Fluorine-containing ether compounds, fluorine-containing ether mixtures, coating agents, articles, and methods for manufacturing articles

Abstract

The present invention pertains to: a fluorine-containing ether compound represented by formula (A) X1-Si(R1)nL2-n-O-X2-O-Si(R1)nL2-n-X1(in formula (A), each X1 independently represents a monovalent organic group having a poly(oxyfluoroalkylene) chain, X2 represents a divalent organic group, atoms at both ends of X2 bound to the two oxygen atoms in formula (A) are both carbon atoms, each R1 independently represents a monovalent hydrocarbon group, each L independently represents a hydrolysable group or a hydroxyl group, and each n independently represents an integer of 0-2; a method for producing said compound; a fluorine-containing ether mixture and a coating agent that contain said compound; and an article using said compound and a method for manufacturing said article.

Description

[Technical Field]

[0001] This disclosure relates to fluorine-containing ether compounds, fluorine-containing ether mixtures, coatings, articles, and methods for producing 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 fluorine-containing compounds, fluorine-containing ether compounds having poly(oxyfluoroalkylene) chains in which ether bonds exist in the fluoroalkylene chain are compounds with excellent flexibility and are particularly excellent at removing oils and greases.

[0003] As fluorine-containing ether compounds, compounds having a poly(oxyperfluoroalkylene) chain and a hydrolyzable silyl group at the terminal are widely used. For example, Patent Document 1 describes that a surface treatment layer having water-repellent, oil-repellent, stain-resistant, and waterproof properties, as well as excellent abrasion resistance, can be formed using a mixture of a poly(oxyperfluoroalkylene) group-containing silane compound and a fluorine-containing compound. Patent Document 2 describes a fluorine-containing ether composition for vapor deposition that comprises a compound having a poly(oxyperfluoroalkylene) chain and a hydrolyzable silyl group, and a partial condensate of the said compound, and capable of forming a vapor-deposited film with excellent friction resistance. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2016-132719 [Patent Document 2] International Publication No. 2018 / 221520 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] In recent years, the required level of the friction resistance of the surface layer by coating has been increasing. Therefore, the inventors have tried to develop a fluorine-containing ether compound capable of forming a surface layer having more excellent friction resistance than conventional compounds described in Patent Documents 1 and 2. The present disclosure relates to a fluorine-containing ether compound, a fluorine-containing ether mixture, and a coating agent capable of forming a surface layer having excellent friction resistance, and an article using these and a method for producing the same.

Means for Solving the Problems

[0006] The means for solving the above problems include the following aspects. <1> A fluorine-containing ether compound represented by the following formula (A). Formula (A): X 1 -Si(R 1 ) n L 2-n -O-X 2 -O-Si(R 1 ) n L 2-n -X 1 In formula (A), X 1 each independently represents a monovalent organic group having a poly(oxyfluoroalkylene) chain, X 2 represents a divalent organic group, provided that the atoms at both ends of X 2 bonded to the two oxygen atoms in formula (A) are carbon atoms, R 1 each independently represents a monovalent hydrocarbon group, L each independently represents a hydrolyzable group or a hydroxyl group, n each independently represents an integer of 0 to 2. <2> The fluorine-containing ether compound according to <1>, wherein in formula (A), X 2 contains an alkylene group, a fluoroalkylene group, or an ether oxygen atom-containing group having an ether oxygen atom between carbon atoms of an alkylene group or a fluoroalkylene group. <3> In formula (A), X2 contains a poly(oxyperfluoroalkylene) group, <1> or <2> The fluorine-containing ether compounds described above. <4> In formula (A), X 2 (OCF2) m21 (OCF2CF2) m22 The structure is represented by}, where m21 is an integer greater than or equal to 1, m22 is an integer greater than or equal to 1, and m21 + m22 is an integer between 2 and 500. <3> The fluorine-containing ether compounds described above. <5> The aforementioned {(OCF2) m21 (OCF2CF2) m22 In}, m21 > m22, <4> The fluorine-containing ether compounds described above. <6> In formula (A), X 2 but, Poly(oxyperfluoroalkylene) group and A divalent organic group selected from the group consisting of an alkylene group, an etheric oxygen atom-containing group having an etheric oxygen atom between carbon atoms of the alkylene group, a perfluoroalkylene group, and combinations thereof, which links a poly(oxyperfluoroalkylene) group to at least one of the two oxygen atoms in formula (A), It is a group having, <3> ~ <5> A fluorine-containing ether compound as described in any one of the items. <7> In the presence of a catalyst, a compound represented by the following formula (Cs) and a compound represented by the following formula (Cd) are transesterified to obtain: <1> ~ <6> A fluorine-containing ether compound as described in any one of the items. Formula(Cs):X 1 -Si(R 1 ) n L 3-n Equation (Cd): HO-X 2 -OH In the formula (Cs), X 1 This represents a monovalent organic group having a poly(oxyfluoroalkylene) chain. R 1 Each of these independently represents a monovalent hydrocarbon group. Each L independently represents a hydrolyzable group or a hydroxyl group. n represents an integer between 0 and 2. In equation (Cd), X 2 represents a divalent organic group, where X is bonded to the two hydroxyl groups in formula (Cd). 2 The atoms at both ends are carbon atoms. <8> In the transesterification described above, the amount M of the compound represented by formula (Cd) Cd The amount M of the compound represented by the above formula (Cs) relative to Cs Mole ratio (M Cs / M Cd ) is between 1.5 and 4.0. <7> The fluorine-containing ether compounds described above. <9> The catalyst comprises at least one selected from the group consisting of carboxylic acids, Lewis acids, substituted or unsubstituted pyridines, substituted or unsubstituted imidazoles, tertiary phosphines, amine compounds, and solid catalysts. <7> or <8> The fluorine-containing ether compounds described above. <10> Transesterification is performed between a compound represented by the following formula (Cs) and a compound represented by the following formula (Cd) in the presence of a catalyst. <1> ~ <6> A method for producing a fluorine-containing ether compound as described in any one of the items. Formula(Cs):X 1 -Si(R 1 ) n L 3-n Equation (Cd): HO-X 2 -OH In the formula (Cs), X 1 This represents a monovalent organic group having a poly(oxyfluoroalkylene) chain. R 1 Each of these independently represents a monovalent hydrocarbon group. Each L independently represents a hydrolyzable group or a hydroxyl group. n represents an integer between 0 and 2. In equation (Cd), X 2 represents a divalent organic group, where X is bonded to the two hydroxyl groups in formula (Cd). 2 The atoms at both ends are carbon atoms. <11> In the transesterification described above, the amount M of the compound represented by formula (Cd) CdThe amount M of the compound represented by the above formula (Cs) relative to Cs Mole ratio (M Cs / M Cd ) is between 1.5 and 4.0. <10> A method for producing the fluorine-containing ether compound described above. <12> The catalyst comprises at least one selected from the group consisting of carboxylic acids, Lewis acids, substituted or unsubstituted pyridines, substituted or unsubstituted imidazoles, tertiary phosphines, amine compounds, and solid catalysts. <10> or <11> A method for producing the fluorine-containing ether compound described above. <13> <1> ~ <9> It contains two or more fluorine-containing ether compounds as described in any one of the items, or <1> ~ <9> One or more fluorine-containing ether compounds as described in any one of the items and <1> ~ <9> A fluorine-containing ether mixture comprising a fluorine-containing ether compound other than the fluorine-containing ether compound described in any one of the items. <14> <1> ~ <9> A fluorine-containing ether compound as described in any one of the items or <13> A coating agent containing the fluorine-containing ether mixture described above. <15> Furthermore, including a liquid medium, <14> The coating agent described above. <16> Substrate and <14> or <15> An article having a surface layer formed on the substrate by the coating agent described above. <17> <14> A method for manufacturing an article, comprising applying the coating agent described above to the surface of a substrate by a dry coating method to form a surface layer on the substrate. <18> <15> The coating agent described above is applied to the surface of the substrate by a wet coating method, The substrate to which the coating agent has been applied is dried to form a surface layer on the substrate, A method for manufacturing articles, including [Effects of the Invention]

