78, the compound represented by formula (11-20) above (10.2 g) was used, and the same operation as in Example 78 was performed to obtain 10.4 g of compound (DD1).

[1010] The resulting compound (DD1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[1011] 1 ¹H-NMR (acetone-d6): δ [ppm] = 3.40-4.20 (46H)

[1012] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[1013] [Example 82]

[1014] The compound (DE1) shown in the above formula (DE1) was obtained by the method shown below (in formula (DE1), xe1, which represents the average degree of polymerization, is 3.4, and ye1, which represents the average degree of polymerization, is 3.4).

[1015] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (11-13) above (7.28 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 15.0 g of compound (DE1).

[1016] The resulting compound (DE1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[1017] 1 ¹H-NMR (acetone-d6): δ [ppm] = 3.40-4.20 (38H)

[1018] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[1019] [Example 83]

[1020] The compound (DF1) shown in the above formula (DF1) was obtained by the method shown below (in formula (DF1), xf1, representing the average degree of polymerization, is 3.4, and yf1, representing the average degree of polymerization, is 3.4).

[1021] Instead of the compound represented by formula (11-2) used in Example 1, the compound represented by formula (11-14) above (8.54 g) was used, and otherwise the same operation as in Example 1 was performed to obtain 15.4 g of compound (DF1).

[1022] The resulting compound (DF1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[1023] 1 ¹H NMR (acetone-d6): δ [ppm] = 2.10 (2H), 3.40-4.20 (39H)

[1024] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[1025] [Example 84]

[1026] The compound (DG1) represented by the above formula (DG1) was obtained by the method shown below (in formula (DG1), xg1, which represents the average degree of polymerization, is 3.4, and yg1, which represents the average degree of polymerization, is 3.4).

[1027] Instead of the compound represented by formula (11-2) used in Example 16, the compound represented by formula (11-14) above (8.54 g) was used, and otherwise the same operation as in Example 16 was performed to obtain 15.0 g of compound (DG1_).

[1028] The resulting compound (DG1) was subjected to... 1 H-NMR and 19 The structure was identified by F-NMR measurements, and the following results were obtained.

[1029] 1 ¹H NMR (acetone-d6): δ [ppm] = 2.10 (2H), 3.40-4.20 (39H)

[1030] 19 F-NMR (acetone-d6): δ [ppm] = -51.99 to -55.72 (6.8F), -78.48 (2F), -80.66 (2F), -89.16 to -91.14 (13.6F)

[1031] [Comparative Example 1]

[1032] The compound (XA1) shown in the following formula (XA1) was synthesized by the method described in Patent Document 5.

[1033] [Comparative Example 2]

[1034] The compound (XB1) shown in the following formula (XB1) was synthesized by the method described in Patent Document 4.

[1035] [Comparative Example 3]

[1036] The compound (XC1) shown in the following formula (XC1) was synthesized by the method described in Patent Document 7.

[1037] [Comparative Example 4]

[1038] The compound (XD1) shown in the following formula (XD1) was synthesized by the method described in Patent Document 7.

[1039] [Comparative Example 5]

[1040] The compound (XE1) shown in the following formula (XE1) was synthesized by the method described in Patent Document 1.

[1041] [Comparative Example 6]

[1042] The compound (XF1) shown in the following formula (XF1) was synthesized by the method described in Patent Document 8.

[1043] [Comparative Example 7]

[1044] The compound (XG1) shown in the following formula (XG1) was synthesized by the method described in Patent Document 8.

[1045]

[1046]

[1047]

[1048] (In equation (XA1), maa, representing the average degree of polymerization, is 3.4, and naa, representing the average degree of polymerization, is 3.4.)

[1049] (In equation (XB1), mgb, representing the average degree of polymerization, is 3.4, and nbb, representing the average degree of polymerization, is 3.4.)

[1050] (In equation (XC1), mcc, representing the average degree of polymerization, is 3.4, and ncc, representing the average degree of polymerization, is 3.4.)

