WO2022270318A1

WO2022270318A1 - Fluorine-containing ether compound, fluorine-containing ether mixture, coating agent, article, and article manufacturing method

Info

Publication number: WO2022270318A1
Application number: PCT/JP2022/023183
Authority: WO
Inventors: 隆太高下; 剛長谷川; 祥一齊藤; 英樹富澤
Original assignee: Ａｇｃ株式会社
Priority date: 2021-06-21
Filing date: 2022-06-08
Publication date: 2022-12-29
Also published as: JPWO2022270318A1; TW202300560A; KR20240024804A; CN117545792A

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

Fluorine-containing ether compound, fluorine-containing ether mixture, coating agent, article, and method for producing article

The present disclosure relates to fluorine-containing ether compounds, fluorine-containing ether mixtures, coating agents, articles, and methods for producing articles.

Fluorine-containing compounds exhibit high lubricity, water and oil repellency, and are therefore suitable for use as surface treatment agents. By imparting water and oil repellency to the surface of the base material with the surface treatment agent, dirt on the surface of the base material can be easily wiped off and the removability of the dirt can be improved. Among fluorine-containing compounds, a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain in which an ether bond is present in the fluoroalkylene chain is a compound with excellent flexibility, and is particularly excellent in removing stains such as oils and fats.

As the fluorine-containing ether compound, compounds having a poly(oxyperfluoroalkylene) chain and having a hydrolyzable silyl group at the end thereof are widely used.
For example, in Patent Document 1, a mixture of a poly(oxyperfluoroalkylene) group-containing silane compound and a fluorine-containing compound has water repellency, oil repellency, antifouling properties, and waterproof properties, and also exhibits excellent friction durability. It is described that it is possible to form a surface treatment layer having
Patent Document 2 discloses a fluorine-containing ether for vapor deposition, which contains a compound having a poly(oxyperfluoroalkylene) chain and a hydrolyzable silyl group, and a partial condensate of the compound, and is capable of forming a vapor deposition film having excellent friction durability. A composition is described.

JP 2016-132719 A WO2018/221520

In recent years, the level of demand for abrasion resistance of the surface layer by coating has increased. Therefore, the inventors have attempted to develop a fluorine-containing ether compound capable of forming a surface layer with even better abrasion resistance than the conventional compounds described in Patent Documents 1 and 2. The present disclosure relates to a fluorine-containing ether compound, a fluorine-containing ether mixture, a coating agent capable of forming a surface layer with excellent abrasion resistance, an article using these, and a method for producing the same.

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 -OX 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 both terminal atoms of X ² bonded to two oxygen atoms in formula (A) are carbon atoms,
each R ¹ 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> In formula (A), X ² includes an alkylene group, a fluoroalkylene group, or an etheric oxygen atom-containing group having an etheric oxygen atom between the carbon atoms of an alkylene group or a fluoroalkylene group, < The fluorine-containing ether compound according to 1>.
<3> The fluorine-containing ether compound according to <1> or <2>, wherein in formula (A), X ² contains a poly(oxyperfluoroalkylene) group.
<4> In formula (A), X ² includes a structure represented by {(OCF ₂ ) _m21 (OCF ₂ CF ₂ ) _m22 }, wherein m21 is an integer of 1 or more and m22 is 1 or more The fluorine-containing ether compound according to <3>, wherein m21+m22 is an integer of 2 to 500.
<5> The fluorine-containing ether compound according to <4>, wherein in {( _OCF2 ) _m21 ( _OCF2CF2 ) _m22 }, _m21 >m22.
<6> In formula (A), X ² is
a poly(oxyperfluoroalkylene) group;
An alkylene group, an etheric oxygen having an etheric oxygen atom between the carbon atoms of the alkylene group, which connects between the poly(oxyperfluoroalkylene) group and at least one of the two oxygen atoms in the formula (A) a divalent organic group selected from the group consisting of atom-containing groups, perfluoroalkylene groups, and combinations thereof;
The fluorine-containing ether compound according to any one of <3> to <5>, which is a group having
<7> Any one of <1> to <6>, which is obtained by transesterifying a compound represented by the following formula (Cs) and a compound represented by the following formula (Cd) in the presence of a catalyst: The fluorine-containing ether compound according to .
Formula (Cs): X ¹ -Si(R ¹ ) _n L _3-n
Formula (Cd): HO—X ² —OH
In formula (Cs),
X ¹ represents a monovalent organic group having a poly(oxyfluoroalkylene) chain,
each R ¹ independently represents a monovalent hydrocarbon group,
L each independently represents a hydrolyzable group or a hydroxyl group,
n represents an integer of 0 to 2;
In formula (Cd),
X2 represents a ^divalent organic group, provided that both terminal atoms of X2 bonded to ^two hydroxyl groups in formula (Cd) are carbon atoms.
<8> In the transesterification, the molar ratio (M _Cs /M _Cd ) of the amount M _Cs of the compound represented by the formula (Cs) to the amount M _Cd of the compound represented by the formula (Cd) is 1 .5 to 4.0, the fluorine-containing ether compound according to <7>.
<9> The catalyst contains 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. The fluorine-containing ether compound according to <7> or <8>.
<10> Any one of <1> to <6>, wherein the compound represented by the following formula (Cs) and the compound represented by the following formula (Cd) are transesterified in the presence of a catalyst: A method for producing a fluorine-containing ether compound.
Formula (Cs): X ¹ -Si(R ¹ ) _n L _3-n
Formula (Cd): HO—X ² —OH
In formula (Cs),
X ¹ represents a monovalent organic group having a poly(oxyfluoroalkylene) chain,
each R ¹ independently represents a monovalent hydrocarbon group,
L each independently represents a hydrolyzable group or a hydroxyl group,
n represents an integer of 0 to 2;
In formula (Cd),
X2 represents a ^divalent organic group, provided that both terminal atoms of X2 bonded to ^two hydroxyl groups in formula (Cd) are carbon atoms.
<11> In the transesterification, the molar ratio (M _Cs /M _Cd ) of the amount M _Cs of the compound represented by the formula (Cs) to the amount M _Cd of the compound represented by the formula (Cd) is 1 .5 to 4.0, the method for producing a fluorine-containing ether compound according to <10>.
<12> The catalyst contains 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. A method for producing a fluorine-containing ether compound according to <10> or <11>.
<13> Contains two or more fluorine-containing ether compounds according to any one of <1> to <9>, or containing the fluorine-containing ether compound according to any one of <1> to <9> A fluorine-containing ether mixture containing one or more fluorine-containing ether compounds other than the fluorine-containing ether compound according to any one of <1> to <9>.
<14> A coating agent comprising the fluorine-containing ether compound according to any one of <1> to <9> or the fluorine-containing ether mixture according to <13>.
<15> The coating agent according to <14>, further comprising a liquid medium.
<16> An article comprising a base material and a surface layer formed on the base material by the coating agent according to <14> or <15>.
<17> A method for producing an article, comprising applying the coating agent according to <14> to a surface of a substrate by a dry coating method to form a surface layer on the substrate.
<18> Applying the coating agent according to <15> to the surface of the substrate by a wet coating method;
drying the substrate to which the coating agent is applied to form a surface layer on the substrate;
A method of manufacturing an article, comprising:

According to the present disclosure, a fluorine-containing ether compound, a fluorine-containing ether mixture, a coating agent capable of forming a surface layer with excellent abrasion resistance, an article using these, and a method for producing the same are provided.