[0007] This disclosure provides fluorine-containing ether compounds, fluorine-containing ether mixtures, and coating agents capable of forming a surface layer with excellent abrasion resistance, as well as articles using these and methods for manufacturing the same. [Modes for carrying out the invention]

[0008] The embodiments for carrying out the embodiments of this disclosure will be described in detail below. However, the embodiments of this disclosure are not limited to the embodiments described below. In the embodiments described below, the components (including elemental steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the embodiments of this disclosure.

[0009] In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes, provided that the purpose of such process is achieved. In this disclosure, the numerical range indicated using "~" includes the numbers before and after "~" as the minimum and maximum values, respectively. In this disclosure, each component may contain multiple types of the corresponding substance. If multiple types of the substance corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple types of substances present in the composition, unless otherwise specified. In this disclosure, the terms “alkyl group” and “alkylene group” mean an unsubstituted alkyl group and an unsubstituted alkylene group, respectively, unless otherwise specified.

[0010] <Fluorine-containing ether compounds> The fluorine ether compounds of this disclosure are represented by the following formula (A). Formula (A):X 1 -Si(R 1 ) n L 2-n -OX 2 -O-Si(R 1 ) n L 2-n -X 1 In formula (A), X 1 Each of these independently represents a monovalent organic group having a poly(oxyfluoroalkylene) chain. X 2represents a divalent organic group, where X is bonded to the two oxygen atoms in formula (A). 2 The atoms at both ends are carbon atoms. R 1 Each of these independently represents a monovalent hydrocarbon group. Each L independently represents a hydrolyzable group or a hydroxyl group. Each n represents an independent integer between 0 and 2.

[0011] In this disclosure, the fluorine-containing ether compound is also referred to as a "specific fluorine-containing ether compound." In this disclosure, each group of a specific fluorine-containing ether compound may be referred to as follows: (S) Base: In the above formula (A), X 1 -Si(R 1 ) n L 2-n A monovalent organic group represented by -O- (D) Base: In the above formula (A), -X 2 - A divalent group The specific fluorine ether compound has a structure represented by (S) group-(D) group-(S) group. The two (S) groups may be the same or different. From the viewpoint of ease of manufacture, it is preferable that the two (S) groups are the same.

[0012] The inventors discovered that using a specific fluorine-containing ether compound allows for the formation of a surface layer with excellent abrasion resistance. While the reason for this is not entirely clear, it is speculated to be as follows: For example, Patent Document 1 describes a composition obtained by mixing a poly(oxyperfluoroalkylene) group-containing silane compound with a monovalent poly(oxyperfluoroalkylene) group-containing alcohol compound. On the other hand, since specific fluorine-containing ether compounds have a structure in which multiple (S) groups having poly(oxyfluoroalkylene) chains are linked via (D) groups, it is thought that a stronger coating is formed when a surface layer is formed using a specific fluorine-containing ether compound. Furthermore, in the partial condensate of the compound having poly(oxyperfluoroalkylene) chains and hydrolyzable silyl groups described in Patent Document 2, multiple poly(oxyperfluoroalkylene) chains are linked via Si-O-Si bonds. In contrast, in the specific fluorine-containing ether compound, multiple poly(oxyfluoroalkylene) chains are linked via Si-OC bonds. Since multiple (S) groups are linked via (D) groups, it is thought that a stronger film is formed when a surface layer is formed using the specific fluorine-containing ether compound.

[0013] Specific fluorine ether compounds can be obtained, for example, by transesterifying a compound having a poly(oxyfluoroalkylene) chain and a hydrolyzable silyl group with a diol in a molar ratio of approximately 2:1 in the presence of a catalyst. In this reaction, a Si-OC bond is formed between the hydrolyzable silyl group and the two hydroxyl groups of the diol. The following details the structure of each group in specific fluorine-containing ether compounds.

[0014] [X 1 -Si(R 1 ) n L 2-n A monovalent organic group ((S) group) represented by -O- The fluorine-containing ether compounds of this disclosure have two (S) groups. Preferably, the (S) groups are structures derived from the compound represented by formula (Cs) described below.

[0015] (S) Motochu, X 1 It is a monovalent organic group having a poly(oxyfluoroalkylene) chain. A poly(oxyfluoroalkylene) chain contains multiple units represented by the following formula. Formula:(OX) In the formula, each X independently represents a fluoroalkylene group.

[0016] From the viewpoint of achieving superior surface layer abrasion resistance, the number of carbon atoms in the fluoroalkylene group within the poly(oxyfluoroalkylene) chain is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. The fluoroalkylene group may be linear, branched, or cyclic. From the viewpoint of achieving superior abrasion resistance of the surface layer, the number of fluorine atoms in the fluoroalkylene group is preferably 1 to 2 times the number of carbon atoms, and more preferably 1.7 to 2 times. The fluoroalkylene group may be a group in which all hydrogen atoms in the fluoroalkylene group are replaced with fluorine atoms (perfluoroalkylene group), and from the viewpoint of having better abrasion resistance of the surface layer, the perfluoroalkylene group is preferred.

[0017] (OX) includes -OCHF-, -OCF2CHF-, -OCHFCF2-, -OCF2CH2-, -OCH2CF2-, -OCF2CF2CHF-, -OCHFCF2CF2-, -OCF2CF2CH2-, -OCH2CF2CF2-, -OCF2CF2CF2CH2-, -OCH2CF2CF2CF2-, -OCH2CF2CF2CF2CH2-, -OCH2CF2CF2CF2CF2-, -O Examples include CF2CF2CF2CF2CF2CH2-, -OCH2CF2CF2CF2CF2CF2-, -OCF2-, -OCF2CF2-, -OCF2CF2CF2-, -OCF(CF3)CF2-, -OCF2CF2CF2CF2-, -OCF(CF3)CF2CF2-, -OCF(CF3)CF2CF2-, -OCF2CF2CF2CF2CF2CF2CF2-, -O-cycloC4F6-, etc. Here, -cycloC4F6- refers to a perfluorocyclobutanediyl group, a specific example of which is the perfluorocyclobutane-1,2-diyl group.

[0018] The number of repetitions m of (OX) is an integer of 2 or more, preferably an integer between 2 and 500, more preferably an integer between 2 and 200, and even more preferably an integer between 5 and 150. (OX) m (OX) may be a repetition of one type, or it may contain two or more types of (OX). The order in which 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, for example, 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, or two or more types of (OX) with the same number of carbon atoms but different in the presence or absence of side chains, type of side chains (number of side chains, number of carbon atoms in side chains, etc.).

