Fluoroether Compound, Method for Producing the Same, Compound, Method for Producing the Same, Fluoroether Composition, Coating Liquid, and Article and Method for Producing the Same

Abstract

Provided are a fluorine-containing ether compound capable of forming a surface layer with excellent durability, a method for producing the same, a fluorine-containing ether composition and a coating liquid, and an article having a surface layer with excellent durability and a method for producing the same. A fluorine-containing ether compound is represented by the following formula (A1) or formula (A2). {R f O-(R f1 O) m1 -(R 1 ) m2 -(CHF) m3 -O-(CHF) m4} n1 -Q 1 (-T 1 ) n2 Formula (A1). (T 2 ) n3 -Q 2 -(CHF) m5 -O-(CHF) m6 -(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -(CHF) m10 -O-(CHF) m11 -Q 3 (-T 3 ) n4 Formula (A2). In the formula, each symbol is as described in the specification.

Description

Technical Field

[0001] The present invention relates to a fluoroether compound, a method for producing the same, a novel compound suitable for producing the fluoroether compound and the like, a method for producing the same, a fluoroether composition, a coating liquid, and an article and a method for producing the same. Background Art

[0002] A fluoroether compound having a perfluoropolyether chain and a hydrolyzable silyl group can form a surface layer exhibiting high lubricity, water and oil repellency, etc. on the surface of a substrate, and thus is suitable for use as a surface treatment agent. A surface treatment agent containing a fluoroether compound is used for applications that require properties such as water and oil repellency that are maintained for a long time without being easily reduced even when the surface layer is repeatedly rubbed with a finger (abrasion resistance) and the property of being able to easily remove fingerprints attached to the surface layer by wiping (fingerprint stain removability), for example, as a surface treatment agent for members forming a finger contact surface of a touch panel, lenses, and the surface of a display of a wearable terminal.

[0003] As a fluoroether compound capable of forming a surface layer excellent in abrasion resistance and fingerprint stain removability on the surface of a substrate, a fluoroether compound having a perfluoropolyether chain and a hydrolyzable silyl group has been proposed (Patent Document 1).

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: WO 2017 / 022437 Summary of the Invention

[0007] Problems to be Solved by the Invention

[0008] It is required that the above surface treatment agent can be applied not only to the display surfaces of, for example, smartphones and tablet terminals, but also to the surface treatment of various materials. There is a demand for further improving the durability of the surface treatment agent.

[0009] An object of the present invention is to provide a fluoroether compound, a fluoroether composition, a coating liquid, an article having a surface layer excellent in durability, and a compound useful as a raw material for the fluoroether compound.

[0010] Means for Solving the Problems

[0011] The present invention provides a fluoroether compound having the following constitution [1] to

[10] , a method for producing the same, a compound, a method for producing the same, a fluoroether composition, a coating liquid, and an article and a method for producing the same.

[0012] [1] A fluoroether compound represented by the following formula (A1) or formula (A2).

[0013] {Rf O-(R f1 O) m1 -(R 1 ) m2 -(CHF) m3 -O-(CHF) m4} n1 -Q 1 (-T 1 ) n2 Formula (A1)

[0014] (T 2 ) n3 -Q 2 -(CHF) m5 -O-(CHF) m6 -(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -(CHF) m10 -O-(CHF) m11 -Q 3 (-T 3 ) n4 Formula (A2)

[0015] Wherein,

[0016] R f is a fluoroalkyl group having 1 to 20 carbon atoms. When there are multiple Rs, f the multiple Rs present f are optionally the same or different from each other,

[0017]

[0018] R f1 and R f2 are each independently a fluoroalkylene group having 1 to 6 carbon atoms. When there are multiple Rs f1 or Rs f2 present, the multiple Rs f1 or Rs f2 are each optionally the same or different from each other,

[0019] R 1 、R 2 and R 3 are each independently an alkylene group optionally having fluorine atoms. When there are multiple Rs 1 present, the Rs 1 are optionally the same or different from each other,

[0019] Q 1 is a linking group having a valence of n1 + n2,

[0020] Q 2 is a linking group having a valence of 1 + n3,

[0021] Q 3 is a 1+n4 valence connecting group,

[0022] T 1 、T 2 and T 3 Each is independently an adhesive group, and there are multiple T 1 、T 2 or T 3 When there are multiple T 1 、T 2 or T 3 are optionally the same as or different from each other,

[0023] m1 and m8 are each independently an integer of 0 to 210. When there are multiple m1s, the m1s may be the same or different from each other.

[0024] m2, m7 and m9 are each independently 0 or 1. When there are multiple m2, the m2 may be the same or different from each other.

[0025] m3 and m4 are each independently 0 or 1, m3+m4 is 1 or 2, and there are multiple (CHF) m3 -O-(CHF) m4 When the combination of m3 and m4 is optionally the same or different from each other,

[0026] m1+m2 is greater than 1,

[0027] m7+m8+m9 is greater than 1,

[0028] m5 and m6 are each independently 0 or 1, m5+m6 is 1 or 2,

[0029] m10 and m11 are each independently 0 or 1, m10+m11 is 1 or 2,

[0030] n1 is an integer from 1 to 10,

[0031] n2, n3 and n4 are each independently an integer of 1 to 20.

[0032] [2] The fluorine-containing ether compound according to [1], wherein the m3, m6 or m10 is 1.

[0033] [3] The fluorine-containing ether compound according to [1] or [2], wherein m4, m5 or m11 is 0.

[0034] [4] A compound represented by the following formula (B1) or formula (B2).

[0035] R f O-(R f1 O) m1-(R 1 ) m2 -CHO formula (B1)

[0036] OHC-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -CHO formula (B2)

[0037] wherein,

[0038] R f is a fluoroalkyl group having 1 to 20 carbon atoms,

[0039] R f1 and R f2 are each independently a fluoroalkylene group having 1 to 6 carbon atoms. When there are multiple Rs f1 or Rs f2 , the multiple Rs f1 or Rs f2 present may be the same or different from each other optionally,

[0040] R 1 , R 2 and R 3 are each independently an alkylene group optionally having a fluorine atom,

[0041] m1 and m8 are each independently an integer from 0 to 210,

[0042] m2, m7 and m9 are each independently 0 or 1.

[0043] [5] A method for producing a fluoroether compound, which comprises reacting a compound represented by the following formula (B1) or formula (B2) with a compound represented by the following formula (C1).

[0044] R f O-(R f1 O) m1 -(R 1 ) m2 -CHO formula (B1)

[0045] OHC-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -CHO formula (B2)

[0046] (CH2=CH-) n5 -Q 4 (-OH) n6 formula (C1)

[0047] Among them,

[0048] R f is a fluoroalkyl group having 1 to 20 carbon atoms,

[0049] R f1 and R f2 are each independently a fluoroalkylene group having 1 to 6 carbon atoms. When there are multiple Rs f1 or Rs f2 , the multiple Rs f1 or Rs f2 each optionally are the same as or different from each other.

[0050] R 1 , R 2 and R 3 are each independently an alkylene group optionally having a fluorine atom.

[0051] Q 4 is a linking group with a valence of n5 + n6.

[0052] m1 and m8 are each independently an integer from 0 to 210.

[0053] m2, m7 and m9 are each independently 0 or 1.

[0054] n5 is an integer from 1 to 20.

[0055] n6 is an integer from 1 to 10.

[0056] [6] A method for producing a compound represented by the following formula (B1) or formula (B2), wherein a compound represented by the following formula (D1) or formula (D2) is reacted with a hydrosilicon compound in the presence of a Lewis acid compound to obtain a compound represented by the following formula (E1) or formula (E2).

[0057] Let Si(R 16 )3 be detached from the compound represented by the following formula (E1) or formula (E2) to obtain a compound represented by the following formula (F1) or formula (F2).

[0058] Heat the compound represented by the following formula (F1) or formula (F2).

[0059] R f O-(R f1 O) m1 -(R 1 ) m2 -C(=O)OR 11 Formula (D1)

[0060] R 11 OC(=O)-(R 2 )m7 -O-(R f2 O) m8 -(R 3 ) m9 -C(=O)OR 11 Formula (D2)

[0061] R f O-(R f1 O) m1 -(R 1 ) m2 -CH(OR 12 )2 formula (E1)

[0062] (R 12 O)2CH-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -CH(OR 13 )2 formula (E2)

[0063] R f O-(R f1 O) m1 -(R 1 ) m2 -CH(OR 14 )2 formula (F1)

[0064] (R 14 O)2CH-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -CH(OR 15 )2 formula (F2)

[0065] R f O-(R f1 O) m1 -(R 1 ) m2 -CHO formula (B1)

[0066] OHC-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -CHO formula (B2)

[0067] Among them,

[0068] R fis a fluoroalkyl group having 1 to 20 carbon atoms,

[0069] R f1 and R f2 each independently is a fluoroalkylene group having 1 to 6 carbon atoms, and when there are a plurality of Rs f1 or Rs f2 exist, the plurality of Rs f1 or Rs f2 are each optionally the same as or different from each other,

[0070] R 1 、R 2 and R 3 each independently is an alkylene group optionally having a fluorine atom,

[0071] R 11 is a hydrogen atom or an alkyl group optionally having a substituent, and when there are a plurality of Rs 11 exist, the plurality of Rs 11 are optionally the same as or different from each other,

[0072] R 12 and R 13 each independently is Si(R 16 )3 or R 11 ,and at least one of each of the plurality of Rs 12 and Rs 13 is Si(R 16 )3,

[0073] R 14 and R 15 each independently is a hydrogen atom or R 11 ,and at least one of each of the plurality of Rs 14 and Rs 15 is a hydrogen atom,

[0074] R 16 is a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an alkoxy group, and the plurality of Rs 16 are optionally the same as or different from each other,

[0075] m1 and m8 each independently are integers from 0 to 210,

[0076] m2, m7 and m9 each independently are 0 or 1.

[0077] [7] A fluoroether composition containing one or more of the fluoroether compounds according to any one of [1] to [3], and other fluoroether compounds.

[0078] [8] A coating liquid containing:

[0079] The fluoroether compound according to any one of [1] to [3] or the fluoroether composition according to [7]; and

[0080] A liquid medium.

[0081] [9] An article having a surface layer formed of the fluoroether compound according to any one of [1] to [3] or the fluoroether composition according to [7].

[0082]

[10] A method for manufacturing an article, wherein a surface layer is formed by using the fluoroether compound according to any one of [1] to [3], the fluoroether composition according to [7], or the coating liquid according to [8] by a dry coating method or a wet coating method.

[0083] Effects of the Invention

[0084] According to the present invention, there are provided a fluoroether compound, a fluoroether composition, and a coating liquid capable of forming a surface layer having excellent durability, an article having a surface layer with excellent durability, and a compound useful as a raw material for the fluoroether compound. BRIEF DESCRIPTION OF THE DRAWINGS

[0085] Figure 1 It is a schematic cross-sectional view showing an example of the article of the present invention. DETAILED DESCRIPTION

[0086] In this specification, the compound represented by the formula (A1) is denoted as compound (A1). The same applies to compounds represented by other formulas and the like.

[0087] The meanings of the following terms in this specification are as follows.

[0088] "Reactive silyl group" refers to the general term for hydrolyzable silyl group and silanol group (Si-OH). "Hydrolyzable silyl group" refers to a group capable of undergoing a hydrolysis reaction to form a silanol group.

[0089] "Surface layer" refers to a layer formed on the surface of a substrate.

[0090] When the fluoroether compound is a mixture of a plurality of fluoroether compounds having different chain lengths of polyfluoropolyether chains, the "molecular weight" of the polyfluoropolyether chain is calculated by 1 H-NMR and 19 F-NMR to calculate the number (average value) of oxyfluoroalkylene units and obtain the number-average molecular weight.

[0091] When the fluoroether compound is a fluoroether compound having a single chain length of polyfluoropolyether chain, the "molecular weight" of the polyfluoropolyether chain is the molecular weight calculated by 1 H-NMR and 19 F-NMR to determine the structure of the polyfluoropolyether chain.

[0092] The "~" indicating a numerical range means that the numerical values described before and after it are included as the lower limit value and the upper limit value.

[0093] [Fluoroether compound]

[0094] The fluoroether compound of the present invention (hereinafter also referred to as "this compound") is a fluoroether compound represented by the following formula (A1) or formula (A2).

[0095] {R f O-(R f1 O) m1 -(R 1 ) m2 -(CHF) m3 -O-(CHF) m4} n1 -Q 1 (-T 1 ) n2 Formula (A1)

[0096] (T 2 ) n3 -Q 2 -(CHF) m5 -O-(CHF) m6 -(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -(CHF) m10 -O-(CHF) m11 -Q 3 (-T 3 ) n4 Formula (A2)

[0097] Among them,

[0098] R f is a fluoroalkyl group having 1 to 20 carbon atoms. When there are multiple Rs f , the multiple Rs f present may be the same or different from each other,

[0099] R f1 and R f2 are each independently a fluoroalkylene group having 1 to 6 carbon atoms. When there are multiple Rs f1 or Rs f2 present, the multiple Rs f1 or Rs f2 present may be the same or different from each other,

[0100] R 1 、R 2 and R 3Each is independently an alkylene group optionally having a fluorine atom, and there are a plurality of Rs 1 When there are a plurality of such Rs 1 they are optionally the same as or different from each other,

[0101] Q 1 is a linking group having a valence of n1 + n2,

[0102] Q 2 is a linking group having a valence of 1 + n3,

[0103] Q 3 is a linking group having a valence of 1 + n4,

[0104] T 1 、T 2 and T 3 are each independently a sealing group, and there are a plurality of Ts 1 、T 2 or T 3 When there are a plurality of Ts present 1 、T 2 or T 3 they are each optionally the same as or different from each other,

[0105] m1 and m8 are each independently an integer from 0 to 210, and when there are a plurality of m1s, the m1s are optionally the same as or different from each other,

[0106] m2, m7 and m9 are each independently 0 or 1, and when there are a plurality of m2s, the m2s are optionally the same as or different from each other,

[0107] m3 and m4 are each independently 0 or 1, m3 + m4 is 1 or 2, and when there are a plurality of (CHF) m3 -O-(CHF) m4 the combinations of m3 and m4 are optionally the same as or different from each other,

[0108] m1 + m2 is 1 or more,

[0109] m7 + m8 + m9 is 1 or more,

[0110] m5 and m6 are each independently 0 or 1, m5 + m6 is 1 or 2,

[0111] m10 and m11 are each independently 0 or 1, m10 + m11 is 1 or 2,

[0112] n1 is an integer from 1 to 10,

[0113] n2, n3 and n4 are each independently an integer from 1 to 20.