Hereinafter, the form for implementing the embodiment of the present disclosure will be described in detail. However, embodiments of the present disclosure are not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and their ranges, which do not limit the embodiments of the present disclosure.

In the present disclosure, the term "process" includes a process that is independent of other processes, and even if the purpose of the process is achieved even if it cannot be clearly distinguished from other processes. .
In the present disclosure, the numerical range indicated using "-" includes the numerical values before and after "-" as the minimum and maximum values, respectively.
In the present disclosure, each component may contain multiple types of applicable substances. When there are multiple types of substances corresponding to each component in the composition, the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition unless otherwise specified. means quantity.
In this disclosure, the terms "alkyl group" and "alkylene group" mean unsubstituted alkyl groups and unsubstituted alkylene groups, respectively, unless otherwise specified that they have substituents.

<Fluorine-containing ether compound>
The fluorine ether compound of the present disclosure is 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 independently represents a monovalent organic group having a poly(oxyfluoroalkylene) chain,
X ² represents a divalent organic group, provided that both terminal atoms of X ² bonded to two oxygen atoms in formula (A) are carbon atoms,
each R ¹ 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;

In the present disclosure, the fluorine-containing ether compound is also referred to as a "specific fluorine-containing ether compound".
In the present disclosure, each group of the specific fluorine-containing ether compound may be indicated as follows.
(S) group: in the above formula (A), a monovalent organic group represented by X ¹ -Si(R ¹ ) _n L _2-n -O- (D) group: in the above formula (A), - Divalent Group Represented by X ² — The specific fluorine ether compound has a structure represented by (S) group-(D) group-(S) group. Note that the two (S) groups may be the same or different. From the viewpoint of manufacturability, the two (S) groups are preferably the same.

The inventors have found that a surface layer having excellent abrasion resistance can be formed by using a specific fluorine-containing ether compound. The reason for this is not necessarily clear, but is presumed as follows.
For example, Patent Document 1 describes a composition obtained by mixing a poly(oxyperfluoroalkylene) group-containing silane compound and a monovalent poly(oxyperfluoroalkylene) group-containing alcohol compound. On the other hand, since the specific fluorine-containing ether compound has a structure in which a plurality of (S) groups having poly(oxyfluoroalkylene) chains are linked via (D) groups, the surface layer is formed using the specific fluorine-containing ether compound. It is believed that a stronger coating is formed when formed.
Further, a partial condensate of a compound having a poly(oxyperfluoroalkylene) chain and a hydrolyzable silyl group described in Patent Document 2 has a plurality of poly(oxyperfluoroalkylene) chains linked via Si—O—Si bonds. It is In contrast, the specific fluorine-containing ether compound has a plurality of poly(oxyfluoroalkylene) chains linked via Si—O—C bonds. Since a plurality of (S) groups are linked via the (D) group, it is believed that a stronger coating is formed when the surface layer is formed using the specific fluorine-containing ether compound.

The specific fluorine ether compound is, for example, reacted with a compound having a poly(oxyfluoroalkylene) chain and a hydrolyzable silyl group and a diol at a molar ratio of about 2:1 in the presence of a catalyst to transesterify. obtained by Said reaction forms a Si--O--C bond between the hydrolyzable silyl group and the two hydroxyl groups of the diol.
The structure of each group of the specific fluorine-containing ether compound is described in detail below.

[A monovalent organic group represented by X ¹ -Si(R ¹ ) _n L _2-n -O- ((S) group)]
The fluorine-containing ether compounds of the present disclosure have two (S) groups. The (S) group preferably has a structure derived from a compound represented by formula (Cs) described below.

In the (S) group, X1 is a ^monovalent organic group having a poly(oxyfluoroalkylene) chain.
A poly(oxyfluoroalkylene) chain includes a plurality of units represented by the following formula.
Formula: (OX)
In the formula, each X independently represents a fluoroalkylene group.

The number of carbon atoms in the fluoroalkylene group in the poly(oxyfluoroalkylene) chain is preferably 1 to 20, more preferably 1 to 10, and 1 to 6 independently from the viewpoint of improving the abrasion resistance of the surface layer. is more preferred.
A 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, more preferably 1.7 to 2 times, from the viewpoint of improving the abrasion resistance of the surface layer.
The fluoroalkylene group may be a group in which all hydrogen atoms in the fluoroalkylene group are substituted with fluorine atoms (perfluoroalkylene group). From the viewpoint of improving the abrasion resistance of the surface layer, the perfluoroalkylene group is preferable.

(OX) includes -OCHF-, -OCF _{2 CHF-, -OCHFCF 2} _- , -OCF ₂ CH ₂ -, -OCH ₂ CF ₂ -, -OCF _{2 CF 2 CHF-, -OCHFCF 2} _CF ₂ _- , _-OCF2CF2CH2- _, _-OCH2CF2CF2- _, _{-OCF2CF2CF2CH2-} _, _{-OCH2CF2CF2CF2-} _, _{-OCF2CF2CF2CF2CH} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _2- _, _{-OCH2CF2CF2CF2CF2-} _, _{-OCF2CF2CF2CF2CF2CH2-} _, _{-OCH2CF2CF2CF2CF2CF2-} _, _-OCF2- _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} , -OCF ₂ CF ₂ -, -OCF ₂ CF ₂ CF ₂ -, -OCF(CF ₃ )CF ₂ -, -OCF ₂ CF ₂ CF ₂ CF ₂ -, -OCF(CF ₃ )CF ₂ CF ₂ -, -OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ -, -OCF _{2 CF 2 CF 2 CF 2 CF 2 CF 2} _- _, _-O _- _cycloC ₄ F ₆ - and the like.
Here, -cycloC ₄ F ₆ - means a perfluorocyclobutanediyl group, a specific example of which is a perfluorocyclobutane-1,2-diyl group.

The repeating number m of (OX) is an integer of 2 or more, preferably an integer of 2 to 500, more preferably an integer of 2 to 200, and even more preferably an integer of 5 to 150.
(OX) _m may be a repetition of one type of (OX), or may contain two or more types of (OX). The binding order of two or more (OX) is not limited, and may be arranged randomly, alternately, or in blocks.
Containing two or more types of (OX) means that, in the specific fluorine-containing ether compound, for example, two or more types of (OX) having different numbers of carbon atoms are present, two or more types of (OX) having different numbers of hydrogen atoms exists, two or more types of (OX) with different positions of hydrogen atoms exist, or the presence or absence of side chains even if the number of carbon atoms is the same, the type of side chain (the number of side chains, the number of side chains It means that there are two or more types of (OX) having different numbers of carbon atoms, etc.).

The poly(oxyfluoroalkylene) chain is preferably a poly(oxyfluoroalkylene) chain mainly composed of (OX), which is an oxyperfluoroalkylene group, from the viewpoint of forming a film having excellent fingerprint stain removability. (OX) In the poly(oxyfluoroalkylene) chain represented by _m , the ratio of the number of (OX) which is an oxyperfluoroalkylene group to the total number m of (OX) is preferably 50 to 100%, and 80 to 100 % is more preferred, and 90 to 100% is even more preferred.

The poly(oxyfluoroalkylene) chain includes a poly(oxyperfluoroalkylene) chain and a poly(oxyperfluoroalkylene) chain having one or two oxyfluoroalkylene units having hydrogen atoms at one end or both ends. more preferred.