[0019] From the viewpoint of forming a film with excellent fingerprint stain removal properties, the poly(oxyfluoroalkylene) chain is preferably a poly(oxyfluoroalkylene) chain mainly composed of the oxyperfluoroalkylene group (OX). (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 even more preferably 90-100%.

[0020] 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.

[0021] In this disclosure, arrangements of two or more (OX) are denoted as follows: 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.

[0022] (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 is preferred. Here, -cycloC4H mg [[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​Note that the above formula represents the type and number of units, not the arrangement of units. That is, m11 to m16 represent the number of units, for example, (OCH ma F (2-ma) ) m11 (OCH ma F (2-ma) ) The unit does not represent a block of m11 consecutive units. Similarly, (OCH ma F (2-ma) )~(O-cycloC4H mg F (6-mg) The order in which the terms are listed does not indicate that they are arranged in that order. In the above formula, if two or more of m11 to m17 are not 0 (i.e., (OX) m If the array consists of two or more types of units, the arrangement of the different units may be random, alternating, block, or a combination of these arrangements. In the above formula, if there are two or more oxyfluoroalkylene units represented by the same formula, each oxyfluoroalkylene unit may be the same or different. For example, if m11 is 2 or more, multiple (OCH ma F (2-ma) ) may be the same or different.

[0025] (OX) m The following structure is preferred. {(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 .

[0026] In the formula, 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.

[0027] (OX) m From the viewpoint of facilitating the production of specific fluorine-containing ether compounds, the following structure is preferred. {(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, m22-2, m25-1, and m28-1 are all integers greater than or equal to 1.

[0028] {(OCF2) m21 (OCF2CF2) m22 In this case, the ratio of m22 to m21 (m22 / m21) is preferably 0.05 to 10.00, more preferably 0.08 to 2.00, particularly preferably 0.10 to 1.00, and most preferably 0.12 to 0.85, from the viewpoint of having superior abrasion resistance and fingerprint stain removal properties of the surface layer. In one embodiment, {(OCF2) m21 (OCF2CF2) m22 In}, it is preferable that m21 > m22. {(OCF2) m21 (OCF2CF2) m22 In this case, it is preferable that m21 is 2 to 200 and m22 is 2 to 100, and more preferably that m21 is 10 to 150 and m22 is 5 to 50.

[0029] (OCF2CF2-OCF2CF2CF2CF2) m25 In this case, m25 is preferably 2 to 100, more preferably 5 to 20, and even more preferably 7 to 15.

[0030] In one embodiment, X 1 R f1 -(OX) m -It may have a group represented by * and a linking group that is linked to *. Here Rf1 (OX) represents a fluoroalkyl group, X independently represents a fluoroalkylene group, and m represents an integer greater than or equal to 2. m Details are as described above. R f1 A perfluoroalkyl group is preferred. From the viewpoint of achieving superior abrasion resistance of the surface layer, the number of carbon atoms in the perfluoroalkyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. The perfluoroalkyl group may be linear, branched, or cyclic. Specific examples of perfluoroalkyl groups include CF3-, CF3CF2-, CF3CF2CF2-, CF3CF2CF2CF2-, CF3CF2CF2CF2CF2-, CF3CF2CF2CF2CF2CF2-, and CF3CF(CF3)-. From the viewpoint of having superior water-repellent and oil-repellent properties of the surface layer, CF3-, CF3CF2-, and CF3CF2CF2- are preferred.

[0031] In another embodiment, X 1 is Z-(OX) m -The group may have a group represented by * and a linking group linked to *. Here, Z represents a monovalent organic group other than a fluoroalkyl group, X independently represents a fluoroalkylene group, and m represents an integer of 2 or more. (OX) m Details are as described above.

[0032] R f1 -(OX) m -* represents the group and Z-(OX) m -The linking groups connected to the * in the group represented by -* are, respectively, these groups and -Si(R 1 ) n L 2-n It is a divalent group that links to the Si atom in the group represented by -O-. Examples of such divalent groups include alkylene groups, fluoroalkylene groups, etheric oxygen atom-containing groups having an etheric oxygen atom between carbon atoms of an alkylene group, and -Si(R 6Examples include -Si(CH3)2-, -Si(CH3)2-Ph-Si(CH3)2-, divalent organopolysiloxane residues, and combinations thereof. In the above linking groups, the atom listed on the left is bonded to *. The above divalent groups can also be -C(O)NR 6 -, -C(O)O-, -C(O)-, -NR 6 -, -S-, -NHC(O)O-, -NHC(O)NR 6 -, -SO2NR 6 -May include, etc. In the formula, R 6 Each of these is independently a hydrogen atom, a C1-C6 alkyl group, or a phenyl group, and Ph is a phenylene group. 6 From the viewpoint of ease of manufacture, the number of carbon atoms in the alkyl group is preferably 1 to 3. *The linking groups that are connected to the alkylene group, the fluoroalkylene group, and the etheric oxygen atom-containing group having an etheric oxygen atom between carbon atoms of the alkylene group, and R 6 At least one hydrogen atom in an alkyl group having 1 to 6 carbon atoms represented by the formula -Si(R 1 ) n L 3-n A group having a reactive silyl group represented by -Si(R 1 ) n L 3-n、 or alkylene group-Si(R 1 ) n L 3-n It may be substituted with. Details of the reactive silyl group are described below. Alkylene group -Si(R 1 ) n L 3-n The number of carbon atoms in the alkylene group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6.

[0033] The alkylene group that is linked to * is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 15 carbon atoms, and even more preferably an alkylene group having 1 to 11 carbon atoms.

[0034] The fluoroalkylene group that is linked to * has at least one fluorine atom, and is preferably a fluoroalkylene group having 1 to 20 carbon atoms, more preferably a fluoroalkylene group having 1 to 10 carbon atoms, and even more preferably a fluoroalkylene group having 1 to 6 carbon atoms. Among these, a perfluoroalkylene group having the aforementioned number of carbon atoms is preferred.

[0035] The total number of carbon atoms in the etheric oxygen atom-containing group, which is a linking group linked to * and has an etheric oxygen atom between carbon atoms of the alkylene group, is preferably 2 to 10, more preferably 2 to 6, and even more preferably 2 to 4. Examples of etheric oxygen atom-containing groups having an etheric oxygen atom between carbon atoms in the alkylene group include poly(oxyalkylene) groups. Examples of poly(oxyalkylene) groups include groups having alkylene groups with 1 to 10 carbon atoms in each oxyalkylene unit, with 1 to 6 carbon atoms being preferred and 1 to 3 carbon atoms being more preferred. The multiple oxyalkylene units in the poly(oxyalkylene group) may be one type or two or more types, and from the viewpoint of ease of manufacture, one or two types are preferred.

[0036] The alkylene group, the fluoroalkylene group, and the etheric oxygen atom-containing group having an etheric oxygen atom between carbon atoms of the alkylene group may each independently be in a linear or branched chain configuration.

[0037] In one embodiment, the linking group to * is -C(O)NR 6 - and combinations of linear or branched alkylene groups which may be substituted with reactive silyl groups.