[1051] (In equation (XD1), mdd, representing the average degree of polymerization, is 3.4, and ndd, representing the average degree of polymerization, is 3.4.)

[1052] (In equation (XE1), mee, representing the average degree of polymerization, is 3.4, and nee, representing the average degree of polymerization, is 3.4.)

[1053] (In equation (XF1), mff, representing the average degree of polymerization, is 3.4, and nff, representing the average degree of polymerization, is 3.4.)

[1054] (In equation (XG1), mgg, representing the average degree of polymerization, is 3.4, and ngg, representing the average degree of polymerization, is 3.4.)

[1055] Next, a lubricant layer forming solution was prepared using the compounds obtained in Examples 1-84 and Comparative Examples 1-7, according to the method shown below. Then, using the obtained lubricant layer forming solution, a lubricant layer of the magnetic recording medium was formed using the method shown below, thus obtaining the magnetic recording media of Examples 1-84 and Comparative Examples 1-7.

[1056] [Solution for forming a lubricating layer]

[1057] The compounds obtained in Examples 1-84 and Comparative Examples 1-7 were dissolved in fluorinated solvent, specifically fluorinated solvent, var. XF (trade name, manufactured by Mitsui Dupont Fluorocec Microcar Co., Ltd.), with the film thickness when coated onto the protective layer as the solvent. The compound was diluted with varnish XF to prepare a lubricant layer forming solution with a concentration of 0.001% to 0.01% by mass.

[1058] [Magnetic recording media]

[1059] An adhesion layer, a soft magnetic layer, a first base layer, a second base layer, a magnetic layer, and a protective layer are sequentially disposed on a substrate with a diameter of 65 mm. The protective layer is formed of carbon nitride.

[1060] On the protective layer of the substrate, which has formed layers up to the protective layer, the lubricating layer forming solutions of Examples 1-84 and Comparative Examples 1-7 were applied by dip coating.

[1061] Then, the magnetic recording medium coated with the lubricant layer forming solution was added to a constant temperature bath at 120°C and subjected to heat treatment for 10 minutes. As a result, a lubricant layer was formed on the protective layer, yielding the magnetic recording media of Examples 1-84 and Comparative Examples 1-7.

[1062] The magnetic recording media of Examples 1-84 and Comparative Examples 1-7 obtained by such operation were evaluated by measuring the film thickness of the lubricating layer, measuring the adhesion (bonding rate) between the lubricating layer and the protective layer, conducting pickup characteristic tests and spin-off characteristic tests, using the methods shown below. The results are shown in Tables 1-5.

[1063] [Measurement of Lubricating Layer Thickness]

[1064] The peak height of the CF vibrational stretching of the lubricating layer was measured using a Fourier transform infrared spectrophotometer (FT-IR, trade name: Nicolet iS50, manufactured by Thermo Fisher Scientific). Then, using the correlation derived later, the film thickness of the lubricating layer was calculated from the measured peak height of the CF vibrational stretching.

[1065] [Method for calculating the correlation formula]

[1066] A disk was prepared with an adhesion layer, a soft magnetic layer, a first base layer, a second base layer, a magnetic layer, and a protective layer sequentially disposed on a substrate with a diameter of 65 mm. On the protective layer of this disk, a 6-… ( The film thickness (as indicated by the scale) forms the lubricating layer.

[1067] Then, for each disk with a lubricating layer, the increase in film thickness compared to the surface of a disk without a lubricating layer was measured using an ellipsometer, and this increase was defined as the film thickness of the lubricating layer. Furthermore, for each disk with a lubricating layer, the peak height in CF vibrational stretching was measured using FT-IR.

[1068] Furthermore, the correlation between the peak height obtained by FT-IR and the film thickness of the lubricating layer obtained by ellipsometer was determined.