[0114] The present compound has: a polyfluoropolyether chain [R f O-(R f1 O)m1 -(R 1 ) m2 or [(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 ; a sealing group [T]; and a specific linking part that links the aforementioned polyfluoropolyether chain and the aforementioned sealing group [-(CHF) p1 -O-(CHF) p2 -Q p3 (wherein, p1 is m3, m6 or m10, p2 is m4, m5 or m11, and p3 is 1, 2 or 3).

[0115] Compound (A1) is a compound having a structure of "n1 monovalent polyfluoropolyether chains - linking group - sealing group", and compound (A2) is a compound having a structure of "sealing group - linking group - divalent polyfluoropolyether chain - linking group - sealing group".

[0116] This compound has a polyfluoropolyether chain. The fingerprint stain removability of the surface layer of this compound having a polyfluoropolyether chain is excellent. In addition, this compound has 2 or more sealing groups at least at one end. This compound having 2 or more sealing groups at the end is firmly chemically bonded to the substrate, and thus, the abrasion resistance of the surface layer is excellent. Furthermore, in the aforementioned linking group of this compound, there is at least 1 -O-CHF- between the polyfluoropolyether chain and the linking group Q p3 . The present inventors found that: by disposing the substituent -O-CHF- in an adjacent manner to the linking group Q p3 , the durability of this compound with respect to the substrate surface is excellent, and thus the present invention was completed. Regarding the effect of the improvement in durability due to this substituent, there is still a part that has not been clarified, but it is speculated that: compared with the hydrogen atom of -O-CH2-, the hydrogen atom of -O-CHF- has a positive charge by the action of the oxygen atom and the fluorine atom. And it is speculated that this hydrogen atom forms a hydrogen bond network such as FCH…FCH…FCH by forming a hydrogen bond with the fluorine atom of -O-CHF- possessed by an adjacent molecule, and thus the film adhesion is improved and high durability can be obtained. It should be noted that "…" represents a hydrogen bond. In addition, by disposing the substituent -O-CHF- in an adjacent manner to the linking group Q p3 , the flexibility of the polyfluoropolyether chain after forming the surface layer can be maintained compared with the case where it is disposed within the polyfluoropolyether chain. Therefore, it is speculated that a surface layer having a large water contact angle can be obtained.

[0117] In this way, the surface layer formed from this compound has the following characteristics: a large water contact angle, excellent removability of fingerprint dirt and the like, and excellent durability such as abrasion resistance, chemical resistance, and light resistance.

[0118] By making R f be a fluoroalkyl group having 1 to 20 carbon atoms, the abrasion resistance and fingerprint dirt removability of the surface layer become more excellent. From the viewpoint of more excellent abrasion resistance and fingerprint dirt removability of the surface layer, R f preferably has 1 to 6 carbon atoms in the fluoroalkyl group, more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms.

[0119] As the fluoroalkyl group of R f , from the viewpoint of more excellent abrasion resistance and fingerprint dirt removability of the surface layer, a perfluoroalkyl group is preferred. The terminal of the compound (A1) in which R f is a perfluoroalkyl group becomes CF3-. According to the compound (A1) having a terminal of CF3-, a surface layer with low surface energy can be formed, and therefore, the abrasion resistance and fingerprint dirt removability of the surface layer are more excellent.

[0120] As the fluoroalkyl group of R f , for example, CF3-, CF3CF2-, CF3CF2CF2-, CF3CF2CF2CF2-, CF3CF2CF2CF2CF2-, CF3CF2CF2CF2CF2CF2-, CF3CF(CF3)- can be cited.

[0121] As (R f1 O) m1 and (R f2 O) m8 , from the viewpoint of more excellent abrasion resistance and fingerprint dirt removability of the surface layer, a structure represented by the following formula (R f -1) is preferred.

[0122] (R f11 O) k1 (R f12 O) k2 (R s f13 O) k3 (R f14 O) k4 (R f15 O) k5 (R f16 O) k6 Formula (R f -1)

[0123] Among them,

[0124] R f11 is a fluoroalkylene group having 1 carbon atom,

[0125] R f12 is a fluoroalkylene group with 2 carbon atoms,

[0126] R f13 is a fluoroalkylene group with 3 carbon atoms,

[0127] R f14 is a fluoroalkylene group with 4 carbon atoms,

[0128] R f15 is a fluoroalkylene group with 5 carbon atoms,

[0129] R f16 is a fluoroalkylene group with 6 carbon atoms,

[0130] k1, k2, k3, k4, k5, k6 each independently represent an integer of 0 or more, and k1 + k2 + k3 + k4 + k5 + k6 is an integer from 0 to 210. There are multiple Rs f11 ~R f16 When there are multiple Rs present, these multiple Rs f11 ~R f16 are each optionally the same as or different from each other.

[0131] It should be noted that the bonding order of (R f -1) in (R f11 O)~(R f16 O) is arbitrary. k1 to k6 in formula (R-1) respectively represent the number of (R f11 O)~(R f16 O), and do not represent the configuration. For example, (R f15 O) k5 represents that the number of (R f15 O) is k5, and does not represent the block configuration structure of (R f5 O) k5 . Similarly, the recording order of (R f11 O)~(R f16 O) does not represent the bonding order of each unit.

[0132] In addition, the fluoroalkylene group with 3 to 6 carbon atoms can be a linear fluoroalkylene group, or a fluoroalkylene group with a branched chain or a ring structure.

[0133] As specific examples of R f11 , CHF and CF2 can be listed. As specific examples of R f12 , CF2CF2, CF2CHF, CF2CH2, etc. can be listed. As specific examples of R f13 , CF2CF2CF2, CF2CF2CHF, CF2CHFCF2, CF2CF2CH2, CF2CH2CF2, CF(CF3)CF2, etc. can be listed. As Rf14 Specific examples include CF2CF2CF2CF2, CF2CF2CF2CH2, CHFCF2CF2CF2, CF2CH2CF2CF2, CF(CF3)CF2CF2, perfluorocyclobutane-1,2-diyl, etc. As R f15 Specific examples include CF2CF2CF2CF2CF2, CF2CF2CF2CF2CH2, CHFCF2CF2CF2CF2, CF2CF2CH2CF2CF2, etc. As R f16 Specific examples include CF2CF2CF2CF2CF2CF2, CF2CF2CF2CF2CF2CH2, CF2CF2CF2CF2CF2CHF, etc.

[0134] (R f1 O) m1 and (R f2 O) m8 Preferably, at least a part thereof has the following structure.

[0135] {(OCF2) k11 (OCF2CF2) k12},

[0136] (OCF2CF2) k13 ,

[0137] (OCF2CF2CF2) k14 ,

[0138] (OCF2CF2 - OCF2CF2CF2CF2) k15 ,

[0139] (OCF2CF2CF2) k16 (OCF2CF2) k17 ,

[0140] (OCF2CF2CF2CF2CF2) k16 (OCF2) k17 ,

[0141] (OCF2CF2CF2CF2CF2) k16 (OCF2CF2) k17 ,

[0142] (OCF2CF2CF2CF2CF2CF2) k16 (OCF2) k17 ,

[0143] (OCF2CF2CF2CF2CF2CF2) k16 (OCF2CF2) k17,

[0144] (OCF2CF2CF2CF2CF2 - OCF2) k18 ,

[0145] (OCF2CF2CF2CF2CF2 - OCF2CF2) k18 ,

[0146] (OCF2CF2CF2CF2CF2CF2 - OCF2) k18 ,

[0147] (OCF2CF2CF2CF2CF2CF2 - OCF2CF2) k18 ,

[0148] (OCF2 - OCF2CF2CF2CF2CF2) k18 ,

[0149] (OCF2 - OCF2CF2CF2CF2CF2CF2) k18 ,

[0150] (OCF2CF2 - OCF2CF2CF2CF2CF2) k18 ,

[0151] (OCF2CF2 - OCF2CF2CF2CF2CF2CF2) k18 ,

[0152] (OCF(CF3)CF2) k19

[0153] (OCF2CF(CF3)) k20 (OCF2CF2CF2) k21 (OCF2CF2) k22 .

[0154] Among them, k11, k12, k13, k14, k15, k16, k17, k18, k19, k20, k21, and k22 are integers greater than or equal to 1, and the upper limit value is adjusted according to the upper limit value of m1 or m8.

[0155] It should be noted that {(OCF2) k11 (OCF2CF2) k12} represents a random configuration of k11 (OCF2) and k12 (OCF2CF2).

[0156] m1 and m8 are each independently 0 to 210. When m1 is 0, (R f1 O) m1 represents a single bond. In addition, when m8 is 0, (R f2 O)m8 represents a single bond. From the viewpoints of water repellency and the like of the obtained surface layer, m1 and m8 are preferably from 1 to 210, more preferably from 2 to 210.

[0157] As (R f1 O) m1 and (R f2 O) m8 , from the viewpoints of various properties of the fluorinated ether compound such as chemical resistance and low refractive index, the fluorination rate represented by the following mathematical formula (1) is preferably 60% or more, more preferably 80% or more, and further preferably substantially 100%, that is, perfluoropolyether.

[0158] Mathematical formula (1): Fluorination rate (%) = (number of fluorine atoms) / {(number of fluorine atoms)+(number of hydrogen atoms)}×100

[0159] R 1 , R 2 and R 3 are each independently an alkylene group optionally having a fluorine atom. From the viewpoints of further excellent friction resistance and fingerprint stain removability of the surface layer, R 1 to R 3 are preferably fluoroalkylene groups. The alkylene groups of R 1 to R 3 are preferably linear fluoroalkylene groups. In addition, the number of carbon atoms of the alkylene groups of R 1 to R 3 is preferably from 1 to 6.

[0160] m2, m7 and m9 are each independently 0 or 1. When m2 is 0, (R 1 ) m2 represents a single bond. When m7 is 0, (R 2 ) m7 represents a single bond. In addition, when m9 is 0, (R 3 ) m9 represents a single bond. From the viewpoints of ease of synthesis of this compound and the like, m2, m7 and m9 are preferably 1.

[0161] This compound has a connecting portion [-(CHF) p1 -O-(CHF)<( p2 -Q p3 (wherein, p1 is m3, m6 or m10, p2 is m4, m5 or m11, and p3 is 1, 2 or ))) that connects the perfluoropolyether chain and the adhesion group T. By making p1 + p2 equal to 1 or 2, the aforementioned hydrogen bond network can be formed. From the viewpoints of water repellency and durability of the obtained surface layer, p1 (m3, m6 or m10) is preferably 1. In addition, from the viewpoints of ease of synthesis of this compound and the like, p2 (m4, m5 or m11) is preferably 0.

[0162] Q 1 is a linking group with a valence of n1 + n2, connecting n2 sealing groups to n1 polyfluoropolyether chains. Q 2 is a linking group with a valence of 1 + n3, Q 3 is a linking group with a valence of 1 + n4, connecting n3 sealing groups at one end of the polyfluoropolyether chain and n4 sealing groups at the other end. In Q 1 、Q 2 and Q 3 (sometimes collectively referred to as Q p3 ) in the case of a divalent linking group, as this Q p3 , a single bond or a linear linking group can be cited. As the linear linking group, an alkylene group optionally having a substituent can be cited. As the alkylene group in Q p3 , an alkylene group having 1 to 6 carbon atoms is preferred. In addition, as the substituent optionally possessed by this alkylene group, a fluorine atom, an alkyl group, etc. can be cited.

[0163] In the case where Q p3 is a linking group with a valence of 3 or more, this linking group is a group having a branching point P. As the branching point P, C, N, Si, a ring structure, an organopolysiloxane residue, etc. can be cited.

[0164] As the ring structure constituting the branching point, from the viewpoints of easy production of this compound and durability of the surface layer formed by this compound, etc., it is preferably one selected from the group consisting of an aliphatic ring having 3 to 8 members, an aromatic ring having 3 to 8 members, a heterocyclic ring having 3 to 8 members, and a condensed ring containing two or more of these rings, and particularly preferably a ring structure listed in the following formula. It should be noted that the ring structure optionally has a substituent such as a halogen atom, an alkyl group (optionally containing an etheric oxygen atom between carbon-carbon atoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group, a bridge oxygen group (=O), etc.

[0165]

[0166] As the organopolysiloxane residue constituting the branching point, the following groups can be cited, for example. Among them, R 5 in the following formula is a hydrogen atom, an alkyl group, an alkoxy group or a phenyl group. The alkyl group and alkoxy group of R 5 preferably have 1 to 10 carbon atoms, and particularly preferably 1.