[0038] The linking group attached to * is the formula -Si(R 1 ) n L 3-n It may have one or more reactive silyl groups represented by the formula -Si(R 1 ) n L 3-nDetails of the reactive silyl group represented by are described below. The total number of reactive silyl groups in the linking group linked to * is preferably 0 to 2.

[0039] Formula Z-(OX) m In the group represented by -*, Z is a monovalent organic group other than a fluoroalkyl group. A monovalent organic group represented by Z is, for example, a linking group linked to * as described above, with the formula -Si(R 1 ) n L 3-n It may also be a linked reactive silyl group represented by . In one embodiment, the monovalent organic group represented by Z is one of the groups described above as a linking group linked to *, with the other bond opposite to the bond site with * being one of the bonds of the formula -Si(R 1 ) n L 3-n It may also be bonded to a reactive silyl group represented by . In one embodiment, a monovalent organic group represented by Z is Z 1 The group may also be represented by -X-, where Z 1 represents a monovalent organic group other than a fluoroalkyl group, and X is (OX) m It is synonymous with X inside, and X is (OX) m The X inside may be the same as or different from the X inside. In one embodiment, Z 1 The other bond of any of the groups described above as linking groups to *, on the opposite side of the bond site to *, is a bond of the formula -Si(R 1 ) n L 3-n It may also be bonded to a reactive silyl group represented by . That is, in this case, X 1 teeth, Si(R 1 ) n L 3-n -(base*)-X-(OX) m -(base*)- It has the structure shown by . Here, (group*) represents any of the groups described above as linking groups linked to *, and the two (groups*) may be the same or different. From the viewpoint of ease of manufacture, it is preferable that the two (groups*) are the same, and the same (group*) is -X-(OX) m -It is more preferable that they are arranged symmetrically with respect to the center. Formula -Si(R 1 ) n L 3-n Details of the reactive silyl group represented by are described below. Z preferably has 1 to 5 reactive silyl groups, and more preferably 1 to 3.

[0040] The following are specific examples of the linking groups that are linked to *. In the examples below, ** represents the linking position to Si in formula (A).

[0041] [ka]

[0042] (S) group, -Si(R 1 ) n L 2-n In the group represented by -O-, R 1 The details of L and the reactive silyl group will be described later.

[0043] [-X 2 - A divalent group ((D) group) represented by - In formula (A), -X 2 In a divalent group represented by -, X 2 represents a divalent organic group, where X is bonded to the two oxygen atoms in formula (A). 2 The atoms at both ends are carbon atoms.

[0044] X 2 Preferably, the group is an alkylene group, a fluoroalkylene group, or an etheric oxygen atom-containing group having an etheric oxygen atom between carbon atoms of the alkylene group or fluoroalkylene group, or a combination thereof.

[0045] X 2 If the alkylene group is present, the number of carbon atoms in the alkylene group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6, from the viewpoint of excellent abrasion resistance.

[0046] X 2 When the group is a fluoroalkylene group, the number of carbon atoms in the fluoroalkylene group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6, from the viewpoint of excellent abrasion resistance. As for the fluoroalkylene group, from the viewpoint of abrasion resistance, a perfluoroalkylene group or a group in which an alkylene group having 1 to 3 carbon atoms is bonded to both or one end of a perfluoroalkylene group is preferred.

[0047] X 2 Examples of etheric oxygen atom-containing groups that have an etheric oxygen atom between carbon atoms of an alkylene group or fluoroalkylene group include poly(oxyalkylene) groups and poly(oxyfluoroalkylene) groups. Examples of poly(oxyalkylene) groups include groups having alkylene groups with 1 to 20 carbon atoms in each oxyalkylene unit, with the number of carbon atoms preferably being 1 to 10, and more preferably 1 to 6. The multiple oxyalkylene units in the poly(oxyalkylene group) may be one type or two or more types, and from the viewpoint of ease of manufacture, it is preferable to have one or two types. Examples of poly(oxyfluoroalkylene) groups include groups in which the alkylene group of the poly(oxyalkylene) group is substituted with one or more fluorine atoms, and poly(oxyperfluoroalkylene) groups are preferred. Among these, (OX) m A poly(oxyfluoroalkylene) group represented by (OX) is preferred. m For details, see (S) group X 1 (OX) m The matters detailed above can be applied.

[0048] Among them, X 2 is {(OCF2) m21 (OCF2CF2)m22 It is preferable to include a structure represented by}. In the formula, m21 is an integer of 1 or more, m22 is an integer of 1 or more, and m21 + m22 is an integer between 2 and 500. {(OCF2) m21 (OCF2CF2) m22 For details on}, see (OX) in the (S) group. m (OCF2) m21 (OCF2CF2) m22 The aforementioned points can be applied to the structure of}. The aforementioned {(OCF2) m21 (OCF2CF2) m22 In}, it is preferable that m21 > m22.

[0049] Among them, -X 2 - is preferably a group having a poly(oxyperfluoroalkylene) group and a divalent organic group selected from the group consisting of an alkylene group, an etheric oxygen atom-containing group having an etheric oxygen atom between carbon atoms of the alkylene group, a perfluoroalkylene group, and combinations thereof, which links the poly(oxyperfluoroalkylene) group to at least one of the two oxygen atoms in formula (A). When the divalent organic group is an alkylene group, the number of carbon atoms in the alkylene group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6, from the viewpoint of excellent abrasion resistance. The alkylene group may be linear or branched. When the divalent organic group is an etheric oxygen atom-containing group having an etheric oxygen atom between the carbon atoms of the alkylene group, the total number of carbon atoms in the etheric oxygen atom-containing group is preferably 2 to 10, more preferably 2 to 6, and even more preferably 2 to 4, from the viewpoint of excellent abrasion resistance. The etheric oxygen atom-containing group may be linear or branched. Examples of etheric oxygen atom-containing groups having an etheric oxygen atom between carbon atoms in the alkylene group include poly(oxyalkylene) groups. Examples of poly(oxyalkylene) groups include groups having alkylene groups with 1 to 10 carbon atoms in each oxyalkylene unit, with 1 to 6 carbon atoms being preferred and 1 to 3 carbon atoms being more preferred. The multiple oxyalkylene units in the poly(oxyalkylene group) may be one type or two or more types, and from the viewpoint of ease of manufacture, one or two types are preferred. As for the perfluoroalkylene group, the (OX) mentioned above m The perfluoroalkylene group, exemplified as X in the compound, is one example.

[0050] [Method for producing fluorine-containing ether compounds] In one embodiment, a fluorine-containing ether compound is obtained by transesterifying a compound represented by the following formula (Cs) with a compound represented by the following formula (Cd) in the presence of a catalyst. Formula(Cs):X 1 -Si(R 1 ) n L 3-n Equation (Cd): HO-X 2 -OH In the formula (Cs), X 1 This represents a monovalent organic group having a poly(oxyfluoroalkylene) chain. R 1 Each of these independently represents a monovalent hydrocarbon group. Each L independently represents a hydrolyzable group or a hydroxyl group. n represents an integer between 0 and 2. In equation (Cd), X 2 represents a divalent organic group, where X is bonded to the two hydroxyl groups in formula (Cd). 2 The atoms at both ends are carbon atoms.