In the present disclosure, two or more (OX) arrangements are represented as follows. For example, the structure represented by {(OCF ₂ ) _m21 (OCF ₂ CF ₂ ) _m22 } indicates that m21 (OCF ₂ ) and m22 (OCF ₂ CF ₂ ) are randomly arranged. show. Further, the structure represented by ₍ OCF ₂ CF ₂ _-OCF ₂ CF ₂ CF ₂ CF ₂ ) _m25 is composed of m25 ₍ _OCF2CF2 ) and m25 ₍ _{OCF2CF2CF2CF2} ) Indicates that they are arranged alternately.

(OX) _m is represented by (OCH _ma F _(2-ma) ) _m11 · (OC ₂ H _mb F _(4-mb) ) _m12 · (OC ₃ H _mc F _(6-mc) ) _m13 · (OC ₄ H _md F _(8-md) ) _m14 .(OC ₅ H _me F _(10-me) ) _m15 .(OC ₆ H _mf F _(12-mf) ) _m16 .(O-cycloC ₄ H _mg F _{(6- mg)} ) _m17 is preferred. Here, -cycloC ₄ H _mg F _(6-mg) represents a fluorocyclobutane-diyl group, preferably a fluorocyclobutane-1,2-diyl group.

In the formula, ma is 0 or 1, mb is an integer of 0 to 3, mc is an integer of 0 to 5, md is an integer of 0 to 7, and me is an integer of 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 independently an integer of 0 or more, preferably 150 or less.
m11+m12+m13+m14+m15+m16+m17 is an integer of 2 or more, preferably an integer of 2 to 500, more preferably an integer of 2 to 200, and even more preferably an integer of 5 to 150.
Among them, m12 is preferably an integer of 2 or more, more preferably an integer of 2 to 200.
C ₃ H _mc F _(6-mc) , C ₄ H _md F _(8-md) , C ₅ H _me F _(10-me) and C ₆ H _mf F _(12-mf) are also linear or a branched chain, and a straight chain is preferred from the standpoint of more excellent abrasion resistance of the surface layer.

Note that the above formula represents the type and number of units, and does not represent the arrangement of the units. That is, m11 to m16 represent the number of units. For example, (OCH _ma F _(2-ma) ) _m11 represents a block in which m11 (OCH _ma F _(2-ma) ) units are consecutive. is not. Similarly, the order of (OCH _ma F _(2-ma) ) to (O-cycloC ₄ H _mg F _(6-mg) ) does not indicate that they are arranged in that order.
In the above formula, when two or more of m11 to m17 are other than 0 (that is, when (OX) _m is composed of two or more types of units), the arrangement of different units is a random arrangement or an alternate arrangement. , block sequences, and combinations thereof.
In the above formula, when there are two or more oxyfluoroalkylene units represented by the same formula, each oxyfluoroalkylene unit may be the same or different. For example, when m11 is 2 or more, multiple (OCH _ma F _(2-ma) ) may be the same or different.

(OX) _m preferably has the following structure.
{( _OCF2 ) _m21 ( _OCF2 _{CF2) 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 _. _{_} _{_}

In the formula, m21 is an integer of 1 or more, m22 is an integer of 1 or more, m21+m22 is an integer of 2 to 500, m23 and m24 are each independently an integer of 2 to 500, and m25 is It is an integer of 1-250, m26 and m27 are each independently an integer of 1 or more, m26+m27 is an integer of 2-500, and m28 is an integer of 1-250.

(OX) _m is preferably the following structure from the viewpoint of easy production of the specific fluorine-containing ether compound.
{( _OCF2 ) _m21 ( _OCF2 _{CF2) m22} _} ,
₍ _OCF2CF2CF2 _{) m24} _,
(OCF ₂ CF ₂ ) ₂ {(OCF ₂ ) _m21 (OCF ₂ CF ₂ ) _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 each an integer of 1 or more.

In {(OCF ₂ ) _m21 (OCF ₂ CF ₂ ) _m22 }, the ratio of m22 to m21 (m22/m21) is from 0.05 to 10.00 is preferred, 0.08 to 2.00 is more preferred, 0.10 to 1.00 is particularly preferred, and 0.12 to 0.85 is most preferred.
In one aspect, in {(OCF ₂ ) _m21 (OCF ₂ CF ₂ ) _m22 }, it is preferable that m21>m22.
In {(OCF ₂ ) _m21 (OCF ₂ CF ₂ ) _m22 }, m21 is preferably 2 to 200 and m22 is 2 to 100, m21 is 10 to 150 and m22 is 5 to 50. is more preferable.

In (OCF ₂ CF ₂ -OCF ₂ CF ₂ CF ₂ CF ₂ ) _m25 , m25 is preferably 2 to 100, more preferably 5 to 20, even more preferably 7 to 15.

In one embodiment, X ¹ may have a group represented by R ^f1 -(OX) _m -* and a linking group linked to *. Here, R ^f1 represents a fluoroalkyl group, each X independently represents a fluoroalkylene group, and m represents an integer of 2 or more. (OX) The details of _m are as described above.
R ^f1 is preferably a perfluoroalkyl group.
The number of carbon atoms in the perfluoroalkyl group is preferably from 1 to 20, more preferably from 1 to 10, even more preferably from 1 to 6, from the viewpoint of improving the abrasion resistance of the surface layer.
Perfluoroalkyl groups may be linear, branched or cyclic.
Specific examples of perfluoroalkyl groups include CF ₃ —, CF ₃ CF ₂ —, CF ₃ CF ₂ CF ₂ —, CF ₃ CF ₂ CF ₂ CF ₂ —, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ —, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ — and CF ₃ CF(CF ₃ )—, and from the viewpoint of more excellent water and oil repellency of the surface layer, CF ₃ —, CF 3 CF 2 —, CF ₃ CF ₂ —, and CF ₃ CF ₂ CF ₂ — are preferred.

In another aspect, X ¹ may have a group represented by Z—(OX) _m —* and a linking group linked to *. Here, Z represents a monovalent organic group other than a fluoroalkyl group, X each independently represents a fluoroalkylene group, and m represents an integer of 2 or more. (OX) The details of _m are as described above.

The linking groups connected to * of the group represented by R ^f1 -(OX) _m -* and the group represented by Z-(OX) _m -* are, respectively, these groups and -Si(R ¹ ) _n L _2-n is a divalent group that connects with the Si atom in the group represented by -O-. Examples of the divalent group include an alkylene group, a fluoroalkylene group, an etheric oxygen atom-containing group having an etheric oxygen atom between the carbon atoms of the alkylene group, -Si(R ⁶ ) ₂ -, - Si(CH ₃ ) ₂ —Ph—Si(CH ₃ ) ₂ —, divalent organopolysiloxane residues and combinations thereof. In the above linking group, the atom described on the left side is bound to *. The divalent group may further include -C(O)NR ⁶ -, -C(O)O-, -C(O)-, -NR ⁶ -, -S-, -NHC(O)O-, - NHC(O)NR ⁶ —, —SO ₂ NR ⁶ — and the like may be included.
In the formula, each R ⁶ is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and Ph is a phenylene group. The number of carbon atoms in the alkyl group of R ⁶ is preferably 1 to 3 from the viewpoint of ease of production.
* is an alkylene group, a fluoroalkylene group, and an etheric oxygen atom-containing group having an etheric oxygen atom between the carbon atoms of the alkylene group and the carbon atom of the alkylene group, and the carbon number represented by R ⁶ is 1 At least one of the hydrogen atoms in the alkyl groups to 6 is a group having a reactive silyl group represented by the formula -Si(R ¹ ) _n L _3-n , for example, -Si(R ¹ ) _n L _{3 -n} or an alkylene group -Si(R ¹ ) _n L _3-n . Details of the reactive silyl group are as described below. The number of carbon atoms in the alkylene group —Si(R ¹ ) _n L _3-n is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 6.