[0167]

[0168] Q p3 optionally has a group selected from -C(O)NR 6 -, -C(O)O-, -C(O)-, -O-, -NR 6-, -S-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -SO2NR 6 -, -Si(R 6 )2-, -OSi(R 6 )2-, -Si(CH3)2-Ph-Si(CH3)2- and at least one bond B selected from the group consisting of divalent organopolysiloxane residues, from the viewpoint of easy production of this compound, is preferably selected from -C(O)NR 6 (-), -C(O)-, -NR 6 (-), and -O-; from the viewpoint of excellent light resistance and chemical resistance of the surface layer, it is more preferably -C(O)NR 6 (-) or -C(O)-. In the above bonds, R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and Ph is a phenylene group. From the viewpoint of easy production of this compound, the alkyl group of R 6 preferably has 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.

[0169] As the divalent organopolysiloxane residue, groups such as the following formula can be exemplified. Among them, R 7 in the following formula is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group.

[0170] R 7 The alkyl group and alkoxy group of preferably have 1 to 10 carbon atoms, and particularly preferably 1 carbon atom.

[0171]

[0172] As Q p3 , combinations of two or more divalent hydrocarbon groups and one or more branching points P, or combinations of two or more hydrocarbon groups, one or more branching points P, and one or more bonds B can be exemplified.

[0173] As the divalent hydrocarbon group, for example, divalent aliphatic hydrocarbon groups (such as alkylene groups, cycloalkylene groups, etc.), divalent aromatic hydrocarbon groups (such as phenylene groups, etc.) can be exemplified. The divalent hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms.

[0174] As the aforementioned Q p3 , from the viewpoint of easy production of this compound, it is preferably a group represented by any one of the following formulas (Q1) to (Q7).

[0175]

[0176] (-A 1 -) e1 C(R 22 )4-e1-e2 (-Q 22 -) e2 Formula (Q2)

[0177] -A 2 -N(-Q 23 -)2 Formula (Q3)

[0178] (-A 3 -) h1 Z 1 (-Q 24 -) h2 Formula (Q4)

[0179] (-A 2 -) i1 Si(R 23 ) 4-i1-i2 (-Q 25 -) i2 Formula (Q5)

[0180] -A 1 -Q 26 - Formula (Q6)

[0181] -A 1 -CH(-Q 22 -)-Si(R 23 ) 3-i3 (-Q 25 -) i3 Formula (Q7)

[0182] Among them, in Formulas (Q1) to (Q7), A 1 , A 2 or A 3 side is connected to the side of the polyfluoropolyether chain, and Q 22 , Q 23 , Q 24 , Q 25 or Q 26 side is connected to the adhesion group T 1 , T 2 or T 3 connection,

[0183] A 1 is a single bond, an alkylene group, or a group having -C(O)NR 26 -, -C(O)-, -NR 26 - or -O- between carbon-carbon atoms of an alkylene group with 2 or more carbon atoms,

[0184] A 2 is an alkylene group, or a group having -C(O)NR 26 -, -C(O)-, -NR 26- or -O-containing group,

[0185] In A 3 When the atom in the Z 1 bonded to A is a carbon atom, A 3 is A 1 ; when the atom in the Z 3 bonded to A is a nitrogen atom, A 1 is A 3 ; 2 ,

[0186] Q 11 is a single bond, -O-, alkylene, or a group having -C(O)NR 26 -,-C(O)-,-NR 26 - or -O- between carbon-carbon atoms of an alkylene having 2 or more carbon atoms,

[0187] Q 22 is alkylene; a group having -C(O)NR 26 -,-C(O)-,-NR 26 - or -O- between carbon-carbon atoms of an alkylene having 2 or more carbon atoms; a group having -C(O)NR 26 -,-C(O)-,-NR 26 - or -O- at the terminal on the side not connected to the sealing group T; or a group having -C(O)NR 26 -,-C(O)-,-NR 26 - or -O- between carbon-carbon atoms of an alkylene having 2 or more carbon atoms and having -C(O)NR 26 -,-C(O)-,-NR 26 - or -O- at the terminal on the side not connected to the sealing group T, Q p3 has 2 or more Q 22 ; when there are 2 or more Q 22 they are optionally the same or different from each other,

[0188] Q 23 is alkylene or a group having -C(O)NR 26 -,-C(O)-,-NR 26 - or -O- between carbon-carbon atoms of an alkylene having 2 or more carbon atoms, and 2 Q 23 are optionally the same or different from each other,

[0189] Q 24 When the atom in the Z 1 bonded to Q is a carbon atom, Q 24 is Q 22 ; Q 24 When the atom in the Z 1When the atom in it is a nitrogen atom, Q 24 is Q 23 and Q p3 has more than 2 Q 24 When there are more than 2 Q 24 are optionally the same as or different from each other,

[0190] Q 25 is an alkylene group, or has -C(O)NR 26 -,-C(O)-,-NR 26 - or -O- between the carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, and Q p3 has more than 2 Q 25 When there are more than 2 Q 25 are optionally the same as or different from each other,

[0191] Q 26 is an alkylene group, or has -C(O)NR 26 -,-C(O)-,-NR 26 - or -O- between the carbon-carbon atoms of an alkylene group having 2 or more carbon atoms,

[0192] Z 1 is a group having a (h1 + h2)-valent ring structure, and the ring structure has a carbon atom or a nitrogen atom directly bonded to A 3 and has a carbon atom or a nitrogen atom directly bonded to Q 24 respectively,

[0193] R 21 is a hydrogen atom or an alkyl group, and Q p3 has more than 2 R 21 When there are more than 2 R 21 are optionally the same as or different from each other,

[0194] R 22 is a hydrogen atom, a hydroxyl group, an alkyl group or an acyloxy group, and Q p3 has more than 2 R 22 When there are more than 2 R 22 are optionally the same as or different from each other,

[0195] R 23 is an alkyl group, and Q p3 has more than 2 R 23 When there are more than 2 R 23 are optionally the same as or different from each other,

[0196] R 26 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group,

[0197] d1 is an integer from 0 to 3, d2 is an integer from 0 to 3, and d1 + d2 is an integer from 1 to 3.

[0198] d3 is an integer from 0 to 3, d4 is an integer from 0 to 3, and d3 + d4 is an integer from 1 to 3.

[0199] d1 + d3 is 1 an integer from 1 to 5 in Q, 2 in Q 3 and Q

[0200] is 1,

[0201] d2 + d4 is an integer from 1 to 5. 1 e1 is an integer from 1 to 3 in Q, 2 in Q 3 and Q

[0202] is 1,

[0203] e2 is an integer from 1 to 3.

[0204] e1 + e2 is an integer from 2 to 4. 1 h1 is an integer of 1 or more in Q, 2 in Q 3 and Q

[0205] is 1,

[0206] h2 is an integer of 1 or more. 1 i1 is an integer from 1 to 3 in Q, 2 in Q 3 and Q

[0207] is 1,

[0208] i2 is an integer from 1 to 3.

[0209] i1 + i2 is an integer from 2 to 4.

[0210] From the viewpoints of ease of manufacturing this compound and more excellent friction resistance, light resistance, and chemical resistance of the surface layer, Q 11 、Q 22 、Q 23 、Q 24 、Q 25 or Q 26 preferably has 1 to 10 carbon atoms in the alkylene group, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms. Among them, the lower limit value of the number of carbon atoms in the alkylene group when having a specific bond between carbon-carbon atoms is 2.

[0211] As the ring structure in Z 1 the above ring structures can be cited, and the preferred forms are also the same.

[0212] From the viewpoint of ease of producing this compound, R 21 , R 22 or R 23 preferably has 1 to 6 carbon atoms in the alkyl group, more preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.

[0213] From the viewpoint of ease of producing this compound, the alkyl moiety of the acyloxy group of R 22 preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.

[0214] From the viewpoints of ease of producing this compound and more excellent friction resistance and fingerprint stain removability of the surface layer, h1 + h2 is preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 or 3.

[0215] As other forms of the aforementioned Q p3 , groups represented by any one of the following formulas (Q11) to (Q17) can be cited.

[0216]

[0217] (-A 1 -) e1 C(R 22 ) 4-e1-e2 (-Q 22 -G) e2 Formula (Q12)

[0218] -A 2 -N(-Q 23 -G)2 Formula (Q13)

[0219] (-A 3 -) h1 Z 1 (-Q 24 -G) h2 Formula (Q14)

[0220] (-A 2 -) i1 Si(R 23 ) 4-i1-i2 (-Q 25 -G) i2 Formula (Q15)

[0221] -A 1 -Q 26 -G Formula (Q16)

[0222] -A 1 -CH(-Q 22 -)-Si(R 23 ) 3-i3 (-Q25 -G) i3 Formula (Q17)

[0223] Among them, in Formulas (Q11) to (Q17), A 1 , A 2 or A 3 is connected to the polyfluoropolyether chain side, and the G side is connected to the adhesion group T 1 , T 2 or T 3 . G is a group represented by the following formula (G1), and two or more Gs in Q p3 are optionally the same as or different from each other. Symbols other than G are the same as those in Formulas (Q1) to (Q7).

[0224] -Si(R 27 ) 3-j1 (-Q 27 -) j1 Formula (G1)

[0225] Among them, in Formula (G1), the Si side is connected to Q 22 , Q 23 , Q 24 , Q 25 or Q 26 , and the Q 27 side is connected to the adhesion group T. R 27 is an alkyl group. Q 27 is an alkylene group, a group having -C(O)NR 28 -, -C(O)-, -NR 28 - or -O- between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or -(OSi(R 29 )2) j2 -O-. Two or more Q 27 are optionally the same as or different from each other. j1 is 2 or 3. R 28 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group.

[0226] R 29 is an alkyl group, a phenyl group or an alkoxy group, and two R 29 are optionally the same or different. j2 is an integer from 0 to 5. When j2 is 2 or more, two or more (OSi(R 29 )2) are optionally the same as or different from each other.

[0227] From the viewpoints of easy preparation of this compound and more excellent friction resistance, light resistance and chemical resistance of the surface layer, the number of carbon atoms of the alkylene group of Q 27 is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. Among them, the lower limit value of the number of carbon atoms of the alkylene group having a specific bond between carbon-carbon atoms is 2.

[0228] From the viewpoint of easy production of this compound, the number of carbon atoms of the alkyl group of R 28 is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2.

[0229] From the viewpoint of easy production of this compound, the number of carbon atoms of the alkyl group of R 29 is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2.

[0230] j2 is preferably 0 or 1.

[0231] T 1 、T 2 and T 3 (Sometimes they are collectively referred to as T) are groups that are disposed on the substrate surface side when forming the surface layer and exhibit adhesion to the substrate. T can form a chemical bond with the substrate surface or the like, or can be chemically adsorbed or physically adsorbed on the substrate surface.

[0232] From the viewpoint of durability, T is preferably chemically bonded to the substrate surface.

[0233] Examples of the adhesion group T include a bromine atom, an iodine atom, a hydroxyl group, an amino group, a carboxyl group, an aldehyde group, an epoxy group, a thiol group, a phosphoric acid group, a phosphonic acid group, an unsaturated hydrocarbon group, an aryl group, a reactive silyl group, etc., and are preferably appropriately selected according to the substrate material to be applied.

[0234] Examples of the amino group in the adhesion group T include -NR 32 R 33 (R 32 、R 33 are each independently a hydrogen atom or an alkyl group), and from the viewpoint of the durability of the surface layer, -NH2 is preferred among them.

[0235] Examples of the phosphoric acid group in the adhesion group T include -OP(=O)(OR 34 )2 (R 34 is a hydrogen atom or an alkyl group, and the plurality of R 34 present may be the same or different from each other), and from the viewpoint of the durability of the surface layer, -OP(=O)(OH)2 is preferred among them.

[0236] Examples of the phosphonic acid group in the adhesion group T include -P(=O)(OR 35 )2 (R 35 is the same as the above R 34 ), and from the viewpoint of the durability of the surface layer, -P(=O)(OH)2 is preferred among them.

[0237] Examples of the unsaturated hydrocarbon group in the adhesion group T include an acryloyl group, a methacryloyl group, a vinyl group, etc.

[0238] Examples of the aryl group in the adhesion group T include a phenyl group, a naphthyl group, an anthryl group, etc.

[0239] In addition, examples of the reactive silyl group in the adhesion group T include a group represented by -Si(R 31 ). 3-c (L 31 ). c The group shown.

[0240] L 31 is a hydrolyzable group or a hydroxyl group, and the reactive silyl group is a group obtained by bonding at least one of a hydrolyzable group and a hydroxyl group to a silicon atom.

[0241] The hydrolyzable group is a group that forms a hydroxyl group through a hydrolysis reaction. That is, the hydrolyzable silyl group forms a silanol group (Si-OH) through a hydrolysis reaction. The silanol group further undergoes a dehydration condensation reaction between molecules to form a Si-O-Si bond. In addition, the silanol group undergoes a dehydration condensation reaction with the hydroxyl group (substrate-OH) on the substrate surface to form a chemical bond (substrate-O-Si).

[0242] Examples of the hydrolyzable group include, for example, an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, an isocyanate group. As the alkoxy group, an alkoxy group having 1 to 6 carbon atoms is preferred. As the aryloxy group, an aryloxy group having 3 to 10 carbon atoms is preferred. As the halogen atom, a chlorine atom is preferred. As the acyl group, an acyl group having 1 to 6 carbon atoms is preferred. As the acyloxy group, an acyloxy group having 1 to 6 carbon atoms is preferred. As L 31 , an alkoxy group having 1 to 4 carbon atoms or a halogen atom is preferred.

[0243] As the hydrolyzable group, from the viewpoint of easy production of this compound, an alkoxy group or a halogen atom is preferred. As the hydrolyzable group, from the viewpoint of less degassing during coating and excellent storage stability of this compound, an alkoxy group having 1 to 4 carbon atoms is preferred. In the case where long-term storage stability of this compound is required, ethoxy is particularly preferred. In the case where the reaction time after coating is set to a short time, methoxy is particularly preferred.

[0244] From the viewpoint of easy production of this compound, the number of carbon atoms of the alkyl group of R 31 is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2.

[0245] From the viewpoint of making the adhesion between the surface layer and the substrate firmer, c is preferably 2 or 3, and more preferably 3.

[0246] Suitable combinations of the adhesive group T, the substrate, and the material are exemplified in the form of "adhesive group T-substrate."

[0247] Bromine atom-silicon nitride, hydrogen-terminated silicon nitride,

[0248] Iodine-hydrogen terminated diamond,

[0249] Hydroxyl-hydrogen terminated silicon, silicon halides, silicon oxide (SiO2), aluminum oxide (Al2O3), diamond-like carbon (DLC),

[0250] Amino-indium tin oxide (ITO), mica,

[0251] Carboxyl-Al2O3, silver oxide (AgO), copper oxide (CuO), zirconium modified alumina (Zr / Al2O3), amine terminal oxide (NH2-terminated oxide), tin oxide (SnO2),

[0252] Aldehyde, epoxy-hydrogen terminated silicon, silicon halide,

[0253] Thiol-gold (Au),

[0254] Phosphoric acid, phosphonic acid - zirconium oxide (ZrO2), titanium oxide (TiO2), Al2O3, tantalum oxide (Ta2O5), Zr / Al2O3,

[0255] Unsaturated hydrocarbon-hydrogen-terminated diamond, hydrogen-terminated silicon, silicon halide, silicon nitride, hydrogen-terminated silicon nitride, polyimide (PI), acrylic,

[0256] Aryl-Al2O3, DLC,

[0257] Reactive silyl - glass, Au, mica, SiO2, tin oxide (SnO2), germanium oxide (GeO2), ZrO2, TiO2, Al2O3, ITO, stainless steel (SUS), lead zirconate titanate (PZT).

[0258] However, the present compound is not limited to these combinations, and can be used in combination with various base materials.

[0259] Specific examples of the present compound include compounds of the following formula: Compounds of the following formula are preferred from the viewpoints of ease of industrial production, ease of handling, superior water and oil repellency, friction resistance, fingerprint removability, lubricity, chemical resistance, light resistance, and chemical resistance of the surface layer, with particularly superior chemical resistance.

[0260]

[0261]

[0262]

[0263] n11 to n33 are integers from 0 to 210.

[0264] (Method for manufacturing this compound)

[0265] The method for manufacturing this compound is not limited to the following method, but according to the following manufacturing method, this compound can be obtained in a high yield. That is, the method for manufacturing the fluorine-containing ether compound described in the present invention (hereinafter also referred to as this manufacturing method) is a method for manufacturing the fluorine-containing ether compound represented by formula (A1) or formula (A2), which includes: reacting the compound represented by the following formula (B1) or formula (B2) with the compound represented by the following formula (C1).

[0266] R f O-(R f1 O) m1 -(R 1 ) m2 -CHO Formula (B1) [[ID=2*]]

[0267] OHC-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -CHO Formula (B2)

[0268] (CH2=CH-) n5 -Q 4 (-OH) n6 Formula (C1)

[0269] Among them, R f , R f1 , R f2 , R 1 , R 2 , R 3 , m1, m2, m7, m8, m9 are the same as the groups in the aforementioned compound (A1) and compound (A2), and the preferred modes are also the same.

[0270] Q 4 is a linking group with a valence of n5 + n6,

[0271] n5 is an integer from 1 to 20,

[0272] n6 is an integer from 1 to 10.

[0273] Q 4 is the Q in compound (A1) 1 or the Q in compound (A2) 2 or Q 3For the part, the preferred method is the same as the aforementioned Q p3 is the same.

[0274] n5 is the part that becomes n2 in compound (A1) or n3 or n4 in compound (A2), and the preferred method is also the same.

[0275] n6 is the part that becomes n1 in compound (A1), and the preferred method is also the same.

[0276] It should be noted that when reacting compound (B2) with compound (C1), a compound with n6 being 1 is selected.

[0277] CH2=CH- in compound (C1) corresponds to the adhesion group T in compounds (A1) and (A2). Additionally, if necessary, it can also react with a compound having other adhesion groups to introduce other adhesion groups.

[0278] For example, if compound (B1) is reacted with compound (C1) with n6 being 1, then R f O-(R f1 O) m1 -(R 1 ) m2 -CH(OH)-O-Q 4 -(CH=CH2) n5 can be obtained. By fluorinating this compound using a fluorinating agent, R f O-(R f1 ) O) m1 -(R 1 ) m2 -CHF-O-Q 4 -(CH=CH2)n5 can be obtained.

[0279] Examples of the fluorinating agent include bis(2-methoxyethyl)aminosulfur trifluoride, diethylaminosulfur trifluoride, perfluoro-1-butanesulfonyl fluoride, 1,1,2,2-tetrafluoro-N,N-dimethylethylamine, (diethylamino)sulfonium difluoride tetrafluoroborate, 4-tert-butyl-2,6-dimethylphenylsulfur trifluoride, 2-chloro-1,3-bis(2,6-diisopropylphenyl)-1H-chloroimidazolium-cesium fluoride, pyridine-2-sulfonyl fluoride, etc.

[0280] When introducing, for example, a reactive silyl group into -(CH=CH2) n5 , it can be produced by a method of hydrosilylation of the aforementioned compound with the following compound 3a.

[0281] HSi(R 31 ) 3-c (L 31 ) cFormula 3a

[0282] Among them, the symbols in Formula 3a are the same as those in the aforementioned compound, and the preferred modes are also the same. Compound 3a can be synthesized or commercially available products can be used.

[0283] The aforementioned compounds (B1) and (B2) are novel compounds suitable for this manufacturing method. The manufacturing methods of compounds (B1) and (B2) are not limited to the following methods, but according to the following manufacturing methods, compounds (B1) and (B2) can be obtained in high yields.

[0284] That is, the manufacturing method of the compound (B1) or (B2) described in the present invention is the manufacturing method of the compound represented by the following formula (B1) or formula (B2), where

[0285] react the compound represented by the following formula (D1) or formula (D2) with a hydrosilicon compound HSi(R 16 )3 in the presence of a Lewis acid compound to obtain the compound represented by the following formula (E1) or formula (E2),

[0286] detach Si(R 16 )3 from the compound represented by the following formula (E1) or formula (E2) to obtain the compound represented by the following formula (F1) or formula (F2),

[0287] heat the compound represented by the following formula (F1) or formula (F2).

[0288] R f O-(R f1 O) m1 -(R 1 ) m2 -C(=O)OR 11 Formula (D1)

[0289] R 11 OC(=O)-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -C(=O)OR 11 Formula (D2)

[0290] R f O-(R f1 O) m1 -(R 1 ) m2 -CH(OR 12 )2 Formula (E1)

[0291] (R 12 O)2CH-(R2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -CH(OR 13 )2 Formula (E2)

[0292] R f O-(R f1 O) m1 -(R 1 ) m2 -CH(OR 14 )2 Formula (F1)

[0293] (R 14 O)2CH-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -CH(OR 15 )2 Formula (F2)

[0294] R f O-(R f1 O) m1 -(R 1 ) m2 -CHO Formula (B1)

[0295] OHC-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -CHO Formula (B2).

[0296] Wherein, R f 、R f1 、R f2 、R 1 、R 2 、R 3 、m1, m2, m7, m8 and m9 are the same as the groups in the foregoing compound of the present invention, and the preferred modes are also the same,

[0297] R 11 is a hydrogen atom or an alkyl group optionally having substituents. When there are multiple R 11 's, the multiple R 11 's present may be the same or different from each other optionally,

[0298] R 12 and R 13 are each independently Si(R 16 )3 or R11 , among the multiple Rs present 12 and R 13 , at least one of each is Si(R 16 )3,

[0299] R 14 and R 15 are each independently a hydrogen atom or R 11 , among the multiple Rs present 14 and R 15 , at least one of each is a hydrogen atom,

[0300] R 16 is a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an alkoxy group, and the multiple Rs present 16 are optionally the same as or different from each other.

[0301] R 11 ~R 16 are moieties that do not remain in compound (B1), compound (B2) and this compound, so they can be appropriately selected from the viewpoints of reactivity and availability.

[0302] As the alkyl group in R 11 , methyl or ethyl is preferred, and from the viewpoint of reactivity, methyl is more preferred. [[ID=4,1]]

[0303] As R 16 , an alkyl group is preferred, and ethyl is more preferred.

[0304] Further, as another production method of this compound, it is characterized by having a step of reacting a compound represented by the following formula (B3) or formula (B4) with a compound represented by the following formula (C2).

[0305] R f O-(R f1 O) m1 -(R 1 ) m2 -OH formula (B3)

[0306] OH-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -CHO formula (B4)

[0307] (CH2=CH-) n5 -Q 4 (-CHO) n6 formula (C2)

[0308] Among them, each symbol in the formula is the same as that in the aforementioned compound (B1), compound (B2), and compound (C1), and the preferred modes are also the same.

[0309] [Fluoroether Composition]

[0310] The fluoroether composition of the present invention (hereinafter also referred to as the present composition) is a composition containing the aforementioned fluorine-containing compound as the present compound and at least any one selected from fluorine-containing compounds other than the present compound and the following impurities. As impurities, compounds that are inevitable in the production of the present compound and other fluorine-containing compounds can be cited. It should be noted that the present composition does not include the liquid medium described later.

[0311] As other fluorine-containing compounds, fluorine-containing compounds by-produced in the production process of the present compound (hereinafter also referred to as by-produced fluorine-containing compounds), well-known fluorine-containing compounds used in the same use as the present compound, etc. can be cited.

[0312] As other fluorine-containing compounds, compounds with a low risk of reducing the properties of the present compound are preferred.

[0313] From the viewpoint of fully exerting the properties of the present compound, the content of other fluorine-containing compounds in the total amount of the present composition is preferably less than 50% by mass, more preferably less than 30% by mass, and further preferably less than 10% by mass.

[0314] As by-produced fluorine-containing compounds, unreacted fluorine-containing compounds in the synthesis of the present compound can be cited. When the present composition contains by-produced fluorine-containing compounds, the purification process for removing or reducing the amount of by-produced fluorine-containing compounds can be simplified.

[0315] As well-known fluorine-containing compounds, compounds described in the following documents can be cited, for example.

[0316] Perfluoropolyether-modified aminosilane described in Japanese Patent Laid-Open No. 11-029585

[0317] Silicone-containing organic fluoropolymer described in Japanese Patent No. 2874715

[0318] Organosilicon compound described in Japanese Patent Laid-Open No. 2000-144097

[0319] Perfluoropolyether-modified aminosilane described in Japanese Patent Laid-Open No. 2000-327772

[0320] Fluorinated siloxane described in Japanese Patent Application Laid-Open No. 2002-506887

[0321] Organosilicon compound described in Japanese Patent Application Laid-Open No. 2008-534696

[0322] The fluorinated modified hydrogen-containing polymer described in Japanese Patent Publication No. 4138936,

[0323] The compounds described in U.S. Patent Application Publication No. 2010 / 0129672, International Publication No. 2014 / 126064, and Japanese Unexamined Patent Application Publication No. 2014-070163,

[0324] The silicone compounds described in International Publication No. 2011 / 060047 and International Publication No. 2011 / 059430,

[0325] The fluorinated organosilane compounds described in International Publication No. 2012 / 064649,

[0326] The polymer containing fluorooxyalkylene described in Japanese Unexamined Patent Application Publication No. 2012-72272,

[0327] The fluorinated ether compounds described in International Publication No. 2013 / 042732, International Publication No. 2013 / 121984, International Publication No. 2013 / 121985, International Publication No. 2013 / 121986, International Publication No. 2014 / 163004, Japanese Unexamined Patent Application Publication No. 2014-080473, International Publication No. 2015 / 087902, International Publication No. 2017 / 038830, International Publication No. 2017 / 038832, and International Publication No. 2017 / 187775,

[0328] The silane compounds containing perfluoro(poly)ether described in Japanese Unexamined Patent Application Publication No. 2014-218639, International Publication No. 2017 / 022437, International Publication No. 2018 / 079743, and International Publication No. 2018 / 143433,

[0329] The polymer-modified silanes containing fluoropolyether groups described in Japanese Unexamined Patent Application Publication No. 2015-199906, Japanese Unexamined Patent Application Publication No. 2016-204656, Japanese Unexamined Patent Application Publication No. 2016-210854, and Japanese Unexamined Patent Application Publication No. 2016-222859,

[0330] The fluorinated ether compounds described in International Publication No. 2018 / 216630, International Publication No. 2019 / 039226, International Publication No. 2019 / 039341, International Publication No. 2019 / 039186, International Publication No. 2019 / 044479, Japanese Unexamined Patent Application Publication No. 2019-44158, International Publication No. 2019 / 044479, and International Publication No. 2019 / 163282.

[0331] In addition, as commercially available products of fluorine-containing compounds, examples include the KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., Afluid (registered trademark) S550 manufactured by AGC Inc., Optool (registered trademark) DSX, Optool (registered trademark) AES, Optool (registered trademark) UF503, Optool (registered trademark) UD509, etc. manufactured by Daikin Industries, Ltd.

[0332] The proportion of the present compound in the present composition is less than 100% by mass, preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more.

[0333] When the present composition contains other fluorine-containing compounds, the proportion of the other fluorine-containing compounds in the present composition relative to the total amount of the present compound and the other fluorine-containing compounds is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less.

[0334] The total proportion of the present compound and the other fluorine-containing compounds in the present composition is preferably 80% by mass or more, more preferably 85% by mass or more.

[0335] If the contents of the present compound and the other fluorine-containing compounds are within the above ranges, the water and oil repellency, abrasion resistance, fingerprint stain removability, lubricity, and appearance of the surface layer are excellent.

[0336] [Coating liquid]

[0337] The coating liquid of the present invention (hereinafter also referred to as the present coating liquid) contains the present compound or the present composition and contains a liquid medium. The present coating liquid only needs to be a liquid and can be a solution or a dispersion.

[0338] The present coating liquid only needs to contain the present compound or the present composition and can contain impurities such as by-products generated in the manufacturing process of the present compound.

[0339] The concentration of the present compound or the present composition in the present coating liquid is preferably 0.001 to 40% by mass, more preferably 0.01 to 20% by mass, and still more preferably 0.1 to 10% by mass.

[0340] As the liquid medium, an organic solvent is preferred. The organic solvent can be a fluorine-based organic solvent, a non-fluorine-based organic solvent, or can contain two solvents.

[0341] Examples of the fluorine-based organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols, etc.

[0342] As the fluorinated alkane, a compound having 4 to 8 carbon atoms is preferred. As commercially available products, for example, C6F 13 H (manufactured by AGC, ASAHIKLIN (registered trademark) AC-2000), C6F 13 C2H5 (manufactured by AGC, ASAHIKLIN (registered trademark) AC-6000), C2F5CHFCHFCF3 (manufactured by Chemours, Vertrel (registered trademark) XF), etc.

[0343] As the fluorinated aromatic compound, for example, hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, bis(trifluoromethyl)benzene, etc. can be mentioned.

[0344] As the fluoroalkyl ether, a compound having 4 to 12 carbon atoms is preferred. As commercially available products, for example, CF3CH2OCF2CF2H (manufactured by AGC, ASAHIKLIN (registered trademark) AE-3000), C4F9OCH3 (manufactured by 3M, Novec (registered trademark) 7100), C4F9OC2H5 (manufactured by 3M, Novec (registered trademark) 7200), C2F5CF(OCH3)C3F7 (manufactured by 3M, Novec (registered trademark) 7300), etc.

[0345] As the fluorinated alkylamine, for example, perfluorotripropylamine, perfluorotributylamine, etc. can be mentioned.

[0346] As the fluoroalcohol, for example, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol, etc. can be mentioned.

[0347] As the non-fluorinated organic solvent, a compound formed only of hydrogen atoms and carbon atoms, and a compound formed only of hydrogen atoms, carbon atoms and oxygen atoms are preferred, and hydrocarbon-based organic solvents, alcohol-based organic solvents, ketone-based organic solvents, ether-based organic solvents, ester-based organic solvents can be mentioned.

[0348] This coating liquid preferably contains 75 to 99.999% by mass of the liquid medium, more preferably contains 85 to 99.99%, and particularly preferably contains 90 to 99.9%.

[0349] In addition to containing this compound or this composition and containing the liquid medium, this coating liquid may also contain other components other than them within the range not impairing the effects of the present invention.

[0350] As other components, for example, known additives such as an acid catalyst and a basic catalyst that promote the hydrolysis and condensation reaction of the hydrolyzable silyl group can be mentioned.

[0351] The content of other components in the coating liquid is preferably 10% by mass or less, more preferably 1% by mass or less.

[0352] The total concentration of the present compound and other components in the coating liquid or the total concentration of the present composition and other components (hereinafter also referred to as the solid component concentration) is preferably 0.001 to 40% by mass, more preferably 0.01 to 20% by mass, still more preferably 0.01 to 10% by mass, and particularly preferably 0.01 to 1% by mass. The solid component concentration of the coating liquid is a value calculated based on the mass of the coating liquid before heating and the mass after heating for 4 hours using a convection dryer at 120°C.

[0353] [Article]

[0354] Figure 1 It is a schematic cross-sectional view showing an example of the article of the present invention. The first article of the present invention is an article 20 having a substrate 12, a base layer 14, and a surface layer 22 in this order.

[0355] The aforementioned base layer contains an oxide containing silicon, and the aforementioned surface layer contains a condensate of the aforementioned present compound.

[0356] The material and shape of the substrate in the above-mentioned first article can be appropriately selected according to the use of the article and the like. Examples of the material of the substrate include glass, resin, sapphire, metal, ceramic, stone, and their composites. The glass can be chemically strengthened. In particular, as the substrate requiring water and oil repellency, substrates for touch panels, substrates for displays, and substrates constituting the housing of electronic devices can be mentioned. The substrates for touch panels and displays have light transmittance. "Having light transmittance" means that the perpendicular incident type visible light transmittance based on JIS R3106:1998 (ISO 9050:1990) is 25% or more. As the material of the substrate for touch panels, glass or transparent resin is preferred.

[0357] The substrate can be a substrate obtained by subjecting the surface to be provided with the base layer to surface treatment such as corona discharge treatment, plasma treatment, or plasma graft polymerization treatment. On the surface where the surface treatment is performed, the adhesiveness between the substrate and the base layer is more excellent, and as a result, the abrasion resistance of the surface layer is further improved. As the surface treatment, from the viewpoint of more excellent abrasion resistance of the surface layer, corona discharge treatment or plasma treatment is preferred.

[0358] The base layer is a layer containing at least an oxide containing silicon, and other elements may also be further contained. By making the base layer contain silicon oxide, a partial structure (2) of the aforementioned present compound undergoes dehydration condensation, and Si-O-Si bonds are formed between the base layers, forming a surface layer with excellent abrasion durability.

[0359] The content of silica in the base layer only needs to be 65% by mass or more, preferably 80% by mass or more, more preferably 85% by mass or more, and further preferably 90% by mass or more. If the content of silica is at least the lower limit value of the foregoing range, Si-O-Si bonds are sufficiently formed in the base layer, and the mechanical properties of the base layer are sufficiently ensured. The content of silica is the remainder obtained by subtracting the mass of the base layer from the total of the total contents of other elements (in the case of oxides, the oxide equivalent).

[0360] From the viewpoint of the durability of the surface layer, the oxide in the base layer preferably further contains one or more elements selected from alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium, molybdenum, and tungsten. By containing these elements, the bonding between the base layer and the foregoing compound becomes stronger, and the abrasion resistance is improved.

[0361] When the base layer contains one or more of iron, nickel, and chromium, their total content is preferably 10 to 1100 mass ppm, more preferably 50 to 1100 mass ppm, further preferably 50 to 500 mass ppm, and particularly preferably 50 to 250 mass ppm, based on the ratio to silica.

[0362] When the base layer contains one or more of aluminum and zirconium, their total content is preferably 10 to 2500 mass ppm, more preferably 15 to 2000 mass ppm, and further preferably 20 to 1000 mass ppm.

[0363] When the base layer contains alkali metal elements, their total content is preferably 0.05 to 15% by mass, more preferably 0.1 to 13% by mass, and further preferably 1.0 to 10% by mass. It should be noted that examples of the alkali metal elements include lithium, sodium, potassium, rubidium, and cesium.

[0364] When the base layer contains platinum group elements, their total content is preferably 0.02 mass ppm or more and 800 mass ppm or less, more preferably 0.04 mass ppm or more and 600 mass ppm or less, and further preferably 0.7 mass ppm or more and 200 mass ppm or less. It should be noted that examples of the platinum group elements include platinum, rhodium, ruthenium, palladium, osmium, and iridium.

[0365] When the base layer contains one or more of boron and phosphorus, from the viewpoint of the abrasion resistance of the surface layer, their total content is preferably 0.003 to 9, more preferably 0.003 to 2, and further preferably 0.003 to 0.5, based on the ratio of the total molar concentration of boron and phosphorus to the molar concentration of silicon.

[0366] When the base layer contains alkaline earth metal elements, from the viewpoint of the abrasion resistance of the surface layer, their total content is preferably 0.005 to 5, more preferably 0.005 to 2, and still more preferably 0.007 to 2 in terms of the ratio of the total molar concentration of the alkaline earth metal elements to the molar concentration of silicon. It should be noted that examples of the alkaline earth metal elements include lithium, sodium, potassium, rubidium, and cesium.

[0367] From the viewpoints of improving the adhesiveness of this compound, improving the water and oil repellency of the article, and improving the abrasion resistance, the base layer is preferably a silica layer containing alkali metal atoms. Among them, in this silica layer, the average value of the concentration of alkali metal atoms in the region with a depth of 0.1 to 0.3 nm from the surface in contact with the aforementioned surface layer is preferably 2.0×10 19 atoms / cm 3 or more. On the other hand, from the viewpoint of sufficiently ensuring the mechanical properties of the silica layer, the average value of the concentration of the aforementioned alkali metal atoms is preferably 4.0×10 22 atoms / cm 3 or less.

[0368] The thickness of the base layer is preferably 1 to 200 nm, and particularly preferably 2 to 20 nm. If the thickness of the base layer is at least the lower limit value of the aforementioned range, it is easy to sufficiently obtain the effect of improving the adhesiveness by using the base layer. If the thickness of the base layer is at most the upper limit value of the aforementioned range, the abrasion resistance of the base layer itself becomes high. As a method for measuring the thickness of the base layer, examples include: a method based on observing the cross-section of the base layer using an electron microscope (SEM, TEM, etc.); a method using an optical interference film thickness meter, a spectroscopic ellipsometer, a surface profiler, etc.

[0369] Examples of the method for forming the base layer include a method of vapor-depositing a vapor-deposited material having the composition of the desired base layer on the surface of the substrate.

[0370] As an example, the vapor deposition method may include a vacuum vapor deposition method. The vacuum vapor deposition method is a method in which the vapor-deposited material is evaporated in a vacuum chamber and adhered to the surface of the substrate.

[0371] The temperature during vapor deposition (for example, when using a vacuum vapor deposition apparatus, it is the temperature of the boat on which the vapor-deposited material is placed) is preferably 100 to 3000 °C, and particularly preferably 500 to 3000 °C.

[0372] The pressure during vapor deposition (for example, when using a vacuum vapor deposition apparatus, it is the absolute pressure in the chamber where the vapor-deposited material is placed) is preferably 1 Pa or less, and particularly preferably 0.1 Pa or less.

[0373] When forming the base layer using a vapor-deposited material, one vapor-deposited material can be used, or two or more vapor-deposited materials containing different elements can be used.

[0374] As evaporation methods of the evaporation material, the following can be cited: a resistance heating method in which the evaporation material is melted and evaporated on a resistance heating boat made of a high melting point metal; an electron gun method in which an electron beam is irradiated to the evaporation material, and the evaporation material is directly heated to melt the surface and evaporate it. As the evaporation method of the evaporation material, from the viewpoints that high melting point substances can be evaporated due to local heating and that there is no concern about reaction with the container or mixing of impurities because the part not in contact with the electron beam is at a low temperature, the electron gun method is preferred. As the evaporation material used in the electron gun method, from the viewpoint that it is not easily scattered even when an air flow is generated, a molten granular body or a sintered body is preferred.

[0375] The surface layer on the base layer contains a condensate of the aforementioned compound. The condensate of the compound includes: a substance in which a silanol group (Si-OH) is formed by a hydrolysis reaction of a hydrolyzable silyl group in the compound, and the silanol groups undergo a condensation reaction between molecules to form a Si-O-Si bond; and a substance in which the silanol group in the compound undergoes a condensation reaction with the silanol group or Si-OM group (where M is an alkali metal element) on the surface of the base layer to form a Si-O-Si bond. In addition, the surface layer may contain a condensate of a fluorine-containing compound other than the aforementioned compound. That is, the surface layer contains a fluorine-containing compound having a reactive silyl group in a state where a part or all of the reactive silyl groups of the fluorine-containing compound have undergone a condensation reaction.

[0376] The thickness of the surface layer is preferably 1 to 100 nm, particularly preferably 1 to 50 nm. If the thickness of the surface layer is at least the lower limit value of the aforementioned range, the effects based on the surface layer can be fully obtained. If the thickness of the surface layer is at most the upper limit value of the aforementioned range, the utilization efficiency is high.

[0377] The thickness of the surface layer is the thickness obtained by using an X-ray diffractometer for thin film analysis. The thickness of the surface layer can be obtained by using an X-ray diffractometer for thin film analysis, obtaining an interference pattern of reflected X-rays by the X-ray reflectivity method, and calculating based on the vibration period of the interference pattern.

[0378] The second article of the present invention is an article 20 having a base material 12 and a surface layer 22 in sequence,

[0379] The aforementioned base material contains an oxide containing silicon,

[0380] The aforementioned surface layer contains a condensate of the aforementioned compound.

[0381] The base material in the second article has the composition of the base layer in the aforementioned first article. Therefore, even if the surface layer is directly formed on the base material, the wear durability of the surface layer is excellent.

[0382] The material of the base material in the second article only needs to have the composition of the aforementioned base layer. For example, it can be a glass base material or the like. The details of the base material material are the same as those of the aforementioned base layer. Therefore, the description here is omitted. In addition, the constitution of the surface layer is also the same as that of the aforementioned first article. Therefore, the description here is omitted.

[0383] [Manufacturing method of the article]

[0384] The manufacturing method of the article according to the present invention is a method of forming a surface layer by using the aforementioned fluorine-containing compound, the composition containing the aforementioned fluorine-containing compound, or the aforementioned coating liquid, and using a dry coating method or a wet coating method.

[0385] This compound and this composition can be directly used in the dry coating method. This compound and this composition are suitable for forming a surface layer with excellent adhesion by the dry coating method. Examples of the dry coating method include vacuum evaporation, CVD, sputtering, and the like. From the viewpoints of suppressing the decomposition of this compound and the simplicity of the apparatus, the vacuum evaporation method can be suitably used.

[0386] In vacuum evaporation, a granular material obtained by supporting this compound on a metal porous body formed of a metal material such as iron or steel can be used. The granular material supporting this compound can be manufactured by impregnating a solution of this compound into the metal porous body and drying to remove the liquid medium. As the solution of this compound, this coating liquid can be used.

[0387] This coating liquid can be suitably used in the wet coating method. Examples of the wet coating method include spin coating, rubbing coating, spraying, squeezy coat method, dip coating, die coating, inkjet printing, flow coating, roll coating, casting, Langmuir-Blodgett method, gravure coating, and the like.

[0388] In order to improve the abrasion resistance of the surface layer, if necessary, an operation for promoting the reaction between this compound and the base material can be performed. Examples of this operation include heating, humidifying, light irradiation, and the like. For example, the base material having a surface layer formed thereon can be heated in an atmosphere containing moisture to promote hydrolysis reactions of hydrolyzable groups, reactions between hydroxyl groups on the surface of the base material and silanol groups, and formation of siloxane bonds by condensation reactions of silanol groups.

[0389] After the surface treatment, compounds in the surface layer that do not chemically bond to other compounds or the base material can be removed as needed. As specific methods, for example, a method of flowing a solvent through the surface layer, a method of wiping with a cloth impregnated with a solvent, and the like can be cited.

[0390] Examples

[0391] Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. Hereinafter, “%” means “mass %” unless otherwise specified. It should be noted that Examples 1 to 4 and 8 to 11 are examples, and Comparative Examples 5 to 7 and 12 to 14 are comparative examples.

[0392] [Synthesis Example 1: Synthesis of Compound (1)]

[0393] Diethyl diallylmalonate (60.0 g), lithium chloride (23.7 g), water (6.45 g), and dimethyl sulfoxide (263 g) were added, and the mixture was stirred at 160°C. After cooling to room temperature, water was added, and the mixture was extracted with ethyl acetate. Hexane was added to the organic phase, and the mixture was washed with saturated brine and dried over sodium sulfate. After filtration, the solvent was distilled off to obtain 39.5 g of the following compound (1).

[0394]

[0395] NMR spectrum of compound (1);

[0396] 1 1H-NMR (400 MHz, chloroform-d) δ (ppm): (ddt, J = 17.1, 10.1, 7.0 Hz, 2H), 5.06 to 4.94 (m, 4H), 4.09 (q, J = 7.1 Hz, 2H), 2.47 (ddd, J = 14.0, 8.0, 6.1 Hz, 1H), 2.33 (dt, J = 14.9, 7.5 Hz, 2H), 2.22 (dt, J = 14.1, 6.5 Hz, 2H), 1.21 (t, J = 7.1 Hz, 3H).

[0397] [Synthesis Example 2: Synthesis of Compound (2)]

[0398] After adding THF (260 mL) and diisopropylamine (41.6 mL), the solution was cooled to -78°C. A hexane solution of n-butyllithium (2.76 M, 96.6 mL) was added, and the temperature was raised to 0°C. After stirring, the solution was cooled to -78°C to prepare a THF solution of lithium diisopropylamide (LDA). The above compound (1) (39.5 g) was added to the THF solution, and after stirring, allyl bromide (24.1 mL) was added. The temperature was raised to 0°C, 1 M hydrochloric acid was added, and THF was distilled off under reduced pressure. After extraction with dichloromethane, sodium sulfate was added. After filtration, the solvent was distilled off, and the following compound (2) (45.0 g) was obtained by performing flash column chromatography using silica gel.

[0399]

[0400] NMR spectrum of compound (2);

[0401] 1 H-NMR (400 MHz, chloroform-d) δ (ppm): 5.74 - 5.62 (m, 3H), 5.04 (dd, J = 13.6, 1.9 Hz, 6H), 4.10 (q, J = 7.1 Hz, 2H), 2.29 (d, J = 7.4 Hz, 6H), 1.22 (t, J = 7.1 Hz, 3H).

[0402] [Synthesis Example 3: Synthesis of Compound (3)]

[0403] Dissolve the above compound (2) (45.0 g) in THF and cool to 0 °C. Add a THF solution of lithium aluminum hydride (104 mL, 260 mmol) and stir. Add water and 15% aqueous sodium hydroxide solution, stir at room temperature, and then dilute with dichloromethane. After filtration, distill off the solvent, and perform flash column chromatography using silica gel to obtain 31.3 g of the following compound (3).

[0404]

[0405] NMR spectrum of Compound (3);

[0406] 1 H-NMR (400 MHz, chloroform-d) δ (ppm): 5.90 - 5.76 (m, 3H), 5.10 - 5.02 (m, 6H), 3.38 (s, 2H), 2.03 (dt, J = 7.5, 1.2 Hz, 6H), 1.45 (s, 1H).

[0407] [Synthesis Example 4: Synthesis of Compound (4)]

[0408] Dissolve the above compound (1) (8.4 g) in THF and cool to 0 °C. Add a THF solution of lithium aluminum hydride (21 mL, 52 mmol) and stir. Add water and 15% aqueous sodium hydroxide solution, stir at room temperature, and then dilute with dichloromethane. After filtration, distill off the solvent, and perform flash column chromatography using silica gel to obtain 5.4 g of the following compound (4).

[0409]

[0410] NMR spectrum of Compound (4);

[0411] 1 H-NMR (400 MHz, chloroform-d) δ (ppm): 5.79 (m, 2H), 5.07 - 4.97 (m, 4H), 3.55 (t, J = 5.5 Hz, 2H), 2.10 (m, 4H), 1.76 - 1.64 (m, 1H).

[0412] [Synthesis Example 5: Synthesis of Compound (5)]

[0413] Dissolve the above compound (4) (2.5 g) in dichloromethane and cool to 0 °C. Add Dess-Martin reagent (10 g) and stir. After filtration, distill off the solvent, and perform flash column chromatography using silica gel to obtain 2.1 g of the following compound (5).

[0414]

[0415] 1H-NMR spectrum of compound (5);

[0416] 1 1H-NMR (400 MHz, chloroform-d) δ (ppm): 9.65 (d, J = 1.9 Hz, 1H), 5.74 (m, 2H), 5.16 - 5.02 (m, 4H), 2.53 - 2.34 (m, 3H), 2.32 - 2.19 (m, 2H).

[0417] [Synthesis Example 6: Synthesis of Compound (6)]

[0418] Dissolve the above compound (5) (2.1 g) in THF and cool to 0 °C. Add an ethyl ether solution of allylmagnesium bromide (30 ml, 21 mmol) and stir. Add 1 M hydrochloric acid, and distill off THF under reduced pressure. After extraction with dichloromethane, add sodium sulfate. After filtration, distill off the solvent, and perform flash column chromatography using silica gel to obtain 1.8 g of the following compound (6).

[0419]

[0420] 1H-NMR spectrum of compound (6);

[0421] 1 1H-NMR (400 MHz, chloroform-d) δ (ppm): 5.89 - 5.72 (m, 3H), 5.18 - 4.98 (m, 6H), 3.66 (s, 1H), 2.37 - 2.01 (m, 6H), 1.71 - 1.57 (m, 1H).

[0422] [Synthesis Example 7: Synthesis of Compound (1-1)]

[0423] According to the method described in Example 6 of International Publication No. WO2013 / 121984, the following compound (1-1) was obtained.

[0424] CF3-O-(CF2CF2O-CF2CF2CF2CF2O) x1(CF2CF2O)-CF2CF2CF2-C(O)OCH3 ··· Formula (1-1)

[0425] Average value of the number of units x1: 14

[0426] [Synthesis Example 8: Synthesis of Compounds (1-2) and (1-3)]

[0427] After adding 1,3-bis(trifluoromethyl)benzene (10 g) to the above compound (1-1) (10.0 g), triethylsilane (450 mg) and tris(pentafluorophenyl)borane (10 mg) were added. After stirring at room temperature for 2 hours, low-boiling components were distilled off, and thus 10.3 g of a mixture of the following compounds (1-2) and (1-3) was obtained.

[0428]

[0429] Average value of the number of units x1: 14

[0430] 1H-NMR spectrum of compound (1-2);

[0431] 1 1H-NMR (400 MHz, chloroform-d) δ (ppm): 5.12 - 5.02 (1H), 3.46 (s, 3H), 1.02 - 0.90 (9H), 0.75 - 0.58 (6H).

[0432] 19 19F-NMR (376 MHz, chloroform-d) δ (ppm): -54.85, -82.32, -86.23, -87.56, -89.70, -124.15, -124.73.

[0433] 1H-NMR spectrum of compound (1-3);

[0434] 1 1H-NMR (400 MHz, chloroform-d) δ (ppm): 5.57 - 5.52 (1H), 1.02 - 0.90 (18H), 0.75 - 0.58 (12H).

[0435] 19 19F-NMR (376 MHz, chloroform-d) δ (ppm): -54.85, -82.32, -86.23, -87.56, -89.70, -124.15, -124.73.

[0436] [Synthesis Example 9: Synthesis of Compounds (1-4) and (1-5)]

[0437] To the mixture (5.0 g) of the above (1-2) and (1-3), 1,3-bis(trifluoromethyl)benzene (10 g) was added, and then methanol (5.0 g) and concentrated sulfuric acid (2.5 g) were added. After stirring at 60 °C for 3 hours, extraction was carried out using AC-6000. By distilling off the solvent, 4.9 g of a mixture of the following compounds (1-4) and (1-5) was obtained.

[0438]

[0439] Average value of the number of units x1: 14

[0440] NMR spectrum of compound (1-4);

[0441] 1 1H-NMR (400 MHz, chloroform-d) δ (ppm): 4.89 - 4.73 (1H), 3.45 (s, 3H).

[0442] 19 19F-NMR (376 MHz, chloroform-d) δ (ppm): -54.84, -82.31, -86.22, -87.54, -89.69, -124.70, -125.25, -128.63.

[0443] NMR spectrum of compound (1-5);

[0444] 1 1H-NMR (400 MHz, chloroform-d) δ (ppm): 5.34 - 5.21 (1H).

[0445] 19 19F-NMR (376 MHz, chloroform-d) δ (ppm): -54.84, -82.31, -86.22, -87.54, -89.69, -124.70, -125.25, -128.63.

[0446] [Synthesis Example 10: Synthesis of Compound (1-6)]

[0447] The mixture (4.9 g) of the above (1-4) and (1-5) was put into a vacuum drying oven and concentrated under reduced pressure at 100 °C for 16 hours, whereby 4.8 g of the following compound (1-6) was obtained.

[0448]

[0449] Average value of the number of units x1: 14

[0450] NMR spectrum of compound (1-6);

[0451] 1H-NMR (400 MHz, chloroform-d) δ (ppm): 9.42 (t, J = 3.3 Hz, 1H).

[0452] 19 F-NMR (376 MHz, chloroform-d) δ (ppm): -54.85, -82.32, -86.24, -87.56, -89.68, -124.73, -125.27, -126.50.

[0453] [Synthesis Example 11: Synthesis of Compound (1-7)]

[0454] After adding 1,3-bis(trifluoromethyl)benzene (1.0 g) to the above compound (1-6) (1.0 g), the above compound (3) (60 mg) was added. After stirring at room temperature for 1 hour, bis(2-methoxyethyl)aminosulfur trifluoride (300 mg) was added. After heating to 80 °C and stirring for 1 hour, methanol was added, and extraction was carried out using AC-6000. The solvent was distilled off, and column chromatography was performed using silica gel to obtain 0.85 g of the following compound (1-7).

[0455]

[0456] Average value of the number of units x1: 14

[0457] NMR spectrum of Compound (1-7);

[0458] 1 H-NMR (400 MHz, chloroform-d) δ (ppm): 5.83~5.67 (3H), 5.56~5.30 (1H), 5.14~4.96 (6H), 3.79~3.69 (1H), 3.43~3.34 (1H), 2.07~1.96 (6H).

[0459] 19 F-NMR (376 MHz, chloroform-d) δ (ppm): -54.85, -82.32, -86.23, -87.56, -89.70, -124.73, -125.0, -125.21, -125.43, -125.98, -126.15, -141.30~-141.80.

[0460] [Example 1: Synthesis of Fluoroether Compound (1-8)]

[0461] Add AC-6000 (1.0 g), the above compound (1-7) (0.5 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 8.3 mg), aniline (2.6 mg), and trimethoxysilane (125 mg). After stirring at 40 °C, the solvent was distilled off under reduced pressure, and thus 0.51 g of the following fluorinated ether compound (1-8) was obtained.

[0462]

[0463] Average value of the number of units x1: 14

[0464] NMR spectrum of compound (1-8);

[0465] 1 1H-NMR (400 MHz, chloroform-d) δ (ppm): 5.61 - 5.25 (1H), 3.80 - 3.68 (1H), 3.64 - 3.45 (27H), 3.44 - 3.31 (1H), 1.57 - 1.29 (12H), 0.75 - 0.47 (6H).

[0466] 19 19F-NMR (376 MHz, chloroform-d) δ (ppm): -54.85, -82.32, -86.23, -87.56, -89.70, -124.73, -125.0, -125.21, -125.43, -125.98, -126.15, -141.30 - -141.80.

[0467] [Synthesis Example 12: Synthesis of Compound (2-1)]

[0468] After adding 1,3-bis(trifluoromethyl)benzene (1.0 g) to the above compound (1-6) (1.0 g), 1,6-heptadien-4-ol (40 mg) was added. After stirring at room temperature for 5 hours, bis(2-methoxyethyl)aminosulfur trifluoride (300 mg) was added. After heating to 80 °C and stirring for 1 hour, methanol was added, and extraction was carried out using AC-6000. The solvent was distilled off, and column chromatography was performed using silica gel, and thus 0.65 g of the following compound (2-1) was obtained.

[0469]

[0470] Average value of the number of units x1: 14

[0471] NMR spectrum of compound (2-1);

[0472] 1H-NMR (400 MHz, chloroform-d) δ (ppm): 5.85 - 5.50 (3H), 5.13 - 4.93 (4H), 3.88 - 3.78 (1H), 2.42 - 2.19 (4H).

[0473] 19 F-NMR (376 MHz, chloroform-d) δ (ppm): -54.85, -82.33, -86.24, -87.57, -89.71, -124.74, -124.94, -125.18, -136.79 - -137.11.

[0474] [Example 2: Synthesis of Fluoroether Compound (2-2)]

[0475] Add AC-6000 (1.0 g), the above compound (2-1) (0.5 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 8.3 mg), aniline (2.6 mg), trimethoxysilane (83 mg), stir at 40 °C, and then distill off the solvent under reduced pressure to obtain 0.5 g of the following fluoroether compound (2-2).

[0476]

[0477] Average value of the number of units x1: 14

[0478] NMR spectrum of compound (2-2);

[0479] 1 H-NMR (400 MHz, chloroform-d) δ (ppm): 5.77 - 5.51 (1H), 3.98 - 3.75 (1H), 3.65 - 3.43 (18H), 1.78 - 1.49 (8H), 0.88 - 0.71 (4H).

[0480] 19 F-NMR (376 MHz, chloroform-d) δ (ppm): -54.85, -82.33, -86.24, -87.57, -89.71, -124.74, -124.94, -125.18, -136.79 - -137.11.

[0481] [Synthesis Example 13: Synthesis of Compound (3-1)]

[0482] To the above compound (1-6) (1.0 g), 1,3-bis(trifluoromethyl)benzene (1.0 g) was added, and then the above compound (6) (60 mg) was added. After stirring at room temperature for 72 hours, bis(2-methoxyethyl)aminosulfur trifluoride (300 mg) was added. After heating to 80 °C and stirring for 1 hour, methanol was added, and extraction was carried out using AC-6000. The solvent was distilled off, and column chromatography was performed using silica gel, whereby 0.55 g of the following compound (3-1) was obtained.

[0483]

[0484] Average value of the number of units x1: 14

[0485] NMR spectrum of compound (3-1);

[0486] 1 H-NMR (400 MHz, chloroform-d) δ (ppm): 5.77 - 5.33 (4H), 5.08 - 4.62 (6H), 3.93 - 3.66 (1H), 2.36 - 1.46 (7H).

[0487] 19 F-NMR (376 MHz, chloroform-d) δ (ppm): -54.85, -82.34, -86.24, -87.57, -89.70, -124.75, -125.26, -133.46 - -133.84, -136.50 - -136.89.

[0488] [Example 3: Synthesis of fluorinated ether compound (3-2)]

[0489] AC-6000 (1.0 g), the above compound (3-1) (0.5 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 8.3 mg), aniline (2.6 mg), and trimethoxysilane (125 mg) were added, and after stirring at 40 °C, the solvent was distilled off under reduced pressure, whereby 0.51 g of the following fluorinated ether compound (3-2) was obtained.

[0490]

[0491] Average value of the number of units x1: 14

[0492] NMR spectrum of compound (3-2);

[0493] 11H-NMR (400 MHz, chloroform-d) δ (ppm): 5.80 - 5.50 (1H), 4.01 - 3.86 (1H), 3.78 - 3.30 (27H), 1.86 - 1.37 (13H), 0.85 - 0.45 (6H).

[0494] 19 19F-NMR (376 MHz, chloroform-d) δ (ppm): -54.85, -82.34, -86.24, -87.57, -89.70, -124.75, -125.26, -133.46 - -133.84, -136.50 - -136.89.

[0495] [Synthesis Example 14: Synthesis of Compound (4-1)]

[0496] To the above compound (1-6) (1.0 g), 1,3-bis(trifluoromethyl)benzene (1.0 g) was added, and then allyl alcohol (20 mg) was added. After stirring at room temperature for 1 hour, bis(2-methoxyethyl)aminosulfur trifluoride (300 mg) was added. After heating to 80 °C and stirring for 1 hour, methanol was added, and extraction was carried out using AC-6000. The solvent was distilled off, and column chromatography was performed using silica gel to obtain 0.77 g of the following compound (4-1).

[0497]

[0498] NMR spectrum of Compound (4-1);

[0499] 1 1H-NMR (400 MHz, chloroform-d) δ (ppm): 5.90 - 5.73 (1H), 5.68 - 5.43 (1H), 5.35 - 5.13 (2H), 4.41 - 4.13 (2H)

[0500] 19 19F-NMR (376 MHz, chloroform-d) δ (ppm): -54.85, -82.34, -86.24, -87.57, -89.70, -124.67, -125.14 - -125.29, -126.16, -142.64 - -143.30

[0501] [Example 4: Synthesis of Fluoroether Compound (4-2)]

[0502] AC-6000 (1.0 g), the above compound (4-1) (0.5 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3%, 8.0 mg), aniline (2.8 mg), and trimethoxysilane (50 mg) were added. After stirring at 40 °C, the solvent was distilled off under reduced pressure, and 0.51 g of the following fluorinated ether compound (4-2) was thus obtained.

[0503]

[0504] NMR spectrum of compound (4-2);

[0505] 1 1H-NMR (400 MHz, chloroform-d) δ (ppm): 5.65 - 5.36 (1H), 3.77 - 3.39 (13H), 1.87 - 1.71 (2H), 0.76 - 0.63 (2H)

[0506] 19 19F-NMR (376 MHz, chloroform-d) δ (ppm): -54.85, -82.34, -86.24, -87.57, -89.70, -124.67, -125.14 - -125.29, -126.16, -142.64 - -143.30

[0507] [Example 5: Synthesis of compound (5-1)]

[0508] According to the methods described in Synthesis Examples 1 - 3 of International Publication No. 2017 / 022437, the following compound (5-1) was obtained.

[0509]

[0510] The average value of the repeat unit number x2 was 21, and the average value of the repeat unit number x3 was 19.

[0511] [Example 6: Synthesis of compound (6-1)]

[0512] According to the method described in Example 5 of International Publication No. 2017 / 038830, the following compound (6-1) was obtained.

[0513]

[0514] The average value of the repeat unit number x2 was 21, and the average value of the repeat unit number x3 was 19.

[0515] [Synthesis of compound (7-1)]

[0516] According to the method described in Example 7 of International Publication No. 2013 / 121984, the following compound (7-1) was obtained.

[0517] CF3-O-(CF2CF2O-CF2CF2CF2CF2O) X1 (CF2CF2O)-CF2CF2CF2-CH2OH ··· Formula (7-1)

[0518] Average value of the number of units x1: 14

[0519] [Synthesis of Compound (7-2)]

[0520] After adding 1,3-bis(trifluoromethyl)benzene (1.0 g) to the above compound (7-1) (1.0 g), cesium carbonate (5.0 g) and allyl bromide (200 mg) were added. After stirring overnight at 60 °C, hydrochloric acid was added and extraction was carried out. The solvent was distilled off, and column chromatography was performed using silica gel to obtain 0.83 g of the following compound (7-2).

[0521]

[0522] 1H-NMR spectrum of compound (7-2);

[0523] 1 1H-NMR (400 MHz, chloroform-d) δ (ppm): 5.85 - 5.69 (1H), 5.29 - 5.04 (2H), 4.08 - 3.98 (2H), 3.94 - 3.81 (2H)

[0524] 19 19F-NMR (376 MHz, chloroform-d) δ (ppm): -54.85, -82.34, -86.24, -87.57, -89.70, -118.86, -124.67, -125.97

[0525] [Example 7: Synthesis of Compound (7-3)]

[0526] AC-6000 (1.0 g), the above compound (7-2) (0.5 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 8.0 mg), aniline (2.8 mg), and trimethoxysilane (50 mg) were added, and after stirring at 40 °C, the solvent was distilled off under reduced pressure to obtain 0.51 g of the following fluorinated ether compound (7-3).

[0527]

[0528] 1H-NMR spectrum of compound (7-3);

[0529] 1 1H-NMR (400 MHz, chloroform-d) δ (ppm): 3.98 - 3.81 (2H), 3.65 - 3.47 (11H), 1.79 - 1.63 (2H), 0.73 - 0.59 (2H)

[0530] 19 19F-NMR (376 MHz, chloroform-d) δ (ppm): -54.85, -82.34, -86.24, -87.57, -89.70, -118.86, -124.67, -125.97

[0531] [Examples 8 - 14: Manufacture and Evaluation of Articles]

[0532] Using the respective compounds obtained in Examples 1 - 7, the substrates were surface-treated to obtain the articles of Examples 8 - 14. As the surface treatment method, the following dry coating method and wet coating method were used respectively for each example. As the substrate, chemically strengthened glass was used. The obtained articles were evaluated by the following method. The results are shown in Table 1.

[0533] (Dry Coating Method)

[0534] Dry coating was carried out using a vacuum evaporation apparatus (manufactured by ULVAC, Inc., VTR350M) (vacuum evaporation method). 0.5 g of each compound was filled into a molybdenum boat in the vacuum evaporation apparatus, and the inside of the vacuum evaporation apparatus was evacuated to 1×10 -3 Pa or less. The boat containing the compound was heated at a heating rate of 10 °C / min or less. When the evaporation rate based on a crystal oscillator type film thickness gauge exceeded 1 nm / sec, the shutter was opened to start film formation on the surface of the substrate. When the film thickness reached about 50 nm, the shutter was closed to end film formation on the surface of the substrate. The substrate with the compound deposited thereon was heat-treated at 200 °C for 30 minutes and then cleaned with 1,1,2-trichloro-1,2,2-trifluoroethane (manufactured by AGC Inc., AK-225) to obtain an article having a surface layer on the surface of the substrate.

[0535] (Evaluation Method)

[0536] (Method for Measuring Contact Angle)

[0537] Using a contact angle measuring apparatus (manufactured by Kyowa Interface Science Co., Ltd., DM-500), the contact angles of about 2 μL of distilled water or n-hexadecane placed on the surface of the surface layer were measured. The measurements were carried out at 5 different positions on the surface of the surface layer, and the average value was calculated. The 2θ method was used in the calculation of the contact angle.

[0538] (Initial Contact Angle)

[0539] For the surface layer, the initial water contact angle and the initial n-hexadecane contact angle are measured using the aforementioned measurement method. The evaluation criteria are as described below.

[0540] Initial water contact angle:

[0541] 〇 (Good): 115 degrees or more.

[0542] × (Not acceptable): Less than 115 degrees.

[0543] <Abrasion resistance (steel wool)>

[0544] For the surface layer, in accordance with JIS L0849:2013 (ISO 105-X12:2001), using a reciprocating horizontal tester (manufactured by KNT Corporation), after the steel wool BONSTAR (#0000) reciprocates 10,000 times under the conditions of pressure: 98.07 kPa and speed: 320 cm / minute, the water contact angle is measured using the aforementioned method. The smaller the decrease in water repellency (water contact angle) after friction, the smaller the performance degradation caused by friction, and the more excellent the abrasion resistance. The evaluation criteria are as described below.

[0545] ◎ (Excellent): The change in the water contact angle after reciprocating 10,000 times is 4 degrees or less.

[0546] 〇 (Good): The change in the water contact angle after reciprocating 10,000 times exceeds 4 degrees and is up to 8 degrees.

[0547] × (Not acceptable): The change in the water contact angle after reciprocating 10,000 times exceeds 8 degrees.

[0548] <Light resistance>

[0549] For the surface layer, using a bench-top xenon arc lamp type light resistance promotion tester (product name: SUNTEST XLS+, manufactured by Toyo Seiki Co., Ltd.), under the condition of blackboard temperature: 63 °C, after irradiating light (650 W / m 2 , 300 - 700 nm) for 500 hours, the water contact angle is measured using the aforementioned method. The evaluation criteria are as described below.

[0550] ◎ (Excellent): The change in the water contact angle after the light resistance promotion test is 5 degrees or less.

[0551] ○ (Good): The change in the water contact angle after the light resistance promotion test exceeds 5 degrees and is up to 10 degrees.

[0552] × (Not acceptable): The change in the water contact angle after the light resistance promotion test exceeds 10 degrees.

[0553] [Table 1]

[0554] Table 1

[0555]

[0556] As shown in Table 1, even for the articles of Examples 12 and 14 obtained using the compounds of Examples 5 and 7, the initial contact angle and light resistance are good, but in particular, a decrease in the water contact angle after the friction test was confirmed. In addition, for the article obtained using the compound of Example 6 in which the O-CHF group is arranged at a position separated from the adhesion group, the initial water repellency is insufficient.

[0557] On the other hand, for the articles of Examples 8 to 11 obtained using the fluorinated ether compounds of Examples 1 to 4 having an O-CHF group at the connecting portion between the polyfluoropolyether chain and the adhesion group, a decrease in the water contact angle can be suppressed even after the friction test and the light resistance test, indicating that they have excellent durability.

[0558] Industrial Applicability

[0559] As an example, an article having a surface layer containing this compound is useful as an optical article, a touch panel, an antireflection film, an antireflection glass, an SiO2-treated glass, a tempered glass, a sapphire glass, a quartz substrate, a die metal, etc., which are parts of the following products.

[0560] Products: car navigation, mobile phone, digital camera, digital video camera, personal digital assistant (PDA), portable music player, car audio, game machine, lens, camera lens, lens filter, sunglasses, medical equipment (such as gastroscope), copier, personal computer (PC), liquid crystal display, organic EL display, plasma display, touch panel display, protective film, antireflection film, antireflection glass, nanoimprint template, die, etc.

[0561] This application claims priority based on Japanese Patent Application No. 2020-102409 filed on June 12, 2020, and incorporates all of its disclosure herein.

[0562] Explanation of Reference Numerals

[0563] 10: Substrate with a base layer, 12: Substrate, 14: Base layer,

[0564] 20: Article, 22: Surface layer

Claims

1. A fluoroether compound represented by the following formula (A1) or formula (A2), {R f O-(R f1 O) m1 -(R 1 ) m2 -(CHF) m3 -O-(CHF) m4} n1 -Q 1 (-T 1 ) n2 Formula (A1), (T 2 ) n3 -Q 2 -(CHF) m5 -O-(CHF) m6 -(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -(CHF) m10 -O-(CHF) m11 -Q 3 (-T 3 ) n4 Formula (A2) wherein, R f is a fluoroalkyl group having 1 to 20 carbon atoms, and there are multiple Rs f When there are multiple Rs f optionally the multiple Rs are the same as or different from each other R f1 and R f2 each independently represents a fluoroalkylene group having 1 to 6 carbon atoms, and there are multiple Rs f1 or R f2 When there are multiple Rs f1 or R f2 each may be the same as or different from each other, R 1 、 R 2 and R 3 each independently represents an alkylene group optionally having a fluorine atom, and when there are a plurality of R 1 's, the R 1 's are optionally the same as or different from each other. Q 1 is a linking group with a valence of n1 + n2, Q 2 is a linking group with a valence of 1 + n3, Q 3 is a linking group with a valence of 1 + n4 Q 1 、Q 2 and Q 3 each independently represents a group represented by any one of the following formulas (Q1) to (Q7): (-A 1 -) e1 C(R 22 ) 4-e1-e2 (-Q 22 -) e2 Formula (Q2) -A 2 -N(-Q 23 -)2 formula (Q3) (-A 3 -) h1 Z 1 (-Q 24 -) h2 Formula (Q4) (-A 2 -) i1 Si(R 23 ) 4-i1-i2 (-Q 25 -) i2 Formula (Q5) -A 1 -Q 26 - formula (Q6) -A 1 -CH(-Q 22 -)-Si(R 23 ) 3-i3 (-Q 25 -) i3 Formula (Q7) In formulas (Q1) to (Q7), A 1 , A 2 or A 3 is connected to the perfluoropolyether chain side, and Q 22 , Q 23 , Q 24 , Q 25 or Q 26 is connected to the sealing group T 1 , T 2 or T 3 . A 1 is a single bond, an alkylene group, or a group having -C(O)NR- between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms 26 -, -C(O)-, -NR- 26 -, or -O-, A 2 is an alkylene group, or a group having -C(O)NR-,-C(O)-,-NR- or -O- between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms 26 -、-C(O)-、-NR 26 -, or -O- At A 3 When the atom in the bonded Z 1 is a carbon atom, A 3 is A 1 ; when the atom in the bonded Z 3 is a nitrogen atom, A 1 is A 3 is A 2 , Q 11 is a single bond, -O-, an alkylene group, or an alkylene group having 2 or more carbon atoms and having -C(O)NR between carbon-carbon atoms 26 -, -C(O)-, -NR 26 -, or a group of -O-, Q 22 is an alkylene group; having -C(O)NR between carbon-carbon atoms of an alkylene group with 2 or more carbon atoms 26 -, -C(O)-, -NR 26 -, or -O-; a group having -C(O)NR 1 , T 2 , or T 3 at the terminal on the side not connected to the adhesion group T 26 -, -C(O)-, -NR 26 -, or -O-; alternatively, having -C(O)NR between carbon-carbon atoms of an alkylene group with 2 or more carbon atoms 26 -, -C(O)-, -NR 26 -, or -O- and having -C(O)NR 1 , T 2 , or T 3 at the terminal on the side not connected to the adhesion group T 26 -, -C(O)-, -NR 26 -, or -O-, Q 1 , Q 2 , or Q 3 has 2 or more Qs 22 When there are 2 or more Qs 22 they are optionally the same as or different from each other Q 23 is an alkylene group, or an alkylene group having 2 or more carbon atoms and having -C(O)NR 26 -, -C(O)-, -NR 26 -, or -O-; two Qs 23 are optionally the same as or different from each other Q 24 When the atom in the bonded Z 1 is a carbon atom, Q 24 is Q 22 , Q 24 When the atom in the bonded Z 1 is a nitrogen atom, Q 24 is Q 23 , Q 1 , Q 2 or Q 3 When there are two or more Q 24 , two or more Q 24 are optionally the same as or different from each other, Q 25 is an alkylene group, or a group having -C(O)NR- between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, 26 -C(O)-, -NR 26 -, or -O-, Q 1 , Q 2 or Q 3 having 2 or more Q 25 When there are 2 or more Q 25 they are optionally the same as or different from each other, Q 26 is an alkylene group, or has -C(O)NR- between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms 26 -, -C(O)-, -NR 26 -, or -O- group Z 1 is a group having a ring structure with a valence of (h1 + h2), and the ring structure has a carbon atom or a nitrogen atom directly bonded to A 3 and has a carbon atom or a nitrogen atom directly bonded to Q 24 and has a carbon atom or a nitrogen atom directly bonded thereto, R 21 is a hydrogen atom or an alkyl group, Q 1 , Q 2 or Q 3 has two or more Rs 21 When there are two or more Rs 21 they are optionally the same as or different from each other R 22 is a hydrogen atom, a hydroxyl group, an alkyl group or an acyloxy group, Q 1 , Q 2 or Q 3 When there are two or more Rs 22 among the two or more Rs 22 are optionally the same as or different from each other R 23 is an alkyl group, Q 1 , Q 2 or Q 3 has two or more Rs 23 When there are two or more Rs 23 they are optionally the same as or different from each other R 26 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group, d1 is an integer from 0 to 3, d2 is an integer from 0 to 3, and d1 + d2 is an integer from 1 to 3, d3 is an integer from 0 to 3, d4 is an integer from 0 to 3, and d3 + d4 is an integer from 1 to 3, d1 + d3 in Q 1 is an integer from 1 to 5 in Q 2 and Q 3 is 1 in d2 + d4 is an integer from 1 to 5, e1 is an integer from 1 to 3 in Q 1 and is 1 in Q 2 and Q 3 and is 1 in e2 is an integer from 1 to 3, e1 + e2 is an integer from 2 to 4, h1 is an integer of 1 or more in Q 1 and is 1 in Q 2 and Q 3 and is 1 h2 is an integer of 1 or more, i1 is an integer from 1 to 3 in Q 1 and is 1 in Q 2 and Q 3 and is 1 in i2 is an integer from 1 to 3, i1 + i2 is an integer from 2 to 4, i3 is an integer from 1 to 3; T 1 、T 2 and T 3 Each is independently an adhesive group, and there are multiple T 1 、T 2 or T 3 When there are multiple T 1 、T 2 or T 3 are optionally the same as or different from each other, m1 and m8 are each independently an integer from 0 to 210. When there are multiple m1s, the m1s may be the same as or different from each other optionally, m2, m7, and m9 are each independently 0 or 1. When there are multiple m2s, the m2s may be the same as or different from each other optionally, m3 and m4 are each independently 0 or 1, m3 + m4 is 1 or 2, and there are multiple (CHF) m3 -O-(CHF) m4 When present, the combinations of m3 and m4 are optionally the same as or different from each other m1 + m2 is 1 or more, m7 + m8 + m9 is 1 or more, m5 and m6 are each independently 0 or 1, and m5 + m6 is 1 or 2, m10 and m11 are each independently 0 or 1, and m10 + m11 is 1 or 2, n1 is an integer from 1 to 10, n2, n3, and n4 are each independently an integer from 1 to 20.

2. The fluoroether compound according to claim 1, wherein m3, m6, or m10 is 1.

3. The fluoroether compound according to claim 1 or 2, wherein m4, m5, or m11 is 0.

4. A compound represented by the following formula (B1) or formula (B2), R f O-(R f1 O) m1 -(R 1 ) m2 -CHO formula (B1) OHC-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -CHO formula (B2) wherein, R f is a perfluoroalkyl group having 1 to 20 carbon atoms, R f1 and R f2 each independently represents a fluoroalkylene group having 1 to 6 carbon atoms, and there are multiple Rs f1 or R f2 When there are multiple Rs f1 or R f2 each may be the same as or different from each other, R 1 、R 2 and R 3 each independently represents an alkylene group which may optionally have a fluorine atom, m1 is an integer from 1 to 210, and m8 is an integer from 0 to 210, m2, m7, and m9 are each independently 0 or 1.

5. A method for producing a fluoroether compound, comprising: React a compound represented by the following formula (B1) or formula (B2) with a compound represented by the following formula (C1), R f O-(R f1 O) m1 -(R 1 ) m2 -CHO formula (B1) OHC-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -CHO formula (B2) (CH2=CH-) n5 -Q 4 (-OH) n6 Formula (C1) wherein, R f is a fluoroalkyl group having 1 to 20 carbon atoms, R f1 and R f2 each independently represents a fluoroalkylene group having 1 to 6 carbon atoms, and there are multiple Rs f1 or R f2 When there are multiple Rs f1 or R f2 each may be the same as or different from one another, R 1 、R 2 and R 3 each independently represents an alkylene group optionally having a fluorine atom, Q 4 is a linking group having a valence of n5 + n6, m1 and m8 are each independently an integer from 0 to 210, m2, m7, and m9 are each independently 0 or 1, n5 is an integer from 1 to 20, n6 is an integer from 1 to 10.

6. A method for producing a compound represented by the following formula (B1) or formula (B2), wherein, React a compound represented by the following formula (D1) or formula (D2) with a hydrosilicon compound in the presence of a Lewis acid compound to obtain a compound represented by the following formula (E1) or formula (E2), Detaching Si(R 16 )3 from a compound represented by the following formula (E1) or formula (E2) to obtain a compound represented by the following formula (F1) or formula (F2), Heat a compound represented by the following formula (F1) or formula (F2), R f O-(R f1 O) m1 -(R 1 ) m2 -C(=O)OR 11 Formula (D1) R 11 OC(=O)-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -C(=O)OR 11 Formula (D2) R f O-(R f1 O) m1 -(R 1 ) m2 -CH(OR 12 )2 Formula (E1) (R 12 O)2CH-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -CH(OR 13 )2 Formula (E2) R f O-(R f1 O) m1 -(R 1 ) m2 -CH(OR 14 )2 Formula (F1) (R 14 O)2CH-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -CH(OR 15 )2 Formula (F2) R f O-(R f1 O) m1 -(R 1 ) m2 -CHO of formula (B1) OHC-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -CHO formula (B2) wherein, R f is a fluoroalkyl group having 1 to 20 carbon atoms, R f1 and R f2 each independently represents a fluoroalkylene group having 1 to 6 carbon atoms, and there are multiple Rs f1 or R f2 When there are multiple Rs f1 or R f2 each may be the same as or different from each other optionally R 1 、R 2 and R 3 each independently represents an alkylene group which may optionally have a fluorine atom. R 11 is a hydrogen atom or an alkyl group optionally having a substituent, and there are a plurality of Rs 11 When there are a plurality of Rs 11 they are optionally the same as or different from each other R 12 and R 13 each independently is Si(R 16 )3 or R 11 , at least one of each of the multiple Rs 12 and Rs 13 present is Si(R 16 )3, R 14 and R 15 each independently represents a hydrogen atom or R 11 For multiple Rs present, 14 and R 15 at least one of each of them is a hydrogen atom. R 16 is a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an alkoxy group, and a plurality of Rs present 16 are optionally the same as or different from each other m1 and m8 are each independently an integer from 0 to 210, m2, m7, and m9 are each independently 0 or 1.

7. A fluoroether composition containing one or more of the fluoroether compounds described in any one of claims 1 to 3, and other fluoroether compounds.

8. A coating liquid containing: the fluoroether compound described in any one of claims 1 to 3 or the fluoroether composition described in claim 7; and a liquid medium.

9. An article having a surface layer formed of the fluoroether compound described in any one of claims 1 to 3 or the fluoroether composition described in claim 7.

10. A method for manufacturing an article, wherein, Use the fluoroether compound described in any one of claims 1 to 3, the fluoroether composition described in claim 7, or the coating liquid described in claim 8 to form a surface layer by a dry coating method or a wet coating method.

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