[1069] [Determination of the adhesion (bonding rate) between the lubricating layer and the protective layer]

[1070] Regarding the magnetic recording medium with the lubricating layer formed, after the film thickness of the lubricating layer was measured using the method described above, it was washed by immersing it in Burberry XF as a solvent for 10 minutes and then removing it. The immersion speed of the magnetic recording medium in the solvent was set to 10 mm / s, and the removal speed was set to 1.2 mm / s. Then, the film thickness of the lubricating layer after solvent immersion was measured using the same method as the film thickness measurement performed before washing.

[1071] Furthermore, the film thickness of the lubricating layer before washing was defined as α, and the film thickness of the lubricating layer after washing (after solvent impregnation) was defined as β. The binding rate (adhesion rate) of the lubricant was calculated from the ratio of α to β ((β / α)×100(%)). Using the calculated adhesion rate, the adhesion between the lubricating layer and the protective layer was evaluated according to the criteria shown below.

[1072] The adhesion ratio can be used as an indicator of the bonding strength between the lubricating layer and the protective layer. If the adhesion between the lubricating layer and the protective layer is poor, some of the fluorinated ether compounds contained in the lubricating layer will dissolve into the varnish XF and be washed away. Therefore, the film thickness of the lubricating layer becomes smaller after washing, and the adhesion ratio decreases.

[1073] Evaluation criteria for "adhesion (bonding rate)"

[1074] ◎(Excellent): Adhesion rate of 75% or higher

[1075] ○ (Good): Adhesion rate 70%–74%

[1076] △ (Qualified): Adhesion rate 50%~69%

[1077] × (Unacceptable): Adhesion rate below 49%

[1078] [Pickup Characteristics Test]

[1079] A magnetic recording medium and a magnetic head were mounted on a spin mount and rotated under reduced pressure at room temperature (approximately 250 Torr) to allow the magnetic head to float at a fixed point for 10 minutes. The surface of the magnetic head opposite the magnetic recording medium was then analyzed using an ESCA (Electron Spectroscopy for Chemical Analysis) analyzer. The intensity of the fluorine-derived peak (signal intensity (au)) obtained using the ESCA analyzer represents the amount of lubricant adhering to the magnetic head. The pickup characteristics were evaluated using the obtained signal intensity according to the evaluation criteria shown below.

[1080] Evaluation Criteria for Pickup Characteristics

[1081] ◎(Excellent): Signal strength below 160 (very low adhesion)

[1082] ○ (Good): Signal strength 161-300 (low adhesion)

[1083] △ (Pass): Signal strength 301~1000 (high adhesion amount)

[1084] × (Unacceptable): Signal strength above 1001 (extremely high adhesion amount)

[1085] [Spin-off Characteristics Test]

[1086] A magnetic recording medium was mounted on a spin mount and rotated at 10,000 rpm for 72 hours at 80°C. Before and after this operation, the film thickness of the lubricant layer at a radius of 20 mm from the center of the magnetic recording medium was measured using FT-IR, and the reduction rate of the lubricant layer thickness was calculated. Using the calculated reduction rate, the spin-off characteristics were evaluated according to the evaluation criteria shown below.

[1087] Evaluation Criteria for Spin-Off Properties

[1088] ◎(Excellent): Film thickness reduction rate is less than 2%

[1089] ○ (Good): Film thickness reduction rate exceeds 2% but is less than 3%.

[1090] △ (Qualified): Film thickness reduction rate exceeding 3% but below 8%

[1091] × (Unacceptable): Film thickness reduction rate exceeds 8%

[1092] Based on these results, a comprehensive evaluation was conducted according to the evaluation criteria shown below.

[1093] "Overall Evaluation"

[1094] ◎(Excellent): The evaluation of adhesion rate, pickup characteristics, and spin-off characteristics are all ◎.

[1095] ○ (Good): The evaluation of adhesion rate, lifting characteristics and spin characteristics is ◎ or ○, with more than one of them being ○.

[1096] △ (Pass): One or more of the following evaluation criteria are △: adhesion rate, pick-up characteristics, and spin-off characteristics. No × is given.