The alkylene group that is the linking 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 still more preferably an alkylene group having 1 to 11 carbon atoms.

The fluoroalkylene group, which is a linking group 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. 1 to 6 fluoroalkylene groups are more preferred. Among them, a perfluoroalkylene group having the number of carbon atoms described above is preferable.

The total carbon number of the etheric oxygen atom-containing group having an etheric oxygen atom between the carbon atoms of the alkylene group, which is the linking group linked to *, is preferably 2 to 10, more preferably 2 to 6. , 2 to 4 are more preferred.
The etheric oxygen atom-containing group having an etheric oxygen atom between the carbon atoms of the alkylene group includes poly(oxyalkylene) groups and the like.
Examples of the poly(oxyalkylene) group include groups having an alkylene group having 1 to 10 carbon atoms in each oxyalkylene unit, and the number of carbon atoms is preferably 1 to 6, more preferably 1 to 3. The plurality of oxyalkylene units in the poly(oxyalkylene group) may be one or two or more, and preferably one or two from the viewpoint of ease of production.

An alkylene group, a fluoroalkylene group, and an etheric oxygen atom-containing group having an etheric oxygen atom between the carbon atoms of the alkylene group may each independently be linear or branched. .

In one embodiment, the linking group that is linked to * includes a combination of —C(O)NR ⁶ — and a linear or branched alkylene group optionally substituted with a reactive silyl group. be done.

The linking group linked to * may have one or more reactive silyl groups represented by the formula —Si(R ¹ ) _n L _3-n . The details of the reactive silyl group represented by the formula —Si(R ¹ ) _n L _3-n are as described later. The total number of reactive silyl groups in the linking group linked to * is preferably 0-2.

Z in the group represented by the formula Z-(OX) _m -* is a monovalent organic group other than a fluoroalkyl group.
The monovalent organic group represented by Z is, for example, a reactive silyl group represented by the formula —Si(R ¹ ) _n L _3-n added to the above-described group described as the linking group linked to *. It may be connected.
In one aspect, in the monovalent organic group represented by Z, any of the groups described as the linking groups linked to * above, the other bond on the side opposite to the bonding site with * is It may be bonded to a reactive silyl group represented by the formula —Si(R ¹ ) _n L _3-n .
In one embodiment, the monovalent organic group represented by Z may be a group represented by Z ¹ -X-, where Z ¹ represents a monovalent organic group other than a fluoroalkyl group, X has the same definition as X in (OX) _m , and X may be the same as or different from X in (OX) _m . In one aspect, Z ¹ is a group of the formula —Si(R ¹ ) _n It may be bonded to a reactive silyl group represented by L _3-n . That is, in this case, X ¹ is
Si(R ¹ ) _n L _3-n -(group*)-X-(OX) _m -(group*)-
has a structure represented by Here, (group *) represents any of the groups described as the linking groups linked to * above, and two (groups *) may be the same or different. From the viewpoint of ease of production, the two (groups*) are preferably the same, and the same (groups*) are more preferably arranged symmetrically about -X-(OX) _m -. preferable.
The details of the reactive silyl group represented by the formula —Si(R ¹ ) _n L _3-n are as described later. The number of reactive silyl groups that Z has is preferably 1 to 5, more preferably 1 to 3.

Specific examples of the linking group linked to * are as follows. ** in the following specific example represents the linking position to Si in formula (A).

Among the (S) groups, in the group represented by -Si(R ¹ ) _n L _2-n -O-, the details of R ¹ and L are as described below for the reactive silyl group.

[Divalent group represented by -X ² - ((D) group)]
In formula (A), in the divalent group represented by -X ² -, X ² represents a divalent organic group, provided that both of X ² bonded to two oxygen atoms in formula (A) The terminal atoms are carbon atoms.

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

When X ² is an alkylene group, the number of carbon atoms in the alkylene group is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 6, from the viewpoint of excellent abrasion resistance.

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

The etheric oxygen atom-containing group having an etheric oxygen atom between the carbon atoms of an alkylene group or a fluoroalkylene group contained in X ² includes a poly(oxyalkylene) group and a poly(oxyfluoroalkylene) group. mentioned.
Examples of the poly(oxyalkylene) group include groups having an alkylene group having 1 to 20 carbon atoms in each oxyalkylene unit, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. The plurality of oxyalkylene units in the poly(oxyalkylene group) may be one or two or more, and preferably one or two from the viewpoint of ease of production.
Examples of the poly(oxyfluoroalkylene) group include groups in which the alkylene group of the poly(oxyalkylene) group is substituted with one or more fluorine atoms, and a poly(oxyperfluoroalkylene) group is preferred. Among them, a poly(oxyfluoroalkylene) group represented by (OX) _m is preferable. Here, the details of (OX) _m can be applied to the details of (OX) _m in X ¹ of the (S) group.

Among them, X ² preferably includes a structure represented by {(OCF ₂ ) _m21 (OCF ₂ CF ₂ ) _m22 }. 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 of 2-500. Details of {(OCF ₂ ) _m21 (OCF ₂ CF ₂ ) _m22 } are described above for the structure of {(OCF ₂ ) _m21 (OCF ₂ CF ₂ ) _m22 }, which is an aspect of (OX) _m in the (S) group. applicable.
In {(OCF ₂ ) _m21 (OCF ₂ CF ₂ ) _m22 }, it is preferable that m21>m22.

Among them, -X ² - is a poly(oxyperfluoroalkylene) group, an alkylene group connecting between the poly(oxyperfluoroalkylene) group and at least one of the two oxygen atoms in the formula (A), an alkylene group A divalent organic group selected from the group consisting of a carbon atom-an ethereal oxygen atom-containing group having an etheric oxygen atom between the carbon atoms, a perfluoroalkylene group, and combinations thereof preferable.
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, even more preferably 1 to 6, from the viewpoint of excellent abrasion resistance. Alkylene groups 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 carbon number of the etheric oxygen atom-containing group is From the standpoint of superiority, 2 to 10 are preferred, 2 to 6 are more preferred, and 2 to 4 are even more preferred. The etheric oxygen atom-containing group may be linear or branched.
The etheric oxygen atom-containing group having an etheric oxygen atom between the carbon atoms of the alkylene group includes poly(oxyalkylene) groups and the like.
Examples of the poly(oxyalkylene) group include groups having an alkylene group having 1 to 10 carbon atoms in each oxyalkylene unit, and the number of carbon atoms is preferably 1 to 6, more preferably 1 to 3. The plurality of oxyalkylene units in the poly(oxyalkylene group) may be one or two or more, and preferably one or two from the viewpoint of ease of production.
Examples of the perfluoroalkylene group include the perfluoroalkylene groups exemplified as X in (OX) _m described above.

[Method for producing fluorine-containing ether compound]
In one aspect, the fluorine-containing ether compound is obtained by subjecting a compound represented by the following formula (Cs) and a compound represented by the following formula (Cd) to transesterification in the presence of a catalyst.
Formula (Cs): X ¹ -Si(R ¹ ) _n L _3-n
Formula (Cd): HO—X ² —OH
In formula (Cs),
X ¹ represents a monovalent organic group having a poly(oxyfluoroalkylene) chain,
each R ¹ independently represents a monovalent hydrocarbon group,
L each independently represents a hydrolyzable group or a hydroxyl group,
n represents an integer of 0 to 2;
In formula (Cd),
X2 represents a ^divalent organic group, provided that both terminal atoms of X2 bonded to ^two hydroxyl groups in formula (Cd) are carbon atoms.