[0051] The above manufacturing method allows for the production of specific fluorine-containing ether compounds. Hereinafter, compounds represented by formula (Cs) will be referred to as "compound (Cs)," and compounds represented by formula (Cd) will be referred to as "compound (Cd)."

[0052] X1 and X 2 The details are as described above.

[0053] -Si(R) in equation (Cs) 1 ) n L 3-n This is a reactive silyl group. A reactive silyl group refers to a hydrolyzable silyl group and a silanol group (Si-OH). A hydrolyzable silyl group becomes a silanol group represented by Si-OH through hydrolysis. The silanol group can further form a Si-OC bond with the hydroxyl group of a compound represented by (Cd) through transesterification.

[0054] R 1 Each of these is independently a monovalent hydrocarbon group, and a monovalent saturated hydrocarbon group is preferred. 1 The number of carbon atoms is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2.

[0055] Each L independently represents either a hydrolyzable group or a hydroxyl group. A hydrolyzable group represented by L is a group that becomes a hydroxyl group through hydrolysis.

[0056] Examples of hydrolyzable groups L include alkoxy groups, aryloxy groups, halogen atoms, acyl groups, acyloxy groups, and isocyanate groups (-NCO). As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferred. The preferred aryloxy group is one having 3 to 10 carbon atoms. However, the aryl group of the aryloxy group may be an aryl group that does not contain a heteroatom, or it may be a heteroaryl group. A chlorine atom is preferred as the halogen atom. As the acyl group, an acyl group having 1 to 6 carbon atoms is preferred. As the acyloxy group, an acyloxy group having 1 to 6 carbon atoms is preferred.

[0057] From the viewpoint of easier production of fluorine-containing ether compounds, C1-C4 alkoxy groups and halogen atoms are preferred for L. From the viewpoint of minimizing outgassing during coating and providing excellent storage stability of fluorine-containing ether compounds, C1-C4 alkoxy groups are preferred for L, ethoxy groups are more preferred when long-term storage stability of fluorine-containing ether compounds is required, and methoxy groups are more preferred when the reaction time after coating is short.

[0058] n is an integer between 0 and 2. n is preferably 0 or 1, and more 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 a single molecule may be the same or different. From the viewpoint of ease of obtaining raw materials and ease of manufacturing fluorine-containing ether compounds, it is preferable that the multiple L atoms are the same. If n is 2, then there are multiple R in one molecule. 2 These may be the same or different. From the viewpoint of ease of obtaining raw materials and ease of manufacturing fluorine-containing ether compounds, it is preferable that they be the same.

[0059] From the viewpoint of efficiently producing specific fluorine-containing ether compounds, in transesterification, the amount M of compound (Cd) Cd The amount of compound (Cs) M Cs Mole ratio (M Cs / M Cd ) is preferably 1.1 to 10, more preferably 1.3 to 7.0, and even more preferably 1.5 to 4.0.

[0060] The transesterification reaction between compound (Cs) and compound (Cd) is carried out, for example, by adding a catalyst to a mixture of compound (Cs) and compound (Cd), or a mixture of these dissolved in a solvent, and reacting the two compounds.

[0061] Examples of catalysts include acid catalysts and nucleophilic catalysts. Examples of acid catalysts include Lewis acids such as titanium alkoxides, and acids such as sulfonic acids, phosphonic acids, hydrochloric acid, sulfuric acid, and carboxylic acids. Among these, carboxylic acids are preferred, and acetic acid is more preferred from the viewpoint of efficient transesterification. Examples of nucleophilic catalysts include substituted or unsubstituted pyridines; substituted or unsubstituted imidazoles; tertiary phosphines such as triphenylphosphine; and amine compounds such as 1,4-diazabicyclo[2.2.2]octane. Among these, substituted or unsubstituted pyridines are preferred from the viewpoint of efficient transesterification. Examples of catalysts include solid catalysts such as zeolites and amberlists. From the viewpoint of efficient production of specific fluorine-containing ether compounds, the catalyst is preferably at least one selected from the group consisting of carboxylic acids, Lewis acids, substituted or unsubstituted pyridines, substituted or unsubstituted imidazoles, tertiary phosphines, amine compounds, and solid catalysts.

[0062] The solvent is not particularly limited and can be appropriately adjusted depending on the type of compound (Cs), compound (Cd), and catalyst. As a solvent, for example, it can be appropriately selected from fluorinated organic solvents and non-fluorinated organic solvents or mixed solvents thereof that can be used in the coating agent described later.

[0063] The reaction temperature and reaction time can be appropriately adjusted depending on the type of compound (Cs), compound (Cd), and catalyst, for example, the reaction may be carried out at 80-120°C for 10-100 hours.

[0064] <Fluorine-containing ether mixture> The fluorine-containing ether mixtures of this disclosure contain two or more specific fluorine-containing ether compounds, or contain one or more specific fluorine-containing ether compounds and fluorine-containing ether compounds other than specific fluorine-containing ether compounds. Hereinafter, the fluorine-containing ether mixture will also be referred to as the "specific fluorine-containing ether mixture." The specific fluorine-containing ether mixture is a mixture of two or more fluorine-containing ether compounds, including a specific fluorine-containing ether compound. Fluorine-containing ether compounds other than specific fluorine-containing ether compounds may be used individually or in combination of two or more.

[0065] Examples of fluorine-containing ether compounds other than specific 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, A fluorooxyalkylene group-containing polymer as described in Japanese Patent Publication No. 2012-72272, International Publication No. 2013 / 042732, International Publication No. 2013 / 121984, International Publication No. 2013 / 121985, International Publication No. 2013 / 121986, International Publication No. 2014 / 163004, Japanese Patent Publication No. 2014-080473, International Publication No. 2015 / 087902, International Publication No. 2017 / 038830, International Publication No. 2017 / 038832, International Publication No. 201 Fluorine-containing ether compounds described in 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 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 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 described in International Publication No. 2019 / 039083 and International Publication No. 2019 / 049754, and Fluorine-containing ether compounds as described in International Publication No. 2020 / 111010.

[0066] Examples of commercially available fluorine-containing ether compounds other than specific 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., Optool® DSX, Optool® AES, Optool® UF503, Optool® UD509 from Daikin Industries Ltd., Fomblin® and Fluorolink® from Solvay Inc., and Krytox® from Chemours Inc.

[0067] In addition, fluorine-containing ether compounds other than specific fluorine-containing ether compounds include fluorine-containing ether compounds that are produced as by-products in the manufacturing process of specific fluorine-containing ether compounds. As a by-product of fluorine-containing ether compounds, CF3CF2CF2O[CF2CF2OCF2CF2CF2CF2CF2CF2O]CF2CF2O{(CF2O)} is obtained as a by-product of fluorine-containing ether compounds produced by the method described in Example 13-7 of International Publication No. 2018 / 216630. x1 (CF2CF2O) x2 CF2CF2OCF2CF2[OCF2CF2CF2CF2CF2CF2OCF2CF2]OCF2CF2CF3, a fluorine-containing ether compound CF3-(OCF2CF2OCF2CF2CF2CF2) produced by the method described in Example 6 of International Publication No. 2013 / 121984. m Examples include OCF2CF2OCF2CF2CF2-C(=O)OCH3.