[1097] × (Unacceptable): If one or more of the following evaluation criteria are met: adhesion rate, pick-up characteristics, or spin-off characteristics, the result will be ×.

[1098]

[1099]

[1100]

[1101]

[1102]

[1103] As shown in Tables 1 to 5, the magnetic recording media of Examples 1 to 84, which use the fluorinated ether compound represented by Formula (1) to form a lubricating layer, are evaluated as ◎ (excellent) or ○ (good) for adhesion rate, pickup characteristics, and spin-off characteristics, and are evaluated as ◎ (excellent) or ○ (good) for overall performance.

[1104] In contrast, for fluorinated ether compounds that do not possess the -[C]-[D]-R group shown in formula (1) 3 Compared with the magnetic recording media of Examples 1 to 84, the magnetic recording media of Comparative Examples 1 to 7 all showed poor results in terms of adhesion rate, pickup characteristics, and spin-off characteristics.

[1105] For the compound (XF1) of Comparative Example 6, although the terminal groups having two primary hydroxyl groups are arranged at both ends of the molecule, it does not contain divalent linkers corresponding to the -[B]-[A]- and -[C]-[D]- structures in the fluorinated ether compounds shown in Formula (1). Therefore, it is presumed that the compound (XF1) of Comparative Example 6 has a weaker adsorption force on the protective layer compared to the compounds of Examples 1 to 84.

[1106] Furthermore, regarding the compound (XG1) of Comparative Example 7, although the terminal groups having two primary hydroxyl groups are arranged at both ends of the molecule, it does not contain divalent linkers equivalent to the -[B]-[A]- structure and the -[C]-[D]- structure. Therefore, it is speculated that the adsorption force on the protective layer is poor compared with the compounds of Examples 1 to 84.

[1107] Industry availability

[1108] Fluorinated ether compounds are provided that can form a lubricating layer with good adhesion to the protective layer and can suppress pickup and spin-off, making them suitable as materials for use as lubricants for magnetic recording media.

[1109] Explanation of symbols

[1110] 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 fluorinated ether compound, characterized in that, It is represented by the following formula (1), R 1 -[B]-[A]-CH2-R 2 -CH2-[C]-[D]-R 3 (1) In equation (1), R 2 It is a perfluoropolyether chain and is any one of the following formulas (8-1) to (8-4); [A] is represented by the following formula (2-1), where a is an integer from 0 to 3; [B] is represented by the following formula (2-2), where b is an integer from 0 to 3 and c is an integer from 2 to 5; wherein the sum of the values ​​of a and b is 1 to 3; [A] and [B] can be interchanged in formula (1); [C] is represented by the following formula (3-1), where d is an integer from 0 to 2; [D] is represented by the following formula (3-2), where e is an integer from 0 to 2 and f is an integer from 2 to 5; wherein the sum of the values ​​of d and e is 1 or 2; [C] and [D] can be interchanged in formula (1); R 3 It is a branched terminal group with 3 to 30 carbon atoms, and is any one of the branched terminal groups in formulas (5-1) to (5-3) below; R 1 To be able to work with R 3 The same or different terminal groups; -CF2O-(CF2CF2O) m -(CF2O) n -CF2-(8-1) In equation (8-1), m and n represent the average degree of polymerization, each ranging from 0 to 30; where m or n is 0.1 or higher. -CF(CF3)-(OCF(CF3)CF2) w -OCF(CF3)-(8-2) In equation (8-2), w represents the average degree of polymerization, ranging from 0.1 to 30. -CF2CF2O-(CF2CF2CF2O) x -CF2CF2-(8-3) In equation (8-3), x represents the average degree of polymerization, ranging from 0.1 to 30. -CF2CF2CF2O-(CF2CF2CF2CF2O) y -CF2CF2CF2-(8-4) In equation (8-4), y represents the average degree of polymerization, ranging from 0.1 to 30. In equation (5-1), g represents an integer from 1 to 6; X 1 and X 2 Represented by equation (6); X 1 With X 2 They can be the same or different; In equation (5-2), h represents an integer from 0 to 6; i and j each independently represent an integer from 1 to 6; X 3 and X 4 It can be represented by a hydrogen atom or by formula (6); X 3 With X 4 They can be the same or different; In equation (5-3), k represents an integer from 0 to 6; p, q, and r each independently represent an integer from 1 to 6; X 5 X 6 and X 7 It can be represented by a hydrogen atom or by formula (6); X 5 X 6 and X 7 They can be different from each other, or they can be partially or completely the same; In equation (6), s represents an integer from 2 to 6, and t represents 1 or 2.