A specific fluorine-containing ether compound can be produced by the production method described above.
Hereinafter, the compound represented by formula (Cs) may be referred to as "compound (Cs)", and the compound represented by formula (Cd) may be referred to as "compound (Cd)".

^The details of X1 and X2 ^are as described above.

—Si(R ¹ ) _n L _3-n in formula (Cs) is a reactive silyl group. A reactive silyl group means a hydrolyzable silyl group and a silanol group (Si—OH). A hydrolyzable silyl group becomes a silanol group represented by Si—OH through a hydrolysis reaction. The silanol group can further form a Si--O--C bond by transesterification with the hydroxyl group of the compound represented by (Cd).

Each R ¹ is independently a monovalent hydrocarbon group, preferably a monovalent saturated hydrocarbon group. The number of carbon atoms in R ¹ is preferably 1-6, more preferably 1-3, even more preferably 1-2.

Each L is independently a hydrolyzable group or a hydroxyl group. The hydrolyzable group represented by L is a group that becomes a hydroxyl group through a hydrolysis reaction.

Examples of the hydrolyzable group L include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, and an isocyanate group (--NCO).
As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable.
As the aryloxy group, an aryloxy group having 3 to 10 carbon atoms is preferred. However, the aryl group of the aryloxy group may be an aryl group containing no heteroatom or a heteroaryl group.
A chlorine atom is preferable 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.

From the viewpoint of easier production of fluorine-containing ether compounds, L is preferably an alkoxy group having 1 to 4 carbon atoms and a halogen atom. L is preferably an alkoxy group having 1 to 4 carbon atoms from the viewpoint of less outgassing during application and excellent storage stability of the fluorine-containing ether compound, and when long-term storage stability of the fluorine-containing ether compound is required. is more preferably an ethoxy group, and a methoxy group is more preferable when the reaction time after coating is shortened.

n is an integer of 0-2.
n is preferably 0 or 1, more preferably 0. By having a plurality of L's, the adhesion of the surface layer to the base material becomes stronger.
When n is 1 or less, multiple Ls present in one molecule may be the same or different. From the viewpoint of availability of raw materials and ease of production of the fluorine-containing ether compound, it is preferable that the plurality of L's are the same.
When n is 2, multiple R ² present in one molecule may be the same or different. From the viewpoint of the availability of raw materials and the ease of production of the fluorine-containing ether compound, they are preferably the same.

From the viewpoint of efficiently producing the specific fluorine-containing ether compound, in transesterification, the molar ratio (M _Cs /M _Cd ) of the amount M _Cs of the compound (Cs) to the amount M _Cd of the compound (Cd) is 1. 1 to 10 are preferred, 1.3 to 7.0 are more preferred, and 1.5 to 4.0 are even more preferred.

The transesterification reaction between the compound (Cs) and the compound (Cd) is performed, for example, by adding a catalyst to a mixture of the compound (Cs) and the compound (Cd) or a mixture of these dissolved in a solvent to react both compounds. It is done by

Catalysts include acid catalysts and nucleophilic catalysts.
Acid catalysts include Lewis acids such as titanium alkoxide; and acids such as sulfonic acid, phosphonic acid, hydrochloric acid, sulfuric acid, and carboxylic acids. is more preferred.
Nucleophilic catalysts include substituted or unsubstituted pyridine; substituted or unsubstituted imidazole; tertiary phosphines such as triphenylphosphine; amine compounds such as 1,4-diazabicyclo[2.2.2]octane; Of these, substituted or unsubstituted pyridine is preferred from the viewpoint of efficient transesterification.
The catalyst also includes solid catalysts such as zeolite and amberlyst.
From the viewpoint of efficient production of a specific fluorine-containing ether compound, the catalyst consists of a carboxylic acid, a Lewis acid, a substituted or unsubstituted pyridine, a substituted or unsubstituted imidazole, a tertiary phosphine, an amine compound, and a solid catalyst. At least one selected from the group is preferred.

The solvent is not particularly limited, and may be adjusted as appropriate according to the type of compound (Cs), compound (Cd) and catalyst. The solvent can be appropriately selected from, for example, fluorine-based organic solvents and non-fluorine-based organic solvents that can be used in coating agents described later, or mixed solvents thereof.

The reaction temperature and reaction time may be appropriately adjusted according to the type of compound (Cs), compound (Cd), catalyst, etc. For example, the reaction may be carried out at 80-120°C for 10-100 hours.

<Fluorine-containing ether mixture>
The fluorine-containing ether mixture of the present disclosure contains two or more specific fluorine-containing ether compounds, or one or more specific fluorine-containing ether compounds and a fluorine-containing ether compound other than the specific fluorine-containing ether compounds. Hereinafter, the fluorine-containing ether mixture is also referred to as "specific fluorine-containing ether mixture". A specific fluorine-containing ether mixture is a mixture of two or more fluorine-containing ether compounds containing a specific fluorine-containing ether compound.
The fluorine-containing ether compounds other than the specific fluorine-containing ether compound may be used singly or in combination of two or more.

Examples of fluorine-containing ether compounds other than the specific fluorine-containing ether compounds include those described in the following documents.
perfluoropolyether-modified aminosilanes described in JP-A-11-029585 and JP-A-2000-327772;
a silicon-containing organic fluorine-containing polymer described in Japanese Patent No. 2874715;
Organosilicon compounds described in JP-A-2000-144097,
Fluorinated siloxane described in JP-T-2002-506887,
Organosilicone compounds described in JP-T-2008-534696,
a fluorinated modified hydrogen-containing polymer described in Japanese Patent No. 4138936;
The compounds described in US Patent Application Publication No. 2010/0129672, WO 2014/126064 and JP 2014-070163,
organosilicon compounds described in WO2011/060047 and WO2011/059430;
A fluorine-containing organosilane compound described in WO 2012/064649,
A fluorooxyalkylene group-containing polymer described in JP-A-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, JP 2014-080473, International Publication WO 2015/087902, WO 2017/038830, WO 2017/038832, WO 2017/187775, WO 2018/216630, WO 2019/039186, WO 2019 /039226, International Publication No. 2019/039341, International Publication No. 2019/044479, International Publication No. 2019/049753, International Publication No. 2019/163282 and Fluorine-containing ether compounds described in JP-A-2019-044158 ,
JP 2014-218639, WO 2017/022437, WO 2018/079743, and WO 2018/143433 perfluoro (poly) ether-containing silane compounds described,
A perfluoro(poly)ether group-containing silane compound described in WO 2018/169002,
fluoro(poly)ether group-containing silane compounds described in WO 2019/151442;
(poly)ether group-containing silane compounds described in WO 2019/151445,
A perfluoropolyether group-containing compound described in WO 2019/098230,
Fluoropolyether group-containing polymer-modified silanes described in JP-A-2015-199906, JP-A-2016-204656, JP-A-2016-210854 and JP-A-2016-222859,
The fluorine-containing compounds described in WO2019/039083 and WO2019/049754, and the fluorine-containing ether compounds described in WO2020/111010.