[0068] The content of fluorine-containing ether compounds other than the specified fluorine-containing ether compounds is preferably 0% by mass or more and less than 90% by mass, more preferably 0% by mass or more and less than 70% by mass, even more preferably 0% by mass or more and less than 50% by mass, and particularly preferably 0% by mass or more and less than 30% by mass, relative to the total mass of the specified fluorine-containing ether compounds.

[0069] <Coating agent> The coating agent of this disclosure comprises a specific fluorine-containing ether compound or a specific fluorine-containing ether mixture. A specific fluorine-containing ether compound or a specific fluorine-containing ether mixture can be used alone to form a surface layer on a substrate (dry coating method described later). Alternatively, a composition containing other components besides the specific fluorine-containing ether compound or specific fluorine-containing ether mixture may be used to form a surface layer on a substrate (dry coating method and wet coating method described later). In this disclosure, specific fluorine-containing ether compounds, specific fluorine-containing ether mixtures, and compositions containing specific fluorine-containing ether compounds or specific fluorine-containing ether mixtures with other components, used for coating substrates, are all referred to as "coating agents."

[0070] The coating agent may contain a liquid medium. Examples of liquid media include water and organic solvents. A liquid medium is defined as a medium that is liquid at 25°C. The liquid medium preferably contains an organic solvent, and more preferably contains an organic solvent with a boiling point of 35 to 250°C from the viewpoint of excellent coating properties. Here, the boiling point refers to the standard boiling point. Examples of organic solvents include fluorinated organic solvents and non-fluorinated organic solvents, with fluorinated organic solvents being preferred from the viewpoint of excellent solubility. One type of organic solvent may be used alone, or two or more types may be used in combination.

[0071] Examples of fluorinated organic solvents include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols. Fluorinated alkanes are preferably compounds having 4 to 8 carbon atoms. Examples of compounds having 4 to 8 carbon atoms include C6F 13 H (AC-2000: Product name, manufactured by AGC Corporation), C6F 13 Examples include C2H5 (AC-6000: product name, manufactured by AGC Corporation) and C2F5CHFCHFCF3 (Bartrell: product name, manufactured by Chemours Corporation). 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. Examples of fluoroalkyl ethers include 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). Examples of fluorinated alkylamines include perfluorotripropylamine and perfluorotributylamine. Examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.

[0072] 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. Examples of such compounds include hydrocarbon organic solvents, ketone organic solvents, ether organic solvents, ester organic solvents, and alcohol organic solvents. Examples of hydrocarbon organic solvents include hexane, heptane, and cyclohexane. Examples of ketone-based organic solvents include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of ether-based organic solvents include diethyl ether, tetrahydrofuran, and tetraethylene glycol dimethyl ether. Examples of ester-based organic solvents include ethyl acetate and butyl acetate. Examples of alcoholic organic solvents include isopropyl alcohol, ethanol, and n-butanol.

[0073] If the coating agent contains a liquid medium, the liquid medium content is preferably 70.00 to 99.99% by mass, and more preferably 75.00 to 99.50% by mass, relative to the total mass of the coating agent.

[0074] The coating agent may contain components other than specific fluorine-containing ether compounds, fluorine-containing ether compounds other than specific fluorine-containing ether compounds, and liquid media. For example, the coating agent may include by-products generated in the manufacturing process of specific fluorine-containing ether compounds and other fluorine-containing ether compounds used as needed, as well as residual unreacted raw materials and catalysts. Furthermore, the coating agent may contain additives such as acid catalysts and basic catalysts that promote the hydrolysis and condensation reactions of hydrolyzable silyl groups. Examples of acid catalysts include hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, and p-toluenesulfonic acid. Examples of basic catalysts include sodium hydroxide, potassium hydroxide, and ammonia.

[0075] If the coating agent contains a specific fluorine-containing ether compound, a fluorine-containing ether compound other than the specific fluorine-containing ether compound, and components other than the liquid medium, the content of such components is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and even more preferably 0 to 1% by mass, relative to the total mass of the components of the coating agent excluding the liquid medium.

[0076] <Goods> The articles of this disclosure include a substrate and a surface layer formed on the substrate by the coating agent. The surface layer contains compounds obtained by hydrolysis and condensation reactions of specific fluorine-containing ether compounds.

[0077] The thickness of the surface layer is preferably 1 to 100 nm, and more preferably 1 to 50 nm. When the thickness of the surface layer is above the lower limit, the effect of the surface layer is obtained well. When the thickness of the surface layer is below the upper limit, the utilization efficiency of the coating agent is high. The thickness of the surface layer can be calculated using an X-ray diffractometer for thin film analysis (product name "ATX-G", manufactured by RIGAKU Corporation), by obtaining the interference pattern of reflected X-rays using the X-ray reflectivity method (XRR), and then calculating it from the oscillation period of this interference pattern.

[0078] Preferred substrates include those that may come into contact with other articles (such as styluses) or human fingers during use, those that may be held by human fingers during operation, and those that may be placed on other articles (such as stands). The coating agent of this disclosure can impart water-repellent and oil-repellent properties and abrasion resistance to the substrate, making it particularly useful when using a substrate for which water-repellent and oil-repellent properties and abrasion resistance are required. Examples of substrate materials include metals, resins, glass, sapphires, ceramics, stones, fibers, nonwoven fabrics, paper, wood, natural leather, artificial leather, and composite materials thereof. The glass may be chemically strengthened. The substrate is preferably a substrate for touch panels or a display substrate, with the touch panel substrate being more preferred. The touch panel substrate is preferably light-transmitting. "Light-transmitting" means that the normal incidence visible light transmittance, in accordance with JIS R3106:2019 (ISO 9050:2003), is 25% or more. The material of the touch panel substrate is preferably glass or transparent resin. Other suitable base materials include building materials; decorative building materials; interior furnishings; transportation equipment (automobiles, etc.); signs or bulletin boards; drinking utensils or tableware; aquariums; ornamental equipment (frames, boxes, etc.); laboratory equipment; furniture, textile products, packaging containers; and glass or resin used in art, sports, or games. Glass or resin used in the exterior parts (excluding display parts) of devices such as mobile phones (smartphones, etc.), personal digital assistants, game consoles, and remote controls is also preferred as a base material. The substrate may be in the form of a plate, film, or other shapes.

[0079] In particular, the article is a touch panel, and the surface layer is preferably formed on the surface of a component that constitutes the surface of the touch panel that is touched by a finger.

[0080] 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. Examples of such other films 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, SiO2, etc.

[0081] <Method of manufacturing articles> The articles of this disclosure can be manufactured, for example, by the following methods: A method for manufacturing an article, comprising applying the coating agent of the present disclosure to the surface of a substrate by a dry coating method to form a surface layer on the substrate. A method for manufacturing an article, comprising: applying a coating agent of the present disclosure, which includes a liquid medium, to the surface of a substrate by a wet coating method; and drying the substrate to which the coating agent has been applied to form a surface layer on the substrate.

[0082] Examples of dry coating methods include vacuum deposition, CVD, and sputtering. Among these, vacuum deposition is preferred from the viewpoint of suppressing the decomposition of specific fluorine-containing ether compounds and from the viewpoint of simplicity of the equipment. In vacuum deposition, a pellet-like material may be used in which a coating agent containing a liquid medium is impregnated into a porous metal body such as iron or steel and then dried.

