Fluorine-containing ether compounds, compositions, and articles

Abstract

To provide fluorine-containing ether compounds, compositions, and articles that can form a surface layer with excellent light resistance. [Solution] The fluorine-containing ether compound of the present invention has a poly(oxyfluoroalkylene) chain, a reactive silyl group, and a group (A) represented by -NR-C(O)- (wherein R is a hydrogen atom or an alkyl group), wherein the carbon atom of -C(O)- in group (A) is bonded to a carbon atom, and the poly(oxyfluoroalkylene) chain is located on the nitrogen atom side of group (A).

Description

[Technical Field]

[0001] This invention relates to fluorine-containing ether compounds, compositions, and articles. [Background technology]

[0002] Fluorine-containing compounds are suitable for use as surface treatment agents because they exhibit high lubricity, water-repellent and oil-repellent properties. By imparting water-repellent and oil-repellent properties to the surface of a substrate using a surface treatment agent, dirt on the substrate surface becomes easier to wipe off, improving the ability to remove dirt. Among the above-mentioned fluorine-containing compounds, fluorine-containing ether compounds having poly(oxyfluoroalkylene) chains in which an ether bond (-O-) exists in the middle of the fluoroalkylene chain are compounds with excellent flexibility and are particularly excellent at removing oils and greases. As the fluorine-containing ether compounds mentioned above, compounds having a poly(oxyperfluoroalkylene) chain and a hydrolyzable silyl group at the terminal are widely used (Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2017 / 038830 [Overview of the project] [Problems that the invention aims to solve]

[0004] In recent years, the performance requirements for surface layers formed using fluorine-containing ether compounds have increased; for example, there is a demand for surface layers with excellent light resistance. The present inventors evaluated an article having a surface layer formed on the surface of a substrate using a fluorine-containing ether compound as described in Patent Document 1, and found that there is room for improvement in light resistance.

[0005] The present invention has been made in view of the above problems and aims to provide a fluorine-containing ether compound, composition, and article that can form a surface layer with excellent light resistance. [Means for Solving the Problems]

[0006] As a result of intensive studies on the above problems, the present inventors have found that a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain, a reactive silyl group, and a group (A) represented by -NR-C(O)-, wherein the carbon atom of -C(O)- in the group (A) is bonded to a carbon atom and the poly(oxyfluoroalkylene) chain is located on the nitrogen atom side of the group (A) can form a surface layer excellent in light resistance, leading to the present invention.

[0007] That is, the inventors have found that the above problems can be solved by the following configuration. [1] A fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain, a reactive silyl group, and a group (A) represented by -NR-C(O)- (wherein R is a hydrogen atom, an alkyl group, or an alkyl group having a reactive silyl group), wherein the carbon atom of -C(O)- in the group (A) is bonded to a carbon atom, and the poly(oxyfluoroalkylene) chain is located on the nitrogen atom side of the group (A). [2] Further, a fluorine-containing ether compound according to [1], having a group (B) represented by -R 1 - (wherein R 1 is an alkylene group having 1 to 10 carbon atoms and the alkylene group does not have a fluorine atom), and the group (B) is bonded to the nitrogen atom of the group (A).

[0008] [3] The fluorine-containing ether compound according to [1] or [2], which is a compound represented by formula (1). Z[-R f -R 1 -NR-C(O)-Y-{Si(R 2 ) n L 3-n} g j ···(1) However, in formula (1), R f ​R is a fluoroalkylene group. f Medium, R 1 The carbon atom bonded to it has at least one fluorine atom bonded to it. R 1 This is an alkylene group having 1 to 10 carbon atoms. R is a hydrogen atom, an alkyl group, or an alkyl group having a reactive silyl group. Y is an organic group with a (g+1) valency and has a carbon atom bonded to the carbon atom of -C(O)- in formula (1). R 2 It is a monovalent hydrocarbon group. L is a hydrolyzable group or a hydroxyl group. n is an integer between 0 and 2. g is an integer greater than or equal to 1. j is either 1 or 2. If j is 1, then Z is R f1 -(OX) m A monovalent group represented by -O-, where j is 2, then Z is -(OX) m It is a divalent group represented by -O-. f1 is a perfluoroalkyl group. X is a fluoroalkylene group. m is an integer greater than or equal to 2. [4] The fluorine-containing ether compound of [3], wherein the organic group in Y in formula (1) is a hydrocarbon group which may have a heteroatom. [5] Y is {Si(R 2 ) n L 3-n} g A fluorine-containing ether compound of [3] or [4] having a carbon atom bonded to a silicon atom. [6] The compound represented by formula (1) is such that Z is R f1 -(OX) m It is a monovalent group represented by -O-, where X is a fluoroalkylene group having 1 to 6 carbon atoms, (OX) m A fluorine-containing ether compound from any of [3] to [5], wherein the compound contains two or more (OX) groups. [7] The compound represented by formula (1) is such that Z is -(OX) mIt is a divalent group represented by -O-, where X is a fluoroalkylene group having 1 to 6 carbon atoms, (OX) m A fluorine-containing ether compound from any of [3] to [5], wherein the compound contains two or more (OX) groups.

[0009] [8] A composition characterized by comprising two or more fluorine-containing ether compounds from any of [1] to [7] above, or comprising one or more fluorine-containing ether compounds from any of [1] to [7] and a fluorine-containing ether compound other than any of [1] to [7]. [9] The composition of [8] comprising the fluorine-containing ether compound having one of the groups (A) and the fluorine-containing ether compound having two of the groups (A).

[10] The fluorine-containing ether compound having one of the groups (A) is a fluorine-containing ether compound in formula (1) where j is 1, The composition of [9], wherein the fluorine-containing ether compound having two of the group (A) is a fluorine-containing ether compound in formula (1) where j is 2.

[11] A coating composition characterized by comprising any fluorine-containing ether compound from [1] to [7] or any composition from [8] to

[10] , and a liquid medium.

[12] An article characterized by having a base material and a surface layer formed on the base material from any of the fluorine-containing ether compounds from [1] to [7] or any of the compositions from [8] to

[10] . [Effects of the Invention]

[0010] According to the present invention, it is possible to provide fluorine-containing ether compounds, compositions, and articles that can form a surface layer with excellent light resistance. [Modes for carrying out the invention]

[0011] In this specification, an atomic group based on one monomer molecule directly formed by the polymerization of monomers, and an atomic group obtained by chemically transforming a part of the above atomic group, are referred to as "units." Furthermore, an oxyfluoroalkylene group constituting a poly(oxyfluoroalkylene) chain is also referred to as a "unit." Note that poly(oxyfluoroalkylene) groups such as a di(oxyfluoroalkylene) group derived from one monomer molecule may also be referred to as a "unit." A compound represented by formula (1) is referred to as compound (1). Compounds represented by other formulas are referred to similarly. A group represented by formula (A) is referred to as group (A). Groups represented by other formulas are referred to similarly. In this specification, when it is stated that "the alkylene group may have an A group," the alkylene group may have an A group between carbon atoms in the alkylene group, or it may have an A group at its terminal, such as alkylene-A-group-.

[0012] A "divalent organopolysiloxane residue" is the group represented by the following formula. In the following formula, R x g1 is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group. g1 is an integer of 1 or more, preferably an integer from 1 to 9, and particularly preferably an integer from 1 to 4.

[0013] [ka]

[0014] "Sylphenylene skeleton group" refers to -Si(R y )2PhSi(R y )2-(However, Ph is a phenylene group, R y It is a monovalent organic group. ) It is a group represented by R y As such, alkyl groups (preferably having 1 to 10 carbon atoms) are preferred. The "dialkylsilylene group" is -Si(R z )2-(However, R z The group is an alkyl group (preferably having 1 to 10 carbon atoms). The "number-average molecular weight" of a compound is, 1 H-NMR and 19It is calculated by determining the number (average value) of oxyfluoroalkylene groups based on the terminal groups using F-NMR.

[0015] [Fluorine-containing ether compounds] The fluorine-containing ether compound of the present invention is a compound having a poly(oxyfluoroalkylene) chain, a reactive silyl group, and a group (A) represented by -NR-C(O)- (wherein R is a hydrogen atom, an alkyl group, or an alkyl group having a reactive silyl group), wherein the carbon atom of -C(O)- in group (A) is bonded to a carbon atom, and the poly(oxyfluoroalkylene) chain is located on the nitrogen atom side of group (A) (hereinafter also referred to as "specific fluorine-containing ether compound"). The inventors have found that when a specific fluorine-containing ether compound is used in which the nitrogen atom of group (A) is bonded to the poly(oxyfluoroalkylene) chain side, a surface layer with superior light resistance can be obtained compared to when a fluorine-containing ether compound is used in which the carbon atom of group (A) is bonded to the poly(oxyfluoroalkylene) chain side. Although the details of this reason are unclear, it is presumed that when a specific fluorine-containing ether compound is used, the visible light absorption range of group (A) shifts to the shorter wavelength side, resulting in higher visible light transmittance. This suppresses the decomposition of the surface layer and improves the light resistance of the surface layer.

[0016] Group (A) is represented by formula (A), where the carbon atom of -C(O)- in group (A) is bonded to another carbon atom, and the poly(oxyfluoroalkylene) chain is located on the nitrogen atom side of group (A). In other words, the poly(oxyfluoroalkylene) chain and group (A) are bonded directly or via a linking group, and the nitrogen atom of group (A) is located on the poly(oxyfluoroalkylene) chain side. -NR-C(O)- ···(A)

[0017] R is a hydrogen atom, an alkyl group, or an alkyl group having a reactive silyl group, and a hydrogen atom is preferred from the viewpoint of ease of production of specific fluorine-containing ether compounds. The number of carbon atoms in the alkyl group is preferably 1 to 10, and particularly preferably 1 to 6. The alkyl group may be linear or branched. The number of reactive silyl groups in the alkyl group having a reactive silyl group is preferably 1 to 3, and particularly preferably 1 to 2. The number of carbon atoms in the alkyl group having a reactive silyl group is preferably 1 to 20, and particularly preferably 1 to 15.

[0018] The number of groups (A) in the specific fluorine-containing ether compound is one or more, and preferably one to two. If there are multiple groups (A) in one molecule, the multiple groups (A) may be the same or different. From the viewpoint of the availability of raw materials and the ease of manufacturing specific fluorine-containing ether compounds, it is preferable that they be the same.

[0019] The specific fluorine-containing ether compound is preferably one that has a group (B) that bonds with the nitrogen atom of group (A) because it exhibits superior light resistance of the surface layer. -R 1 - ···(B)

[0020] R 1 This is an alkylene group having 1 to 10 carbon atoms and does not contain a fluorine atom. The number of carbon atoms in the alkylene group is preferably 1 to 6, and particularly preferably 1 to 4, from the viewpoint of having better light resistance of the surface layer, as well as the availability of raw materials and the ease of manufacturing the fluorine-containing ether compound. The alkylene group may be in a linear or branched chain configuration.

[0021] If a specific fluorine-containing ether compound has group (B), it is preferable that the number of groups (B) is the same as the number of groups (A). If there are multiple groups (B) in one molecule, the multiple groups (B) may be the same or different. From the viewpoint of the availability of raw materials and the ease of manufacturing the fluorine-containing ether compound, it is preferable that they be the same.

[0022] A poly(oxyfluoroalkylene) chain contains multiple units represented by formula (C). (OX) ···(C)

[0023] X is a fluoroalkylene group. The number of carbon atoms in the fluoroalkylene group is particularly preferably 1 to 6, as this provides superior light resistance to the surface layer. The fluoroalkylene group may be linear, branched, or cyclic. The number of fluorine atoms in the fluoroalkylene group is preferably 1 to 2 times the number of carbon atoms, and particularly preferably 1.7 to 2 times, from the standpoint of providing superior corrosion resistance to the surface layer. The fluoroalkylene group may be a group in which all hydrogen atoms in the fluoroalkylene group are replaced with fluorine atoms (perfluoroalkylene group), and the perfluoroalkylene group is preferred because it has better abrasion resistance for the surface layer.

[0024] Specific examples of (OX) include -OCHF-, -OCF2CHF-, -OCHFCF2-, -OCF2CH2-, -OCH2CF2-, -OCF2CF2CHF-, -OCHFCF2CF2-, -OCF2CF2CH2-, -OCH2CF2CF2-, -OCF2CF2CF2CH2-, -OCH2CF2CF2CF2CH2-, -OCF2CF2CF2CF2CH2-, -OCH2CF2CF2CF2CF2-, Examples include -OCF2CF2CF2CF2CF2CH2-, -OCH2CF2CF2CF2CF2CF2-, -OCF2-, -OCF2CF2-, -OCF2CF2CF2-, -OCF(CF3)CF2-, -OCF2CF2CF2CF2-, -OCF(CF3)CF2CF2-, -OCF(CF3)CF2CF2-, -OCF2CF2CF2CF2CF2CF2-, and -O-cycloC4F6-. Here, -cycloC4F6- refers to a perfluorocyclobutanediyl group, a specific example of which is the perfluorocyclobutane-1,2-diyl group.