Commercially available fluorine-containing ether compounds other than specific fluorine-containing ether compounds include KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., Afluid (registered trademark) manufactured by AGC. ) S550, Optool (registered trademark) DSX, Optool (registered trademark) AES, Optool (registered trademark) UF503, Optool (registered trademark) UD509 manufactured by Daikin Industries, Ltd., Fomblin (registered trademark) of Solvay, Fluorolink (registered trademark) and Krytox (registered trademark) manufactured by Chemours.

Fluorine-containing ether compounds other than the specific fluorine-containing ether compound also include fluorine-containing ether compounds that are by-produced in the production process of the specific fluorine-containing ether compound.
Examples of the by-product fluorine-containing ether compound include CF ₃ CF ₂ CF ₂ O[CF ₂ obtained as a by-product of the fluorine-containing ether compound produced by the method described in Example 13-7 of WO 2018/216630. _{CF2OCF2CF2CF2CF2CF2CF2O} _] _CF2CF2O _{ ₍ _CF2O ₎ _x1 ₍ _CF2CF2O ₎ _x2 _} _{CF2CF2OCF2CF2} _[ _OCF2CF2 _{_} _{_} _{_} _{_} CF ₂ CF ₂ CF ₂ CF ₂ OCF ₂ CF ₂ ]OCF ₂ CF ₂ CF ₃ , a fluorine-containing ether compound CF ₃ -(OCF ₂ CF ₂ produced by the method described in Example 6 of WO 2013/121984 OCF ₂ CF ₂ CF ₂ CF ₂ ) _m OCF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ —C(=O)OCH ₃ and the like.

The content of the fluorine-containing ether compound other than the specific fluorine-containing ether compound 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, based on the total mass of the specific fluorine-containing ether compound. , 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.

<Coating agent>
The coating agent of the present disclosure contains 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). Moreover, in order to form a surface layer on the substrate, a composition containing other components than the specific fluorine-containing ether compound or the specific fluorine-containing ether mixture may be used (dry coating method and wet coating method described later). .
In the present disclosure, a specific fluorine-containing ether compound, a specific fluorine-containing ether mixture, and a composition containing a specific fluorine-containing ether compound or a specific fluorine-containing ether mixture and other components, which are used for coating a substrate, are all ""coatingagent".

The coating agent may contain a liquid medium. Examples of liquid media include water and organic solvents. A liquid medium refers to a medium that is liquid at 25°C.
The liquid medium preferably contains an organic solvent, and more preferably contains an organic solvent having a boiling point of 35 to 250° C. from the viewpoint of excellent coatability. Here, boiling point means normal boiling point.
Examples of the organic solvent include fluorine-based organic solvents and non-fluorine-based organic solvents, and from the viewpoint of excellent solubility, fluorine-based organic solvents are preferred. An organic solvent may be used individually by 1 type, and may use 2 or more types together.

Fluorinated organic solvents include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols and the like.
The fluorinated alkane is preferably a compound having 4 to 8 carbon atoms. Examples of compounds having 4 to 8 carbon atoms include C ₆ F ₁₃ H (AC-2000: product name, manufactured by AGC), C ₆ F ₁₃ C ₂ H ₅ (AC-6000: product name, manufactured by AGC), C ₂ F ₅ CHFCHFCF ₃ (Vertrell: product name, manufactured by Chemours) and the like.
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 CF ₃ CH ₂ OCF ₂ CF ₂ H (AE-3000: product name, manufactured by AGC), C ₄ F ₉ OCH ₃ (Novec-7100: product name, manufactured by 3M), and C ₄ F. _9OC ₂ H ₅ (Novec-7200: product name, manufactured by 3M), C ₂ F ₅ CF(OCH ₃ )C ₃ F ₇ (Novec-7300: product name, manufactured by 3M), and the like.
Fluorinated alkylamines include perfluorotripropylamine, perfluorotributylamine, and the like.
Fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol and the like.

As the non-fluorine organic solvent, a compound consisting only of hydrogen atoms and carbon atoms, and a compound consisting only of hydrogen atoms, carbon atoms and oxygen atoms are preferable. Examples of such compounds include hydrocarbon-based organic solvents, ketone-based organic solvents, ether-based organic solvents, ester-based organic solvents, and alcohol-based organic solvents.
Examples of hydrocarbon-based organic solvents include hexane, heptane, cyclohexane, and the like.
Ketone organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like.
Examples of ether-based organic solvents include diethyl ether, tetrahydrofuran, tetraethylene glycol dimethyl ether, and the like.
Ethyl acetate, butyl acetate, etc. are mentioned as an ester type organic solvent.
Examples of alcoholic organic solvents include isopropyl alcohol, ethanol, n-butanol and the like.

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

The coating agent may contain components other than the specific fluorine-containing ether compound, the fluorine-containing ether compound other than the specific fluorine-containing ether compound, and the liquid medium.
For example, the coating agent may contain by-products produced in the manufacturing process of the specific fluorine-containing ether compound and optionally other fluorine-containing ether compounds, residual unreacted raw materials, catalysts, and the like.
The coating agent may also contain additives such as acid catalysts and basic catalysts that promote hydrolysis and condensation reaction of the hydrolyzable silyl groups. Acid catalysts include hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, p-toluenesulfonic acid and the like. Basic catalysts include sodium hydroxide, potassium hydroxide, ammonia and the like.

When 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 the total mass of the components of the coating agent excluding the liquid medium. 0 to 10% by mass is preferable, 0 to 5% by mass is more preferable, and 0 to 1% by mass is even more preferable.

<Goods>
An article of the present disclosure has a substrate and a surface layer formed on the substrate with the coating agent. The surface layer contains a compound obtained by hydrolysis reaction and condensation reaction of a specific fluorine-containing ether compound.

The thickness of the surface layer is preferably 1 to 100 nm, more preferably 1 to 50 nm. When the thickness of the surface layer is equal to or greater than the lower limit, the effect of the surface layer can be obtained satisfactorily. When the thickness of the surface layer is equal to or less than the upper limit, the utilization efficiency of the coating agent is high.
The thickness of the surface layer is determined by obtaining an interference pattern of reflected X-rays by the X-ray reflectance method (XRR) using an X-ray diffractometer for thin film analysis (product name “ATX-G”, manufactured by RIGAKU). It can be calculated from the vibration period of the interference pattern.

Substrates include other items (stylus, etc.), substrates that may be used in contact with human fingers, substrates that may be held with human fingers during operation, and other items (placing table, etc.). A substrate or the like on which it may be placed is preferred. Since the coating agent of the present disclosure can impart water and oil repellency and abrasion resistance to a substrate, it is particularly useful when using a substrate that requires imparting water and oil repellency and abrasion resistance.
Materials for the substrate include metal, resin, glass, sapphire, ceramic, stone, fiber, non-woven fabric, paper, wood, natural leather, artificial leather, and composite materials thereof. The glass may be chemically strengthened.
The base material is preferably a touch panel base material or a display base material, and more preferably a touch panel base material. The touch panel substrate preferably has translucency. The term "having translucency" means that the vertical incidence type visible light transmittance according to JIS R3106:2019 (ISO 9050:2003) is 25% or more. Glass or transparent resin is preferable as the material of the touch panel substrate.
Interior goods; transportation equipment (automobiles, etc.); signboards or bulletin boards; drinking vessels or tableware; water tanks; packaging containers; glass or resin used for art, sports or games; As the base material, glass or resin used for exterior parts (excluding display parts) of devices such as mobile phones (smartphones, etc.), personal digital assistants, game machines, remote controllers, etc. is also preferable.
The shape of the substrate may be plate-like, film-like, or the like.