[0083] Examples of wet coating methods include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, Langmuir-Bludget coating, and gravure coating. It is preferable to wet coat the coating solution and then dry the coating film. The drying temperature of the coating film is preferably 20 to 200°C, and more preferably 80 to 160°C. In the wet coating method, a specific fluorine-containing ether compound may be hydrolyzed beforehand using a catalyst such as an acid catalyst or a basic catalyst, and a composition containing the hydrolyzed compound and a liquid medium may be used as a coating agent. [Examples]

[0084] The embodiments of this disclosure will now be described in detail with reference to examples, but the embodiments of this disclosure are not limited to these examples. In the following examples, Examples 1 to 8 are examples, and Examples 9 and 10 are comparative examples.

[0085] <Synthesis of fluorine-containing ether compounds> [Compound (A-1)] Compound (A-1) below was synthesized using the same method as compound (1-1) described in International Publication No. 2020 / 166487. (Mean value of n: 13)

[0086] [ka]

[0087] [Compound (A-2)] Compound (A-2) was synthesized using the same method as compound (1-3a-2) described in International Publication No. 2013 / 121984. (Mean value of n: 7)

[0088] [ka]

[0089] [Compound (A-3)] Compound (A-3) was synthesized using the same method as compound (B) in Japanese Patent Publication No. 2019-90045. (Average value of m: 18, average value of l: 19)

[0090] [ka]

[0091] [Compound (A-4)] Compound (A-4) below was synthesized using the same method as compound (2-C) described in International Publication No. 2020 / 166488. (Average value of n: 10)

[0092] [ka]

[0093] [Compound (B-1)] Fluorolink D4000 (trade name, manufactured by Solvay Specialty Polymers; see compound below) was used. (Average value of m: 20, average value of l: 22)

[0094] [ka]

[0095] [Compound (B-2)] The following two compounds were used as raw materials. (In both cases, the average value of m was 28, and the average value of l was 16.)

[0096] [ka]

[0097] [ka]

[0098] 6.0 g of a mixture containing the two compounds mentioned above was dissolved in 5.0 g of 1,3-bis(trifluoromethyl)benzene and 1.3 g of tetrahydrofuran (THF). 3.0 g of Red-Al toluene solution (70%) (sodium bis(2-methoxyethoxy)aluminum hydride solution) was added, and the mixture was stirred at 50°C. After adding hydrochloric acid, the mixture was extracted using AE3000 (trade name, AGC). After solvent removal, flash column chromatography using silica gel (developing solvent: AE3000) was performed to obtain 0.24 g of the following compound (B-2). (Average m: 28, Average l: 16)

[0099] [ka]

[0100] [Compound (B-3)] The following compounds (X3-4) described in International Publication No. 2020 / 166488 were used as raw materials. (Average value of n: 10)

[0101] [ka]

[0102] 6.0 g of compound (X3-4) was dissolved in 5.0 g of 1,3-bis(trifluoromethyl)benzene and 1.3 g of THF. 3.0 g of Red-Al toluene solution (70%) was added, and the mixture was stirred at 50°C. Hydrochloric acid was added, and the mixture was extracted using AE3000 (trade name, AGC). After solvent removal, 4.2 g of compound (B-3) was obtained by flash column chromatography using silica gel (developing solvent: AE3000). (Average value of n: 10)

[0103] [ka]

[0104] <Preparation of Composition> [Example 1] A mixture containing 0.50 g of compound (A-1) and 0.15 g of compound (B-1) was dissolved in hydrofluoroether (3M, trade name: Novec HFE-7300) to a concentration of 20% by mass. 1.0 mg of acetic acid was added, and the mixture was reacted at 100°C. Composition 1 was then obtained by removing the solvent under reduced pressure.

[0105] [Example 2] A mixture containing 0.30 g of compound (A-2) and 0.15 g of compound (B-1) was dissolved in hydrofluoroether (3M, trade name: Novec HFE-7300) to a concentration of 20% by mass. 1.0 mg of acetic acid was added, and the mixture was reacted at 100°C. Composition 2 was then obtained by removing the solvent under reduced pressure.

[0106] [Example 3] A mixture containing 0.40 g of compound (A-3) and 0.15 g of compound (B-1) was dissolved in hydrofluoroether (3M, trade name: Novec HFE-7300) to a concentration of 20% by mass. 1.0 mg of acetic acid was added, and the mixture was reacted at 100°C. Composition 3 was obtained by removing the solvent under reduced pressure.

[0107] 〔Example 4〕 A mixture containing 0.44 g of compound (A-4) and 0.15 g of compound (B-1) was dissolved in hydrofluoroether (manufactured by 3M, trade name: Novec HFE-7300) to a concentration of 20% by mass. 1.0 mg of acetic acid was added, and after reacting at 100 °C, the solvent was distilled off under reduced pressure to obtain Composition 4.

[0108] 〔Example 5〕 A mixture containing 0.50 g of compound (A-1) and 0.15 g of compound (B-2) was dissolved in hydrofluoroether (manufactured by 3M, trade name: Novec HFE-7300) to a concentration of 20% by mass. 1.0 mg of acetic acid was added, and after reacting at 100 °C, the solvent was distilled off under reduced pressure to obtain Composition 5.

[0109] 〔Example 6〕 A mixture containing 0.50 g of compound (A-1) and 0.15 g of compound (B-3) was dissolved in hydrofluoroether (manufactured by 3M, trade name: Novec HFE-7300) to a concentration of 20% by mass. 1.0 mg of acetic acid was added, and after reacting at 100 °C, the solvent was distilled off under reduced pressure to obtain Composition 6.

[0110] 〔Example 7〕 A mixture containing 0.50 g of compound (A-1) and 0.15 g of compound (B-1) was dissolved in hydrofluoroether (manufactured by 3M, trade name: Novec HFE-7300) to a concentration of 20% by mass. 1.0 mg of acetic acid was added, and after reacting at 100 °C, Composition 7 was obtained.

[0111] 〔Example 8〕 0.50 g of compound (A-1), 0.15 g of compound (B-1) and 1.0 mg of pyridine were added and reacted at 100 °C, and then concentrated under reduced pressure to obtain Composition 8.

[0112] 〔Example 9〕 Composition 9 was obtained by mixing 0.50 g of compound (A-1) and 0.15 g of compound (B-1).

[0113] [Example 10] 0.50 g of compound (A-1) was dissolved in hydrofluoroether (3M Novec HFE-7300) to a concentration of 20% by mass. 1.0 mg of water was added, and the mixture was reacted at 100°C. Composition 10 was then obtained by removing the solvent under reduced pressure.

[0114] <Confirmation of the product> Gel permeation chromatography (GPC) peak observations confirmed that specific fluorine-containing ether compounds were obtained from compositions 1 to 8. Furthermore, composition 10 was confirmed to contain a self-condensed product of compound (A-1).

[0115] <Method for forming the surface layer> [Dry coating] A substrate (alkali-free glass (Eagle XG: product name, manufactured by Corning, 50mm x 50mm, 0.5mm thick)) is placed inside the vacuum deposition apparatus, and the inside of the vacuum deposition apparatus is 5 x 10 -3 The system was evacuated until the pressure was below Pa. A deposition container containing the composition prepared above was heated to 300°C by resistance heating at a distance of 1000 mm opposite one of the main surfaces of the substrate, and the composition was vacuum deposited to form a surface layer with a thickness of 10 nm. The temperature of the composition in each example was 300°C. After that, the substrate with the surface layer was heated at 200°C for 30 minutes (post-treatment).

[0116] [Wet coating] The composition prepared above was mixed with C4F9OC2H5 (Novec-7200: trade name, manufactured by 3M) as a liquid medium to prepare a coating solution in which the fluorine-containing ether compound content of the coating agent was 0.1% by mass. Alkali-free glass (Eagle XG: trade name, manufactured by Corning, 50 mm x 50 mm, 0.5 mm thick) was prepared as the substrate.

[0117] A coating agent was spray-coated onto one main surface of the substrate using a Nordson spray at a rate of 6.0 g / second. The coating film formed on the substrate was then dried at 120°C for 10 minutes to obtain a substrate with a surface layer. In each example, the thickness of the surface layer was 10 nm.

[0118] <Evaluation Method> [Initial water contact angle] The 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 (Kyowa Interface Science Co., Ltd., DM-500). Measurements were taken at five different locations on the surface of the surface layer, and the average value was calculated. The 2θ method was used to calculate the contact angle. The evaluation criteria are as follows. A: 115 degrees or higher. B: 105 degrees or higher and less than 115 degrees.

[0119] [Abrasion resistance (steel wool)] For the surface layer, a reciprocating traverse tester (manufactured by KNT Co., Ltd.) was used in accordance with JIS L0849:2013 (ISO 105-X12:2001). Steel wool bonstar (#0000) was traversed 10,000 times at a pressure of 98.07 kPa and a speed of 320 cm / min, and then the water contact angle was measured. The smaller the decrease in water repellency (water contact angle) after friction, the smaller the performance degradation due to friction and the superior abrasion resistance. The evaluation criteria are as follows. A: The change in the water contact angle after 10,000 round trips is 2 degrees or less. B: The change in water contact angle after 10,000 cycles is greater than 2 degrees and less than or equal to 3 degrees. C: The change in water contact angle after 10,000 cycles is greater than 3 degrees and less than or equal to 4 degrees. D: The change in water contact angle after 10,000 cycles exceeds 4 degrees.

[0120] The evaluation results for each example are shown in the table below. In the table below, compounds (A-1) to (A-4) are shown as "Compound A," and compounds (B-1) to (B-3) are shown as "Compound B." "-" indicates that the compound is not applicable.

[0121] [Table 1]

[0122] As shown in the table, the surface layer exhibited excellent abrasion resistance in Examples 1-8. On the other hand, in Example 9, where compounds (A-1) and (B-1) were mixed without using a catalyst, the abrasion resistance of the surface layer was inferior to that of Examples 1-8. Even in Example 10, where a self-condensed product of compound (A-1) was formed, the abrasion resistance of the surface layer was inferior to that of Examples 1-8. The initial contact angle evaluations were all favorable.

[0123] The disclosure of Japanese Patent Application No. 2021-102685 is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

Claims

1. A fluorine-containing ether compound represented by the following formula (A). Formula (A): X １ -Si(R １ ) ｎ L ２－ｎ -O-X ２ -O-Si(R １ ) ｎ L ２－ｎ -X １ In formula (A), X １ Each of these independently represents a monovalent organic group having a poly(oxyfluoroalkylene) chain. X ２ represents a divalent organic group containing a poly(oxyperfluoroalkylene) group, where X is bonded to the two oxygen atoms in formula (A). ２ The atoms at both ends are carbon atoms. R １ Each of these independently represents a monovalent hydrocarbon group. Each L independently represents a hydrolyzable group or a hydroxyl group. Each n represents an independent integer between 0 and 2.

2. In formula (A), X ２ The fluorine-containing ether compound according to claim 1, wherein the compound comprises an alkylene group, a fluoroalkylene group, or an etheric oxygen atom-containing group having an etheric oxygen atom between carbon atoms of the alkylene group or fluoroalkylene group.

3. In formula (A), X ２ But {(OCF ２ ) ｍ２１ (OCF ２ CF ２ ) ｍ２２ The fluorine-containing ether compound according to claim 1, comprising a structure represented by}, wherein m21 is an integer of 1 or more, m22 is an integer of 1 or more, and m21 + m22 is an integer from 2 to 500.

4. The aforementioned {(OCF ２ ) ｍ２１ (OCF ２ CF ２ ) ｍ２２ The fluorine-containing ether compound according to claim 3, wherein m21 > m22 in the given expression.

5. In formula (A), X ２ but, Poly(oxyperfluoroalkylene) group and A divalent organic group selected from the group consisting of an alkylene group, an etheric oxygen atom-containing group having an etheric oxygen atom between carbon atoms of the alkylene group, a perfluoroalkylene group, and combinations thereof, which links a poly(oxyperfluoroalkylene) group to at least one of the two oxygen atoms in formula (A), A fluorine-containing ether compound according to claim 1, wherein the group has a group having the same properties.

6. A method for producing a fluorine-containing ether compound according to any one of claims 1 to 5, comprising transesterifying a compound represented by the following formula (Cs) with a compound represented by the following formula (Cd) in the presence of a catalyst. Formula (Cs): X １ -Si(R １ ) ｎ L ３－ｎ Formula (Cd): HO-X ２ -OH In the formula (Cs), X １ This represents a monovalent organic group having a poly(oxyfluoroalkylene) chain. R １ Each of these independently represents a monovalent hydrocarbon group. Each L independently represents a hydrolyzable group or a hydroxyl group. n represents an integer between 0 and 2. In equation (Cd), X ２ represents a divalent organic group, where X is bonded to the two hydroxyl groups in formula (Cd). ２ The atoms at both ends are carbon atoms.

7. In the transesterification described above, the amount M of the compound represented by formula (Cd) Ｃｄ The amount M of the compound represented by the above formula (Cs) relative to Ｃｓ Mole ratio (M Ｃｓ / M Ｃｄ A method for producing a fluorine-containing ether compound according to claim 6, wherein the ratio is 1.5 to 4.

0.

8. The method for producing a fluorine-containing ether compound according to claim 6, wherein the catalyst comprises at least one selected from the group consisting of carboxylic acids, Lewis acids, substituted or unsubstituted pyridines, substituted or unsubstituted imidazoles, tertiary phosphines, amine compounds, and solid catalysts.

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

10. A coating agent comprising a fluorine-containing ether compound according to any one of claims 1 to 5.

11. The coating agent according to claim 10, further comprising a liquid medium.

12. An article having a base material and a surface layer formed on the base material by the coating agent described in claim 10.

13. The article according to claim 12, wherein the article is a touch panel, and the surface layer is formed on the surface of a member that constitutes the surface of the touch panel that is touched by a finger.

14. A method for manufacturing an article, comprising applying the coating agent described in claim 10 to the surface of a substrate by a dry coating method to form a surface layer on the substrate.

15. A method for manufacturing an article, comprising applying the coating agent described in claim 11 to the surface of a substrate by a dry coating method to form a surface layer on the substrate.

16. The coating agent described in claim 11 is applied to the surface of the substrate by a wet coating method, The substrate to which the coating agent has been applied is dried to form a surface layer on the substrate, A method for manufacturing articles, including

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