[0025] The number of repetitions m of (OX) is an integer of 2 or more, more preferably an integer between 2 and 200, even more preferably an integer between 5 and 150, particularly preferably an integer between 5 and 100, and most preferably an integer between 10 and 50. (OX) m It may contain two or more types of (OX). The order in which the two or more types of (OX) are combined is not limited and may be random, alternating, or arranged in blocks. "Containing two or more types of (OX)" means that in a specific fluorine-containing ether compound, there are two or more types of (OX) with different numbers of carbon atoms, two or more types of (OX) with different numbers of hydrogen atoms, two or more types of (OX) with different positions of hydrogen atoms, and two or more types of (OX) with the same number of carbon atoms but different in the presence or absence of side chains or the type of side chains (number of side chains, number of carbon atoms in side chains, etc.). The poly(oxyfluoroalkylene) chain is preferably a poly(oxyfluoroalkylene) chain mainly composed of the oxyperfluoroalkylene group (OX) in order to create a film with excellent fingerprint stain removal properties. (OX) m In the poly(oxyfluoroalkylene) chain represented by , the ratio of the number of oxyperfluoroalkylene groups (OX) to the total number of (OX) groups is preferably 50-100%, more preferably 80-100%, and particularly preferably 90-100%. More preferably, the poly(oxyperfluoroalkylene) chain is a poly(oxyperfluoroalkylene) chain, and a poly(oxyperfluoroalkylene) chain having one or two oxyfluoroalkylene units, each having a hydrogen atom at one or both ends. For arrangements of two or more types of (OX), for example, {(OCF2) m21 (OCF2CF2) m22 The structure represented by} represents that m21 (OCF2) and m22 (OCF2CF2) are randomly arranged. Also, (OCF2CF2-OCF2CF2CF2CF2) m25 The structure represented by indicates that m25 (OCF2CF2) and m25 (OCF2CF2CF2CF2) are arranged alternately.

[0026] (OX) m (OCH ma F (2-ma) ) m11 ·(OC2H mb F (4-mb) ) m12 ·(OC3H mc F (6-mc) ) m13 ·(OC4H md F (8-md) ) m14 ·(OC5H me F (10-me) ) m15 ·(OC6H mf F (12-mf) ) m16 ·(O-cycloC4H mg F (6-mg) ) m17 This is preferable. Here, -cycloC4H mg F (6-mg) represents a fluorocyclobutane-diyl group, with a fluorocyclobutane-1,2-diyl group being preferred. ma is 0 or 1, mb is an integer from 0 to 3, mc is an integer from 0 to 5, md is an integer from 0 to 7, me is an integer from 0 to 9, mf is an integer from 0 to 11, and mg is an integer from 0 to 5. m11, m12, m13, m14, m15, m16, and m17 are each independent integers greater than or equal to 0, preferably 100 or less. m11+m12+m13+m14+m15+m16+m17 are integers greater than or equal to 2, more preferably integers between 2 and 200, more preferably integers between 5 and 150, even more preferably integers between 5 and 100, and particularly preferably integers between 10 and 50. In particular, m12 is preferably an integer of 2 or greater, and especially preferably an integer between 2 and 200. Also, C3H mc F (6-mc) C4H md F (8-md) , C5H me F (10-me) and C6H mf F (12-mf)It may be linear or branched, and a linear structure is preferred in terms of better abrasion resistance of the surface layer.

[0027] Note that the above formula represents the type and number of units, not the arrangement of units. That is, m11~m16 represent the number of units. For example, (OCH ma F (2-ma) ) m11 does not represent a block in which m11 (OCH ma F (2-ma) ) units are consecutive. Similarly, the order of description of (OCH ma F (2-ma) )~(O-cycloC4H mg F (6-mg) ) does not mean that they are arranged in that order. In the above formula, when two or more of m11~m17 are not zero (that is, when (OX) m1 is composed of two or more types of units), the arrangement of different units may be any of a random arrangement, an alternating arrangement, a block arrangement, and combinations of these arrangements. Furthermore, each of the above units may also be different when two or more of them are included. For example, when m11 is 2 or more, the plurality of (OCH ma F (2-ma) ) may be the same or different. (OX) m Preferably has the following structure. {(OCF2) m21 (OCF2CF2) m22}, (OCF2CF2) m23 , (OCF2CF2CF2) m24 , (OCF2CF2-OCF2CF2CF2CF2) m25 , (OCF2CF2CF2CF2CF2) m26 (OCF2) m27 , (OCF2CF2CF2CF2CF2) m26 (OCF2CF2) m27, (OCF2CF2CF2CF2CF2CF2) m26 (OCF2) m27 , (OCF2CF2CF2CF2CF2CF2) m26 (OCF2CF2) m27 , (OCF2CF2CF2CF2CF2-OCF2) m28 , (OCF2CF2CF2CF2CF2-OCF2CF2) m28 , (OCF2CF2CF2CF2CF2CF2-OCF2) m28 , (OCF2CF2CF2CF2CF2CF2-OCF2CF2 m28 , (OCF2-OCF2CF2CF2CF2CF2) m28 , (OCF2-OCF2CF2CF2CF2CF2CF2) m28 , (OCF2CF2-OCF2CF2CF2CF2CF2) m28 , (OCF2CF2-OCF2CF2CF2CF2CF2CF2) m28 . However, m21 is an integer greater than or equal to 1, m22 is an integer greater than or equal to 1, m21 + m22 is an integer between 2 and 500, m23 and m24 are each independently integers between 2 and 500, m25 is an integer between 1 and 250, m26 and m27 are each independently integers greater than or equal to 1, m26 + m27 is an integer between 2 and 500, and m28 is an integer between 1 and 250. (OX) m The following are preferred because they facilitate the production of specific fluorine-containing ether compounds. {(OCF2) m21 (OCF2CF2) m22}, (OCF2CF2CF2) m24 , (OCF2CF2)2{(OCF2) m21 (OCF2CF2) m22-2}, (OCF2CF2-OCF2CF2CF2CF2) m25-1 OCF2CF2, (OCF2CF2CF2CF2CF2-OCF2) m28 , (OCF2CF2CF2CF2CF2CF2-OCF2) m28 , (OCF2CF2-OCF2CF2CF2CF2CF2) m28-1 OCF2CF2, (OCF2CF2-OCF2CF2CF2CF2CF2CF2) m28-1 OCF2CF2. However, for m22-2, m25-1, and m28-1, the numbers m22, m25, and m28 are selected such that they are integers greater than or equal to 1. Especially {(OCF2) m21 (OCF2CF2) m22 In this case, m22 / m21 is preferably 0.1 to 10, more preferably 0.2 to 5.0, even more preferably 0.2 to 2.0, particularly preferably 0.2 to 1.5, and most preferably 0.2 to 0.85, from the standpoint of superior abrasion resistance and fingerprint stain removal of the surface layer.

[0028] Reactive silyl groups refer to hydrolyzable silyl groups and silanol groups (Si-OH). Specific examples of hydrolyzable silyl groups include those represented by formula (D) below, where L is a hydrolyzable group. Hydrolyzable silyl groups undergo hydrolysis to form silanol groups represented by Si-OH. These silanol groups then undergo dehydration condensation to form Si-O-Si bonds. Furthermore, silanol groups can form Si-O-Si bonds by undergoing dehydration condensation with silanol groups present on the surface of the substrate.

[0029] The reactive silyl group is preferably group (D). -Si(R 2 ) n L 3-n ...(D)

[0030] The number of groups (D) in the specific fluorine-containing ether compound is one or more, preferably two or more, more preferably 2 to 10, and particularly preferably 2 to 6, in terms of superior abrasion resistance of the surface layer. If there are multiple groups (D) in one molecule, the multiple groups (D) may be the same or different. From the viewpoint of the availability of raw materials and the ease of manufacturing the fluorine-containing ether compound, it is preferable that they be the same.

[0031] R 2 R is a monovalent hydrocarbon group, and a monovalent saturated hydrocarbon group is preferred. 2 The number of carbon atoms is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2.

[0032] L is a hydrolyzable group or a hydroxyl group. The hydrolyzable group L is a group that becomes a hydroxyl group through hydrolysis. That is, a hydrolyzable silyl group represented as Si-L becomes a silanol group represented as Si-OH through hydrolysis. The silanol groups further react with each other to form Si-O-Si bonds. In addition, silanol groups can undergo dehydration condensation reactions with silanol groups derived from oxides contained in the substrate to form Si-O-Si bonds.

[0033] Specific examples of the hydrolyzable group L include alkoxy groups, aryloxy groups, halogen atoms, acyl groups, acyloxy groups, and isocyanate groups (-NCO). For alkoxy groups, alkoxy groups having 1 to 4 carbon atoms are preferred. For aryloxy groups, aryloxy groups having 3 to 10 carbon atoms are preferred. However, the aryl group of the aryloxy group includes heteroaryl groups. For halogen atoms, chlorine atoms are preferred. For acyl groups, acyl groups having 1 to 6 carbon atoms are preferred. For acyloxy groups, acyloxy groups having 1 to 6 carbon atoms are preferred. As L, alkoxy groups having 1 to 4 carbon atoms and halogen atoms are preferred because they facilitate the production of fluorine-containing ether compounds. As L, alkoxy groups having 1 to 4 carbon atoms are preferred because they result in less outgassing during coating and provide better storage stability for fluorine-containing ether compounds. Ethoxy groups are particularly preferred when long-term storage stability of the fluorine-containing ether compound is required, and methoxy groups are particularly preferred when the reaction time after coating is short.

[0034] n is an integer between 0 and 2. n is preferably 0 or 1, and particularly preferably 0. The presence of multiple L values ​​strengthens the adhesion of the surface layer to the substrate. When n is 1 or less, the multiple L atoms present in one molecule may be the same or different. From the viewpoint of the availability of raw materials and the ease of manufacturing the fluorine-containing ether compound, it is preferable that they be the same. When n is 2, the multiple R atoms present in one molecule 2 They may be the same or different. However, from the standpoint of ease of obtaining raw materials and ease of manufacturing fluorine-containing ether compounds, it is preferable that they be the same.

[0035] The fluorine-containing ether compound is preferably structured such that the poly(oxyalkylene) chain is located on the nitrogen atom side of group (A) and the reactive silyl group is located on the carbon atom side of group (A), and is particularly preferably structured such that group (B) is located between group (A) and the poly(oxyalkylene) chain, in order to have superior light resistance and abrasion resistance of the surface layer.

[0036] The specific fluorine-containing ether compound is preferably compound (1) because it exhibits superior light resistance to the surface layer. Z[-R f -R 1 -NR-C(O)-Y-{Si(R 2 ) n L 3-n} g ] j ...(1)

[0037] R fR is a fluoroalkylene group. f Medium, R 1 The carbon atom bonded to it has at least one fluorine atom bonded to it. The number of carbon atoms in the fluoroalkylene group is preferably 1 to 6, and particularly preferably 1 to 3. The fluoroalkylene group may be linear or branched, but a linear configuration is preferred because it provides superior effects in the present invention. The fluoroalkylene group has one or more fluorine atoms, and since it has better light resistance of the surface layer, it is preferably 1 to 10, and particularly preferably 1 to 6. The fluoroalkylene group may also be a perfluoroalkylene group in which all hydrogen atoms in the fluoroalkylene group are replaced with fluorine atoms. R f Specific examples of these include -CF2CHF-, -CHFCF2-, -CH2CF2-, -CF2CF2CHF-, -CHFCF2CF2-, -CH2CF2CF2-, -CH2CF2CF2CF2-, -CH2CF2CF2CF2CF2-, -CH2CF2CF2CF2CF2CF2-, -CF2-, -CF2CF2-, -CF2CF2CF2-, -CF(CF3)CF2-, -CF2CF2CF2CF2-, -CF(CF3)CF2CF2-, -CF2CF2CF2CF2CF2-, and -CF2CF2CF2CF2CF2CF2-. If j is 2, then multiple R f They may be the same or different.

[0038] R 1 , R, R 2 The definitions of L and n are as described above. If j is 2, then multiple R 1 , R, R 2 L and n may be the same or different, respectively.

[0039] Y is an organic group with a (g+1) valency and has a carbon atom bonded to the carbon atom of -C(O)- in formula (1). Examples of organic groups include carbon atoms, hydrocarbon groups which may have heteroatoms, and organopolysiloxane residues, with hydrocarbon groups which may have heteroatoms being preferred. Furthermore, if Y is a hydrocarbon group having a heteroatom, it is preferable that the heteroatom is located between carbon atoms. That is, Y is {Si(R 2 ) n L 3-n} g It is preferable that Y is a hydrocarbon group having a carbon atom bonded to a silicon atom. Furthermore, Y is {Si(R 2 ) n L 3-n} g It is particularly preferable that the molecule has a trimethylene group at the terminal end that bonds with the silicon atom. Examples of hydrocarbon groups include saturated hydrocarbon groups and unsaturated hydrocarbon groups, and they may be linear, branched, or cyclic. Note that aromatic hydrocarbon groups are also included in the category of cyclic unsaturated hydrocarbon groups. The number of carbon atoms in the hydrocarbon group is preferably 1 to 20, and particularly preferably 1 to 10. Examples of heteroatoms include etheric oxygen atoms, nitrogen atoms, silicon atoms, and sulfur atoms, with etheric oxygen atoms, nitrogen atoms, and silicon atoms being preferred. If j is 2, then multiple Ys may be the same or different.

[0040] g is an integer greater than or equal to 1, and is preferably an integer between 2 and 4, more preferably 2 or 3, and particularly preferably 3, from the standpoint of having superior abrasion resistance of the surface layer. If g is 2 or more, multiple {Si(R 2 ) n L 3-n The} may be the same or different.

[0041] j is either 1 or 2. If j is 1, then Z is R f1 -(OX) m It is a monovalent group represented by -O-. If j is 2, then Z is -(OX) m It is a divalent group represented by -O-. The definitions of X and m are as described above. R f1 It is a perfluoroalkyl group. The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6, from the viewpoint of having better abrasion resistance of the surface layer. The perfluoroalkyl group may be linear, branched, or cyclic. Specific examples of perfluoroalkyl groups include CF3-, CF3CF2-, CF3CF2CF2-, CF3CF2CF2CF2-, CF3CF2CF2CF2CF2-, CF3CF2CF2CF2CF2CF2-, and CF3CF(CF3)-. CF3-, CF3CF2-, and CF3CF2CF2- are preferred because they offer superior water-repellent and oil-repellent properties to the surface layer.

[0042] -Y-{Si(R 2 ) n L 3-n} g The group represented is preferably the group (1-1A). -Q a -X 11 (-Q b -Si(R 2 ) n L 3-n ) h (-R 11 ) i ...(1-1A)

[0043] R 2 The definitions of L and n are as described above.

[0044] Q a These are single-bonded or divalent organic groups. Examples of divalent organic groups include divalent hydrocarbon groups, divalent heterocyclic groups, -O-, -S-, -SO2-, -C(O)-, and -Si(R a )2- and groups formed by combining two or more of these are examples. Here, R aThis is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group. d This is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms). Examples of the above-mentioned divalent hydrocarbon groups include divalent saturated hydrocarbon groups, divalent aromatic hydrocarbon groups, alkenylene groups, and alkylylene groups. Divalent saturated hydrocarbon groups may be linear, branched, or cyclic, and examples include alkylene groups. The number of carbon atoms in the divalent saturated hydrocarbon group is preferably 1 to 20. Divalent aromatic hydrocarbon groups are preferably 5 to 20 carbon atoms, and examples include phenylene groups. As for alkenylene groups, alkenylene groups with 2 to 20 carbon atoms are preferred, and as for alkylylene groups, alkylylene groups with 2 to 20 carbon atoms are preferred. Furthermore, groups formed by combining two or more of the above include, for example, -OC(O)-, an alkylene group having an etheric oxygen atom, an alkylene group having -OC(O)-, and an alkylene group -Si(R a )2-phenylene group-Si(R a )2 is one example.

[0045] X 11 This is a single bond, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom, or a 2-8 valent organopolysiloxane residue. However, Q a If it is a single bond, X 11 It is an alkylene group or a carbon atom. The alkylene group may have -O-, a sylphenylene skeleton, a divalent organopolysiloxane residue, or a dialkylsilylene group. The alkylene group may have multiple groups selected from the group consisting of -O-, a sylphenylene skeleton, a divalent organopolysiloxane residue, and a dialkylsilylene group. X 11 The number of carbon atoms in the alkylene group represented by is preferably 1 to 20, and particularly preferably 1 to 10. Examples of organopolysiloxane residues with 2-8 valencies include divalent organopolysiloxane residues and (w2+1) valencies, which will be discussed later.

[0046] Q b These are single-bonded or divalent organic groups. The definition of a divalent organic group is as described above in Q a This is synonymous with the definition explained earlier.

[0047] R 11 These are hydroxyl groups, alkyl groups, or fluoroalkyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1. The number of carbon atoms in the fluoroalkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1. The fluoroalkyl group may also be a perfluoroalkyl group in which all hydrogen atoms in the fluoroalkyl group are replaced with fluorine atoms.

[0048] X 11 If it is a single bond or an alkylene group, then h is 1 and i is 0. X 11 If it is a nitrogen atom, then h is an integer from 1 to 2, i is an integer from 0 to 1, and h+i=2 satisfies, X 11 If the atom is a carbon atom or a silicon atom, then h is an integer from 1 to 3, i is an integer from 0 to 2, and the condition h+i=3 is met. X 11 If the organopolysiloxane residue is 2-8 valent, then h is an integer from 1 to 7, i is an integer from 0 to 6, and so that h+i=1-7. (-Q b -Si(R 2 ) n L 3-n If there are two or more (-Q) then b -Si(R 2 ) n L 3-n ) may be the same or different. 11 If there are two or more (-R 11 ) may be the same or different.

[0049] The preferred group(s) are (1-1A-1) to (1-1A-6). -Qb1 -SiR 2 n L 3-n ...(1-1A-1) -Q a2 -N[-Q b2 -Si(R 2 ) n L 3-n ]2···(1-1A-2) -Q a3 -G(R g )[-Q b3 -Si(R 2 ) n L 3-n ]2···(1-1A-3) -Q a4 -(O) t4 -C[-(O) u4 -Q b4 -Si(R 2 ) n L 3-n ] 3-w1 (-R 11 ) w1 ...(1-1A-4) -Q a5 -4[-Q b5 -Si(R 2 ) n L 3-n ]3···(1-1A-5) -Q a6 -Z a [-Q b6 -Si(R 2 ) n L 3-n ] w2 ...(1-1A-6) Note that in equations (1-1A-1) to (1-1A-6), R 2 The definitions of L and n are as described above.

[0050] Q b1 This is an alkylene group. The alkylene group may have -O-, a sylphenylene skeleton, a divalent organopolysiloxane residue, or a dialkylsilylene group. The alkylene group may have multiple groups selected from the group consisting of -O-, a sylphenylene skeleton, a divalent organopolysiloxane residue, and a dialkylsilylene group. Furthermore, if the alkylene group has an -O-, a sylphenylene skeleton group, a divalent organopolysiloxane residue, or a dialkylsilylene group, these groups are present between carbon atoms.

[0051] Q b1 The number of carbon atoms in the alkylene group represented by is preferably 1 to 10, and particularly preferably 2 to 6.

[0052] Q b1 Examples include -CH2OCH2CH2CH2-, -CH2OCH2CH2OCH2CH2CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2OCH2CH2CH2Si(CH3)2OSi(CH3)2CH2CH2-, and -CH2CH2OCH2CH2CH2- positivity (where the right side is bonded to Si). Q b1 These groups make it easier to manufacture compounds.

[0053] Q a2 This refers to an alkylene group, -C(O)-, or a group having an etheric oxygen atom, -C(O)-, -C(O)O-, -OC(O)-, or -NH- between carbon atoms of an alkylene group having 2 or more carbon atoms. Q a2 The number of carbon atoms in the alkylene group represented by is preferably 1 to 10, and particularly preferably 1 to 6. Q a2 The number of carbon atoms in an alkylene group having 2 or more carbon atoms, represented by , which has an etheric oxygen atom, -C(O)-, -C(O)O-, -OC(O)-, or -NH- between carbon atoms, is preferably 2 to 10, and particularly preferably 2 to 6.

[0054] Q a2 From the standpoint of ease of compound production, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2OCH2CH2-, -CH2NHCH2CH2-, -CH2CH2OC(O)CH2CH2-, and -C(O)- are preferred (however, the right side is bonded to N).

[0055] Q b2This refers to an alkylene group, or an alkylene group having 2 or more carbon atoms with a divalent organopolysiloxane residue, an etheric oxygen atom, or an -NH- group between carbon atoms. Q b2 The number of carbon atoms in the alkylene group represented by is preferably 1 to 10, and particularly preferably 2 to 6. Q b2 The number of carbon atoms in the alkylene group having 2 or more carbon atoms represented by the formula, which has a divalent organopolysiloxane residue, an etheric oxygen atom, or an -NH- between carbon atoms, is preferably 2 to 10, and particularly preferably 2 to 6.

[0056] Q b2 As for the compounds, -CH2CH2CH2- and -CH2CH2OCH2CH2CH2- are preferred because they are easy to produce (however, the right side is bonded to Si).

[0057] 2 [-Q b2 -Si(R 2 ) n L 3-n ] may be the same or different.

[0058] Q a3 This is an alkylene group which may have a single bond or an etheric oxygen atom, and a single bond is preferred because it facilitates the production of compounds. However, if the alkylene group has an etheric oxygen atom, the etheric oxygen atom does not directly bond to the carbon atom of -C(O)- in formula (1) above. The alkylene group, which may have an etheric oxygen atom, preferably has 1 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.

[0059] G is a carbon or silicon atom. However, Q a3 If it is a single bond, then G is a carbon atom. R g R is a hydroxyl group or an alkyl group. g The number of carbon atoms in the alkyl group represented by is preferably 1 to 4. G(R g) are C(OH) or Si(R) because they are easy to manufacture. ga )(However, R ga is an alkyl group. The alkyl group preferably has 1 to 10 carbon atoms, and a methyl group is particularly preferred.

[0060] Q b3 This refers to an alkylene group, or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms of an alkylene group having 2 or more carbon atoms. Q b3 The number of carbon atoms in the alkylene group represented by is preferably 1 to 10, and particularly preferably 2 to 6. Q b3 The number of carbon atoms in the alkylene group having 2 or more carbon atoms, represented by the formula, which has an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms, is preferably 2 to 10, and particularly preferably 2 to 6. Q b3 As for the ease of compound production, -CH2CH2-, -CH2CH2CH2-, and -CH2CH2CH2CH2CH2CH2CH2CH2- GMP are preferred.

[0061] 2 [-Q b3 -Si(R 2 ) n L 3-n ] may be the same or different.

[0062] Q a4 is an alkylene group which may have a single bond or an etheric oxygen atom. However, when t4 is 1, Q a4 This is an alkylene group which may have an etheric oxygen atom. When the alkylene group has an etheric oxygen atom, the etheric oxygen atom does not directly bond with the carbon atom of -C(O)- in formula (1) above. The alkylene group, which may have an etheric oxygen atom, preferably has 1 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms. t4 is 0 or 1 (however Q a4 The value is 0 if it is a single bond. -Qa4 -(O) t4 As for the components, single bonds, -CH2-, and -CH2CH2- are preferred because they facilitate the production of compounds.

[0063] Q b4 This is an alkylene group, and the alkylene group may have -O-, a sylphenylene skeleton group, a divalent organopolysiloxane residue, or a dialkylsilylene group. Furthermore, if the alkylene group has an -O- or sylphenylene skeleton group, it is preferable that the -O- or sylphenylene skeleton group is present between carbon atoms. Also, if the alkylene group has a dialkylsilylene group or a divalent organopolysiloxane residue, it is preferable that the -O- or sylphenylene skeleton group is present between carbon atoms or (O) u4 It is preferable to have these groups at the terminal end that binds to the other end. Q b4 The number of carbon atoms in the alkylene group represented by is preferably 1 to 10, and particularly preferably 2 to 6.

[0064] u4 is either 0 or 1. -(O) u4 -Q b4 -As for the compounds, -CH2CH2-, -CH2CH2CH2-, -CH2OCH2CH2CH2-, -CH2OCH2CH2CH2CH2CH2-, -OCH2CH2CH2-, -OSi(CH3)2CH2CH2CH2-, -OSi(CH3)2OSi(CH3)2CH2CH2CH2-, and -CH2CH2CH2Si(CH3)2PhSi(CH3)2CH2CH2- are preferred because they are easy to manufacture (however, the right side is bonded to Si).

[0065] w1 is an integer between 0 and 2, preferably 0 or 1, and particularly preferably 0. [-(O) u4 -Q b4 -Si(R 2 ) n L 3-n If there are two or more ], then there are two or more [-(O) u4 -Q b4 -Si(R 2 ) n L3-n ] may be the same or different. R 11 If there are two or more (-R 11 ) may be the same or different. 11 The definition is as stated above.

[0066] Q a5 This is an alkylene group which may have an etheric oxygen atom. However, if the alkylene group has an etheric oxygen atom, the etheric oxygen atom does not directly bond with the carbon atom of -C(O)- in formula (1) above. The alkylene group, which may have an etheric oxygen atom, preferably has 1 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms. Q a5 From the standpoint of ease of compound production, -CH2OCH2CH2CH2-, -CH2OCH2CH2OCH2CH2CH2-, -CH2CH2-, and -CH2CH2CH2- are preferred (however, the right side is bonded to Si).

[0067] Q b5 This refers to an alkylene group, or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms of an alkylene group having 2 or more carbon atoms. Q b5 The number of carbon atoms in the alkylene group represented by is preferably 1 to 10, and particularly preferably 2 to 6. Q b5 The number of carbon atoms in the alkylene group having 2 or more carbon atoms, represented by the formula, which has an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms, is preferably 2 to 10, and particularly preferably 2 to 6. Q b5 As for the compounds, -CH2CH2CH2- and -CH2CH2OCH2CH2CH2- are preferred because they are easy to produce (however, the right side is bonded to Si).

[0068] 3 [-Q b5 -Si(R 2 ) n L 3-nmay be the same or different.

[0069] Q a6 is an alkylene group which may have an ether oxygen atom. However, when the alkylene group has an ether oxygen atom, the ether oxygen atom is not directly bonded to the carbon atom of -C(O)- in the above formula (1). The number of carbon atoms of the alkylene group which may have an ether oxygen atom is preferably 1 to 10, particularly preferably 2 to 6. Q a6 From the viewpoint of ease of producing the compound, -CH2OCH2CH2CH2-, -CH2OCH2CH2OCH2CH2CH2-, -CH2CH2-, -CH2CH2CH2- are preferable (however, the right side is bonded to Z a .).

[0070] Z a is a (w2 + 1)-valent organopolysiloxane residue. w2 is an integer of 2 to 7. Examples of the (w2 + 1)-valent organopolysiloxane residue include the following groups. However, R in the following formula is as described above. a is as described above.

[0071] [Chemical formula]

[0072] Q b6 is an alkylene group or a group having an ether oxygen atom or a divalent organopolysiloxane residue between carbon atoms of an alkylene group having 2 or more carbon atoms. Q b6 The number of carbon atoms of the alkylene group represented by is preferably 1 to 10, particularly preferably 2 to 6. Q b6 The number of carbon atoms of the group having an ether oxygen atom or a divalent organopolysiloxane residue between carbon atoms of an alkylene group having 2 or more carbon atoms represented by is preferably 2 to 10, particularly preferably 2 to 6. Q b6From the viewpoint of ease of compound production, -CH2CH2- and -CH2CH2CH2- are preferred.

[0073] w2 of [-Q b6 -Si(R 2 ) n L 3-n may be the same or different.

[0074] In the following, the specific examples of the partial structure represented by R f -R 1 -NR-C(O)-Y-{Si(R 2 ) n L 3-n}<00​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​

[0079]

Chem.

[0080]

Chem.

Chem.

[0081] As an example of a preferred embodiment of compound (1), Z in the above formula (1) is R f1 -(OX) m -O-, a monovalent group, X is a fluoroalkylene group having 1 to 6 carbon atoms, and (OX) m includes two or more (OX) (hereinafter also referred to as "compound (1-X)"). By using compound (1-X), a surface layer with excellent abrasion resistance and water / oil repellency can be obtained.

[0082] As another example of a preferred embodiment of compound (1), Z in the above formula (1) is -(OX) m -O-, a divalent group, X is a fluoroalkylene group having 1 to 6 carbon atoms, and (OX) m includes two or more (OX) (hereinafter also referred to as "compound (1-Y)"). By using compound (1-Y), a surface layer with excellent abrasion resistance and water / oil repellency can be obtained.

[0083] Compound (1-X) and compound (1-Y) preferably have a unit (hereinafter also referred to as "unit α") in which X in (OX) of formula (1) is a perfluoroalkylene group having 5 or 6 carbon atoms, and a unit β (hereinafter also referred to as "unit β") in which X in (OX) of formula (1) is a perfluoroalkylene group having 1 to 4 carbon atoms, from the viewpoint of obtaining a surface layer with excellent abrasion resistance and water / oil repellency. The unit α is preferably at least one of -OCF2CF2CF2CF2CF2- and -OCF2CF2CF2CF2CF2CF2-, as this provides a surface layer with superior abrasion resistance and water / oil repellency. The unit β is preferably at least one of -OCF2- and -OCF2CF2-, as this provides a surface layer with superior abrasion resistance and water / oil repellency. When compounds (1-X) and (1-Y) have units α and β, the ratio of the number of repeating units of unit α to the total number of repeating units of unit β (number of repeating units of unit α / (number of repeating units of unit α + number of repeating units of unit β)) is preferably 0.002 to 0.5, and particularly preferably 0.005 to 0.2. By using compounds in which the above ratio falls within the above range, a surface layer with superior abrasion resistance and water / oil repellency can be obtained. The number of repeating units α is preferably 1, as this yields a surface layer with superior abrasion resistance and water / oil repellency.

[0084] If compound (1-X) has units α and β, then all positions of unit α correspond to R represented by Z in formula (1) above. f1 -(OX) m -O-'s R f1 Counting from the side, the [0.5 × m]th is R f1 It is preferable that it be on the side. That is, R f1 It is preferable that the element is located between the 1st and 0.5 × mth elements from the side. However, if m is an odd number, it must be a natural number not exceeding 0.5 times m. Note that the [0.5 × m]th m represents the number of m in (OX)m.

[0085] [Composition] The composition of the present invention (hereinafter also referred to as "Composition (X)") is a composition containing two or more of the above-mentioned specific fluorine-containing ether compounds, or a composition containing one or more of the above-mentioned specific fluorine-containing ether compounds and a fluorine-containing ether compound other than the above-mentioned specific fluorine-containing ether compounds. Since Composition (X) contains one or more specific fluorine-containing ether compounds, it can form a surface layer with excellent light resistance.

[0086] Composition (X) may also contain a specific fluorine-containing ether compound having one group (A) (hereinafter also referred to as "specific fluorine-containing ether compound (A1)") and a specific fluorine-containing ether compound having two groups (A) (hereinafter also referred to as "specific fluorine-containing ether compound (A2)"), in order to provide superior light resistance of the surface layer. The specific fluorine-containing ether compound (A1) and the specific fluorine-containing ether compound (A2) may be used individually or in combination of two or more types.

[0087] A specific example of the specified fluorine-containing ether compound (A1) is the specified fluorine-containing ether compound in formula (1) above where j is 1. Furthermore, a specific example of the specified fluorine-containing ether compound (A2) is the specified fluorine-containing ether compound in formula (1) above, where j is 2.

[0088] This composition (X) may contain fluorine-containing ether compounds other than the specified fluorine-containing ether compound (hereinafter also referred to as "other fluorine-containing ether compounds"). Other fluorine-containing ether compounds include those having a poly(oxyfluoroalkylene) chain and a reactive silyl group, and even if they have the aforementioned group (A), they have a structure in which the nitrogen atom of group (A) is not located on the poly(oxyfluoroalkylene) chain side. Other fluorine-containing ether compounds may be used individually or in combination of two or more.

[0089] Of the other fluorine-containing ether compounds, compound (2) is preferred because it provides a surface layer with superior abrasion resistance and water / oil repellency. [A 2 -(OX 2 ) m2 -] j2 Z 2 [-Si(R 3 ) n2 L 2 3-n2 ] g2 ...(2)

[0090] R in equation (2) 3 , L 2 The definitions of and n2 are given by R in equation (1), respectively. 2 , is synonymous with L and n. X in equation (2) 2 The definitions of and m2 are given by R represented by Z in equation (1), respectively. f1 -(OX) m This is equivalent to X and m in -O-.

[0091] A 2 is a perfluoroalkyl group or -Q 2 [-Si(R 3 ) n2 L 2 3-n2 ] k2 That is the case. The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 6, and particularly preferably 1 to 3, from the viewpoint of having better abrasion resistance of the film. The perfluoroalkyl group may be linear or branched. However, A is -Q 2 [-Si(R 3 ) n2 L 2 3-n2 ] k2 If so, then j2 is 1.

[0092] Examples of perfluoroalkyl groups include CF3-, CF3CF2-, CF3CF2CF2-, CF3CF2CF2CF2-, CF3CF2CF2CF2CF2-, CF3CF2CF2CF2CF2CF2-, and CF3CF(CF3)-. As perfluoroalkyl groups, CF3-, CF3CF2-, and CF3CF2CF2- are preferred because they exhibit superior water-repellent and oil-repellent properties on the surface layer.

[0093] Q 2 Q is a linking group with (k2+1) valence. As will be explained later, k2 is an integer from 1 to 10. Therefore, Q 2Examples include 2- to 11-valent linking groups. Q 2 The group can be any group that does not impair the effects of the present invention, and examples include an alkylene group which may have an etheric oxygen atom or a divalent organopolysiloxane residue, a carbon atom, a nitrogen atom, a silicon atom, or a divalent to octavalent organopolysiloxane residue. However, Q 2 If it contains a group (A) represented by -NR-C(O)- (wherein R is a hydrogen atom or an alkyl group), the nitrogen atom of group (A) is -[-Si(R 3 ) n2 L 2 3-n2 ] k2 It connects to the side.

[0094] Z 2 This is a (j2+g2) valence linking group. Z 2 The group can be any group that does not impair the effects of the present invention, and examples include an alkylene group which may have an etheric oxygen atom or a divalent organopolysiloxane residue, a carbon atom, a nitrogen atom, a silicon atom, or a divalent to octavalent organopolysiloxane residue. However, Z 2 If it contains a group (A) represented by -NR-C(O)- (wherein R is a hydrogen atom or an alkyl group), the nitrogen atom of group (A) is -[-Si(R 3 ) n2 L 2 3-n2 ] g2 It connects to the side.

[0095] j2 is an integer greater than or equal to 1, and is preferably an integer from 1 to 5 in that it provides superior water-repellent and oil-repellent properties to the surface layer, and is particularly preferably 1 in that it facilitates the production of compound (3). g2 is an integer greater than or equal to 1, and is preferably an integer between 2 and 4, more preferably 2 or 3, and particularly preferably 3, from the standpoint of having superior abrasion resistance of the surface layer.

[0096] Other specific examples of fluorine-containing ether compounds include those described in the following literature. Perfluoropolyether-modified aminosilanes described in Japanese Patent Publication No. 11-029585 and Japanese Patent Publication No. 2000-327772, Silicon-containing organic fluorine polymer as described in Japanese Patent Publication No. 2874715, Organosilicon compounds as described in Japanese Patent Publication No. 2000-144097, Fluorinated siloxane as described in Japanese Patent Publication No. 2002-506887, Organic silicone compounds as described in Japanese Patent Publication No. 2008-534696, Fluorine-modified hydrogen-containing polymer as described in Japanese Patent Publication No. 4138936, The compounds described in U.S. Patent Application Publication No. 2010 / 0129672, International Publication No. 2014 / 126064, and Japanese Patent Publication No. 2014-070163, Organosilicon compounds described in International Publication No. 2011 / 060047 and International Publication No. 2011 / 059430, Fluorine-containing organosilane compounds described in International Publication No. 2012 / 064649, Fluoroxyalkylene group-containing polymers as described in Japanese Patent Publication No. 2012-72272, International Publication Nos. 2013 / 042732, 2013 / 121984, 2013 / 121985, 2013 / 121986, 2014 / 163004, Japanese Patent Publication No. 2014-080473, 2015 / 087902, 2017 / 038830, 2017 / 038832, and 201 Fluorine-containing ether compounds described in International Publication No. 7 / 187775, International Publication No. 2018 / 216630, International Publication No. 2019 / 039186, International Publication No. 2019 / 039226, International Publication No. 2019 / 039341, International Publication No. 2019 / 044479, International Publication No. 2019 / 049753, International Publication No. 2019 / 163282 and Japanese Patent Publication No. 2019-044158, Perfluoro(poly)ether-containing silane compounds as described in Japanese Patent Publication No. 2014-218639, International Publication No. 2017 / 022437, International Publication No. 2018 / 079743, and International Publication No. 2018 / 143433. Perfluoro(poly)ether group-containing silane compounds described in International Publication No. 2018 / 169002, Fluoro(poly)ether group-containing silane compounds described in International Publication No. 2019 / 151442, (Poly)ether group-containing silane compounds described in International Publication No. 2019 / 151445, perfluoropolyether group-containing compounds described in International Publication No. 2019 / 098230, Fluoropolyether group-containing polymer-modified silanes as described in Japanese Patent Publication No. 2015-199906, Japanese Patent Publication No. 2016-204656, Japanese Patent Publication No. 2016-210854, and Japanese Patent Publication No. 2016-222859 Fluorine-containing compounds as described in International Publication No. 2019 / 039083 and International Publication No. 2019 / 049754.

[0097] Other commercially available fluorine-containing ether compounds include the KY-100 series (KY-178, KY-185, KY-195, etc.) from Shin-Etsu Chemical Co., Ltd., Afluid® S550 from AGC Inc., and Optool® DSX, Optool® AES, Optool® UF503, and Optool® UD509 from Daikin Industries, Ltd.

[0098] The content of the specific fluorine-containing ether compound is preferably 50 to 100% by mass, and more preferably 80 to 100% by mass, based on the total mass of the composition (X). When the composition (X) contains a specific fluorine-containing ether compound (A1) and a specific fluorine-containing ether compound (A2), the mass ratio of the content of the specific fluorine-containing ether compound (A2) to the content of the specific fluorine-containing ether compound (A1) (specific fluorine-containing ether compound (A2) / specific fluorine-containing ether compound (A1)) is preferably greater than 0 and 100 or less, and particularly preferably greater than 0 and 20 or less. If the composition (X) contains other fluorine-containing ether compounds, the mass ratio of the content of other fluorine-containing ether compounds to the content of the specific fluorine-containing ether compound (other fluorine-containing ether compound / specific fluorine-containing ether compound) is preferably greater than 0 and 50 or less, and particularly preferably greater than 0 and 10 or less.

[0099] <Composition for coatings> The specific fluorine-containing ether compound and composition (X) can be used alone to form a surface layer on a substrate (dry coating method described later), or a composition containing other components can be used (dry coating method or wet coating method described later). The latter coating composition containing other components will also be referred to as composition (Y) below.

[0100] Examples of composition (Y) include a specific fluorine-containing ether compound or a composition (X) and a liquid medium. Specific examples of the liquid medium include water and organic solvents. The liquid medium preferably contains an organic solvent, and more preferably contains an organic solvent with a boiling point of 35 to 250°C, in terms of excellent coating properties. Here, the boiling point refers to the standard boiling point. Specific examples of organic solvents include fluorinated organic solvents and non-fluorinated organic solvents, with fluorinated organic solvents being preferred due to their superior solubility. Organic solvents may be used individually or in combination of two or more.

[0101] Specific examples of fluorinated organic solvents include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols. Fluorinated alkanes are preferably compounds with 4 to 8 carbon atoms, for example, C6F 13 H (AC-2000: Product name, manufactured by AGC Corporation), C6F 13 Examples include C2H5 (AC-6000: product name, manufactured by AGC) and C2F5CHFCHFCF3 (Bartrell: product name, manufactured by DuPont). Specific examples of fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, 1,3-bis(trifluoromethyl)benzene, and 1,4-bis(trifluoromethyl)benzene. Fluoroalkyl ethers are preferably compounds having 4 to 12 carbon atoms, such as CF3CH2OCF2CF2H (AE-3000: product name, manufactured by AGC), C4F9OCH3 (Novec-7100: product name, manufactured by 3M), C4F9OC2H5 (Novec-7200: product name, manufactured by 3M), and C2F5CF(OCH3)C3F7 (Novec-7300: product name, manufactured by 3M). Specific examples of fluorinated alkylamines include perfluorotripropylamine and perfluorotributylamine. Specific examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.

[0102] As nonfluorinated organic solvents, compounds consisting only of hydrogen atoms and carbon atoms, and compounds consisting only of hydrogen atoms, carbon atoms, and oxygen atoms are preferred. Specifically, examples include hydrocarbon organic solvents, ketone organic solvents, ether organic solvents, ester organic solvents, and alcohol organic solvents. Specific examples of hydrocarbon organic solvents include hexane, heptane, and cyclohexane. Specific examples of ketone organic solvents include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Specific examples of ether-based organic solvents include diethyl ether, tetrahydrofuran, and tetraethylene glycol dimethyl ether. Specific examples of ester-based organic solvents include ethyl acetate and butyl acetate. Specific examples of alcoholic organic solvents include isopropyl alcohol, ethanol, and n-butanol.

[0103] If composition (Y) contains a liquid medium, the content of the liquid medium is preferably 70 to 99.99% by mass, and particularly preferably 80 to 99.9% by mass, relative to the total mass of the specific fluorine-containing ether compound or composition (X).

[0104] Composition (Y) may contain components other than the liquid medium described above, as long as they do not impair the effects of the present invention. Other components include by-products generated during the manufacturing process of specific fluorine-containing ether compounds and other fluorine-containing ether compounds, as well as unreacted raw materials and other unavoidable compounds in the manufacturing process. Other additives include acid catalysts and basic catalysts that promote the hydrolysis and condensation reactions of hydrolyzable silyl groups. Specific examples of acid catalysts include hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, and p-toluenesulfonic acid. Specific examples of basic catalysts include sodium hydroxide, potassium hydroxide, and ammonia. The content of other components is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and particularly preferably 0 to 1% by mass, relative to the content of the specific fluorine-containing ether compound in composition (Y).

[0105] [Goods] The article of the present invention comprises a base material and a surface layer formed on the base material from the above-mentioned specific fluorine-containing ether compound or composition (X).

[0106] The surface layer contains compounds obtained by hydrolysis and condensation reactions of specific fluorine-containing ether compounds. The thickness of the surface layer is preferably 1 to 100 nm, and particularly preferably 1 to 50 nm. If the thickness of the surface layer is above the lower limit, the effect of the surface layer is sufficiently obtained. If the thickness of the surface layer is below the upper limit, the utilization efficiency is high. The thickness of the surface layer can be calculated using an X-ray diffractometer for thin-film analysis. The interference pattern of reflected X-rays is obtained by the X-ray reflectivity method (XRR), and the vibration period of this interference pattern is used to determine the thickness.

[0107] Preferred substrates include those that may come into contact with other articles (e.g., styluses) or human fingers during use, those that may be held by human fingers during operation, and / or those that may be placed on other articles (e.g., stands). Since water-repellent and oil-repellent properties can be imparted, substrates for which water-repellent and oil-repellent properties are required are particularly preferred. Specific examples of substrate materials include metals, resins, glass, sapphires, ceramics, stones, and composite materials thereof. Glass may be chemically strengthened. The substrate is preferably a substrate for touch panels and a substrate for displays, with the substrate for touch panels being particularly preferred. The substrate for touch panels is preferably light-transmitting. "Light-transmitting" means that the normal incidence visible light transmittance, in accordance with JIS R3106:1998 (ISO 9050:1990), is 25% or more. Glass and transparent resin are preferred materials for the substrate for touch panels. Examples of substrates include: glass or resin used in building materials, decorative building materials, interior goods, transportation equipment (e.g., automobiles), signs and notice boards, drinking utensils and tableware, aquariums, ornamental equipment (e.g., frames, boxes), laboratory equipment, furniture, and art, sports, and games. Glass or resin used in the exterior parts (excluding display parts) of devices such as mobile phones (e.g., smartphones), personal digital assistants, game consoles, and remote controls is also preferred as a substrate. The substrate may be in the form of a plate or a film.

[0108] The surface layer may be formed directly on the surface of the substrate, or it may be formed on the substrate via another film formed on the surface of the substrate. Specific examples of the above-mentioned other film include a base film formed on the surface of the substrate by pre-treating the substrate with compounds described in paragraphs 0089-0095 of International Publication No. 2011 / 016458 or SiO2, etc.

[0109] The above-mentioned articles can be manufactured, for example, by the following method: A method for obtaining the above-mentioned article by treating the surface of a substrate by a dry coating method using a specific fluorine-containing ether compound or the present composition (X). A method for obtaining the above-mentioned article by applying a composition (Y) containing a liquid medium to the surface of a substrate by a wet coating method and drying it. In addition, in the wet coating method, a specific fluorine-containing ether compound may be hydrolyzed in advance using an acid catalyst or a basic catalyst, and a composition containing the hydrolyzed compound and a liquid medium may be used.

[0110] Specific examples of dry coating methods include vacuum deposition, CVD, and sputtering. Among these, vacuum deposition is preferred because it suppresses the decomposition of specific fluorine-containing ether compounds and because of the simplicity of the equipment. In vacuum deposition, a pellet-like material may be used, which is made by impregnating a porous metal body such as iron or steel with a composition (Y) containing a liquid medium and then drying it. Specific examples of wet coating methods include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, cast coating, Langmuir-Bludget coating, and gravure coating. [Examples]

[0111] The present invention will be described in detail below with reference to examples. However, the present invention is not limited to these examples. The amounts of each component are given on a mass basis. Of Examples 1 to 16, Examples 1 to 12 are examples, and Examples 13 to 16 are comparative examples.

[0112] [Evaluation Method] (Method for measuring water contact angle) The contact angle (water contact angle) of approximately 2 μL of distilled water placed on the surface of the surface layer was measured using a contact angle measuring device (DM-500: product name, manufactured by Kyowa Interface Science Co., Ltd.). Measurements were taken at five different locations on the surface of the surface layer, and the average value was calculated to determine the initial contact angle. The 2θ method was used to calculate the contact angle. The judgment criteria are shown below. ○ (Good): The initial contact angle is 100 degrees or more. × (Defective): The initial contact angle is less than 100 degrees.

[0113] (Test method for lightfastness) The surface layer was irradiated with light (650 W / m2, 300-700 nm) for 2,000 hours at a black panel temperature of 63°C using a benchtop xenon arc lamp type accelerated lightfastness tester (SUNTEST XLS+: product name, manufactured by Toyo Seiki Co., Ltd.), and then the water contact angle of the surface layer was measured using the method described above. The smaller the decrease in the water contact angle after accelerated lightfastness testing, the less the performance degradation due to light, and the better the lightfastness of the surface layer. The evaluation criteria are as follows. ○ (Good): The change in water contact angle after accelerated lightfastness testing is 5 degrees or less. × (Defective): The change in water contact angle after accelerated lightfastness testing is more than 5 degrees.

[0114] [Synthesis Example 1] (Synthesis Example 1-1) Compound (A-1) was obtained according to the method described in Example 2 of the Examples in International Publication No. 2013 / 121984 (specifically, Example 2-3). CF3(OCF2CF2OCF2CF2CF2CF2) m OCF2CF2OCF2CF2CF2-C(=O)OCH3...(A-1) Average value of m: 13

[0115] (Synthesis Example 1-2) 15 g of compound (A-1), 50 g of Asahiclean AK-225 (product name, manufactured by AGC Inc.), and 7.5 g of 2.0 M ammonia-methanol solution were placed in a 100 mL pressure reactor and stirred at room temperature for 6 hours. After that, the solvent was removed by distillation to obtain 14.8 g of the target compound (A-2) (yield 99%). CF3(OCF2CF2OCF2CF2CF2CF2) m OCF2CF2OCF2CF2CF2-C(=O)NH2···(A-2)

[0116] NMR spectrum of compound (A-2): 19 F-NMR: -55(3F), -82(53F), -87(53F), -90(2F), -119(2F), -123~-128(55F)

[0117] (Synthesis Examples 1-3) 15 g of compound (A-2), 75 g of AK-225, and 30 g of diethyl ether were added to a 300 mL round-bottom flask and stirred under ice. Then, 0.31 g of lithium aluminum hydride was slowly added and stirred at room temperature for 20 hours. After that, 0.3 mL of saturated sodium sulfate solution was added and the precipitated solid was removed by Celite filtration. The obtained filtrate was concentrated and purified by silica gel column chromatography to obtain 6.8 g of the target compound (A-3) (yield 45%). CF3(OCF2CF2OCF2CF2CF2CF2) m OCF2CF2OCF2CF2CF2-CH2NH2···(A-3)

[0118] NMR spectrum of compound (A-3): 1 H-NMR: 3.2(2H) 19 F-NMR: -55(3F), -82(59F), -87(59F), -90(2F), -122(2F), -123~-128(61F)

[0119] (Synthesis Examples 1-4) 0.2 g of HO(C=O)C(CH2CH=CH2)3, 10 mL of dichloromethane, and 0.2 mL of oxalyl chloride were added to a 50 mL round-bottom flask and stirred under ice cooling. Then, 0.0118 g of DMF (N,N-dimethylformamide) was added. After stirring at room temperature for 3 hours, the mixture was concentrated to obtain 0.18 g of Cl(C=O)C(CH2CH=CH2)3. In a separate 50 mL round-bottom flask, 3.0 g of compound (A-3) and 0.35 mL of triethylamine were added, and the above-mentioned Cl(C=O)C(CH2CH=CH2)3 and 2 mL of 1,3-bistrifluoromethylbenzene were added. The mixture was stirred for 1 hour, and the solvent was removed by distillation. The resulting crude product was purified by silica gel column chromatography to obtain 1.7 g of compound (A-4) (yield 54%). CF3(OCF2CF2OCF2CF2CF2CF2) mOCF2CF2OCF2CF2CF2-CH2NH(C=O)C(CH2CH=CH2)3...(A-4)

[0120] NMR spectrum of compound (A-4): 1 H-NMR:6.1(1H), 5.8(3H), 5.2(6H), 4.1(2H), 2.4(6H) 19 F-NMR: -55(3F), -82(49F), -87(51F), -120(2F), -126(49F)

[0121] (Synthesis Examples 1-5) In a nitrogen-purged 50 mL round-bottom flask, 1.0 g of compound (A-4), 0.003 g of xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass), 0.0009 g of aniline, and 1.0 g of AC-6000 (product name, manufactured by AGC) were added. Then, 0.11 g of trimethoxysilane was added and the mixture was stirred at 40°C for 4 hours. Subsequently, the same amount of xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass), aniline, and AC-6000 was added and the mixture was stirred for 7 hours. After the solvent was removed by distillation, 1.1 g of compound (1-A) was obtained (yield 95%). CF3(OCF2CF2OCF2CF2CF2CF2) m OCF2CF2OCF2CF2CF2-CH2NH(C=O)C[CH2CH2CH2Si(OCH3)3]3...(1-A)

[0122] NMR spectrum of compound (1-A): 1 H-NMR:6.0(1H), 4.1(2H), 3.6(27H), 1.7(6H), 1.4(6H), 0.7(6H) 19 F-NMR: -55(3F), -82(49F), -87(51F), -120(2F), -126(49F) m was approximately 13.

[0123] [Synthesis Example 2] Compound (1-B) was synthesized using the same method as in Synthesis Example 1, except that HO(C=O)C(CH2CH=CH2)3 was changed to HO(C=O)CH(CH2CH=CH2)2. CF3(OCF2CF2OCF2CF2CF2CF2) m OCF2CF2OCF2CF2CF2-CH2NH(C=O)CH[CH2CH2CH2Si(OCH3)3]2...(1-B) m was approximately 13.

[0124] [Synthesis Example 3] Compound (C-1) was obtained according to the method described in Example 1 of the Examples in International Publication No. 2017 / 038830 (specifically, Examples 1-1 to 1-4). CF3CF2CF2(OCF2CF2)(OCF2CF2){(OCF2) n (OCF2CF2) p}OCF2C(=O)OCH3···(C-1) n was approximately 21 and p was approximately 20.

[0125] (Synthesis Example 3-1) Compound (1-C) was synthesized using the same method as in Synthesis Example 1, except that compound (A-1) was replaced with compound (C-1). CF3CF2CF2(OCF2CF2)(OCF2CF2){(OCF2) n (OCF2CF2) p}OCF2CH2NH(C=O)C[CH2CH2CH2Si(OCH3)3]3...(1-C) n was approximately 21 and p was approximately 20.

[0126] [Synthesis Example 4] Compound (1-D) was synthesized using the same method as in Synthesis Example 2, except that HO(C=O)C(CH2CH=CH2)3 was changed to HO(C=O)CH(CH2CH=CH2)2. CF3CF2CF2(OCF2CF2)(OCF2CF2){(OCF2) n (OCF2CF2) p}OCF2CH2NH(C=O)CH[CH2CH2CH2Si(OCH3)3]2···(1-D) n was approximately 21 and p was approximately 20.

[0127] [Synthesis Example 5] (Synthesis Example 5-1) In a 200 mL round-bottom flask, 16.2 g of HO-CH2CF2CF2CH2-OH and 13.8 g of potassium carbonate were added and stirred at 120°C. Then, 278 g of CF2=CFO-CF2CF2CF2CH2OH obtained according to the method described in Example 1-1 of International Publication No. 2013 / 121984 was added and stirred at 120°C for 2 hours. The mixture was then cooled to 25°C and heated in AC-2000 (product name, manufactured by AGC, C6F). 13 50 g each of H and hydrochloric acid were added, and the mixture was separated to concentrate the organic phase. The resulting crude reaction solution was purified by column chromatography to obtain 117.7 g of compound (E-2) (40% yield).

[0128] [ka] (E-2)

[0129] NMR spectrum of compound (E-2): 1 ¹H-NMR (300.4 MHz, solvent: CDCl3, reference: tetramethylsilane (TMS)) δ (ppm): 6.0 (12H), 4.6 (20H), 4.2 (4H), 4.1 (4H). 19 F-NMR (282.7 MHz, solvent: CDCl3, reference: CFCl3) δ (ppm): -85 (24F), -90 (24F), -120 (20F), -122 (4F), -123 (4F), -126 (24F), -144 (12F) The average value of the number of units m+n was 10.

[0130] (Synthesis Example 5-2) 20 g of compound (E-2), 2.4 g of sodium fluoride powder, 20 g of AC-2000, and 18.8 g of CF3CF2CF2OCF(CF3)COF were added to a 50 mL round-bottom flask connected to a reflux condenser. The mixture was stirred at 50°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the sodium fluoride powder was removed using a pressure filter, and then the excess CF3CF2CF2OCF(CF3)COF and AC-2000 were removed by distillation under reduced pressure to obtain 24 g of compound (E-3) (100% yield).

[0131] [ka] (E-3)

[0132] NMR spectrum of compound (E-3): 1 ¹H-NMR (300.4 MHz, solvent: CDCl3, reference: tetramethylsilane (TMS)) δ (ppm): 6.0 (12H), 5.0 (4H), 4.6 (20H), 4.2 (4H). 19 F-NMR (282.7 MHz, solvent: CDCl3, reference: CFCl3) δ (ppm): -79 (4F), -81 (6F), -82 (6F), -85 (24F), -90 (24F), -119 (4F), -120 (20F), -122 (4F), -126 (24F), -129 (4F), -131 (2F), -144 (12F) The average value of the number of units m+n was 10.

[0133] (Synthesis Example 5-3) 250 mL of ClCF2CFClCF2OCF2CF2Cl (hereinafter referred to as "CFE-419") was added to a 500 mL nickel reactor, and nitrogen gas was bubbled in. After the oxygen gas concentration had sufficiently decreased, 20 vol% fluorine gas diluted with nitrogen gas was bubbled in for 1 hour. A CFE-419 solution of compound (E-3) (concentration: 10 mass%, compound (E-3): 24 g) was added over 6 hours. The ratio of the fluorine gas introduction rate (mol / hour) to the hydrogen atom introduction rate in compound (E-3) (mol / hour) was controlled to 2:1. After the addition of compound (E-3) was complete, a CFE-419 solution of benzene (concentration: 0.1 mass%, benzene: 0.1 g) was added intermittently. After the addition of benzene was complete, fluorine gas was bubbled in for 1 hour, and finally the reactor was thoroughly purged with nitrogen gas. The solvent was removed by distillation to obtain 25.3 g of compound (E-4) (90% yield). CF3CF2CF2-OCF(CF3)-C(=O)-O-CF2CF2CF2CF2-(OCF2CF2-OCF2CF2CF2CF2) l -OCF2CF2-OCF2CF2CF2CF2-OC(=O)-CF(CF3)O-CF2CF2CF3...(E-4)

[0134] NMR spectrum of compound (E-4): 19 F-NMR (282.7 MHz, solvent: CDCl3, reference: CFCl3) δ (ppm): -79 (4F), -81 (6F), -82 (6F), -83 (48F), -87 (44F), -124 (48F), -129 (4F), -131 (2F). The average value of units l was 10.

[0135] (Synthesis Example 5-4) 25.3 g of compound (E-4), 2.2 g of sodium fluoride, and 25 mL of AC-2000 were placed in a 50 mL round-bottom flask and stirred in an ice bath. 1.7 g of methanol was added and stirred at 25°C for 1 hour. After filtration, the filtrate was purified by column chromatography. 15 g of compound (E-5) (80% yield) was obtained. CH3-OC(=O)-CF2CF2CF2-(OCF2CF2-OCF2CF2CF2CF2) l -OCF2CF2-OCF2CF2CF2-C(=O)-O-CH3...((E-5)

[0136] NMR spectrum of compound (E-5): 1 ¹H-NMR (300.4 MHz, solvent: CDCl3, reference: tetramethylsilane (TMS)) δ (ppm): 4.2 (6H). 19 F-NMR (282.7 MHz, solvent: CDCl3, reference: CFCl3) δ (ppm): -83 (44F), -87 (44F), -119 (4F), -124 (44F).

[0137] (Synthesis Example 5-5) 15 g of compound (E-5), 50 g of AK-225, and 7.5 g of 2.0 M ammonia-methanol solution were placed in a 100 mL pressure reactor and stirred at room temperature for 6 hours. The solvent was then removed by distillation to obtain 15.0 g of the target compound (E-6) (100% yield). H2NC(=O)CF2CF2CF2-(OCF2CF2-OCF2CF2CF2CF2) l -OCF2CF2-OCF2CF2CF2C(=O)NH2...(E-6)

[0138] NMR spectrum of compound (E-6): 19 F-NMR: -83(44F), -87(44F), -120(4F), -124(44F)

[0139] (Synthesis Examples 5-6) 15 g of compound (E-6), 75 g of AK-225, and 30 g of diethyl ether were added to a 300 mL round-bottom flask and stirred under ice. Then, 0.70 g of lithium aluminum hydride was slowly added and stirred at room temperature for 20 hours. After that, 0.3 mL of saturated sodium sulfate solution was added and the precipitated solid was removed by Celite filtration. The obtained filtrate was concentrated and purified by silica gel column chromatography to obtain 9.8 g of the target compound (E-7) (yield 65%). H2NCH2CF2CF2CF2-(OCF2CF2-OCF2CF2CF2CF2) l -OCF2CF2-OCF2CF2CF2CH2NH2...(E-7)

[0140] NMR spectrum of compound (E-7): 1 H-NMR: 3.2(4H) 19 F-NMR: -83(44F), -87(44F), -122(4F), -124(44F)

[0141] (Synthesis Examples 5-7) 0.5 g of HO(C=O)C(CH2CH=CH2)3, 20 mL of dichloromethane, and 0.5 mL of oxalyl chloride were added to a 50 mL round-bottom flask and stirred under ice cooling. Then 0.01 g of DMF was added. After stirring at room temperature for 3 hours, the mixture was concentrated to obtain 0.45 g of Cl(C=O)C(CH2CH=CH2)3. In a separate 50 mL round-bottom flask, 3.0 g of compound (E-7) and 0.7 mL of triethylamine were added, and the above-mentioned Cl(C=O)C(CH2CH=CH2)3 and 2 mL of 1,3-bistrifluoromethylbenzene were added. The mixture was stirred for 1 hour, and the solvent was removed by distillation. The resulting crude product was purified by silica gel column chromatography to obtain 2.2 g of compound (E-8) (70% yield). (CH2=CHCH2)3C(C=O)NHCH2CF2CF2CF2O-(CF2CF2O-CF2CF2CF2CF2O) l -CF2CF2O-CF2CF2CF2CH2NH(C=O)C(CH2CH=CH2)3...(E-8)

[0142] NMR spectrum of compound (E-8): 1 H-NMR:6.1(2H), 5.8(6H), 5.2(12H), 4.1(4H), 2.4(12H) 19 F-NMR: -83(44F), -87(44F), -120(4F), -124(44F)

[0143] (Synthesis Examples 5-8) In a 50 mL round-bottom flask purged with nitrogen, 1.0 g of compound (E-8), 0.003 g of xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass), 0.001 g of aniline, and 1.0 g of AC-6000 were added. Then, 0.21 g of trimethoxysilane was added and the mixture was stirred overnight at 40°C. After that, the solvent was removed by distillation to obtain 1.2 g of compound (1-E) (100% yield). [(CH3O)3SiCH2CH2CH2]3C-C(=O)-NH-CH2-CF2CF2CF2-(OCF2CF2-OCF2CF2CF2CF2) l -OCF2CF2-OCF2CF2CF2CH2-NH-(C=O)-C[CH2CH2CH2Si(OCH3)3]3...(1-E)

[0144] NMR spectrum of compound (1-E): 1 H-NMR:6.0(2H), 4.1(4H), 3.6(54H), 1.7(12H), 1.4(12H), 0.7(12H) 19 F-NMR: -83(44F), -87(44F), -120(4F), -124(44F) The average value of units l was 10.

[0145] [Synthesis Example 6] (Synthesis Example 6-1) Compound (F-1) was obtained according to the method described in Example 1-1 of International Publication No. 2013-121984. CF2=CFO-CF2CF2CF2CH2OH (F-1)

[0146] (Synthesis Example 6-2) 10 g of compound (F-1) was placed in a 100 mL stainless steel reactor and stirred at 175 °C for 200 hours. The resulting organic phase was concentrated to obtain 6 g of compound (F-2).

[0147] [ka] (F-2)

[0148] NMR spectrum of compound (F-2): 1 ¹H-NMR (300.4 MHz, solvent: CDCl3, reference: tetramethylsilane (TMS)) δ (ppm): 4.1 (4H). 19 F-NMR (282.7 MHz, solvent: CDCl3, reference: CFCl3) δ (ppm): -80 (2F), -85 (2F), -123 (4F), -126 (4F), -128 (2F), -131 (2F), -137 (1F), -139 (1F)

[0149] (Synthesis Example 6-3) Compound (1-F) was synthesized using the same method as in Example 5, except that HO-CH2CF2CF2CH2-OH was replaced with compound (F-2).

[0150] [ka] (1-F)

[0151] In equation (1-F), the average value of the number of units m+n was 10.

[0152] [Synthesis Example 7] (Synthesis Example 7-1) Compounds (G-1) and (I-1) were synthesized using the same synthesis method as described in Synthesis Examples 1-4 of Japanese Patent No. 6024816. CH3OCOCF2-{(OCF2) x1 -(OCF2CF2) x2}-OCF2CO2CH3 Compound (G-1): A compound in which x1 has an average of 42 and x2 has an average of 10 in the above formula. Compound (I-1): A compound in which x1 has an average of 26 and x2 has an average of 22 in the above formula.

[0153] (Synthesis Example 7-2) Compound (G-2) was synthesized according to the methods described in (Examples 13-1) to (Examples 13-2) of International Publication No. 2018 / 216630. CF3CF2CF2-O-CHF-CF2OCH2CH2CH2CH2CH2CH2OTs...(G-2) (OTs represents -O-SO2-Ph-CH3, and Ph represents the phenylene group.)

[0154] (Synthesis Example 7-3) In a 300 mL three-necked flask, 4 g of compound (G-2), 30 g of compound (G-1), and 160 g of 1,3-bis(trifluoromethyl)benzene were placed, and 12 g of cesium carbonate was added. The mixture was stirred at 70°C under a nitrogen atmosphere. After filtering the solid, it was washed with water and the organic phase was recovered. After concentration under reduced pressure, it was purified by silica gel column chromatography to obtain 12 g of product (G-3). CF3CF2CF2-O-CHF-CF2OCH2CH2CH2CH2CH2CH2O-CH2-CF2-{(OCF2) x1 (OCF2CF2) x2}-OCF2-CH2-OH ···(G-3)

[0155] NMR spectrum of compound (G-3): 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 1.3 (4H), 1.7 (4H), 2.5 (1H), 3.5 (2H), 3.8 (2H), 4.0 (2H), 4.2 (2H), 5.8 (1H). 19F-NMR (282.7 MHz, solvent: CDCl3, reference: CFCl3) δ (ppm): -52 to -56 (84F), -79 (1F), -80 (1F), -81 (1F), -82 (3F), -84 (1F), -85 to -88 (2F), -89 to -91 (40F), -130 (2F), -146 (1F). Average value for 1 unit: 42, Average value for 2 units: 10.

[0156] (Synthesis Example 7-4) In a 100 mL round-bottom flask, 12 g of compound (G-3) and 2.3 g of sodium fluoride powder were placed, and 11 g of CF3CF2CF2OCF(CF3)C(O)F was added. The mixture was stirred under a nitrogen atmosphere. After removing the sodium fluoride powder by filtration, the excess CF3CF2CF2OCF(CF3)C(O)F was removed by distillation under reduced pressure to obtain 12 g of compound (G-4). CF3CF2CF2-O-CHF-CF2OCH2CH2CH2CH2CH2CH2O-CH2-CF2-{(OCF2) x1 (OCF2CF2) x2}-OCF2-CH2-OC(O)CF(CF3)OCF2CF2CF3...(G-4)

[0157] NMR spectrum of compound (G-4): 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 1.3 (4H), 1.7 (4H), 2.5 (1H), 3.5 (2H), 4.0 (2H), 4.2 (2H), 4.7 (2H), 5.8 (1H). 19 F-NMR (282.7 MHz, solvent: CDCl3, reference: CFCl3) δ (ppm): -52 to -56 (84F), -79 to -88 (16F), -89 to -91 (40F), -130 (4F), -133 (2F), -146 (1F). Average value for 1 unit: 42, Average value for 2 units: 10.

[0158] (Synthesis Example 7-5) A condenser maintained at 20°C, a NaF pellet packed bed, and another condenser maintained at 0°C were installed in series at the gas outlet of a 1L nickel autoclave. A liquid return line was installed to return the condensed liquid from the 0°C condenser back to the autoclave. 750g of ClCF2CFClCF2OCF2CF2Cl (hereinafter also referred to as CFE-419) was placed in an autoclave and stirred while maintaining a temperature of 25°C. Nitrogen gas was blown into the autoclave at 25°C for 1 hour, and then 20% fluorine gas was blown in at 25°C at a flow rate of 2.0 L / hour for 1 hour. While blowing in 20% fluorine gas at the same flow rate, a solution of 6.0g of compound (G-4) dissolved in 54g of CFE-419 was injected into the autoclave over 1 hour. While blowing in 20% fluorine gas at the same flow rate, the internal pressure of the autoclave was increased to 0.15 MPa (gauge pressure). 4 mL of a benzene solution containing 0.05 g / mL of benzene in CFE-419 was injected into the autoclave while heating from 25°C to 40°C, and the benzene solution inlet of the autoclave was closed. After stirring for 15 minutes, another 4 mL of benzene solution was injected while maintaining a temperature of 40°C, and the inlet was closed. This procedure was repeated three more times. The total amount of benzene injected was 0.17 g. Stirring was continued for 1 hour while blowing in 20% fluorine gas at the same flow rate. The pressure inside the autoclave was reduced to atmospheric pressure, and nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated using an evaporator to obtain 6.1 g of compound (G-5). CF3CF2CF2-O-CF2-CF2OCF2CF2CF2CF2CF2CF2O-CF2-CF2-{(OCF2) x1 (OCF2CF2) x2}-OCF2-CF2-OC(O)CF(CF3)OCF2CF2CF3...(G-5)

[0159] NMR spectrum of compound (G-5): 19 F-NMR (282.7 MHz, solvent: CDCl3, reference: CFCl3) δ (ppm): -52 to -56 (84F), -79 to -88 (20F), -89 to -91 (48F), -121 (4F), -124 (4F), -130 (4F), -133 (1F). Average value for 1 unit: 42, Average value for 2 units: 10.

[0160] (Synthesis Example 7-6) 6.1 g of compound (G-5) and 10 g of AK-225 were placed in a round-bottom flask made of PFA. The mixture was stirred while cooling in an ice bath, and 10 g of methanol was slowly added dropwise from a dropping funnel under a nitrogen atmosphere. The mixture was stirred for 12 hours. The reaction mixture was concentrated using an evaporator to obtain 5.5 g of compound (G-6). CF3CF2CF2-O-CF2-CF2OCF2CF2CF2CF2CF2CF2O-CF2-CF2-{(OCF2) x1 (OCF2CF2) x2}-OCF2-C(O)OCH3···(G-6)

[0161] NMR spectrum of compound (G-6): 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 3.9 (3H). 19 F-NMR (282.7 MHz, solvent: CDCl3, reference: CFCl3) δ (ppm): -52 to -56 (84F), -79 to -88 (10F), -89 to -91 (48F), -121 (4F), -124 (4F), -130 (2F). Average value for 1 unit: 42, Average value for 2 units: 10.

[0162] (Synthesis Example 7-7) Compound (1-G) was synthesized using the same method as in Synthesis Example 1, except that compound (A-1) was replaced with compound (G-6). CF3CF2CF2-O-CF2-CF2OCF2CF2CF2CF2CF2CF2O-CF2-CF2-{(OCF2) x1 (OCF2CF2) x2}-OCF2-CH2NH(C=O)C[CH2CH2CH2Si(OCH3)3]3...(1-G) Average value for 1 unit: 58, Average value for 2 units: 13.

[0163] [Synthesis Example 8] Compound (1-H) was synthesized using the same method as in Synthesis Example 7, except that HO(C=O)C(CH2CH=CH2)3 was changed to HO(C=O)CH(CH2CH=CH2)2. CF3CF2CF2-O-CF2-CF2OCF2CF2CF2CF2CF2CF2O-CF2-CF2-{(OCF2) x1 (OCF2CF2) x2}-OCF2-CH2NH(C=O)CH[CH2CH2CH2Si(OCH3)3]2···(1-H) Average value for 1 unit: 58, Average value for 2 units: 13.

[0164] [Synthesis Example 9] Compound (1-I) was synthesized using the same method as in Synthesis Example 7, except that compound (G-1) was replaced with compound (I-1). CF3CF2CF2-O-CF2-CF2OCF2CF2CF2CF2CF2CF2O-CF2-CF2-{(OCF2) x1 (OCF2CF2) x2}-OCF2-CH2NH(C=O)C[CH2CH2CH2Si(OCH3)3]3...(1-I) Average value for 1 unit: 26, Average value for 2 units: 22.

[0165] [Synthesis Example 10] Compound (1-J) was synthesized using the same method as in Synthesis Example 7, except that HO(C=O)C(CH2CH=CH2)3 was changed to HO(C=O)CH(CH2CH=CH2)2. CF3CF2CF2-O-CF2-CF2OCF2CF2CF2CF2CF2CF2O-CF2-CF2-{(OCF2) x1 (OCF2CF2) x2}-OCF2-CH2NH(C=O)CH[CH2CH2CH2Si(OCH3)3]2···(1-J) Average value for 1 unit: 26, Average value for 2 units: 22.

[0166] [Synthesis Example 11] Compound (2-A) was obtained according to the method described in Example 11 of International Publication No. 2017 / 038830. CF3-(OCF2CF2-OCF2CF2CF2CF2) n OCF2CF2-OCF2CF2CF2(C=O)NH-CH2-C[CH2CH2CH2-Si(OCH3)3]3...(2-A) Average value of unit number n: 13

[0167] [Synthesis Example 12] Compound (2-B) was synthesized using the same method as in Synthesis Example 7, except that H2NCH2C(CH2CH=CH2)3 was changed to H2NCH2CH(CH2CH=CH2)2. CF3-(OCF2CF2-OCF2CF2CF2CF2) n OCF2CF2-OCF2CF2CF2(C=O)NH-CH2-CH[CH2CH2CH2-Si(OCH3)3]2...(2-B)

[0168] [Synthesis Example 13] The compound (2-C) used is CF3-(OCF2CF2-OCF2CF2CF2CF2) n The synthesis was carried out using the same method as in Synthesis Example 11, except that OCF2CF2-OCF2CF2CF2(C=O)OCH3 (average value of unit number n is 13) was changed to compound (G-6). CF3CF2CF2-O-CF2-CF2OCF2CF2CF2CF2CF2CF2O-CF2-CF2-{(OCF2) x1 (OCF2CF2) x2}-OCF2-(C=O)NHCH2C[CH2CH2CH2Si(OCH3)3]3...(2-C) Average value for 1 unit: 58, Average value for 2 units: 13.

[0169] [Synthesis Example 14] Compound (2-D) was synthesized using the same method as in synthesis example 10, except that H2NCH2C(CH2CH=CH2)3 was changed to H2NCH2CH(CH2CH=CH2)2. CF3CF2CF2-O-CF2-CF2OCF2CF2CF2CF2CF2CF2O-CF2-CF2-{(OCF2) x1 (OCF2CF2) x2}-OCF2-(C=O)NHCH2CH[CH2CH2CH2Si(OCH3)3]2···(2-D) Average value for 1 unit: 58, Average value for 2 units: 13.

[0170] [Synthesis Example 15] (Synthesis Example 15-1) 50 g of compound (A-1), 50 g of AC2000, and 0.7 g of allylamine were placed in a 100 mL round-bottom flask and stirred at 40°C for 6 hours. The crude reaction solution was then purified by silica gel chromatography to obtain 33 g of the target compound (K-1) (yield 66%). CF3(OCF2CF2OCF2CF2CF2CF2) m OCF2CF2OCF2CF2CF2-C(=O)NHCH2CH=CH2...(K-1) NMR spectrum of compound (K-1): 1 H-NMR:6.0(1H), 5.8(1H), 5.2(2H), 4.0(2H) 19 F-NMR: -55(3F), -82(54F), -87(52F), -90(2F), -120(2F), -123~-128(54F)

[0171] (Synthesis Example 15-2) In a 300 mL three-necked flask equipped with a Liebig condenser, 33 g of compound (K-1) and 49 g of 1,3-bistrifluoromethylbenzene were added under a dry nitrogen atmosphere and stirred in an ice bath. Then, 15 mL of 2.5 M lithium aluminum hydride-tetrahydrofuran solution was slowly added and stirred at room temperature for 30 minutes, followed by stirring at 100 °C for 5 hours. Sodium sulfate decahydrate was then added until the foaming subsided, and the solid was removed by Celite filtration. The resulting filtrate was concentrated to obtain 31 g of the target compound (K-2) (yield 93%). CF3(OCF2CF2OCF2CF2CF2CF2) m OCF2CF2OCF2CF2CF2-CH2NHCH2CH=CH2...(K-2) NMR spectrum of compound (K-2): 1H-NMR:5.8(1H), 5.2(2H), 3.4(2H), 3.2(2H) 19 F-NMR: -55(3F), -82(54F), -87(52F), -90(2F), -118(2F), -123~-128(54F)

[0172] (Synthesis Example 15-3) In a 50 mL three-necked flask equipped with a Liebig condenser, 10 g of compound (K-2), 7.4 g of triethylamine, 0.3 g of N,N-dimethylaminopyridine, and 10 g of 1,3-bistrifluoromethylbenzene were added under a dry nitrogen atmosphere. 7.4 g of Cl(C=O)C(CH2CH=CH2)3 was added while stirring at room temperature. The mixture was stirred at 100°C for 4 days. The crude reaction solution was then purified by silica gel chromatography to obtain 2.6 g of the target compound (K-3) (yield 25%). CF3(OCF2CF2OCF2CF2CF2CF2) m OCF2CF2OCF2CF2CF2-CH2N(CH2CH=CH2)(C=O)C(CH2CH=CH2)3...(K-3) NMR spectrum of compound (K-3): 1 H-NMR:5.8(4H), 5.3(2H), 5.2(6H), 4.4(2H), 4.4(2H), 4.2(2H), 1.4(6H) 19 F-NMR: -55(3F), -82(54F), -87(52F), -115(2F), -126(54F)

[0173] (Synthesis Example 15-4) In a 10 mL round-bottom flask purged with nitrogen, 0.9 g of compound (K-3), 0.003 g of xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass), 0.002 g of aniline, and 0.9 g of AC-6000 were added. Then, 0.11 g of trimethoxysilane was added and the mixture was stirred at 40°C for 4 hours. After that, the solvent was removed by distillation to obtain 1.1 g of compound (1-K) (yield 98%). CF3(OCF2CF2OCF2CF2CF2CF2) mOCF2CF2OCF2CF2CF2-CH2N[CH2CH2CH2Si(OCH3)3](C=O)C[CH2CH2CH2Si(OCH3)3]3...(1-K) NMR spectrum of compound (1-K): 1 H-NMR:4.2(2H), 3.8(2H), 3.6(36H), 1.7(8H), 1.4(8H), 0.7(8H) 19 F-NMR: -55(3F), -82(54F), -87(52F), -115(2F), -126(54F) m was approximately 13.

[0174] [Synthesis Example 16] (Synthesis Example 16-1) In a 50 mL three-necked flask under a dry nitrogen atmosphere, 10 g of compound (K-2), 1.2 g of triethylamine, and 10 g of 1,3-bistrifluoromethylbenzene were added. 0.9 g of Cl(C=O)CH(CH2CH=CH2)2 was added while stirring at room temperature. The mixture was stirred at room temperature for 1 hour. The crude reaction solution was then purified by silica gel chromatography to obtain 2.3 g of the target compound (L-1) (yield 23%). CF3(OCF2CF2OCF2CF2CF2CF2) m OCF2CF2OCF2CF2CF2-CH2N(CH2CH=CH2)(C=O)CH(CH2CH=CH2)2...(L-1) NMR spectrum of compound (L-1): 1 H-NMR:5.8(3H), 5.2(2H), 5.0(4H), 4.2(6H), 2.8(1H), 2.3(4H) 19 F-NMR: -55(3F), -82(54F), -87(52F), -116(2F), -126(54F)

[0175] (Synthesis Example 16-2) In a 10 mL round-bottom flask purged with nitrogen, 1.0 g of compound (L-1), 0.004 g of xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass), 0.001 g of aniline, and 1.0 g of AC-6000 were added. Then, 0.10 g of trimethoxysilane was added and the mixture was stirred at 40°C for 4 hours. After that, the solvent was removed by distillation to obtain 1.1 g of compound (1-L) (yield 99%). CF3(OCF2CF2OCF2CF2CF2CF2) m OCF2CF2OCF2CF2CF2-CH2N[CH2CH2CH2Si(OCH3)3](C=O)CH[CH2CH2CH2Si(OCH3)3]2...(1-L) NMR spectrum of compound (1-L): 1 H-NMR:4.2(2H), 3.6(27H), 2.8(1H), 1,8(4H), 1.4(6H), 0.7(6H) 19 F-NMR: -55(3F), -82(54F), -87(52F), -115(2F), -126(54F) m was approximately 13.

[0176] [Synthesis Example 17] (Synthesis Example 17-1) 50 g of compound (A-1), 50 g of AC2000, and 1.5 g of H2NCH2(C=O)CH(CH2CH=CH2)2 were placed in a 100 mL round-bottom flask and stirred at 40°C for 6 hours. The crude reaction solution was then purified by silica gel chromatography to obtain 26 g of the target compound (M-1) (yield 52%). CF3(OCF2CF2OCF2CF2CF2CF2) m OCF2CF2OCF2CF2CF2-CH2NHCH2(C=O)CH(CH2CH=CH2)2...(M-1) NMR spectrum of compound (M-1): 1 H-NMR:6.4(1H), 5.6(2H), 4.9(4H), 3.2(2H), 2.0(4H), 1.6(1H) 19F-NMR: -55(3F), -82(54F), -87(52F), -120(2F), -126(54F)

[0177] (Synthesis Example 17-2) In a 300 mL three-necked flask equipped with a Liebig condenser, 26 g of compound (M-1) and 46 g of 1,3-bistrifluoromethylbenzene were added under a dry nitrogen atmosphere and stirred in an ice bath. Then, 7 mL of 2.5 M lithium aluminum hydride-tetrahydrofuran solution was slowly added and stirred at room temperature for 30 minutes, followed by stirring at 100 °C for 5 hours. Sodium sulfate decahydrate was then added until the foaming subsided, and the solid was removed by Celite filtration. The resulting filtrate was concentrated to obtain 25 g of the target compound (M-2) (yield 95%). CF3(OCF2CF2OCF2CF2CF2CF2) m NMR spectrum of compound (M-2): OCF2CF2OCF2CF2CF2-CH2NHCH2CH2CH(CH2CH=CH2)2···(M-2) 1 H-NMR:6.0(2H), 5.3(4H), 3.5(2H), 2.9(2H), 2.3(4H), 1.8(1H) 19 F-NMR: -55(3F), -82(54F), -87(52F), -118(2F), -126(54F)

[0178] (Synthesis Example 17-3) In a 50 mL three-necked flask under a dry nitrogen atmosphere, 10 g of compound (M-2), 1.1 g of triethylamine, and 10 g of 1,3-bistrifluoromethylbenzene were added. 1.0 g of Cl(C=O)CH(CH2CH=CH2)2 was added while stirring at room temperature. The mixture was stirred at room temperature for 24 hours. The crude reaction solution was then purified by silica gel chromatography to obtain 2.7 g of the target compound (M-3) (yield 27%). CF3(OCF2CF2OCF2CF2CF2CF2) m OCF2CF2OCF2CF2CF2-CH2N[CH2CH2CH(CH2CH=CH2)2](C=O)CH(CH2CH=CH2)2...(M-3) NMR spectrum of compound (M-3): 1 H-NMR:5.8(4H), 5.0(8H), 4.3(2H), 3.5(2H), 3.0(1H), 2.5(2H), 2.3(2H), 2.2(2H) 19 F-NMR: -55(3F), -82(54F), -87(52F), -117(2F), -126(54F)

[0179] (Synthesis Example 17-4) In a 10 mL round-bottom flask purged with nitrogen, 1.0 g of compound (M-3), 0.004 g of xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass), 0.009 g of aniline, and 1.0 g of AC-6000 were added. Then, 0.14 g of trimethoxysilane was added and the mixture was stirred at 40°C for 4 hours. After that, the solvent was removed by distillation to obtain 1.1 g of compound (1-M) (yield 98%). CF3(OCF2CF2OCF2CF2CF2CF2) m OCF2CF2OCF2CF2CF2-CH2N[CH2CH(CH2CH2CH2Si(OCH3)3)2](C=O)CH[CH2CH2CH2Si(OCH3)3]2...(1-M) NMR spectrum of compound (1-M): 1 H-NMR:4.5(2H), 3.8(36H), 3.0(1H), 2.0(3H), 1.7(8H), 1.5(8H), 0.7(8H) 19 F-NMR: -55(3F), -82(54F), -87(52F), -115(2F), -126(54F) m was approximately 13.

[0180] [Synthesis Example 18] (Synthesis Example 18-1) In a 50 mL three-necked flask under a dry nitrogen atmosphere, 10 g of compound (M-2), 1.0 g of triethylamine, and 10 g of 1,3-bistrifluoromethylbenzene were added. 0.9 g of Cl(C=O)CH2CH2CH=CH2 was added while stirring at room temperature. The mixture was stirred at room temperature for 24 hours. The crude reaction solution was then purified by silica gel chromatography to obtain 1.3 g of the target compound (N-1) (yield 13%). CF3(OCF2CF2OCF2CF2CF2CF2) m OCF2CF2OCF2CF2CF2-CH2N(CH2CH2CH=CH2)(C=O)CH(CH2CH=CH2)2...(N-1) NMR spectrum of compound (N-1); 1 H-NMR:5.8(3H), 5.0(6H), 4.4(2H), 3.6(2H), 2.1(9H) 19 F-NMR: -55(3F), -82(54F), -87(52F), -115(2F), -126(54F)

[0181] (Synthesis Example 18-2) In a 10 mL round-bottom flask purged with nitrogen, 0.6 g of compound (N-1), 0.003 g of xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass), 0.0006 g of aniline, and 0.6 g of AC-6000 were added. Then, 0.07 g of trimethoxysilane was added and the mixture was stirred at 40°C for 4 hours. After that, the solvent was removed by distillation to obtain 0.6 g of compound 1-N (yield 98%). CF3(OCF2CF2OCF2CF2CF2CF2) m OCF2CF2OCF2CF2CF2-CH2N[CH2CH2CH2CH2Si(OCH3)3](C=O)CH[CH2CH2CH2Si(OCH3)3]2...(1-N) NMR spectrum of compound (1-N); 1 H-NMR:4.5(2H), 3.8(27H), 2.1(1H), 1.7(8H), 1.5(6H), 0.7(6H) 19F-NMR: -55(3F), -82(54F), -87(52F), -115(2F), -126(54F)

[0182] [Examples 1-16] The compounds obtained in each synthesis example were mixed with Novec-7200 (product name, manufactured by 3M, C4F9OC2H5, boiling point 76°C) as an organic solvent in a mass ratio of 1 / 9 (compound / organic solvent) to obtain the coating compositions of Examples 1 to 16.

[0183] [Creation of evaluation samples] Using the compounds obtained in the synthesis examples and the coating compositions obtained above, the substrate surface was treated by the following dry coating or wet coating method to obtain evaluation samples (articles) in which a surface layer was formed on the surface of the substrate (chemically strengthened glass). The evaluation results are shown in Tables 1 and 2.

[0184] (Dry coating method) Dry coating of the substrate was performed using a vacuum deposition apparatus (ULVAC, VTR-350M). Specifically, first, 0.5 g of the compound obtained in each example was packed into a molybdenum boat in the vacuum deposition apparatus, and the inside of the vacuum deposition apparatus was filled to 1 × 10⁻⁶ -3 The air was evacuated to below Pa. The boat containing the compound was heated at a heating rate of 10°C / min or less, and when the deposition rate measured by a quartz crystal film thickness gauge exceeded 1 nm / second, the shutter was opened to begin film deposition on the substrate surface. When the film thickness reached approximately 50 nm, the shutter was closed to end film deposition on the substrate surface. The substrate on which the compound had been deposited was heat-treated at 200°C for 30 minutes, and then washed with Asahi Clean AK-225 (product name, manufactured by AGC Inc.) to obtain an evaluation sample (article) with a surface layer on the substrate surface.

[0185] (Wet coating method) The substrate was dipped into each coating composition, left for 30 minutes, and then removed (dip-coating method). The coating film was dried at 200°C for 30 minutes and then washed with AK-225 to obtain evaluation samples (articles) with a surface layer on the substrate surface.

[0186] [Table 1]

[0187] [Table 2]

[0188] As shown in Tables 1 and 2, it was found that using specific fluorine-containing ether compounds allows for the formation of a surface layer with superior light resistance compared to cases where specific fluorine-containing ether compounds are not used. Furthermore, the entire contents of the specifications, claims, and abstracts of Japanese Patent Application No. 2018-222871, filed on November 28, 2018, Japanese Patent Application No. 2018-222872, filed on November 28, 2018, and Japanese Patent Application No. 2019-089666, filed on May 10, 2019, are incorporated herein by reference as disclosure of the specification of the present invention.

Claims

1. A fluorine-containing ether compound represented by formula (1). Z[-R ｆ -R １ -NR-C(O)-Y-{Si(R ２ ) ｎ L ３－ｎ } ｇ ] ｊ ・・・(1) However, in equation (1), R ｆ is a fluoroalkylene group. However, in R ｆ , at least one fluorine atom is bonded to the carbon atom bonded to R １ [[ID=] R １ This is an alkylene group having 1 to 10 carbon atoms. R is a hydrogen atom, an alkyl group, or an alkyl group having a reactive silyl group. R2 is a monovalent hydrocarbon group. L is a hydrolyzable group or a hydroxyl group. n is an integer between 0 and 2. g is an integer greater than or equal to 1. j is either 1 or 2. If j is 1, then Z is R ｆ１ - (OX) ｍ It is a monovalent group represented by -O-, and when j is 2, Z is -(OX) ｍ It is a divalent group represented by -O-. ｆ１ is a perfluoroalkyl group. X is a fluoroalkylene group. m is an integer greater than or equal to 2. The group represented by Y-{Si(R2)nL3-n}g is the following group (1-1A). -Q a -X 11 (-Q b -Si(R 2 ) n L 3-n ) h (-R 11 ) i ... (1-1A) Qa is a divalent saturated hydrocarbon group having 1 to 20 carbon atoms. X11 is either a nitrogen atom or a silicon atom. Qb is a divalent saturated hydrocarbon group having 1 to 20 carbon atoms. R11 is a hydrogen atom, a hydroxyl group, an alkyl group, or a fluoroalkyl group. If X11 is a nitrogen atom, then h is an integer between 1 and 2, i is an integer between 0 and 1, and the equation h + i = 2 is satisfied. If X11 is a silicon atom, then h is an integer from 1 to 3, i is an integer from 0 to 2, and the equation h + i = 3 is satisfied.

2. The fluorine-containing ether compound according to Claim 1, wherein the group (1-1A) is the following group (1-1A-2), group (1-1A-3), or (1-1A-5). -Q a2 -N [-Q b2 -Si(R 2 ) n L 3-n ] 2 ... (1-1A-2) -Q a3 -G(R g ) [-Q b3 -Si(R 2 ) n L 3-n ] 2...(1-1A －３） -Q a5 -Si [-Q b5 -Si(R 2 ) n L 3-n ] 3 ... (1-1A-5) however, Q a2, Q b2, Q a3, Q b3, Q a5, and Q b5 are each independently divalent saturated hydrocarbon groups having 1 to 20 carbon atoms. G represents a silicon atom. R g is an alkyl group having 1 to 10 carbon atoms.

3. The compound represented by formula (1) is such that Z is R ｆ１ - (OX) ｍ It is a monovalent group represented by -O-, where X is a fluoroalkylene group having 1 to 6 carbon atoms, (OX) ｍ The fluorine-containing ether compound according to claim 1 or 2, wherein is a compound containing two or more (OX) elements.

4. The compound represented by formula (1) is such that Z is -(OX) ｍ It is a divalent group represented by -O-, where X is a fluoroalkylene group having 1 to 6 carbon atoms, (OX) ｍ The fluorine-containing ether compound according to claim 1 or 2, wherein is a compound containing two or more (OX) elements.

5. A composition characterized by comprising two or more fluorine-containing ether compounds described in any one of claims 1 to 4, or comprising one or more fluorine-containing ether compounds described in any one of claims 1 to 4 and a fluorine-containing ether compound other than the fluorine-containing ether compounds described in any one of claims 1 to 4.

6. The composition according to claim 5, comprising: the fluorine-containing ether compound having one group (A) represented by -NR-C(O)-; and the fluorine-containing ether compound having two groups (A).

7. The fluorine-containing ether compound having one of the groups (A) is a fluorine-containing ether compound in formula (1) where j is 1. The composition according to claim 6, wherein the fluorine-containing ether compound having two of the group (A) is a fluorine-containing ether compound in formula (1) where j is 2.

8. A fluorine-containing ether compound according to any one of claims 1 to 4 or a composition according to any one of claims 5 to 7, A coating composition characterized by containing a liquid medium.

9. An article characterized by having a base material and a surface layer formed on the base material from a fluorine-containing ether compound according to any one of claims 1 to 4 or a composition according to any one of claims 5 to 7.