Above all, it is preferable that 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.

The surface layer may be formed directly on the surface of the substrate, or may be formed on the substrate via another film formed on the surface of the substrate. Examples of the other films include compounds described in paragraphs 0089 to 0095 of International Publication No. WO 2011/016458, base films formed on the surface of the base material by treating the base material with SiO ₂ or the like. be done.

<Product manufacturing method>
Articles of the present disclosure can be manufactured, for example, in the following manner.
- A method of 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.
- Applying the coating agent of the present disclosure containing a liquid medium to the surface of a substrate by a wet coating method, and drying the substrate to which the coating agent is applied to form a surface layer on the substrate. , a method of manufacturing an article.

Dry coating methods include vacuum deposition, CVD, and sputtering. Among them, the vacuum deposition method is preferable from the viewpoint of suppressing the decomposition of the specific fluorine-containing ether compound and from the viewpoint of the simplicity of the apparatus. At the time of vacuum deposition, a pellet-like material obtained by impregnating a metal porous material such as iron or steel with a coating agent containing a liquid medium and drying may be used.

Wet coating methods include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet, flow coating, roll coating, casting, Langmuir-Blodgett, and gravure. A coat method and the like can be mentioned. After wet-coating the coating liquid, it is preferable to dry the coating film. The drying temperature of the coating film is preferably 20 to 200°C, more preferably 80 to 160°C.
In the wet coating method, a specific fluorine-containing ether compound is hydrolyzed in advance using a catalyst such as an acid catalyst or a basic catalyst, and a composition containing the hydrolyzed compound and a liquid medium is used as a coating agent. good too.

Next, the embodiments of the present disclosure will be specifically described with examples, but the embodiments of the present disclosure are not limited to these examples. In the following examples, Examples 1 to 8 are working examples, and Examples 9 and 10 are comparative examples.

<Synthesis of fluorine-containing ether compound>
[Compound (A-1)]
The following compound (A-1) was synthesized in the same manner as compound (1-1) of WO2020/166487. (Average value of n: 13)

[Compound (A-2)]
The following compound (A-2) was synthesized in the same manner as compound (1-3a-2) of WO 2013/121984. (average value of n: 7)

[Compound (A-3)]
The following compound (A-3) was synthesized in the same manner as compound (B) of JP-A-2019-90045. (Average value of m: 18, Average value of l: 19)

[Compound (A-4)]
The following compound (A-4) was synthesized in the same manner as compound (2-C) of WO 2020/166488. (Average value of n: 10)

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

[Compound (B-2)]
The following two compounds were used as raw materials. (Average value of m: 28, average value of l: 16)

　6.0 g of the mixture containing the above two compounds 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%) (bis(2-methoxyethoxy)aluminum sodium hydride solution) was added and stirred at 50°C. After adding hydrochloric acid, extraction was performed with AE3000 (trade name, manufactured by AGC). After distilling off the solvent, flash column chromatography using silica gel (developing solvent: AE3000) was performed to obtain 0.24 g of the following compound (B-2). (Average value of m: 28, Average value of l: 16)

[Compound (B-3)]
As a raw material, the following compound (X3-4) described in International Publication 2020/166488 was used. (Average value of n: 10)

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 stirred at 50°C. Hydrochloric acid was added and extracted with AE3000 (trade name, manufactured by AGC). After distilling off the solvent, flash column chromatography using silica gel (developing solvent: AE3000) was performed to obtain 4.2 g of the following compound (B-3). (Average value of n: 10)

<Preparation of composition>
[Example 1]
A mixture containing 0.50 g of compound (A-1) and 0.15 g of compound (B-1) was added to hydrofluoroether (manufactured by 3M, trade name: Novec HFE-7300) so as to have a concentration of 20% by mass. Dissolved. After adding 1.0 mg of acetic acid and reacting at 100° C., composition 1 was obtained by distilling off the solvent under reduced pressure.

[Example 2]
A mixture containing 0.30 g of compound (A-2) and 0.15 g of compound (B-1) was added to hydrofluoroether (manufactured by 3M, trade name: Novec HFE-7300) so as to have a concentration of 20% by mass. Dissolved. After adding 1.0 mg of acetic acid and reacting at 100° C., composition 2 was obtained by distilling off the solvent under reduced pressure.

[Example 3]
A mixture containing 0.40 g of compound (A-3) and 0.15 g of compound (B-1) was added to hydrofluoroether (manufactured by 3M, trade name: Novec HFE-7300) so as to have a concentration of 20% by mass. Dissolved. After adding 1.0 mg of acetic acid and reacting at 100° C., composition 3 was obtained by distilling off the solvent under reduced pressure.

[Example 4]
A mixture containing 0.44 g of compound (A-4) and 0.15 g of compound (B-1) was added to hydrofluoroether (manufactured by 3M, trade name: Novec HFE-7300) so as to have a concentration of 20% by mass. Dissolved. After adding 1.0 mg of acetic acid and reacting at 100° C., composition 4 was obtained by distilling off the solvent under reduced pressure.

[Example 5]
A mixture containing 0.50 g of compound (A-1) and 0.15 g of compound (B-2) was added to hydrofluoroether (manufactured by 3M, trade name: Novec HFE-7300) so as to have a concentration of 20% by mass. Dissolved. After adding 1.0 mg of acetic acid and reacting at 100° C., composition 5 was obtained by distilling off the solvent under reduced pressure.

[Example 6]
A mixture containing 0.50 g of compound (A-1) and 0.15 g of compound (B-3) was added to hydrofluoroether (manufactured by 3M, trade name: Novec HFE-7300) so as to have a concentration of 20% by mass. Dissolved. After adding 1.0 mg of acetic acid and reacting at 100° C., composition 6 was obtained by distilling off the solvent under reduced pressure.

[Example 7]
A mixture containing 0.50 g of compound (A-1) and 0.15 g of compound (B-1) was added to hydrofluoroether (manufactured by 3M, trade name: Novec HFE-7300) so as to have a concentration of 20% by mass. Dissolved. 1.0 mg of acetic acid was added and reacted at 100° C. to obtain composition 7.

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

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

[Example 10]
0.50 g of compound (A-1) was dissolved in hydrofluoroether (Novec HFE-7300, manufactured by 3M) to a concentration of 20% by mass. After adding 1.0 mg of water and reacting at 100° C., composition 10 was obtained by distilling off the solvent under reduced pressure.

<Confirmation of product>
Observation of the peaks of gel permeation chromatography (GPC) confirmed that compositions 1 to 8 yielded specific fluorine-containing ether compounds. It was also confirmed that composition 10 yielded a self-condensate of compound (A-1).

<Method of Forming Surface Layer>
[Dry coating]
A base material (non-alkali glass (Eagle XG: trade name, manufactured by Corning, 50 mm × 50 mm, thickness 0.5 mm)) is placed in a vacuum deposition apparatus, and the pressure in the vacuum deposition apparatus is 5 × 10 ^-3 Pa or less. was evacuated to a pressure of A deposition vessel containing the composition prepared above at a distance of 1000 mm so as to face one main surface of the substrate is heated to 300 ° C. by resistance heating, and the composition is vacuum-deposited to a thickness of 10 nm. A surface layer was formed. The temperature of the composition in each example was 300°C. After that, the obtained substrate with a surface layer was heated at a temperature of 200° C. for 30 minutes (post-treatment).