2. The fluorinated ether compound according to claim 1, wherein R in formula (1) 1 It is a branched terminal group with 3 to 30 carbon atoms, represented by the following formula (4); L in formula (4) represents an integer from 0 to 6; Y in formula (4) 1 and Y 2 Each is independently a hydrocarbon group containing one primary hydroxyl group and may contain an ether oxygen atom; Y in formula (4) 3 It is a hydrocarbon group containing one primary hydroxyl group and may contain an ether oxygen atom, or a hydrogen atom; 。 3. The fluorinated ether compound according to claim 1 or 2, wherein R in formula (1) 1 With R 3 Both are branch-type terminal groups in equations (5-1) to (5-3).

4. The fluorinated ether compound according to claim 1 or 2, wherein R in formula (1) 1 -[B]-[A]-and-[C]-[D]-R 3 same.

5. The fluorinated ether compound according to claim 1, wherein R in formula (1) 1 It is represented by the following formula (7), In equation (7), u represents an integer from 2 to 6, and v represents 0 or 1; R 4 It is any one of the following: a hydrogen atom, an alkyl group that may have substituents that do not contain a hydroxyl group, or an organogroup having at least one double or triple bond; wherein, The alkyl group and the organic group can be straight-chain or branched.

6. The fluorinated ether compound according to claim 5, wherein R in formula (7) 4 It is an alkyl group having 1 to 6 carbon atoms.

7. The fluorinated ether compound according to claim 5, wherein R in formula (7) 4 It is an alkyl group having 1 to 6 carbon atoms and a substituent, wherein the substituent is a fluorinated group or a cyano group.

8. The fluorinated ether compound according to claim 5, wherein R in formula (7) 4 It is any one of the following: an organogroup having 6 to 12 carbon atoms with an aromatic hydrocarbon group, an organogroup having 3 to 10 carbon atoms with an aromatic heterocycle, an alkenyl group having 2 to 8 carbon atoms, and an alkynyl group having 3 to 8 carbon atoms.

9. The fluorinated ether compound according to claim 5, wherein R in formula (7) 4 It is one group selected from methyl, ethyl, n-propyl, isopropyl, 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2,2,2,2,2,2-hexafluoroisopropyl, 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl, phenyl, methoxyphenyl, cyanophenyl, phenethyl, thienylethyl, N-methylpyrazolylmethyl, allyl, 3-butenyl, 4-pentenyl, propyneyl, 3-butynyl, and 4-pentynyl.

10. The fluorinated ether compound according to claim 5, wherein R in formula (7) 4 It is a hydrogen atom.

11. The fluorinated ether compound according to claim 1 or 2, wherein the number average molecular weight is in the range of 500 to 10000.

12. A lubricant for magnetic recording media, characterized in that, The compound comprising any one of claims 1 to 11.

13. A magnetic recording medium, characterized in that, It is a magnetic recording medium on which at least a magnetic layer, a protective layer, and a lubricating layer are sequentially disposed on a substrate. The lubricating layer comprises any one of the fluorinated ether compounds according to claims 1 to 11.

14. The magnetic recording medium according to claim 13, wherein the average film thickness of the lubricating layer is 0.5 nm to 2.0 nm.

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