[Wet coating]
The composition prepared above was mixed with C ₄ F ₉ OC ₂ H ₅ (Novec-7200: trade name, manufactured by 3M) as a liquid medium, and the content of the fluorine-containing ether compound in the coating agent was A coating liquid of 0.1% by mass was prepared. Alkali-free glass (Eagle XG: trade name, manufactured by Corning Incorporated, 50 mm×50 mm, thickness 0.5 mm) was prepared as the substrate.

After spray-coating the coating agent on one main surface of the substrate at a coating amount of 6.0 g/sec using a Nordson spray, the coating agent formed on the substrate is heated at 120 ° C. for 10 It was dried for a minute to obtain a base material with a surface layer. In each example, the thickness of the surface layer was 10 nm.

<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 measurement device (manufactured by Kyowa Interface Science Co., Ltd., DM-500). Measurements were performed at five different points on the surface of the surface layer, and the average value was calculated. The 2θ method was used to calculate the contact angle. Evaluation criteria are as follows.
A: 115 degrees or more.
B: 105 degrees or more and less than 115 degrees.

[Abrasion resistance (steel wool)]
For the surface layer, using a reciprocating traverse tester (manufactured by KNT) in accordance with JIS L0849: 2013 (ISO 105-X12: 2001), Steel Wool Bonster (#0000) Pressure: 98.07 kPa, speed: 320 cm After reciprocating 10,000 times per minute, the water contact angle was measured. The smaller the drop in water repellency (water contact angle) after rubbing, the smaller the drop in performance due to friction, and the better the rub resistance. Evaluation criteria are as follows.
A: Change in water contact angle after 10,000 reciprocations is 2 degrees or less.
B: Change in water contact angle after 10,000 reciprocations is more than 2 degrees and 3 degrees or less.
C: Change in water contact angle after 10,000 reciprocations is more than 3 degrees and 4 degrees or less.
D: Change in water contact angle after 10,000 reciprocations exceeds 4 degrees.

The evaluation results for each example are shown in the table below. In the table below, compounds (A-1) to (A-4) are indicated as "compound A", and compounds (B-1) to (B-3) are indicated as "compound B". "-" means not applicable.

As shown in the table, in Examples 1 to 8, the abrasion resistance of the surface layer was excellent.
On the other hand, in Example 9, in which the compounds (A-1) and (B-1) were mixed without using a catalyst, the abrasion resistance of the surface layer was inferior to those in Examples 1-8.
In Example 10, in which a self-condensate of compound (A-1) was formed, the abrasion resistance of the surface layer was inferior to those in Examples 1-8.
All evaluations of the initial contact angle were good.

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

Claims

A fluorine-containing ether compound 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 independently represents a monovalent organic group having a poly(oxyfluoroalkylene) chain,
X 2 represents a divalent organic group, provided that both terminal atoms of X 2 bonded to two oxygen atoms in formula (A) are carbon atoms,
each R 1 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;
wherein X 2 in formula (A) comprises an alkylene group, a fluoroalkylene group, or an etheric oxygen atom-containing group having an etheric oxygen atom between carbon atoms of an alkylene group or a fluoroalkylene group; The fluorine-containing ether compound described.
The fluorine-containing ether compound according to claim 1 or 2 , wherein in formula (A), X2 contains a poly(oxyperfluoroalkylene) group.
In formula (A), X 2 contains a structure represented by {(OCF 2 ) m21 (OCF 2 CF 2 ) m22 }, wherein m21 is an integer of 1 or more and m22 is an integer of 1 or more 4. The fluorine-containing ether compound according to claim 3, wherein m21+m22 is an integer of 2-500.
5. The fluorine-containing ether compound according to claim 4, wherein m21 >m22 in {( OCF2 ) m21 ( OCF2CF2 ) m22 }.
In formula (A), X 2 is
a poly(oxyperfluoroalkylene) group;
An alkylene group, an etheric oxygen having an etheric oxygen atom between the carbon atoms of the alkylene group, which connects between the poly(oxyperfluoroalkylene) group and at least one of the two oxygen atoms in the formula (A) a divalent organic group selected from the group consisting of atom-containing groups, perfluoroalkylene groups, and combinations thereof;
The fluorine-containing ether compound according to any one of claims 3 to 5, which is a group having
The fluorine-containing according to any one of claims 1 to 6, which is obtained by transesterifying a compound represented by the following formula (Cs) and a compound represented by the following formula (Cd) in the presence of a catalyst. Ether compounds.
Formula (Cs): X 1 -Si(R 1 ) n L 3-n
Formula (Cd): HO—X 2 —OH
In formula (Cs),
X 1 represents a monovalent organic group having a poly(oxyfluoroalkylene) chain,
each R 1 independently represents a monovalent hydrocarbon group,
L each independently represents a hydrolyzable group or a hydroxyl group,
n represents an integer of 0 to 2;
In formula (Cd),
X2 represents a divalent organic group, provided that both terminal atoms of X2 bonded to two hydroxyl groups in formula (Cd) are carbon atoms.
In the transesterification, the molar ratio (M Cs /M Cd ) of the amount M Cs of the compound represented by the formula (Cs) to the amount M Cd of the compound represented by the formula (Cd) is 1.5 to 8. The fluorine-containing ether compound according to claim 7, which is 4.0.
Claim 7, 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. Or the fluorine-containing ether compound according to 8.
The fluorine-containing ether compound according to any one of claims 1 to 6, wherein a compound represented by the following formula (Cs) and a compound represented by the following formula (Cd) are transesterified in the presence of a catalyst. Production method.
Formula (Cs): X 1 -Si(R 1 ) n L 3-n
Formula (Cd): HO—X 2 —OH
In formula (Cs),
X 1 represents a monovalent organic group having a poly(oxyfluoroalkylene) chain,
each R 1 independently represents a monovalent hydrocarbon group,
L each independently represents a hydrolyzable group or a hydroxyl group,
n represents an integer of 0 to 2;
In formula (Cd),
X2 represents a divalent organic group, provided that both terminal atoms of X2 bonded to two hydroxyl groups in formula (Cd) are carbon atoms.
In the transesterification, the molar ratio (M Cs /M Cd ) of the amount M Cs of the compound represented by the formula (Cs) to the amount M Cd of the compound represented by the formula (Cd) is 1.5 to 4.0, the method for producing a fluorine-containing ether compound according to claim 10.
Claim 10, 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. 12. The method for producing a fluorine-containing ether compound according to 11.
Two or more fluorine-containing ether compounds according to any one of claims 1 to 9, or one or more of the fluorine-containing ether compounds according to any one of claims 1 to 9 and claim 1 A fluorine-containing ether mixture containing a fluorine-containing ether compound other than the fluorine-containing ether compound according to any one of items 1 to 9.
A coating agent containing the fluorine-containing ether compound according to any one of claims 1 to 9 or the fluorine-containing ether mixture according to claim 13.
The coating agent according to claim 14, further comprising a liquid medium.
An article comprising a substrate and a surface layer formed on the substrate with the coating agent according to claim 14 or 15.
A method for producing an article, comprising applying the coating agent according to claim 14 to the surface of a substrate by a dry coating method to form a surface layer on the substrate.
Applying the coating agent according to claim 15 to the surface of a substrate by a wet coating method;
drying the substrate to which the coating agent is applied to form a surface layer on the substrate;
A method of manufacturing an article, comprising: