JP2022001653A - Fluorine-containing ether composition, coating liquid, and article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorine-containing ether composition and a coating liquid capable of forming a surface layer excellent in lubricity and durability, and an article having a surface layer excellent in lubricity and durability. SOLUTION: The poly (oxyperfluoroalkylene) chain containing a fluorine-containing ether compound (A) and a fluorine-containing ether compound (B), wherein the fluorine-containing ether compound (A) contains a (CF2O) unit and the following formula ( A compound having a group represented by I), wherein the fluorine-containing ether compound (B) has a poly (oxyperfluoroalkylene) chain containing no (CF2O) unit and a group represented by the above formula (I). A fluorine-containing ether composition that is a compound. -SiRnL3-n ... (I); where L is a hydroxyl group or a hydrolyzable group and R is a hydrogen atom or a monovalent hydrocarbon group. [Selection diagram] None

Description

The present invention relates to fluorine-containing ether compositions, coating liquids and articles.

Fluorine-containing compounds are used as surface treatment agents because they exhibit high lubricity, water repellency, oil repellency, and the like. For example, when a surface layer is formed on the surface of the base material by the surface treatment agent, lubricity, water repellency, oil repellency and the like are imparted, dirt on the surface of the base material can be easily wiped off, and dirt removal property is improved. Among the fluorine-containing compounds, the fluorine-containing ether compound having a poly (oxyperfluoroalkylene) chain in which an ether bond (-O-) is present in the middle of the perfluoroalkyl chain is excellent in removing stains such as oils and fats.

As a fluorine-containing ether compound, a compound having a hydrolyzable silyl group has been proposed. Such a fluorine-containing ether compound has a performance that the water and oil repellency does not easily decrease even if it is repeatedly rubbed with a finger (friction resistance) and a performance that can easily remove fingerprints adhering to the surface by wiping (fingerprint stain removing property). Is used for applications that are required to be maintained for a long period of time, for example, as a surface treatment agent for a member of a touch panel that constitutes a surface to be touched by a finger.

A fluorine-containing ether composition in which a fluorine-containing oil, that is, a non-reactive fluorine-containing ether compound having no hydrolyzable silyl group is blended with a fluorine-containing ether compound having a hydrolyzable silyl group in order to enhance lubricity. Has been proposed (for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2014-65884

However, according to the present inventor, the surface layer formed by the above-mentioned fluorine-containing ether composition tends to deteriorate in performance such as lubricity, water repellency, and oil repellency when friction with a finger or the like is repeated. It turned out to be (low durability). Therefore, it is difficult to achieve both lubricity and durability at a high level.

An object of the present invention is to provide a fluorine-containing ether composition and a coating liquid capable of forming a surface layer excellent in lubricity and durability, and an article having a surface layer excellent in lubricity and durability.

The present invention provides a fluorine-containing ether composition, a coating liquid and an article having the following configurations [1] to [15].
[1] A fluorine-containing ether compound (A) and a fluorine-containing ether compound (B) are included.
The fluorine-containing ether compound (A) is a compound having _{a poly (oxyperfluoroalkylene) chain containing a (CF 2} O) unit and a group represented by the following formula (I).
The fluorine-containing ether compound (B) is a compound having a _{poly (oxyperfluoroalkylene) chain containing no (CF 2} O) unit and a group represented by the formula (I). Composition.
−SiR _n L _3-n ... (I)
However, L is a hydroxyl group or a hydrolyzable group, and is
R is a hydrogen atom or a monovalent hydrocarbon group,
n is an integer from 0 to 2
When n is 0 or 1, the (3-n) L's may be the same or different.
When n is 2, n Rs may be the same or different.
The groups represented by the formula (I) of each of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) may be the same or different.

[2] Both the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) are fluorine-containing ether compounds represented by the following formula (A / B).
^{R f} in the fluorine-containing ether compound (A) is a poly (oxyperfluoroalkylene) chain containing a (CF ₂ O) unit, and is a poly (oxyperfluoroalkylene) chain.
The fluorine-containing ether composition according to [1], ^{wherein R f} in the fluorine-containing ether compound (B) is a poly (oxyperfluoroalkylene) chain containing no (CF _{2 O) unit.
^{[R f1 -O-Q-R}} f -] r Z [-SiR n L 3-n] s ··· (A / B)
However, R ^f1 is a perfluoroalkyl group and is a perfluoroalkyl group.
Q is a polyoxyfluoroalkylene group having a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group having 2 to 5 bonds of the oxyfluoroalkylene group, and the polyoxyfluoroalkylene group is used. The constituent oxyfluoroalkylene groups may all be the same or different.
R ^f is a poly (oxyperfluoroalkylene) chain and
Z is a linking group of (r + s) valence,
−SiR _n L _3-n is a group represented by the above formula (I).
When r is 2 or more, r [R ^f1- O-Q-R ^f- ] are the same group.
When s is 2 or more, the s groups represented by the formula (I) are the same group.
r and s are integers of 1 or more, respectively, and r + s is 3 to 8.

[3] The _{poly (oxyperfluoroalkylene) chain containing the (CF 2} O) unit is a poly (oxyperfluoroalkylene) chain containing the (CF ₂ O) unit and the (CF ₂ CF ₂ O) unit. The fluorine-containing ether composition of 1] or [2].
[4] The _{poly (oxyperfluoroalkylene) chain containing no (CF 2} O) unit is composed of (CF ₂ CF ₂ O) units, (CF ₂ CF ₂ CF ₂ O) units and (CF ₂ CF ₂ CF ₂ CF). ₂ O) The fluorine-containing ether composition according to any one of [1] to [3], which is a poly (oxyperfluoroalkylene) chain containing at least one selected from units.
[5] The _(CF 2 O) units containing no poly (oxyperfluoroalkylene) _chain, a poly (oxyperfluoroalkylene) chain comprising _{(CF 2 CF 2 OCF 2 CF} 2 CF 2 CF 2 O) units, The fluorine-containing ether composition according to any one of [1] to [4].
[6] Any of [1] to [5], wherein at least one of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) has three or more groups represented by the formula (I). Fluorine-containing ether composition.
[7] Any of [1] to [5], wherein both the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) have two or more groups represented by the formula (I). Fluorine-containing ether composition.
[8] Any of [1] to [5], wherein both the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) have three or more groups represented by the formula (I). Fluorine-containing ether composition.
[9] The fluorine-containing ether composition according to any one of [1] to [8], wherein the fluorine-containing ether compound (A) has a number average molecular weight of 2,000 to 20,000.
[10] The fluorine-containing ether composition according to any one of [1] to [9], wherein the fluorine-containing ether compound (B) has a number average molecular weight of 2,000 to 20,000.
[11] Any of [1] to [10] containing 10 to 80% by mass of the fluorine-containing ether compound (A) with respect to the total of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B). Fluorine-containing ether composition.

[12] A fluorine-containing ether composition comprising a fluorine-containing ether compound (A1) represented by the following formula (A1) and a fluorine-containing ether compound (B1) represented by the following formula (B1).
[R ^f1a- O-Q ^a- R ^fa- ] _ra Z ^a [-SiR ^a _na L ^a _3-na ] _sa ... (A1)
_{^{[R f1b -O-Q b -R}} fb -] rb Z b [-SiR b nb L b 3-nb] sb ··· (B1)
^{However, R f1a} and ^{R f1b} is a perfluoroalkyl group,
Q ^a and Q ^b are a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group having 2 to 5 bonds of the oxyfluoroalkylene group, and the polyoxy. The oxyfluoroalkylene groups constituting the fluoroalkylene group may be the same or different.
R ^fa is a _{poly (oxyperfluoroalkylene) chain containing (CF 2} O) units and is a poly (oxyperfluoroalkylene) chain.
R ^fb is a _{poly (oxyperfluoroalkylene) chain containing no (CF 2} O) unit and is a poly (oxyperfluoroalkylene) chain.
Z ^a is a linking group of (ra + sa) valence,
Z ^b is a linking group of (rb + sb) valence.
L ^a and ^{L b} are hydroxyl group or a hydrolyzable group,
R ^a and R ^b are hydrogen atoms or monovalent hydrocarbon groups.
na and nb are integers from 0 to 2 and
^{The (3-na) L a} when na is 0 or 1, and the (3-nb) L ^b when nb is 0 or 1, may be the same or different, respectively.
na number of ^R a when na is 2, each nb number of ^{R b} when nb is 2, may be the same or different and
ra and rb are integers of 1 or more, and when ra is 2 or more, ra [R ^f1a −O−Q ^a −R ^fa −] may be the same or different, and rb is 2. or when the rb pieces ^{[R f1b -O-Q b -R} fb -] may be the same or different and
sa and sb are integers of 1 or more, and when sa is 2 or more, sa [-SiR ^a _na L ^a _3-na ] may be the same or different, and sb is 2 or more. When sb [-SiR ^b _nb L ^b _3-nb ] may be the same or different.
[13] The fluorine-containing ether composition of [12] containing 10 to 80% by mass of the fluorine-containing ether compound (A1) with respect to the total of the fluorine-containing ether compound (A1) and the fluorine-containing ether compound (B1). ..
[14] A coating liquid comprising the fluorine-containing ether composition according to any one of the above [1] to [13] and a liquid medium.
[15] An article having a surface layer formed from the fluorine-containing ether composition according to any one of the above [1] to [13].

According to the fluorine-containing ether composition and the coating liquid of the present invention, a surface layer having excellent lubricity and durability can be formed.
The article of the present invention has a surface layer having excellent lubricity and durability.

In the present specification, the compound represented by the formula (1) is referred to as compound (1). Compounds represented by other formulas are also described in the same manner.
The meanings of the following terms in the present specification are as follows.
The "hydrolyzable silyl group" means a group capable of forming a silanol group (Si-OH) by a hydrolytic reaction. For example, L in the formula (I) is a group that is a hydrolyzable group.
The chemical formula of the oxyperfluoroalkylene group shall represent the oxygen atom described on the right side of the perfluoroalkylene group.
"Surface layer" means a layer formed on the surface of a substrate.
“Drying” by applying the coating liquid means applying the coating liquid to the base material to form a coating film of the coating liquid on the base material, and then evaporating and removing the liquid medium from the coating film. ..

[Fluorine-containing ether composition]
The fluorine-containing ether composition of the present invention (hereinafter, also referred to as the present composition) includes a fluorine-containing ether compound (A) (hereinafter, also referred to as compound (A)) and a fluorine-containing ether compound (B) (hereinafter, also referred to as the present composition). Also referred to as compound (B)). This composition does not contain a liquid medium, as will be described later. The present composition may be composed of the compound (A) and the compound (B), and as described later, a fluorine-containing ether compound other than the compound (A) and the compound (B), the compound (A), and the compound ( It may contain impurities other than B) and other fluorine-containing ether compounds.
Compound (A) has a _{poly (oxyperfluoroalkylene) chain containing (CF 2} O) units (hereinafter, also referred to as A chain), and a group (I).
Compound (B) has a poly (oxyperfluoroalkylene) chain (hereinafter, also referred to as B chain) containing no _{(CF 2 O) unit, and a group (I).} Compound (B) does not have an A chain.
−SiR _n L _3-n ... (I)
However, L is a hydroxyl group or a hydrolyzable group, and is
R is a hydrogen atom or a monovalent hydrocarbon group,
n is an integer from 0 to 2
When n is 0 or 1, the (3-n) L's may be the same or different.
When n is 2, n Rs may be the same or different.
The group (I) contained in each of the compound (A) and the compound (B) may be the same or different.

The compound (A) and the compound (B) can each further have a group (II). When both compound (A) and compound (B) have a group (II), the group (II) of each may be the same or different.
R ^f1- O-Q-... (II)
However,
R ^f1 is a perfluoroalkyl group and
Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group having 2 to 5 bonds of the oxyfluoroalkylene group. The oxyfluoroalkylene groups constituting the polyoxyfluoroalkylene group may be the same or different.

(A chain)
Examples of the A chain include a poly (oxyperfluoroalkylene) chain containing _{(CF 2} O) units and (R ^f2 O) units represented by the following formula (a1).
{(CF ₂ O) _m1 (R ^f2 O) _m2 } ... (a1)
However, R ^f2 is a perfluoroalkylene group having 2 or more carbon atoms, and is a perfluoroalkylene group.
m1 is an integer of 1 or more, m2 is an integer of 0 or more, and (m1 + m2) is an integer of 2 to 200.
When m2 is 1 or more, _{the binding order of m1 CF 2} O and m2 R ^f2 O is not limited.
When m2 is 2 or more (R ^f2 O) _m2 may consist of two or more types of R ^f2 O having different carbon atoms.

R ^f2 may be branched or linear, and is preferably linear from the viewpoint of further excellent lubricity of the surface layer.
The carbon number of R ^f2 is preferably 2 to 6 from the viewpoint of further excellent durability and lubricity of the surface layer, more preferably 2 to 4, and particularly preferably 2 from the viewpoint of further excellent lubricity of the surface layer.

(M1 + m2) is an integer of 2 to 200. Therefore, when m1 is 1, the minimum value of m2 is 1, and there is at least one (R ^f2 O). When m1 is 2 or more, the minimum value of m2 is 0, and (R ^f2 O) may or may not be present. (M1 + m2) is preferably an integer of 10 to 150, and particularly preferably an integer of 20 to 100. When (m1 + m2) is at least the lower limit of the above range, the lubricity of the surface layer is excellent. When (m1 + m2) is not more than the upper limit of the above range, the durability of the surface layer is excellent. That is, if the number average molecular weight of compound (A) is too large, the number of groups (I) present per unit molecular weight decreases, and the durability decreases.

The ratio of m1 to m2 (m1 / m2) is preferably 100/0 to 30/70, and particularly preferably 90/10 to 40/60. The higher the ratio of m1 within the above range, the better the lubricity of the surface layer tends to be.

(CF ₂ O) _m1 (R ^f2 O) In _m2 , when m2 is 1 or more, that is, when two or more kinds of oxyperfluoroalkylene groups having different carbon atoms are present, each oxyperfluoroalkylene group (m1 CF _2). The binding order of O and m2 R ^f2 O) is not limited. For example, each oxyperfluoroalkylene group may be randomly, alternately or blocked. In particular, _{it is preferable that the (CF 2} O) unit and the (R ^f2 O) unit are randomly arranged.
When m2 is 2 or more, (R ^f2 O) _m2 may be composed of two or more kinds of R ^{f2 O having different carbon atoms.} Further, ^{the binding order of m2 R f2} O is not limited.

Specific embodiments of the A chain include the following (a2) to (a6).
(CF ₂ O) _m01 ... (a2)
{(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 } ... (a3)
{(CF ₂ O) _m11 (CF ₂ CF ₂ CF ₂ O) _m12 } ... (a4)
{(CF ₂ O) _m11 (CF ₂ CF ₂ CF ₂ CF ₂ O) _m12 } ... (a5)
{(CF ₂ O) _m11 (CF (CF ₃ ) CF ₂ O) _m12 } ... (a6)
However, m01 is an integer of 2 to 200, m11 is an integer of 1 or more, m12 is an integer of 1 or more, and (m11 + m12) is an integer of 2 to 200.
The preferred ranges of m01 and (m11 + m12) are the same as those of (m1 + m2).
The ratio of m11 to m12 (m11 / m12) is preferably 99/1 to 30/70, and particularly preferably 90/10 to 40/60.
Among the above, (a3) to (a5) are preferable, and (a3) is particularly preferable.
A chain, _(CF 2 O) units and is preferably above (a3) containing a _(CF 2 _CF 2 O) units, _(CF 2 O) units and _(CF 2 _CF 2 O) units and a random It is particularly preferable that the above (a3) is arranged in.

(B chain)
Examples of the B chain include a poly (oxyperfluoroalkylene) chain containing ^{at least one (R f3} O) unit represented by the following formula (b1).
(R ^f3 O) _m3 ... (b1)
However, R ^f3 is a perfluoroalkylene group having 2 or more carbon atoms, and is a perfluoroalkylene group.
m3 is an integer of 2 to 200,
(R ^f3 O) _m3 may consist of two or more types of R ^f2 O having different carbon atoms.
(R ^f3 O) When _m3 consists of two or more types of R ^f2 O having different carbon atoms, the bonding order of each R ^{f2 O is not limited.}

R ^f3 may be branched or linear, and is preferably linear from the viewpoint of further excellent lubricity of the surface layer.
The carbon number of R ^f3 is preferably 2 to 6 from the viewpoint of further excellent durability and lubricity of the surface layer.

m3 is an integer of 2 to 200, preferably an integer of 10 to 150, and particularly preferably an integer of 15 to 100. When m3 is at least the lower limit of the above range, the lubricity of the surface layer is excellent. When m3 is not more than the upper limit of the above range, the durability of the surface layer is excellent. That is, if the number average molecular weight of compound (B) is too large, the number of groups (I) present per unit molecular weight decreases, and the durability decreases.

(R ^f3 O) When _m3 consists of two or more types of R ^f2 O having different carbon atoms, the bonding order of each R ^{f3 O is not limited.} For example, each R ^f3 O may be randomly, alternately, or block.

(R ^f3 O) _{The B chain in the case where m3} is composed of two or more types of R ^f2 O having different carbon atoms is preferably represented by the following formula (b2).
{(CF ₂ CF ₂ O) _m4 (R ^f4 O) _m5 } ... (b2)
However, R ^f4 is a perfluoroalkylene group having 3 to 6 carbon atoms.
m4 is an integer of 1 or more,
m5 is an integer of 1 or more,
(M4 + m5) is an integer of 2 to 200.
The binding order of m4 CF ₂ CF ₂ O and m5 R ^f4 O is not limited.

As R ^f4 , CF ₂ CF ₂ CF ₂ CF ₂ is preferable.
The preferred range of (m4 + m5) is the same as that of m3.
The ratio of m4 to m5 (m4 / m5) is preferably 90/10 to 10/90, and particularly preferably 70/30 to 30/70. The higher the ratio of m4 in the above range, the better the lubricity tends to be. The higher the ratio of m5 within the above range, the better the durability tends to be.

One preferred embodiment of ^{_{{(CF 2 CF 2 O)}} m4 (R f4 O) m5}, {(CF 2 CF 2 O) m41 - (R f4 O) m51} include _m6. However, m41 is an integer of 1 to 3, m51 is an integer of 1 to 3, m6 is an integer of 1 or more, and (m41 + m51) × m6 is an integer of 2 to 200. This poly (oxyperfluoroalkylene) chain is one or more of units in which 1 to 3 units of _{(CF 2} CF ₂ O) and 1 to 3 units of (R ^{f3 O) are connected in series.} It consists of. The preferred range of (m41 + m51) × m6 is the same as (m4 + m5). It is preferable that m41 and m51 are 1 respectively.
_{Incidentally, {(CF 2 CF 2 O} ) m41 - (R f4 O) m51} m6 _{is, {(CF 2 CF 2 O} ) m41 - (R f4 O) m51} to a unit of poly (oxyperfluoroalkylene) chains can also be regarded _as, can be considered as _{(CF 2 CF} 2 _{O) m41} units and ^(R f4 _O) and _m51 units are arranged in alternating poly (oxyperfluoroalkylene) chains.

The B chain is a poly (oxyperfluoroalkylene) containing at least one selected from _{(CF 2} CF ₂ O) units, (CF ₂ CF ₂ CF ₂ O) units and (CF ₂ CF ₂ CF ₂ CF _{2 O) units.} It is preferably a chain. In particular, it is preferably a poly (oxyperfluoroalkylene) chain containing _{(CF 2} CF ₂ OCF ₂ CF ₂ CF ₂ CF _{2 O) units.}
Specific embodiments of the preferred B chain include the following (b3) to (b5).
(CF ₂ CF ₂ O) _m13 ... (b3)
(CF ₂ CF ₂ CF ₂ O) _m14 ... (b4)
(CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _m15 ... (b5)
However, m13 and m14 are integers of 2 to 200, respectively, and m15 is an integer of 1 to 100.
(B5) is a _{poly (oxyperfluoroalkylene) chain containing (CF 2} CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) units, and the poly (oxyperfluoroalkylene) chain is (CF ₂ CF ₂ O). ) Units and (CF ₂ CF ₂ CF ₂ CF ₂ O) units are alternately bonded to form a poly (oxyperfluoroalkylene) chain.

(Group (I))
In group (I), L is a hydroxyl group or a hydrolyzable group.
A hydrolyzable group is a group that becomes a hydroxyl group by a hydrolytic reaction. That is, when L is a hydrolyzable group, Si—L of the group (I) becomes a silanol group (Si—OH) by the hydrolysis reaction.
Examples of the hydrolyzable group include an alkoxy group, a halogen atom, an acyl group, an isocyanate group (-NCO) and the like. The alkoxy group preferably has 1 to 4 carbon atoms. The acyl group preferably has 2 to 5 carbon atoms.

L is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom from the viewpoint of ease of production of the compound (A). As the halogen atom, a chlorine atom is particularly preferable. As L, an alkoxy group having 1 to 4 carbon atoms is preferable because there is little outgas during coating and the compound (A) is excellent in storage stability, and when long-term storage stability of the compound (A) is required. The ethoxy group is particularly preferable, and the methoxy group is particularly preferable when the reaction time after coating is short.

R is a hydrogen atom or a monovalent hydrocarbon group.
Examples of the monovalent hydrocarbon group include a saturated hydrocarbon group such as an alkyl group and a cycloalkyl group, an alkenyl group, an allyl group and the like, and a saturated hydrocarbon group is preferable.
The number of carbon atoms of the monovalent hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2 in that the compound (A) can be easily produced.

n is preferably 0 or 1, and particularly preferably 0. The presence of a plurality of L in one group (I) makes the adhesiveness with the base material stronger, and the durability of the surface layer is further excellent.
When n is 0 or 1, the (3-n) L's may be the same or different. For example, a part of L may be a hydrolyzable group and the remaining L may be a hydroxyl group.

As the group (I), Si (OCH ₃ ) ₃ , SiCH ₃ (OCH ₃ ) ₂ , Si (OCH ₂ CH ₃ ) ₃ , SiCl ₃ , Si (OCOCH ₃ ) ₃ , and Si (NCO) ₃ are preferable. _{Si (OCH 3} ) ₃ is particularly preferable from the viewpoint of ease of handling in industrial manufacturing.

(Group (II))
In group (II), R ^f1 is a perfluoroalkyl group.
The ^{number of carbon atoms of the perfluoroalkyl group in R f1} is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 6, and particularly preferably 1 to 3, from the viewpoint of further excellent lubricity and durability of the surface layer. preferable.
The perfluoroalkyl group may be branched or linear, preferably linear. Examples of the linear perfluoroalkyl group include CF _3- , CF ₃ CF _2- , CF ₃ CF ₂ CF _2- and the like.

Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group having 2 to 5 (preferably 2 to 4) bonds of the oxyfluoroalkylene group. .. In the polyoxyfluoroalkylene group, a plurality of oxyfluoroalkylene groups are usually bonded in series.
When Q is an oxyfluoroalkylene group containing a hydrogen atom or a polyoxyfluoroalkylene group in which 2 to 5 of the oxyfluoroalkylene groups are bonded, the compound (A) and the compound (B) are dissolved in a liquid medium. The sex becomes high. Therefore, the compound (A) and the compound (B) are difficult to aggregate in the coating liquid, and the compound (A) and the compound (B) are difficult to aggregate during drying after being applied to the surface of the base material. The appearance of the surface layer is even better.
The oxyfluoroalkylene group preferably has 1 to 6 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms, and particularly preferably 2 or 3 carbon atoms.
The number of hydrogen atoms in the oxyfluoroalkylene group is 1 or more, preferably 2 or more, and particularly preferably 3 or more, from the viewpoint of excellent appearance of the surface layer. The number of hydrogen atoms in the oxyfluoroalkylene group is preferably (Q carbon number) x 2 or less, and particularly preferably (Q carbon number) or less, from the viewpoint of further excellent water and oil repellency of the surface layer.
The oxyfluoroalkylene group may be branched or linear, and is preferably linear from the viewpoint of further excellent lubricity of the surface layer.
In the polyoxyfluoroalkylene group, 2 to 5 oxyfluoroalkylene groups may be the same or different.
Q is a single bond or -CHFCF ₂ OCH ₂ CF ₂ O-, -CF ₂ CHFCF ₂ OCH ₂ CF ₂ O- _{, -CF 2 CF 2 CHFCF 2 OCH} 2 CF 2 O -, - CF 2 CF 2 OCHFCF 2 OCH 2 CF 2 O -, - CF 2 CF 2 OCF 2 CF 2 OCHFCF 2 OCH 2 CF 2 O -, - CF 2 A _{group selected from the group consisting of CH 2} OCH ₂ CF ₂ O- and -CF ₂ CF ₂ OCF ₂ CH ₂ OCH ₂ CF ₂ O- (however, the left side is ^{bound to R f1-} O). preferable.

The A chain of the compound (A) and the B chain of the compound (B) may be one or two or more, respectively. From the viewpoint of ease of manufacture and handling, 1 to 3 pieces are preferable.
When compound (A) has two or more A chains, each A chain may be the same or different. When compound (B) has two or more B chains, each B chain may be the same or different.

Each of the compound (A) and the compound (B) may have one group (I) or two or more groups (I). Two or more are preferable, and three or more are particularly preferable, because the durability of the surface layer is more excellent due to the increase in the bond with the base material. From the viewpoint that the durability of the surface layer is more excellent by increasing the molecular density bonded to the substrate, 10 or less is preferable, 5 or less is more preferable, and 4 or less is particularly preferable.
Therefore, the number of groups (I) contained in each of the compound (A) and the compound (B) is preferably 1 to 10, more preferably 2 to 5, and particularly preferably 3 to 4.
When the compound (A) and the compound (B) have two or more groups (I), each group (I) may be the same or different. In terms of ease of production of the compound (A) and the compound (B), it is preferable that they all have the same group.

It is preferable that the group (II) is bonded to one end of the A chain and the B chain. That is, compound (A) preferably further has a group (II) attached to one end of the A chain. Compound (B) preferably further has a group (II) attached to one end of the B chain. As a result, the lubricity of the surface layer becomes even better.

The number average molecular weight (Mn) of each of the compound (A) and the compound (B) is preferably 2,000 to 20,000, more preferably 3,000 to 15,000, and particularly preferably 4,000 to 12,000. .. When the number average molecular weights of the compound (A) and the compound (B) are at least the lower limit of the above range, the lubricity of the surface layer is further excellent. When the number average molecular weights of the compound (A) and the compound (B) are at least the lower limit of the above range, the durability of the surface layer is further excellent.
The number average molecular weight (Mn) is measured by the measuring method described in Examples described later.

The compound (A) and the compound (B) are not particularly limited as long as they have an A chain or a B chain and a group (I), respectively. For example, it can be appropriately selected from known fluorine-containing ether compounds as described in the following documents.
Japanese Unexamined Patent Publication No. 2013-91047, Japanese Unexamined Patent Publication No. 2014-80473, International Publication No. 2013/042732, International Publication No. 2013/042733, International Publication No. 2013/121984, International Publication No. 2013/121985, International Publication No. 2013/121986, International Publication No. 2014/163004, International Publication No. 2014/175124, International Publication No. 2015/08792, JP2013-227279A, JP2013-241569A, JP2013- 256643, 2014-15609, 2014-37548, 2014-65884, 2014-21258, 2014-218639, 2015-208844. Japanese Patent Application Laid-Open No. 2015-221888, International Publication No. 2013/146112, International Publication No. 2013/187432, International Publication No. 2014/065922, International Publication No. 2015/099805, International Publication No. 2015/1667660, JP-A-2013-144726, JP-A-2014-77736, JP-A-2013-117012, JP-A-2014-214194, JP-A-2014-198822, JP-A-2015-129230, JP-A. 2015-196723A, 2015-13983A, 2015-199915A, 2015-199906A, etc.

In the present composition, the compound (A) may be a single compound composed of one compound (A) or a mixture composed of two or more compounds (A).
In the present specification, a fluorine-containing ether compound which is the same compound group except that it has a distribution in the number of repetitions of an oxyperfluoroalkylene group in a poly (oxyperfluoroalkylene) chain is regarded as a single compound. For example, in the case of compound (A) in which the poly (oxyperfluoroalkylene) chain is (CF ₂ O) _m1 (R ^f2 O) _m2 , the same compound group is a single compound except that it has distributions in m1 and m2. It is a fluorine-containing ether compound.

(Preferable combination of compound (A) and compound (B))
In a preferred embodiment of the composition, at least one of compound (A) and compound (B) has three or more groups (I), more preferably 3-5. When at least one of them has three or more groups (I), the durability of the surface layer is more excellent.
When only one of them has three or more groups (I), the number of groups (I) of the other is 1 or 2, and 2 is preferable from the viewpoint of durability.

In another preferred embodiment of the composition, both compound (A) and compound (B) have two or more groups (I), more preferably three or more, even more preferably 3-5. When both have two or more groups (I), the durability of the surface layer is more excellent.

When the surface layer is formed by the dry coating method, it is preferable that the difference between the number average molecular weight (Mn) of the compound (A) and the number average molecular weight (Mn) of the compound (B) is small. In the case of the dry coating method, the smaller the molecular weight, the more likely it is to evaporate first and deposit on the substrate. The smaller the difference in the number average molecular weight (Mn), the less uneven the distribution of the compound (A) and the compound (B) occurs in the formed surface layer.
The difference between the number average molecular weight (Mn) of the compound (A) and the number average molecular weight (Mn) of the compound (B) is preferably 3,000 or less, and particularly preferably 2,000 or less.
When the surface layer is formed by the wet coating method, the surface layer is formed even if there is a difference between the number average molecular weight (Mn) of the compound (A) and the number average molecular weight (Mn) of the compound (B). Since uneven distribution of the compound (A) and the compound (B) is unlikely to occur, the difference between them is not particularly limited.

Examples of preferable combinations of the compound (A) and the compound (B) in the present composition include the following combinations.
Combination example 1: A combination of a compound (A) having one A chain and three groups (I) and a compound (B) having one B chain and three groups (I).
Combination example 2: A combination of a compound (A) having two A chains and four groups (I) and a compound (B) having two B chains and four groups (I).
Combination example 3: A combination of a compound (A) having one A chain and five groups (I) and a compound (B) having one B chain and five groups (I).
In each of these combinations, compound (A) preferably has a group (II) attached to one end of the A chain. Further, the compound (B) preferably has a group (II) bonded to one end of the B chain.

Both the compound (A) and the compound (B) are preferably fluorine-containing ether compounds represented by the following formula (A / B). In the formula (A / B) below, R ^f of compound (A) is a poly (oxyperfluoroalkylene) chain containing (CF ₂ ^{O) units, and R f} of compound (B) is (CF ₂ O). It is a poly (oxyperfluoroalkylene) chain containing no unit.
_{^{[R f1 -O-Q-R}} f -] r Z [-SiR n L 3-n] s ··· (A / B)
In the above formula (A / B), R ^f1 is the R ^f1 , Q is the Q, and −SiR _n L _3-n is the group represented by the formula (I). Z is a linking group of (r + s) valence. r is an integer of 1 or more, and is a number corresponding to the number of poly (oxyperfluoroalkylene) chains in the above-mentioned compound (A) and compound (B). s is an integer of 1 or more, and is a number corresponding to the number of groups (I) in the compound (A) and the compound (B).
From the number of poly (oxyperfluoroalkylene) chains and the number of groups (I), r + s is preferably 2 to 13, more preferably 3 to 8, and particularly preferably 4 to 7. Examples of Z as a linking group having a (r + s) value include groups represented by ^{Z a} and Z ^{b described later.}
Further, when r is 2 or more, r [R ^f1- O-Q-R ^f- ] are preferably the same group, and when s is 2 or more, s formula (I) is used. The groups represented by are preferably the same group.

(Preferable aspect)
As a preferred embodiment of the present composition, the compound (A) is a fluorine-containing ether compound (A1) represented by the following formula (A1) (hereinafter, also referred to as a compound (A1)), and the compound (B) is a formula. Examples thereof include a fluorine-containing ether compound (B1) represented by (B1) (hereinafter, also referred to as compound (B1)). That is, the composition of this embodiment contains the compound (A1) and the compound (B1).
[R ^f1a- O-Q ^a- R ^fa- ] _ra Z ^a [-SiR ^a _na L ^a _3-na ] _sa ... (A1)
_{^{[R f1b -O-Q b -R}} fb -] rb Z b [-SiR b nb L b 3-nb] sb ··· (B1)
^{However, R f1a} and ^{R f1b} is a perfluoroalkyl group,
Q ^a and Q ^b are a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group having 2 to 5 bonds of the oxyfluoroalkylene group, and the polyoxy. The oxyfluoroalkylene groups constituting the fluoroalkylene group may be the same or different.
R ^fa is an A chain and
R ^fb is a B chain and
Z ^a is a linking group of (ra + sa) valence,
Z ^b is a linking group of (rb + sb) valence.
L ^a and ^{L b} are hydroxyl group or a hydrolyzable group,
R ^a and R ^b are hydrogen atoms or monovalent hydrocarbon groups.
na and nb are integers from 0 to 2 and
^{The (3-na) L a} when na is 0 or 1, and the (3-nb) L ^b when nb is 0 or 1, may be the same or different, respectively.
na number of ^R a when na is 2, each nb number of ^{R b} when nb is 2, may be the same or different and
ra and rb are integers of 1 or more, and when ra is 2 or more, ra [R ^f1a −O−Q ^a −R ^fa −] may be the same or different, and rb is 2. or when the rb pieces ^{[R f1b -O-Q b -R} fb -] may be the same or different and
sa and sb are integers of 1 or more, and when sa is 2 or more, sa [-SiR ^a _na L ^a _3-na ] may be the same or different, and sb is 2 or more. When sb [-SiR ^b _nb L ^b _3-nb ] may be the same or different.

R ^f1a and ^{R f1b} is the same as ^{R f1} of each of said in group (II), preferable embodiments thereof are also the same.
When ra is 2 or more, ^{it is preferable that ra R f1a} have the same carbon number, and from the viewpoint of ease of manufacture, the same group, that is, the group having the same carbon number and the same chemical structure. Is preferable. A group having the same number of carbon atoms and the same chemical structure means that, for example, when ra is 2, two R ^f1a are CF ₃ CF ₂ CF _2- (of two R ^fa ). It is not a combination of _{CF 3} CF ₂ CF _2- and CF ₃ CF (CF ₃ )-that have the same number of carbon atoms but different chemical structures).
When rb is 2 or more, ^{it is preferable that the rb R f1b} have the same carbon number, and from the viewpoint of ease of manufacture, the same group, that is, the group having the same carbon number and the same chemical structure. Is preferable.

Q ^{a and Q b} are the same as Q in the group (II), and the preferred embodiment is also the same.
The A chain of R ^{fa and the B chain of R fb} are the same as described above, and the preferred embodiments are also the same.
L ^a and L ^b is the same as L in the group (I), preferable embodiments thereof are also the same.
R ^{a and R b} are the same as R in the group (I), and the preferred embodiment is also the same.
na and nb are the same as n in the group (I), and the preferred embodiment is also the same.
The preferred values of ra and rb are the same as the preferred numbers of the A chain of the compound (A) and the B chain of the compound (B), respectively. That is, ra and rb are preferably integers of 1 to 3, respectively.
The preferred values of sa and sb are the same as the preferred number of groups (I) possessed by each of compound (A) and compound (B). That is, sa and sb are preferably integers of 1 to 10, more preferably integers of 2 to 5, and particularly preferably integers of 3 to 4.

As Z ^a , for example, a group or atom other than a hydrocarbon group is provided between carbon-carbon atoms of a substituted or unsubstituted hydrocarbon group having a (ra + sa) valence, a substituted or unsubstituted hydrocarbon group, and / or at the terminal thereof. Examples thereof include a (ra + sa) valent group and a (ra + sa) valent organopolysiloxane group.
Examples of Z ^b are the same as those of ^{Z a} except that the valence is (rb + sb).

The unsubstituted hydrocarbon group includes, for example, a linear or branched saturated hydrocarbon group, an aromatic hydrocarbon ring-type group (for example, (ra + sa) from an aromatic hydrocarbon ring such as a benzene ring or a naphthalene ring, or (ra + sa). rb + sb) group excluding hydrogen atoms), a group consisting of a combination of a linear or branched saturated hydrocarbon group and an aromatic hydrocarbon cyclic group (for example, a substituent to the aromatic hydrocarbon cyclic group). A group to which an alkyl group is bonded, a group having an arylene group such as a phenylene group between carbon atoms of the saturated hydrocarbon group and / or at the terminal thereof, etc.), a group consisting of a combination of two or more aromatic hydrocarbon cyclic groups, etc. Can be mentioned. Among these, linear or branched saturated hydrocarbon groups are preferable. The unsubstituted hydrocarbon group preferably has 20 or less carbon atoms.
A substituted hydrocarbon group is a group in which some or all of the hydrogen atoms of the hydrocarbon group are substituted with a substituent. Examples of the substituent include a halogen atom such as a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an amino group, a nitro group, a cyano group, an aminocarbonyl group and the like.

Examples of the group or atom other than the hydrocarbon group between the carbon atoms of the hydrocarbon group and / or at the terminal thereof include an ethereal oxygen atom (-O-), a thioethery sulfur atom (-S-), and a nitrogen atom (-S-). -N <), silicon atom (> Si <), carbon atom (> C <), -N (R ¹⁵ )-, -C (O) N (R ¹⁵ )-, -OC (O) N (R ¹⁵⁾ )-, -Si (R ¹⁶ ) (R ¹⁷ )-, organopolysiloxane group, -C (O)-, -C (O) -O-, -C (O) -S- and the like. However, R ¹⁵ is a hydrogen atom, an alkyl group or a phenyl group, and R ^{16 to} R ¹⁷ are independently alkyl groups or phenyl groups, respectively. The alkyl group preferably has 1 to 6 carbon atoms.
The organopolysiloxane group may be linear, branched or cyclic, or cyclic.

<Preferable form of compound (A1)>
As the compound (A1), at least one selected from the group consisting of the following compounds (A11), compound (A12) and compound (A13) is selected from the viewpoint of further excellent abrasion resistance and fingerprint stain removing property of the surface layer. preferable.

"Compound (A11)"
The compound (A11) is represented by the following formula (A11).
^{R f1a -O-Q a -R fa} -Q 32a - [C (O) N (R 33a)] pa -R 34a -C [-R 35a -SiR a na L a 3-na] 3 ··· ( A11)
^{However, R f1a, Q a, R} fa, R a, L a and na have the same meanings as defined above,
Q ^32a is a group having an ethereal oxygen atom between carbon atoms of a fluoroalkylene group having 1 to 20 carbon atoms or a fluoroalkylene group having 2 to 20 carbon atoms (however, one end thereof is bonded to the ethereal oxygen atom. The other end is a perfluoroalkylene group except when the fluoroalkylene group bonded to ^{R fa is a perfluoroalkylene group).}
R ^33a is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
pa is 0 or 1 and
R ^34a is a single bond, an alkylene group having 1 to 6 carbon atoms, and an ethereal oxygen at the end of the alkylene group (however, the end on the side bonded to ^{C [-R 34a-} SiR _na L _3-na ] _3). A group having an atom, a group having an ethereal oxygen atom between carbon atoms of an alkylene group having 2 to 6 carbon atoms, or a terminal of an alkylene group having 2 to 6 carbon atoms (however, C [-R ^34a- SiR _na). L _3-na ] ₃ is a group having an ethereal oxygen atom between carbon atoms and a terminal on the side that bonds with 3).
R ^35a is an alkylene group having 1 to 6 carbon atoms, a group having an ethereal oxygen atom at the end of the alkylene group (excluding the end on the side bonded to Si), or an alkylene group having 2 to 6 carbon atoms. A group having an ethereal oxygen atom between carbon atoms of
The three [-R ^34a- SiR _na L _3-na ] may be the same or different.

In the above formula (A1), the compound (A11) has ra of 1, sa of 3, and Z ^a of −Q ^32a − [C (O) N (R ^33a )] _pa −R ^34a −C. [-R ^35a- ] It is a compound of _3.
However, it is preferable that the number of (CF ₂ ^{O) in R fa} is 4 or more and the number of (CF ₂ ^{O) in Q 32a is 0 to 3.}

In Q ^32a , as the fluoroalkylene group having 1 to 20 carbon atoms, a perfluoroalkylene group and a fluoroalkylene group containing one or more hydrogen atoms are preferable. The fluoroalkylene group is preferably linear in terms of friction resistance and lubricity of the surface layer.
Examples of the group having an ethereal oxygen atom between carbon atoms of the fluoroalkylene group having 2 to 20 carbon atoms include the group (ii) described later.
Q ^32a includes a perfluoroalkylene group having 1 to 20 carbon atoms, a fluoroalkylene group having 1 to 20 carbon atoms containing one or more hydrogen atoms, and a fluorocarbon having 2 to 20 carbon atoms containing one or more hydrogen atoms. A group having an ethereal oxygen atom between carbon atoms of the alkylene group is preferable.

When pa is 0 and R ^fa is {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 }, Q ^32a is typically a perfluoroalkylene group having 1 carbon atom.
When pa is 1, the following groups can be mentioned as ^{Q 32a.}
(I) Perfluoroalkylene group.
(Ii) ^{A fluoroalkylene group having R F} CH ₂ O (where R ^F is a perfluoroalkylene group having 1 to 6 carbon atoms) on ^{the side bonded to R fa} and containing one or more hydrogen atoms. A group having (may have an ethereal oxygen atom between carbon atoms) on the side to be bonded ^{to C (O) N (R 33a).}

^{As Q 32a} of (ii), the following groups are preferable from the viewpoints of durability and lubricity of the surface layer and ease of production of the compound (A11).
_{^{-R F CH 2 OCF 2 CHFOCF 2}} CF 2 CF 2 -, - R F CH 2 OCF 2 CHFCF 2 OCF 2 CF 2 -, - R F CH 2 OCF 2 CHFCF 2 OCF 2 CF 2 CF _{^{2 -, - R F CH 2}} OCF 2 CHFOCF 2 CF 2 CF 2 OCF 2 CF 2 -.

[C (O) N (R ^33a )] When the _pa in the pa group is 0 and 1, the characteristics of the fluorine-containing ether compound are almost the same. When pa is 1, it has an amide bond, but it is due to the fact that at least one fluorine atom is bonded to the carbon atom at the terminal on the side that bonds with [C (O) N (R ^{33a )] of Q 32a.} , The polarity of the amide bond becomes small, and the water and oil repellency of the surface layer does not easily decrease. Whether pa is 0 or 1 can be selected from the viewpoint of ease of manufacturing.
[C (O) N (R ^33a )] As the R ^33a _{in the pa} group, a hydrogen atom is preferable from the viewpoint of ease of production of the compound (A11).
When R ^33a is an alkyl group, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms.

When pa is 0, R ^34a _{has a single bond, −CH 2} O− _{, −CH 2} OCH ₂ −, −CH ₂ OCH ₂ CH ₂ O− from the viewpoint of ease of production of compound (A11). and _{-CH 2 OCH 2 CH 2 OCH 2} - selected from the group consisting of the groups (. However, the left side is bonded to ^{Q 32)} are preferred.
When pa is 1, as R ^34a , a group selected from the group consisting of _{a single bond, −CH 2} − and −CH ₂ CH ₂₋ is preferable from the viewpoint of ease of production of the compound (A11).

As R ^35a , from the viewpoint of ease of production of compound (A11), −CH ₂ CH ₂ −, −CH ₂ CH ₂ CH ₂ −, −CH ₂ OCH ₂ CH ₂ CH ₂ −, −OCH ₂ CH _A group selected from the group consisting of 2 CH _2- (where the right side binds to Si) is preferable.
As R ^35a , those having no ethereal oxygen atom are particularly preferable from the viewpoint of excellent light resistance of the surface layer. In touch panels for outdoor use (digital signage such as vending machines and information boards), in-vehicle touch panels, etc., the water- and oil-repellent layer is required to have light resistance.
Three ^{R 35a} in the compound (A11) may be be the same or different.

Examples of the compound (A11) include the compound of the following formula. The compound is preferable because it is industrially easy to manufacture, easy to handle, and is further excellent in water and oil repellency, abrasion resistance, fingerprint stain removing property, lubricity, and appearance of the surface layer.

However, W in these ^{formulas, R f1a -O-Q a -R} fa - a. The preferred form of W is a combination of the ^{preferred R f1a} , Q ^a and R ^{fa described above.} The preferred range of Q ^32a is as described above.

"Compound (A12)"
The compound (A12) is represented by the following formula (A12).
R ^f1a- O-Q ^a- R ^fa- R ^42a- R ^43a- N [-R ^44a- SiR ^a _na L ^a _3-na ] ₂ ... (A12)
^{However, R f1a, Q a, R} fa, R a, L a and na have the same meanings as defined above,
R ^42a is a perfluoroalkylene group having 1 to 6 carbon atoms.
R ^43a is a single bond, an alkylene group having 1 to 6 carbon atoms, a group having an ethereal oxygen atom or −NH− at the end of the alkylene group (excluding the end on the side bonded to N), and the number of carbon atoms. A group having an ethereal oxygen atom or -NH- between carbon-carbon atoms of 2 to 6 alkylene groups, or a terminal of an alkylene group having 2 to 6 carbon atoms (excluding the end on the side bonded to N). And a group having an ethereal oxygen atom or -NH- between carbon and carbon atoms.
R ^44a is an alkylene group having 1 to 6 carbon atoms or a group having an ethereal oxygen atom or -NH- between carbon-carbon atoms of an alkylene group having 2 to 6 carbon atoms.
The two [-R ^44a- SiR _na L _3-na ] may be the same or different.

The compound (A12) is a compound having ra of 1, sa of 2, and Z ^a of −R ^{42a −} R ^43a −N [−R ^44a −] _{2 in} the above formula (A1).

R ^42a is preferably a linear perfluoroalkylene group. If R ^42a is a linear perfluoroalkylene group, the friction resistance and lubricity of the surface layer are further excellent.
R ^42a is typically a perfluoroalkylene group having 1 carbon atom when ^{R fa} is {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12}.

As R ^43a , from the viewpoint of ease of production of the compound (A12), −CH ₂ −, _{−CH 2} CH ₂ −, −CH ₂ CH ₂ CH ₂ −, −CH ₂ OCH ₂ CH ₂ − and −. A group selected from the group consisting of _{CH 2} NHCH ₂ CH _2- ^{(where the left side binds to R 42a} ) is preferable.
Since R ^43a has high polarity and does not have an ester bond having insufficient chemical resistance and light resistance, it is excellent in initial water repellency, chemical resistance and light resistance of the surface layer.

As R ^44a , from the viewpoint of ease of production of the compound (A12), −CH ₂ CH ₂ CH ₂ − and −CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ − (however, the right side is bound to Si). ) Is preferable.
Since R ^44a has high polarity and does not have an ester bond having insufficient chemical resistance and light resistance, it is excellent in initial water repellency, chemical resistance and light resistance of the surface layer.
As R ^44a , one having no ethereal oxygen atom is particularly preferable from the viewpoint of excellent light resistance of the surface layer.
^{The two R 44a in} compound (A12) may be the same or different.

Examples of the compound (A12) include the compound of the following formula. The compound is preferable because it is industrially easy to manufacture, easy to handle, and further excellent in water repellency, oil repellency, abrasion resistance, fingerprint stain removing property, lubricity, chemical resistance, and light resistance.

However, W in these ^{formulas, R f1a -O-Q a -R} fa - a. The preferred form of W is a combination of the ^{preferred R f1a} , Q ^a and R ^{fa described above.} The preferred range of R ^42a is as described above.

"Compound (A13)"
The compound (A13) is represented by the following formula (A13).
[R ^f1a- O-Q ^a- R ^fa- R ^51a- R ^52a- O-] _ea Z ^3a [-O-R ^53a- SiR ^a _na L _3-na ] _fa ... (A13)
^{However, R f1a, Q a, R} fa, R a, L a and na have the same meanings as defined above,
R ^51a is a perfluoroalkylene group having 1 to 6 carbon atoms.
R ^52a is an alkylene group having 1 to 6 carbon atoms.
Z ^3a is a (ea + fa) -valent hydrocarbon group, or a (ea + fa) -valent group having 2 or more carbon atoms and having one or more ethereal oxygen atoms between carbon atoms of the hydrocarbon group.
R ^53a is an alkylene group having 1 to 20 carbon atoms.
ea is an integer greater than or equal to 1 and
fa is an integer of 1 or more,
(Ea + fa) is 3 or more,
When the ea is 2 or more, the ea [R ^f1a- O-Q ^a- R ^fa- R ^51a- R ^52a- O-] may be the same or different.
When the number of fas is 2 or more, the number of fas ^{[-OR 53a- SiR a} _na L ^a _3-na ] may be the same or different.

Compound (A13) is, in the above formula (A1), ra is ea, sa is fa, ^{Z a} is _{^{[-R 51a -R 52a -O-] ea}} Z 3a [-O-R 53a - ] It is a compound of _fa.

The ea is preferably an integer of 1 to 3. The fa is preferably an integer of 1 to 10, more preferably an integer of 2 to 5, and particularly preferably an integer of 3 to 4.

R ^51a is −CF ₂ −, for example, when R ^fa is {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12}.
R ^51a is preferably linear. If R ^51a is a linear compound (A13), a surface layer having better abrasion resistance and lubricity can be formed.

The R ^52a, in terms of the compound (A13) ease of manufacture, preferably an alkylene group having 1 to 4 carbon atoms, -CH ₂ - is particularly preferred.

As the R ^f1a- O-Q ^a- R ^fa- R ^51a -group, the surface layer has water and oil repellency, durability, fingerprint stain removing property, lubricity, and is further excellent in appearance and compound (A13). ^{The group (R f} -1) and the group (R ^f -2) are preferable from the viewpoint of ease of production.
_{^{R f11 O {(CF 2 O}} ) m21 (CF 2 CF 2 O) m22} CF 2 - (R f -1)
_{^{R f11 OCHFCF 2 OCH 2 CF 2}} O {(CF 2 O) m21 (CF 2 CF 2 O) m22} CF 2 - (R f -2)
^{However, R f11} is a linear perfluoroalkyl group with 1 to 20 carbon atoms; m21 and m22 are each an integer of 1 or more, m21 + m22 is an integer of 2 to 200, m21 amino CF _{The binding order of 2} O and m22 CF ₂ CF ₂ O is not limited.

Examples of Z ^3a include residues obtained by removing hydroxyl groups from a polyhydric alcohol having (ea + fa) hydroxyl groups.
As ^{a specific example of Z 3a} , for example, the group of the following formula can be mentioned. As Z ^3a , a residue obtained by removing the hydroxyl group from a polyhydric alcohol having a primary hydroxyl group is preferable from the viewpoint of excellent reactivity of the hydroxyl group, and a group (Z-1) or a group is preferable from the viewpoint of easy availability of a raw material. (Z-2) and group (Z-3) are particularly preferable. However, R ⁴ is an alkyl group, preferably a methyl group or an ethyl group.

As R ^53a , an alkylene group having 3 to 14 carbon atoms is preferable from the viewpoint of ease of production of the compound (A13). Further, during hydrosilylation in the production of the compound (A13) described later, a by-product in which _{a part or all of the allylic group (-CH 2} CH = CH ₂ ) is isomerized to the inner olefin (-CH = CHCH _{3) is generated.} An alkylene group having 4 to 10 carbon atoms is particularly preferable because it is difficult to form.

Examples of the compound (A13) include compounds (A13-1) to (A13-6) of the following formulas. The compound is preferable because it is industrially easy to manufacture, easy to handle, and is further excellent in water and oil repellency, abrasion resistance, fingerprint stain removing property, lubricity, and appearance of the surface layer.

However, W in these ^{formulas, R f1a -O-Q a -R} fa - a. The preferred form of W is a combination of the ^{preferred R f1a} , Q ^a and R ^{fa described above.} The preferred form of R ^51a is as described above.

<Preferable form of compound (B1)>
As the compound (B1), the following compounds (B11), compound (B12) and compound (B13) are preferable from the viewpoint of further excellent friction resistance of the surface layer and fingerprint stain removing property.

"Compound (B11)"
The compound (B11) is represented by the following formula (B11).
^{R f1b -O-Q b -R fb} -Q 32b - [C (O) N (R 33b)] pb -R 34b -C [-R 35b -SiR nb L 3-nb] 3 ··· (B11)
However, R ^f1b , Q ^b , R ^fb , R ^b , L ^b and nb have the same meanings as described above.
Q ^32b is a group having an ethereal oxygen atom between carbon atoms of a fluoroalkylene group having 1 to 20 carbon atoms or a fluoroalkylene group having 2 to 20 carbon atoms (however, one end thereof is bonded to the ethereal oxygen atom. The other end is a perfluoroalkylene group except when the fluoroalkylene group bonded to ^{R fb is a perfluoroalkylene group).}
R ^33b is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
pb is 0 or 1 and
R ^34b is a single bond, an alkylene group having 1 to 6 carbon atoms, and an ethereal oxygen at the end of the alkylene group (however, the end on the side bonded to ^{C [-R 34b-} SiR _nb L _3-nb ] _3). A group having an atom, a group having an ethereal oxygen atom between carbon atoms of an alkylene group having 2 to 6 carbon atoms, or a terminal of an alkylene group having 2 to 6 carbon atoms (however, C [-R ^34b- SiR _nb) L _3-nb ] ₃ is a group having an ethereal oxygen atom between carbon atoms and a terminal on the side that bonds with 3).
R ^35b is an alkylene group having 1 to 6 carbon atoms, a group having an ethereal oxygen atom at the end of the alkylene group (excluding the end on the side bonded to Si), or an alkylene group having 2 to 6 carbon atoms. A group having an ethereal oxygen atom between carbon atoms of
The three [-R ^34b- SiR _nb L _3-nb ] may be the same or different.

In the above formula (B1), the compound (B11) has rb of 1, sb of 3, and Z ^b of −Q ^32b − [C (O) N (R ^33b )] _pb −R ^34b −C. [-R ^35b- ] _{3 is} a compound.

The fluoroalkylene group in Q ^{32b and} the group having an ethereal oxygen atom between the carbon and carbon atoms of the fluoroalkylene group are between the fluoroalkylene group and the carbon-carbon atom of the fluoroalkylene group in ^{Q 32a in the above formula (A11), respectively.} Similar to a group having an ethereal oxygen atom in.
The number of (CF ₂ O) in Q ^32b is preferably 0 to 3.
Q ^32b is typically a perfluoroalkylene group having 1 carbon atom when p1 is 0 and R ^fb is (CF ₂ CF ₂ O) _m13. When p1 is 0 and R ^fb is (CF ₂ CF ₂ CF ₂ O) _m14, it is typically a perfluoroalkylene group having 2 carbon atoms. When p1 is 0 and R ^fb is (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _m15, it is typically a linear perfluoroalkylene group having 3 carbon atoms.
R ^33b , pb, R ^34b , and R ^{35b are the same as R 33a} , pa, R ^34a , and R ^35a in the above formula (A11), respectively, and the preferred embodiments are also the same.

"Compound (B12)"
The compound (B12) is represented by the following formula (B12).
R ^f1b −O−Q ^b −R ^fb −R ^42b −R ^43b −N [−R ^44b −SiR _nb L _3-nb ] ₂ ... (B12)
However, R ^f1b , Q ^b , R ^fb , R ^b , L ^b and nb have the same meanings as described above.
R ^42a is a perfluoroalkylene group having 1 to 6 carbon atoms.
R ^43a is a single bond, an alkylene group having 1 to 6 carbon atoms, a group having an ethereal oxygen atom or −NH− at the end of the alkylene group (excluding the end on the side bonded to N), and the number of carbon atoms. A group having an ethereal oxygen atom or -NH- between carbon-carbon atoms of 2 to 6 alkylene groups, or a terminal of an alkylene group having 2 to 6 carbon atoms (excluding the end on the side bonded to N). And a group having an ethereal oxygen atom or -NH- between carbon and carbon atoms.
R ^44a is an alkylene group having 1 to 6 carbon atoms or a group having an ethereal oxygen atom or -NH- between carbon-carbon atoms of an alkylene group having 2 to 6 carbon atoms.
The two [-R ^44- SiR _n L _3-n ] may be the same or different.

The compound (B12) is a compound having rb of 1, sb of 2, and Z ^b of −R ^42b −R ^43b −N [−R ^44b −] _{2 in} the above formula (B1).

R ^42b , R ^43b , and R ^{44b are the same as R 42a} , R ^43a , and R ^44a in the above formula (A12), respectively.
However, R ^42b is typically a perfluoroalkylene group having 1 carbon atom when ^{R fb} is (CF ₂ CF ₂ O) _m13. When R ^fb is (CF ₂ CF ₂ CF ₂ O) _m14, it is typically a perfluoroalkylene group having 2 carbon atoms. When R ^fb is (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _m15, it is typically a linear perfluoroalkylene group having 3 carbon atoms.

"Compound (B13)"
The compound (B13) is represented by the following formula (B13).
[R ^f1b- O-Q ^b- R ^fb- R ^51b- R ^52b- O-] _eb Z ^3b [-O-R ^53b- SiR ^b _nb L ^b _3-nb ] _f ... (B13)
However, R ^f1b , Q ^b , R ^fb , R ^b , L ^b and nb have the same meanings as described above.
R ^51b is a perfluoroalkylene group having 1 to 6 carbon atoms.
R ^52b is an alkylene group having 1 to 6 carbon atoms.
Z ^3b is a (eb + fb) -valent hydrocarbon group or a (eb + fb) -valent group having 2 or more carbon atoms and having one or more ethereal oxygen atoms between carbon atoms of the hydrocarbon group.
R ^53b is an alkylene group having 1 to 20 carbon atoms.
eb is an integer greater than or equal to 1 and
fb is an integer greater than or equal to 1 and
(Eb + fb) is 3 or more,
When eb is 2 or more, eb [R ^f1b- O-Q-R ^fb- R ^51b- R ^52b- O-] may be the same or different.
When fb is 2 or more, the number of fb [-OR ^53b- SiR ^b _nb L ^b _3-nb ] may be the same or different.

In the compound (B13), in the above formula (B1), rb is eb, sb is fb, and Z ^b is [-R ^51b- R ^52b- O-] _eb Z ^3b [-O-R ^53b-". ] It is a compound of _fb.

R ^51b , R ^52b , Z ^3b , R ^53b , eb, and fb are the same as R ^51a , R ^52a , Z ^3a , R ^53a , ea, and fa in the above formula (A13), respectively.
R ^f1b- O-Q ^b- R ^fb- R ^51b- R ^52b -As a group, the surface layer has water and oil repellency, durability, fingerprint stain removing property, lubricity, and further excellent appearance and compound ( ^{The group (R f-} 3) is preferable from the viewpoint of ease of manufacturing B13).
R ^f11 O (CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) _m25 CF ₂ CF ₂ OCF ₂ CF ₂ CF _2- (R ^f -3)
^{However, R f11} is a linear perfluoroalkyl group with 1 to 20 carbon atoms; m25 is an integer of 1 to 100.

(Other fluorine-containing ether compounds)
The present composition may be composed of the compound (A) and the compound (B), or may further contain a fluorine-containing ether compound other than the compound (A) and the compound (B).
Examples of other fluorine-containing ether compounds include a fluorine-containing ether compound having a poly (oxyperfluoroalkylene) chain and no group (I) (hereinafter, also referred to as compound (C)). The poly (oxyperfluoroalkylene) chain may be an A chain or a B chain.

Examples of the compound (C) include the compound (C1).
_{^{A 31 -O-Q 51 - (}} R F3 O) m30 - [Q 52 -O] p3 -A 32 ··· (C1)
However, A ³¹ and A ³² are independently perfluoroalkyl groups having 1 to 20 carbon atoms; Q ⁵¹ has a single bond and 1 to 6 carbon atoms having no branched structure containing one or more hydrogen atoms. fluoroalkylene group, the ends of one or more fluoro alkylene group having 1 to 6 carbon atoms having no branched structure containing hydrogen atom (except the ends of the side that binds to a ^{31 -O.)} etheric oxygen atom A group having an ethereal oxygen atom between carbon atoms of a fluoroalkylene group having 2 to 6 carbon atoms having no branched structure containing one or more hydrogen atoms, or a group containing one or more hydrogen atoms. end fluoroalkylene group having 2 to 6 carbon atoms having no branched structure (except the ends of the side that binds to a ^{31 -O.)} and carbon - is a group having an etheric oxygen atom between carbon atoms ( However, the number of oxygen is 10 or less.); Q ⁵² has a fluoroalkylene group having 1 to 20 carbon atoms which does not have a branched structure containing one or more hydrogen atoms, or a branched structure containing one or more hydrogen atoms. It is a group having an ethereal oxygen atom between carbon atoms of a fluoroalkylene group having 2 to 6 carbon atoms (however, the oxygen number is 10 or less); ^RF3 does not have a branched structure. It is a perfluoroalkylene group having 1 to 6 carbon atoms; m30 is an integer of ^2~200; (R F3 _{O) m30} may be made of two or more of ^{R F3} O having different numbers of carbon atoms ; ^p3, if ^{Q 51} is a single bond is ^0, if ^{Q 51} is other than a single bond is 1.

As the compound (C1), a compound produced by a known production method may be used, or a commercially available product may be used. For ^{example, Q 51} is a single bond, Examples of commercially available compounds p3 is 0 (C1), FOMBLIN (registered trademark) M, FOMBLIN (registered trademark) Y, FOMBLIN (registered trademark) Z (or, Sorubeiso Lexis), Krytox (registered trademark) (DuPont), Demnam (registered trademark) (Daikin Industries, Ltd.) and the like.

The present composition may contain impurities other than the compound (A), the compound (B) and other fluorine-containing ether compounds. Examples of impurities other than the compound (A), the compound (B) and the other fluorine-containing ether compound include the compound (A), the compound (B) and a compound unavoidable in the production of the other fluorine-containing ether compound.

(Composition of this composition)
In this composition, the content of compound (A) (mass ratio of compound (A) / [compound (A) + compound (B)] to the total of compound (A) and compound (B) is 10 to 80. The mass% is preferable, and 20 to 50% by mass is particularly preferable. The higher the content of compound (A) within the above range, the better the lubricity of the surface layer. The lower the content of the compound (A) within the above range (that is, the higher the content of the compound (B) with respect to the total of the compound (A) and the compound (B)), the better the durability of the surface layer.

In the present composition, the total amount of the compound (A) and the compound (B) is preferably 50% by mass or more, particularly preferably 80% by mass or more, based on the total mass of the present composition. The upper limit is not particularly limited and may be 100% by mass.

[Coating liquid]
The coating liquid of the present invention (hereinafter, also referred to as the present coating liquid) includes the present composition and a liquid medium. The coating liquid may be a liquid, a solution, or a dispersion.
The present coating liquid may contain the present composition, and may contain impurities such as by-products produced in the manufacturing process of the compound (A), the compound (B) and the like.
The concentration of the composition is preferably 0.001 to 50% by mass, more preferably 0.05 to 30% by mass, still more preferably 0.05 to 10% by mass, and 0.1 to 1% by mass in the coating liquid. % Is particularly preferable.

As the liquid medium, an organic solvent is preferable. The organic solvent may be a fluorine-based organic solvent, a non-fluorine-based organic solvent, or may contain both solvents.

Examples of the fluorinated organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols and the like.
As the fluorinated alkane, a compound having 4 to 8 carbon atoms is preferable. Commercially available products include, for example, C ₆ F ₁₃ H (Asahi Glass Co., Ltd., Asahi Clean (registered trademark) AC-2000), C ₆ F ₁₃ C ₂ H ₅ (Asahi Glass Co., Ltd., Asahi Clean (registered trademark) AC-6000). , C ₂ F ₅ CHFCHFCF ₃ (manufactured by The Chemours Company, Bertrel (registered trademark) XF) and the like.
Examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis (trifluoromethyl) benzene.
As the fluoroalkyl ether, a compound having 4 to 12 carbon atoms is preferable. Examples of commercially available products include CF ₃ CH ₂ OCF ₂ CF ₂ H (Asahi Clean (registered trademark) AE-3000), C ₄ F ₉ OCH ₃ (3M, Novec (registered trademark) 7100). Examples thereof include C ₄ F ₉ OC ₂ H ₅ (3M, Novec (registered trademark) 7200), C ₂ F ₅ CF (OCH ₃ ), C ₃ F ₇ (3M, Novec (registered trademark) 7300), and the like. ..
Examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
Examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol and the like.
As the non-fluorine-based organic solvent, a compound consisting only of a hydrogen atom and a carbon atom and a compound consisting only of a hydrogen atom, a carbon atom and an oxygen atom are preferable, and a hydrocarbon-based organic solvent, an alcohol-based organic solvent, a ketone-based organic solvent, etc. Examples thereof include ether-based organic solvents and ester-based organic solvents.
The coating liquid preferably contains 50 to 99.99% by mass of a liquid medium, more preferably 70 to 99.5% by mass, still more preferably 90 to 99.5% by mass, and 99 to 99. It is particularly preferable to contain 9% by mass.

In addition to the composition and the medium, the coating liquid may contain other components as long as the effects of the present invention are not impaired.
Examples of other components include known additives such as an acid catalyst and a basic catalyst that promote the hydrolysis and condensation reaction of the hydrolyzable silyl group.
The content of other components in this coating liquid is preferably 10% by mass or less, and particularly preferably 1% by mass or less.

The solid content concentration of this coating liquid is preferably 0.001 to 50% by mass, more preferably 0.05 to 30, still more preferably 0.05 to 10% by mass, and particularly preferably 0.01 to 1% by mass.
The solid content concentration of the coating liquid is a value calculated from the mass of the coating liquid before heating and the mass after heating in a convection dryer at 120 ° C. for 4 hours.
The concentration of the present composition can be calculated from the solid content concentration and the amount of the present composition, the solvent and the like charged.

[Article]
The article of the present invention has a surface layer formed from the present composition on the surface of the substrate.

(Surface layer)
In this composition, when L in the group (I) in the compound (A) and the compound (B) is a hydrolyzable group, the silanol group (Si-) is reacted by the hydrolysis reaction of the group (I). OH) is formed, and the silanol group reacts between molecules to form a Si—O—Si bond, or the silanol group undergoes a dehydration condensation reaction with a hydroxyl group (base material-OH) on the surface of the base material to chemically react. Bonds (base material-O-Si) are formed. Therefore, the surface layer contains the compound (A) and the compound (B) in a state in which a part or all of the groups (I) of the compound (A) and the compound (B) are hydrolyzed. When L in the group (I) is a hydroxyl group, the above reaction proceeds without undergoing a hydrolysis reaction.

The thickness of the surface layer is preferably 1 to 100 nm, particularly preferably 1 to 50 nm. When the thickness of the surface layer is at least the lower limit of the above range, the effect of the surface treatment can be sufficiently obtained. When the thickness of the surface layer is not more than the upper limit of the above range, the utilization efficiency is high. The thickness of the surface layer is determined by obtaining an interference pattern of reflected X-rays by the X-ray reflectivity method using an X-ray diffractometer for thin film analysis (ATX-G manufactured by RIGAKU), and from the vibration cycle of the interference pattern. Can be calculated.

(Base material)
The base material in the present invention is not particularly limited as long as it is a base material that is required to be imparted with lubricity and water / oil repellency. Examples of the material of the base material include metal, resin, glass, sapphire, ceramic, stone, and a composite material thereof. The glass may be chemically strengthened. _{A base film such as a SiO 2} film may be formed on the surface of the base material.
As the base material, a base material for a touch panel, a base material for a display, and a spectacle lens are suitable, and a base material for a touch panel is particularly suitable. The base material for the touch panel has translucency. "Having translucency" means that the vertically incident visible light transmittance according to JIS R3106: 1998 (ISO 9050: 1990) is 25% or more. Glass and transparent resin are preferable as the material of the base material for the touch panel.

(Manufacturing method of goods)
The article of the present invention can be produced, for example, by the following method.
-A method for obtaining the article of the present invention by treating the surface of a base material by a dry coating method using the present composition.
-A method for obtaining the article of the present invention by applying the present coating liquid to the surface of a base material by a wet coating method and drying it.

<Dry coating method>
This composition can be used as it is in the dry coating method. This composition is suitable for forming a surface layer having excellent adhesion by a dry coating method.
Examples of the dry coating method include a vacuum vapor deposition method, a CVD method, and a sputtering method. The vacuum vapor deposition method is particularly preferable from the viewpoint of suppressing the decomposition of the compound (A) and the compound (B) and the simplicity of the apparatus. At the time of vacuum deposition, a pellet-like substance obtained by impregnating a metal porous body such as iron or steel with the present composition or the present coating liquid may be used.

The temperature at the time of vacuum vapor deposition is preferably 20 to 300 ° C, particularly preferably 30 to 200 ° C. The pressure at the time of vacuum vapor deposition ^{is preferably 1 × 10 -1} Pa or less, and particularly preferably 1 × 10 ^{-2 Pa or less.}

<Wet coating method>
Wet coating methods include spin coating method, wipe coating method, spray coating method, squeegee coating method, dip coating method, die coating method, inkjet method, flow coating method, roll coating method, casting method, Langmuir Brodget method, and gravure. The coat method and the like can be mentioned.

<Post-processing>
In order to improve the friction resistance of the surface layer, an operation for promoting the reaction between the compound (A) and the compound (B) and the substrate may be performed, if necessary. Examples of the operation include heating, humidification, and light irradiation.
For example, a substrate on which a surface layer is formed is heated in a water-containing atmosphere to hydrolyze a hydrolyzable silyl group to a silanol group, a reaction between a hydroxyl group on the surface of the substrate and a silanol group, and silanol. Reactions such as the formation of siloxane bonds by the condensation reaction of groups can be promoted.
After the surface treatment, the compound in the surface layer that is not chemically bonded to other compounds or the substrate may be removed if necessary. Specific methods include, for example, a method of pouring a solvent over the surface layer, a method of wiping with a cloth soaked with the solvent, and the like.

[Action effect]
Since the composition and the coating liquid contain the compound (A) and the compound (B), a surface layer having excellent lubricity and durability can be formed. That is, by forming a surface layer on the surface of the base material using the present composition or the present coating liquid, characteristics such as excellent initial lubricity and water repellency and oil repellency are imparted, and the surface is repeatedly formed. Excellent durability is obtained in which these characteristics are not easily deteriorated even when rubbed. Further, since the water and oil repellency does not easily decrease even if the surface is repeatedly rubbed, the performance of easily removing fingerprint stains on the surface of the base material (fingerprint stain removal property) can be obtained.
Since compound (A) contains (CF ₂ O) units in the A chain, it has excellent lubricity. On the other hand, it is inferior in durability as compared with the case where it does not contain _{(CF 2 O) units.} Since compound (B) _{does not contain (CF 2} O) units in the B chain, it has excellent durability. On the other hand, the lubricity is inferior to that of the case containing _{(CF 2 O) units.} When these are combined, the excellent properties of each are sufficiently maintained, and excellent lubricity and durability can be achieved at the same time. It is considered that the reason for this is that the component having high lubricity (compound (A)) disperses the force applied to wear, and the durability of the component having high durability (compound (B)) is further enhanced.

[Use]
Therefore, the base material having a surface layer thus obtained is suitable as a member constituting the touch panel.
However, the use of the composition, the coating liquid and the article is not limited to the touch panel. For example, display input devices other than touch panels; surface protective coats for transparent glass or transparent plastic (acrylic, polycarbonate, etc.) members, antifouling coats for kitchens; water-repellent and moisture-proof coats for electronic devices, heat exchangers, batteries, etc. Antifouling coat, antifouling coat for toiletry; Coat for parts that require liquid repellency while conducting; Water repellent / waterproof / water-sliding coat for heat exchangers; Used for surface low friction coats such as vibration sieves and cylinder interiors be able to.
As a more specific example of use, a display front protective plate, an antireflection plate, a polarizing plate, an antiglare plate, an antiglare plate on the surface thereof, a touch panel of a device such as a mobile phone or a mobile information terminal. Various devices with display input devices such as sheets and touch panel displays that operate on the screen with human fingers or palms, decorative building materials around water such as toilets, baths, washrooms, kitchens, waterproof coating for wiring boards, and heat exchanger repellent Water / waterproof coat, water repellent coat for solar cells, waterproof / water repellent coat for printed wiring boards, waterproof / water repellent coat for electronic device housings and electronic parts, insulation improvement coat for transmission lines, waterproof / waterproof for various filters Water-repellent coat, waterproof coat for radio wave absorbers and sound-absorbing materials, antifouling coat for baths, kitchen equipment, toiletries, water-repellent / waterproof / water-sliding coat for heat exchangers, low-friction coat on the surface of vibration sieves and cylinders, etc. Examples include surface protective coats for machine parts, vacuum equipment parts, bearing parts, automobile parts, tools and the like.

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto. Hereinafter, "%" is "mass%" unless otherwise specified.
Examples 1-5, 7-11, 13-17, 19-23, 25-29, 42-49, 52-59, 61-65 are examples, and Examples 6, 12, 18, 24, 30-41 are examples. , 50-51, 60, 66-67 are comparative examples.

[Physical characteristics and evaluation]
(Number average molecular weight)
The number average molecular weight of the fluorine-containing ether compound was calculated by determining the number (average value) of the oxyperfluoroalkylene group with respect to the terminal group by ¹ H-NMR and ^{19 F-NMR.} The terminal group is, for example, a group (I) or a group (II).

(Water contact angle)
The contact angle (water contact angle) of about 2 μL of distilled water placed on the surface of the surface layer was measured at 20 ° C. using a contact angle measuring device (DM-701 manufactured by Kyowa Surface Science Co., Ltd.). 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. The larger the water contact angle, the better the water repellency.

(Lubricability)
The dynamic friction coefficient of the surface layer for artificial skin (Idemitsu Technofine Co., Ltd., PBZ13001) was measured using a load-variable friction and wear test system (Shinto Kagaku Co., Ltd., HHS2000), contact area: 3 cm x 3 cm, load: 0.98 N. It was measured under the condition of. The smaller the coefficient of dynamic friction, the better the lubricity.

(Durability 1 (number of times the contact angle is maintained at 100 ° or more))
For the surface layer, use a reciprocating traverse tester (manufactured by KNT) in accordance with JIS L0849: 2013 (ISO 105-X12: 2001), and use a steel wool bon tester (# 0000) with a pressure: 98.07 kPa, speed: It was reciprocated at 320 cm / min. The water contact angle was measured every time the water contact angle was reciprocated 1000 times, and the upper limit number of times the water contact angle of 100 ° or more was maintained (the number of times of maintenance of the contact angle of 100 ° or more) was determined. As the number of times increases, the surface layer is less likely to be damaged by friction, and the durability is excellent.

(Durability 2 (Difficulty in reducing dynamic friction coefficient))
After reciprocating the steel wool bon tester 3,000 times under the condition of <durability 1>, the dynamic friction coefficient was measured under the same conditions as the <lubricity>. The smaller the change in the dynamic friction coefficient, the less the outermost surface is damaged by friction, and the better the durability.

〔material〕
(A-1): The composition (A-1) obtained in Production Example A-1 described later.
(A-2): The composition (A-2) obtained in Production Example A-2 described later.
(A-3): Compound (A-3) obtained in Production Example A-3 described later.
(A-4): Compound (A-4) obtained in Production Example A-4 described later.
(A-5): Compound (A-5) obtained in Production Example A-5 described later.

(B-1): Compound (B-1) obtained in Production Example B-1 described later.
(B-2): The composition (B-2) obtained in Production Example B-2 described later.
(B-3): Compound (B-3) obtained in Production Example B-3 described later.
(B-4): Compound (B-4) obtained in Production Example B-4 described later.
(B-5): Compound (B-5) obtained in Production Example B-5 described later.
(B-6): The solvent of "2634 coating" manufactured by Toray Dow Corning Co., Ltd. was distilled off and used. CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₂₁ CF ₂ CF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ .

(C-1): _{Fluorine-containing ether compound represented by CF 3} O {(CF ₂ O) _r1 (CF ₂ CF ₂ O) _r2 } CF ₃ (r1 / r2 = 20/21) (manufactured by Solbeisolexis) "FOMBLIN M03").

Poly (oxyperfluoroalkylene) chain, a repeating unit of the poly (oxyperfluoroalkylene) chain possessed by the above (A-1) to (A-5), (B-1) to (B-5), (C-1). (Hereinafter, also referred to as the number of PEPE), the number of groups (I) and the number average molecular weight (Mn) are shown in Table 1.
_{The repeating units "(CF 2} O) (CF ₂ CF ₂ O)" in (A-1) to (A-5) and (C-1) _{are (CF 2} O) units and (CF ₂ CF _2). O) Represents that the unit is a randomly arranged poly (oxyperfluoroalkylene) chain.

[Manufacturing Example A-1]
In a 300 mL three-necked flask, 24.4 g of a 24% KOH aqueous solution, 33 g of tert-butyl alcohol, and 220 g of compound (1) (FLUOROLINK (registered trademark) D4000 manufactured by Solbeisolexis) are placed in a CF ₃ CF. ₂ CF _2- O-CF = _{19.4 g of CF 2} (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere. The organic phase was washed once with a dilute aqueous hydrochloric acid solution, and the organic phase was recovered and concentrated with an evaporator to obtain 233 g of a crude product. The crude product was developed by silica gel column chromatography and fractionated. As the developing solvent, C ₆ F ₁₃ CH ₂ CH ₃ (manufactured by Asahi Glass Co., Ltd., AC-6000), AC-6000 / CF ₃ CH ₂ OCF ₂ CF ₂ H (manufactured by Asahi Glass Co., Ltd., AE-3000) = 1/2 ( (Mass ratio) and AE-3000 / ethyl acetate = 9/1 (mass ratio) were used in this order. For each fraction, the average value of the structure of the terminal group and the number of units (x1, x2) of the constituent units was obtained from the integrated values ^{of 1 1} H-NMR and ^{19 F-NMR.} It was found that the crude product contained 42 mol%, 49 mol% and 9 mol% of compound (2), compound (3) and compound (1), respectively. 98.6 g (yield: 44.8%) of compound (2) and 51.9 g (yield: 23.6%) of compound (3) were obtained.
HO-CH _2- (CF ₂ O) {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } -CF _2- CH _2- OH ... (1)
CF ₃ CF ₂ CF _2- O-CHFCF ₂ OCH _2- (CF ₂ O) {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } -CF _2- CH _2- OH ... (2)
CF ₃ CF ₂ CF _2- O-CHFCF ₂ OCH _2- (CF ₂ O) {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } -CF _2- CH ₂ OCF ₂ CHF-O-CF ₂ CF ₂ CF ₃ ... (3)
Compound (2): an average value of 21 units x 1, an average value of 20 units x 2, and a number average molecular weight of 4,150.
Compound (3): an average value of 21 units x 1, an average value of 20 units x 2, and a number average molecular weight of 4,420.

In a 100 mL eggplant flask, 30.0 g of compound (2), 0.9 g of sodium fluoride powder, and 30 g of dichloropentafluoropropane (AK-225 manufactured by Asahi Glass Co., Ltd.) were placed, and CF ₃ CF ₂ CF ₂ OCF ( CF ₃ ) 3.5 g of COF was added. The mixture was stirred at 50 ° C. for 24 hours under a nitrogen atmosphere. After removing the sodium fluoride powder with a pressure filter, excess CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COF and AK-225 were distilled off under reduced pressure. The obtained crude product _{was diluted with C 6} F ₁₃ H (manufactured by Asahi Glass Co., Ltd., AC-2000), passed through a silica gel column, and the recovered solution was concentrated with an evaporator to obtain 31.8 g (yield) of compound (4). 98.8%) was obtained.
CF ₃ CF ₂ CF _2- O-CHFCF ₂ OCH _2- (CF ₂ O) {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } -CF _2- CH _2- OCOCF (CF ₃ ) OCF ₂ CF ₂ CF ₃ ... (4)
Compound (4): an average value of 21 units x 1, an average value of 20 units x 2, and a number average molecular weight of 4,460.

A cooler kept at 20 ° C., a NaF pellet packed bed and a cooler kept at 0 ° C. were installed in series at the gas outlet of a 1 L nickel autoclave. A liquid return line was installed to return the aggregated liquid from the cooler kept at 0 ° C to the autoclave.
750 g of ClCF ₂ CFClCF ₂ OCF ₂ CF ₂ Cl (hereinafter, also referred to as CFE-419) was placed in an autoclave, and the mixture was stirred while maintaining at 25 ° C. After blowing nitrogen gas into the autoclave at 25 ° C. for 1 hour, 20% fluorine gas was blown into the autoclave at 25 ° C. and a flow rate of 2.0 L / hour for 1 hour. A solution of 31.0 g of compound (4) in 124 g of CFE-419 was injected into the autoclave over 4.3 hours while blowing 20% fluorine gas at the same flow rate. The internal pressure of the autoclave was pressurized to 0.15 MPa (gauge pressure) while blowing 20% fluorine gas at the same flow rate. 4 mL of a benzene solution containing 0.05 g / mL of benzene in CFE-419 was poured into the autoclave while heating from 25 ° C. to 40 ° C., and the benzene solution inlet of the autoclave was closed. After stirring for 15 minutes, 4 mL of the benzene solution was injected again while maintaining 40 ° C., and the injection port was closed. The same operation was repeated three more times. The total amount of benzene injected was 0.17 g. Stirring was continued for 1 hour while blowing 20% fluorine gas at the same flow rate. The pressure in the autoclave was increased to atmospheric pressure, and nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated by an evaporator to obtain 31.1 g (yield 98.5%) of compound (5).
CF ₃ CF ₂ CF _2- O- (CF ₂ CF ₂ O) (CF ₂ CF ₂ O) {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } (CF ₂ CF ₂ O) -COCF (CF) ₃ ) OCF ₂ CF ₂ CF ₃ ... (5)
Compound (5): an average value of 21 units x 1, an average value of 20 units x 2, and a number average molecular weight of 4,550.

30.0 g of compound (5) and 60 g of AK-225 were placed in a round-bottom flask made of a tetrafluoroethylene-perfluoro (alkoxyvinyl ether) copolymer (hereinafter, also referred to as PFA). The mixture was stirred while cooling in an ice bath, and 2.0 g of methanol was slowly added dropwise from the dropping funnel under a nitrogen atmosphere. The mixture was stirred for 12 hours while bubbling with nitrogen. The reaction mixture was concentrated by an evaporator to obtain 27.6 g (yield 98.8%) of compound (6).
CF ₃ CF ₂ CF _2- O- (CF ₂ CF ₂ O) (CF ₂ CF ₂ O) {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } -CF _2- COOCCH ₃ ... (6) )
Compound (6): an average value of 21 units x 1, an average value of 20 units x 2, and a number average molecular weight of 4,230.

In a 100 mL three-necked eggplant flask, 0.18 g of lithium chloride was dissolved in 18.3 g of ethanol. While adding 25.0 g of compound (6) and cooling in an ice bath, a solution prepared by dissolving 0.75 g of sodium borohydride in 22.5 g of ethanol was slowly added dropwise. The ice bath was removed, and stirring was continued while slowly raising the temperature to room temperature. After stirring at room temperature for 12 hours, an aqueous hydrochloric acid solution was added dropwise until the liquid became acidic. 20 mL of AC-2000 was added and washed once with water and once with saturated brine to recover the organic phase. The recovered organic phase was concentrated by an evaporator to obtain 24.6 g (yield 99.0%) of compound (7).
CF ₃ CF ₂ CF _2- O- (CF ₂ CF ₂ O) (CF ₂ CF ₂ O) {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } -CF _2- CH ₂ OH ... 7)
Compound (7): an average value of 21 units x 1, an average value of 20 units x 2, and a number average molecular weight of 4,200.

In a 100 mL two-necked eggplant flask, 20.0 g of compound (7), 0.21 g of tetrabutylammonium hydrogen sulfate _{, 1.76 g of BrCH 2} CH = CH ₂ and 2.6 g of a 30% aqueous sodium hydroxide solution are placed. In addition, the mixture was stirred at 60 ° C. for 8 hours. After completion of the reaction, 20 g of AC-2000 was added, and the mixture was washed once with a dilute aqueous hydrochloric acid solution to recover the organic phase. The recovered organic phase was passed through a silica gel column, and the recovered solution was concentrated with an evaporator to obtain 19.8 g (yield 98.2%) of compound (8).
CF ₃ CF ₂ CF _2- O- (CF ₂ CF ₂ O) (CF ₂ CF ₂ O) {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } -CF _{2 -CH 2} OCH ₂ CH = CH ₂ ... (8)
Compound (8): an average value of 21 units x 1, an average value of 20 units x 2, and a number average molecular weight of 4,250.

In a 100 mL PFA eggplant flask, 5.0 g of compound (8) and a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%). Add 0.005 g, 0.25 g of HSi (OCH ₃ ) ₃ , 0.005 g of dimethyl sulfoxide and 0.20 g of 1,3-bis (trifluoromethyl) benzene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) at 40 ° C. The mixture was stirred for 4 hours. After completion of the reaction, the solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter having a pore size of 0.2 μm. 4.9 g (yield 95%) of the composition (A-1) composed of a by-product in which the allyl group of the above was isomerized to the inner olefin (-CH = CHCH _{3) was obtained.} The conversion rate of hydrosilylation was 100%, and compound (8) did not remain. The selectivity for hydrosilylation was 95%.
CF ₃ CF ₂ CF _2- O- (CF ₂ CF ₂ O) (CF ₂ CF ₂ O) {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } -CF _2- CH ₂ OCH ₂ CH ₂ CH _2- Si (OCH ₃ ) ₃ ... (9)

NMR spectrum of compound (9);
^{1 1} H-NMR (300.4 MHz, solvent: CDCl ₃ , reference: TMS) δ (ppm): 0.7 (6H), 1.7 (6H), 3.6 (11H), 3.8 (2H) ..
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: C ₆ F ₆ ) δ (ppm): -52.4 to -55.8 (42F), -78.2 (1F), -80. 2 (1F), -82.2 (3F), -89.4 to -91.1 (90F), -130.5 (2F).
The average value of the number of units x1: 21, the average value of the number of units x2: 20, the number average molecular weight of the compound (9): 4,370.

[Manufacturing Example A-2]
In a 100 mL two-necked eggplant flask, 20.0 g of the compound (7) obtained in Production Example A-1, 20.0 g of 1,3-bis (trifluoromethyl) benzene (manufactured by Tokyo Chemical Industry Co., Ltd.), CF. ₃ SO ₂ Cl (manufactured by Wako Pure Chemical Industries, Ltd.) (1.01 g) and 1.00 g of triethylamine were added, and the mixture was stirred at room temperature for 4 hours under a nitrogen atmosphere. After completion of the reaction, 15 g of AK-225 was added, and the mixture was washed once with water and saturated brine, and the organic phase was recovered. The recovered organic phase was concentrated by an evaporator to obtain 20.3 g (yield 99%) of compound (10).
CF ₃ CF ₂ CF _2- O- (CF ₂ CF ₂ O) (CF ₂ CF ₂ O) {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } -CF _2- CH ₂ OSO ₂ CF ₃ ·.・ ・ (10)
Compound (10): an average value of 21 units x 1, an average value of 20 units x 2, and a number average molecular weight of 4,340.

In a 50 mL eggplant flask, 15.0 g of compound (10), 15.0 g of 1,3-bis (trifluoromethyl) benzene (manufactured by Tokyo Chemical Industry Co., Ltd.), HN (CH ₂ CH = CH ₂ ) ₂ ( 2.27 g of (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.68 g of triethylamine were added, and the mixture was stirred at 90 ° C. for 24 hours under a nitrogen atmosphere. After completion of the reaction, 15 g of AK-225 was added, and the mixture was washed once with water and saturated brine once to recover the organic phase, mixed with 1.5 g of silica gel, and the organic phase was recovered by filter filtration. The recovered organic phase was concentrated by an evaporator to obtain 14.4 g (yield 98%) of compound (11).
CF ₃ CF ₂ CF _2- O- (CF ₂ CF ₂ O) (CF ₂ CF ₂ O) {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } -CF _2- CH _2- N (CH ₂₎ CH = CH ₂ ) ₂ ... (11)
Compound (11): an average value of 21 units x 1, an average value of 20 units x 2, and a number average molecular weight of 4,280.

In a 100 mL PFA eggplant flask, 12.0 g of compound (11) and a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%). Add 0.03 g, 1.3 g of HSi (OCH ₃ ) ₃ , 0.01 g of dimethyl sulfoxide and 0.5 g of 1,3-bis (trifluoromethyl) benzene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) at 40 ° C. The mixture was stirred for 10 hours. After completion of the reaction, the solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter having a pore size of 0.2 μm. 11.9 g (yield 92%) of the composition (A-2) composed of a by-product produced by cyclizing the allyl group of the above in the molecule was obtained. The conversion rate of hydrosilylation was 100%, and compound (11) did not remain. The selectivity for hydrosilylation was 81%.
CF ₃ CF ₂ CF _2- O- (CF ₂ CF ₂ O) (CF ₂ CF ₂ O) {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } -CF _2- CH _2- N [CH ₂ CH ₂ CH _2- Si (OCH ₃ ) ₃ ] ₂ ... (12)

NMR spectrum of compound (12);
^{1 1} H-NMR (300.4 MHz, solvent: CDCl ₃ , reference: TMS) δ (ppm): 0.7 (4H), 1.6 (4H), 2.6 (4H), 3.1 (2H) 3.6 (18H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -52.4 to -55.7 (42F), -74.4 (1F), -76.6 ( 1F), -82.2 (3F), -89.4 to -91.1 (90F), -130.5 (2F). The average value of the number of units x1: 21, the average value of the number of units x2: 20, the number average molecular weight of the compound (12): 4,530.

[Manufacturing Example A-3]
In a 50 mL eggplant flask, 5.0 g of compound (6) obtained in Production Example A-1 and _{0.2 g of H 2} N-CH _2- C (CH ₂ CH = CH ₂ ) ₃ were placed and stirred for 12 hours. did. From NMR, it was confirmed that all the compound (6) was converted to the compound (13). In addition, methanol, which is a by-product, was produced. The obtained solution was diluted with 9.0 g of AE-3000 and purified by silica gel column chromatography (developing solvent: AE-3000) to obtain 4.4 g (yield 85%) of compound (13).
CF ₃ CF ₂ CF _2- O- (CF ₂ CF ₂ O) (CF ₂ CF ₂ O) {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } -CF _2- C (O) NH-CH _2- C (CH ₂ CH = CH ₂ ) ₃ ... (13)
Compound (13): an average value of 21 units x 1, an average value of 20 units x 2, and a number average molecular weight of 4,360.

In a 10 mL PFA sample tube, 4 g of compound (13) and a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%) were added to 0. Add 4 mg, _{0.33 g of HSi (OCH 3} ) ₃ , 0.01 g of dimethyl sulfoxide, and 0.2 g of 1,3-bis (trifluoromethyl) benzene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) for 10 hours at 40 ° C. Stirred. After completion of the reaction, the solvent and the like were distilled off under reduced pressure and filtered through a membrane filter having a pore size of 1.0 μm to obtain 4.3 g (yield 100%) of compound (A-3).
CF ₃ CF ₂ CF _2- O- (CF ₂ CF ₂ O) (CF ₂ CF ₂ O) {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } -CF _2- C (O) NH-CH _2- C [CH ₂ CH ₂ CH _2- Si (OCH ₃ ) ₃ ] ₃ ... (A-3)

NMR spectrum of compound (A-3);
^{1 1} H-NMR (300.4 MHz, solvent: CDCl ₃ , reference: TMS) δ (ppm): 0.75 (6H), 1.3 to 1.6 (12H), 3.4 (2H), 3. 7 (27H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -52.4 to -55.8 (42F), -82.2 (3F), -89.4 to -91.1 (92F), -130.8 (2F).
The average value of the number of units x1 is 21, the average value of the number of units x2 is 20, and the number average molecular weight of the compound (A-3) is 4,720.

[Manufacturing Example A-4]
In a 300 mL three-necked flask, 15.0 g of dipentaerythritol (manufactured by ACROS), 29.5 g of a 48% NaOH aqueous solution, and 150 g of dimethyl sulfoxide were placed. The mixture was heated to 40 ° C., 39.5 g of 5-bromo-1-pentene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred for 4 hours. The mixture was washed once with a dilute aqueous hydrochloric acid solution, 200 g of cyclopentyl methyl ether was added, and the organic phase was recovered. The recovered solution was concentrated by an evaporator to obtain 29.4 g of a crude product. The crude product was developed by silica gel column chromatography to separate 5.3 g of compound (14) and 6.0 g of compound (15).

In a 50 mL two-necked eggplant flask, 1.0 g of compound (14), 0.4 g of 2,6-lutidine, and 5 g of AE-3000 were placed. The mixture was stirred while cooling in an ice bath, and 0.5 g of trifluoromethanesulfonic anhydride was slowly added dropwise under a nitrogen atmosphere. The mixture was further stirred for 1 hour, washed once with a dilute aqueous hydrochloric acid solution, and the organic phase was recovered. The recovered solution was concentrated on an evaporator to obtain a crude product. The crude product was developed by silica gel column chromatography to fractionate 1.2 g of compound (16) in which _{HO − of compound (14) was converted to CF 3} SO _{3 −.}

In a 50 mL eggplant flask, 1.0 g of compound (16), 6.6 g of compound (17) obtained by the method described in Production Example 6 of International Publication No. 2015/08792, 2.7 g of cesium carbonate, 1 , 6.6 g of 3-bis (trifluoromethyl) benzene was added, and the mixture was stirred under reflux conditions at 80 ° C. for 4 hours. 10 g of AE-3000 was added, and the mixture was washed once with a dilute aqueous hydrochloric acid solution to recover the organic phase. The recovered solution was concentrated on an evaporator to obtain a crude product. The crude product was expanded to silica gel column chromatography, _CF 3 SO ₃ compound (16) - is _{CF 3 CF 2 CF 2 O {} (CF 2 O) m21 (CF 2 CF 2 O) m22} CF 2 -CH 6.6 g of compound (18) converted to _{2-O- was fractionated.
CF 3 CF 2 CF 2 O {} (CF 2 O) m21 (CF 2 CF 2 O) m22} CF 2 -CH 2 -OH ··· (17)

In a 100 mL PFA eggplant flask, 6.0 g of compound (18) and a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%). Add 0.03 g, 1.2 g of trimethoxysilane (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 0.01 g of dimethyl sulfoxide and 0.9 g of 1,3-bis (trifluoromethyl) benzene, and stir at 40 ° C. for 4 hours. did. The solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter having a pore size of 0.2 μm to obtain 6.4 g of the compound (A-4) in which the five allyl groups of the compound (18) were hydrosilylated. The conversion rate of hydrosilylation was 100%, and compound (18) did not remain. The selectivity for hydrosilylation was 100%.
Here, the compound (A-4) is a compound in which WR ^51a − of the compound (A13-3) is a group represented by the formula (R ^{f -1).}

[Manufacturing Example A-5]
In the same manner as in Production Example A-4 except that compound (15) obtained in Production Example A-4 was used instead of compound (14), the two HO-s of compound (15) were all CF ₃ SO. Compound (19) converted to _{3- was obtained.} Next, in the same manner as in Production Example A-4 (3) except that compound (19) was used instead of compound (16), the two CF ₃ SO ₃ − of compound (19) were all CF ₃ CF. to give _{2 CF 2 O {(CF 2} O) m21 (CF 2 CF 2 O) m22} CF 2 -CH 2 -O- in the converted compound (20). Next, the compound (A-5) in which the four allylic groups of the compound (20) were hydrosilylated in the same manner as in Production Example A-4 except that the compound (20) was used instead of the compound (18). 6.4 g was obtained.
Here, the compound (A-5) is a compound in which WR ^51a − of the compound (A13-4) is a group represented by the formula (R ^f-1).

[Manufacturing Example B-1]
Compound (B-1) was obtained according to the method described in Example 6 of International Publication No. 2013/121984.
CF _3- O- (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _x3 (CF ₂ CF ₂ O) -CF ₂ CF ₂ CF _2- CONHCH ₂ CH ₂ CH _2- Si (OCH ₃ ) ₃ ... (B-1)
Compound (B-1): Average value 13 of unit number x 3, number average molecular weight 4,870.

[Manufacturing Example B-2]
Compound (21) was obtained according to the method described in Example 7 of International Publication No. 2013/121984.
CF _3- O- (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _x3 (CF ₂ CF ₂ O) -CF ₂ CF ₂ CF _2- CH ₂ OH ... (21)
Compound (21): an average value of 13 units x 3, a number average molecular weight of 4,700.

Production Example A-2 except that the amount of compound (7) was changed to compound (21), the amount of CF ₃ SO ₂ Cl (manufactured by Wako Pure Chemical Industries, Ltd.) was changed to 0.86 g, and the amount of triethylamine was changed to 1.02 g. Similarly, 30.6 g (yield 99%) of compound (22) was obtained.
CF _3- O- (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _x3 (CF ₂ CF ₂ O) -CF ₂ CF ₂ CF _2- CH ₂ OSO ₂ CF ₃ ... (22)
Compound (22): average value of 13 units x 3, number average molecular weight 4,830.

The same as in Production Example A-2 except that compound (10) was changed to compound (22), the amount of HN (CH ₂ CH = CH ₂ ) ₂ was changed to 2.08 g, and the amount of triethylamine was changed to 0.63 g. , 14.6 g (yield 98%) of compound (23) was obtained.
_{CF 3 -O- (CF 2 CF 2} O-CF 2 CF 2 CF 2 CF 2 O) x3 (CF 2 CF 2 O) -CF 2 CF 2 CF 2 -CH 2 -N (CH 2 CH = CH 2) ₂ ... (23)
Compound (23): average value 13 of unit number x 3, number average molecular weight 4,780.

Compound (11) was changed to compound (23), the amount of platinum complex solution _{was changed to 0.029 g, and the amount of HSi (OCH 3} ) ₃ was changed to 1.2 g in the same manner as in Production Example A-2. The composition (B-2) comprising a compound (24) in which the two allyl groups of (23) are hydrosilylated and a by-product produced by cyclizing the two allyl groups of the compound (23) in the molecule. 11.8 g (yield 94%) was obtained. The conversion rate of hydrosilylation was 100%, and compound (23) did not remain. The selectivity for hydrosilylation was 80%.
CF ₃ -O- (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _x3 (CF ₂ CF ₂ O) -CF ₂ CF ₂ CF _2- CH _2- N [CH ₂ CH ₂ CH _2- Si (OCH ₃ ) ₃ ] ₂ ... (24)

NMR spectrum of compound (24);
^{1 1} H-NMR (300.4 MHz, solvent: CDCl ₃ , reference: TMS) δ (ppm): 0.7 (4H), 1.6 (4H), 2.6 (4H), 3.2 (2H) 3.6 (18H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: C ₆ F ₆ ) δ (ppm): -56.3 (3F), -84.0 (54F), -89.2 (54F), -91.4 (2F) -120.9 (2F), -126.6 (54F).
The average value of the number of units x3: 13, the number average molecular weight of the compound (24): 5,020.

[Manufacturing Example B-3]
Compound (25) was obtained according to the method described in Example 6 of International Publication No. 2013/121984.
CF _3- O- (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _x3 (CF ₂ CF ₂ O) -CF ₂ CF ₂ CF _2- C (O) OCH ₃ ... (25)
Compound (25): average value 13 of unit number x 3, number average molecular weight 4,700.

Same as Production Example A-3 except that compound (6) was changed to 9.0 g of compound (25) and the amount of H ₂ N-CH _2- C (CH ₂ CH = CH ₂ ) _{3 was changed to 0.45 g.} To obtain 7.6 g (yield 84%) of compound (26).
CF _3- O- (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _x3 (CF ₂ CF ₂ O) -CF ₂ CF ₂ CF _2- C (O) NH-CH _2- C (CH) ₂ CH = CH ₂ ) ₃ ... (25)
Compound (26): an average value of 13 units x 3, a number average molecular weight of 4,800.

Compound (13) to 6.0 g of compound (26), platinum complex solution to 0.07 g, HSi (OCH ₃ ) ₃ to 0.78 g, dimethylsulfoxide to 0.02 g. 6.7 g (B-3) of compound (B-3) in the same manner as in Production Example A-3 except that the amount of 1,3-bis (trifluoromethyl) benzene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was changed to 0.49 g. Yield 100%) was obtained.
CF _3- O- (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _x3 (CF ₂ CF ₂ O) -CF ₂ CF ₂ CF _2- C (O) NH-CH _2- C [CH ₂ CH ₂ CH _2- Si (OCH ₃ ) ₃ ] ₃ ... (B-3)

NMR spectrum of compound (B-3);
^{1 1} H-NMR (300.4 MHz, solvent: CDCl ₃ , reference: TMS) δ (ppm): 0.75 (6H), 1.3 to 1.6 (12H), 3.4 (2H), 3. 7 (27H). ¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -55.2 (3F), -82.1 (54F), -88.1 (54F), -90 .2 (2F), -119.6 (2F), -125.4 (52F), -126.2 (2F). The average value of the number of units x3: 13, the number average molecular weight of the compound (B-3): 5,400.

[Manufacturing Example B-4]
Instead of compound (17), compound (27) (average value of m25: 13, number average molecular weight: 4,700) obtained by the method described in Example 7 of International Publication No. 2013/121984 was used. _{CF 3} SO ₃ − of compound (16) is CF ₃ O (CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) _m25 CF ₂ CF ₂ OCF ₂ CF _{2 in the same} manner as in Production Example A-4 except. Compound (28) converted to CF _2- CH _{2-O- was obtained.} Next, the compound (B-4) in which the five allyl groups of the compound (28) were hydrosilylated in the same manner as in Production Example A-4 except that the compound (28) was used instead of the compound (18). 6.3 g was obtained.
CF ₃ O (CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) _m25 CF ₂ CF ₂ OCF ₂ CF ₂ CF _2- CH _2- OH ... (27)
Here, the compound (B-4) is a compound in which WR ^51a − of the compound (A13-3) is a group represented by the formula (R ^f-3).

[Manufacturing Example B-5]
In the same manner as in Production Example A-5 except that compound (27) was used instead of compound (17), the two CF ₃ SO ₃ − of compound (19) were all CF ₃ CF ₂ CF ₂ O {(( obtain _{CF 2 O) m21 (CF 2} CF 2 O) m22} CF 2 -CH 2 -O- in the converted compound (29). Next, the compound (B-5) in which the four allylic groups of the compound (29) were hydrosilylated in the same manner as in Production Example A-4 except that the compound (29) was used instead of the compound (18). 6.1 g was obtained.
Here, the compound (B-5) is a compound in which WR ^51a − of the compound (A13-4) is a group represented by the formula (R ^f-3).

[Example 1]
A composition was prepared by mixing 50 parts by mass of (A-1) and 50 parts by mass of (B-1). Using this composition, the surface treatment of the base material was performed by the following dry coating method to obtain the article of Example 1. Chemically tempered glass was used as the base material. The obtained articles were evaluated for durability 1 (the number of times the contact angle was maintained at 100 ° or more), lubricity and durability 2 (difficulty in reducing the dynamic friction coefficient). The results are shown in Tables 3-5.

(Dry coating method)
Dry coating was performed using a vacuum vapor deposition apparatus (SGC-22WA, manufactured by Showa Vacuum Co., Ltd.) (vacuum vapor deposition method). 35 mg of the composition was filled in a molybdenum boat in the vacuum vapor deposition apparatus, and the inside of the vacuum vapor deposition apparatus ^{was exhausted to 5 × 10 -3} Pa or less. A thin-film film was formed on the surface of the substrate by heating the boat on which the composition was placed and depositing the composition on the surface of the substrate. The substrate on which the vapor-film-deposited film was formed was left overnight under the conditions of temperature: 25 ° C. and humidity: 40% to obtain an article having a surface layer on the surface of the substrate.

[Examples 2 to 40]
The composition was prepared in the same manner as in Example 1 except that the types and combinations of the compounds used were changed as shown in Table 2, a surface layer was formed to obtain an article, and the obtained article was evaluated. rice field. In the example of combining two kinds of compounds, the mass ratio of each compound is 50:50. The results are shown in Tables 3-5.

Durability 1 (Number of times to maintain a contact angle of 100 ° or more)

Lubricity (coefficient of dynamic friction)

Durability 2 (Difficulty in reducing dynamic friction coefficient)

The compositions of Examples 1-5, 7-11, 13-17, 19-23, 25-29 in which the compound (A) and the compound (B) are combined do not have the compound (B) and the group (I). Compared with the compositions of Examples 36 to 40 in combination with compound (C-1), the durability and lubricity were excellent. In addition, the lubricity was excellent as compared with Examples 31 to 35 in which the compound (B) was used alone. Further, as the number of the groups (I) contained in each of the compound (A) and the compound (B) increased, the durability tended to improve.

(Examples 41 to 50)
A composition was prepared in the same manner as in Example 15 except that the mixing ratio (mass ratio) of (A-3) and (B-3) was as shown in Table 6, and the base material was prepared by the dry coating method. The surface layer of the above was formed to obtain an article, and the obtained article was evaluated. The results are shown in Table 6.
Further, using each composition, the surface treatment of the base material was performed by the following wet coating method to obtain an article. Chemically tempered glass was used as the base material. Durability 1 and lubricity were evaluated for the obtained articles. The results are shown in Table 7.

(Wet coating method)
Each composition obtained in Examples 41 to 50 and C ₄ F ₉ OC ₂ H ₅ (manufactured by 3M, Novek® 7200) as a liquid medium are mixed to have a solid content concentration of 0.05%. A coating solution was prepared. The base material was dipped in the coating liquid, left for 30 minutes, and then the base material was pulled up (dip coat method). The coating film was dried at 120 ° C. for 30 minutes and washed with AK-225 to obtain an article having a surface treatment layer on the surface of the substrate.

(Examples 51-60)
A composition was prepared in the same manner as in Example 22 except that the mixing ratio (mass ratio) of (A-4) and (B-4) was as shown in Table 8, and the base material was prepared by the dry coating method. The surface layer of the above was formed to obtain an article, and the obtained article was evaluated. The results are shown in Table 8.

By using the compound (A) and the compound (B) in combination, both the lubricity and durability properties could be achieved at a higher level than when each compound was used alone. Durability and lubricity were particularly excellent when the mass ratio of compound (A) / compound (B) was in the range of 20/80 to 50/50.

The present composition and the present coating liquid can be used for various applications in which lubricity and water repellency and oil repellency are required. For example, display input devices such as touch panels; surface protective coats made of transparent glass or transparent plastic materials, antifouling coats for kitchens; water- and moisture-repellent coats for electronic devices, heat exchangers, batteries, etc., antifouling coats, and toiletries. Antifouling coat; Coat for members that require liquid repellency while conducting; Water repellent / waterproof / water-sliding coat for heat exchangers; Can be used for vibration sieves, surface low friction coats such as inside cylinders, and the like.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2017-050558 filed on March 15, 2017 are cited here and incorporated as disclosure of the specification of the present invention. Is.

Claims (15)

Includes a fluorine-containing ether compound (A) and a fluorine-containing ether compound (B),
The fluorine-containing ether compound (A) is a compound having _{a poly (oxyperfluoroalkylene) chain containing a (CF 2} O) unit and a group represented by the following formula (I).
The fluorine-containing ether compound (B) is a compound having a _{poly (oxyperfluoroalkylene) chain containing no (CF 2} O) unit and a group represented by the formula (I). Composition.
−SiR _n L _3-n ... (I)
However, L is a hydroxyl group or a hydrolyzable group, and is
R is a hydrogen atom or a monovalent hydrocarbon group,
n is an integer from 0 to 2
When n is 0 or 1, the (3-n) L's may be the same or different.
When n is 2, n Rs may be the same or different.
The groups represented by the formula (I) of each of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) may be the same or different. Both the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) are fluorine-containing ether compounds represented by the following formula (A / B).
^{R f} in the fluorine-containing ether compound (A) is a poly (oxyperfluoroalkylene) chain containing a (CF ₂ O) unit, and is a poly (oxyperfluoroalkylene) chain.
The fluorine-containing ether composition according to claim 1, ^{wherein R f} in the fluorine-containing ether compound (B) is a poly (oxyperfluoroalkylene) chain containing no (CF _{2 O) unit.
^{[R f1 -O-Q-R}} f -] r Z [-SiR n L 3-n] s ··· (A / B)
However, R ^f1 is a perfluoroalkyl group and is a perfluoroalkyl group.
Q is a polyoxyfluoroalkylene group having a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group having 2 to 5 bonds of the oxyfluoroalkylene group, and the polyoxyfluoroalkylene group is used. The constituent oxyfluoroalkylene groups may all be the same or different.
R ^f is a poly (oxyperfluoroalkylene) chain and
Z is a linking group of (r + s) valence,
−SiR _n L _3-n is a group represented by the above formula (I).
When r is 2 or more, r [R ^f1- O-Q-R ^f- ] are the same group.
When s is 2 or more, the s groups represented by the formula (I) are the same group.
r and s are integers of 1 or more, respectively, and r + s is 3 to 8. 1 or claim 1, wherein the _{poly (oxyperfluoroalkylene) chain containing the (CF 2} O) unit is a poly (oxyperfluoroalkylene) chain containing (CF ₂ O) units and (CF ₂ CF _{2 O) units.} 2. The fluorine-containing ether composition according to 2. The poly (oxyperfluoroalkylene) chain containing no (CF _{2 O) unit is (CF 2} CF ₂ O) unit, (CF ₂ CF ₂ CF ₂ O) unit and (CF ₂ CF ₂ CF ₂ CF ₂ O). The fluorine-containing ether composition according to any one of claims 1 to 3, which is a poly (oxyperfluoroalkylene) chain containing at least one selected from the units. Wherein _(CF 2 O) units containing no poly (oxyperfluoroalkylene) _chain, a poly (oxyperfluoroalkylene) chain comprising _{(CF 2 CF 2 OCF 2 CF} 2 CF 2 CF 2 O) units, claim 1 The fluorine-containing ether composition according to any one of 4 to 4. The invention according to any one of claims 1 to 5, wherein at least one of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) has three or more groups represented by the formula (I). Fluorine-containing ether composition. The invention according to any one of claims 1 to 5, wherein both the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) have two or more groups represented by the formula (I). Fluorine-containing ether composition. The invention according to any one of claims 1 to 5, wherein both the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) have three or more groups represented by the formula (I). Fluorine-containing ether composition. The fluorine-containing ether composition according to any one of claims 1 to 8, wherein the fluorine-containing ether compound (A) has a number average molecular weight of 2,000 to 20,000. The fluorine-containing ether composition according to any one of claims 1 to 9, wherein the fluorine-containing ether compound (B) has a number average molecular weight of 2,000 to 20,000. The invention according to any one of claims 1 to 10, wherein the fluorine-containing ether compound (A) is contained in an amount of 10 to 80% by mass based on the total of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B). Fluorine-containing ether composition. A fluorinated ether composition comprising a fluorinated ether compound (A1) represented by the following formula (A1) and a fluorinated ether compound (B1) represented by the following formula (B1).
[R ^f1a- O-Q ^a- R ^fa- ] _ra Z ^a [-SiR ^a _na L ^a _3-na ] _sa ... (A1)
_{^{[R f1b -O-Q b -R}} fb -] rb Z b [-SiR b nb L b 3-nb] sb ··· (B1)
^{However, R f1a} and ^{R f1b} is a perfluoroalkyl group,
Q ^a and Q ^b are a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group having 2 to 5 bonds of the oxyfluoroalkylene group, and the polyoxy. The oxyfluoroalkylene groups constituting the fluoroalkylene group may be the same or different.
R ^fa is a _{poly (oxyperfluoroalkylene) chain containing (CF 2} O) units and is a poly (oxyperfluoroalkylene) chain.
R ^fb is a _{poly (oxyperfluoroalkylene) chain containing no (CF 2} O) unit and is a poly (oxyperfluoroalkylene) chain.
Z ^a is a linking group of (ra + sa) valence,
Z ^b is a linking group of (rb + sb) valence.
L ^a and ^{L b} are hydroxyl group or a hydrolyzable group,
R ^a and R ^b are hydrogen atoms or monovalent hydrocarbon groups.
na and nb are integers from 0 to 2 and
^{The (3-na) L a} when na is 0 or 1, and the (3-nb) L ^b when nb is 0 or 1, may be the same or different, respectively.
na number of ^R a when na is 2, each nb number of ^{R b} when nb is 2, may be the same or different and
ra and rb are integers of 1 or more, and when ra is 2 or more, ra [R ^f1a −O−Q ^a −R ^fa −] may be the same or different, and rb is 2. or when the rb pieces ^{[R f1b -O-Q b -R} fb -] may be the same or different and
sa and sb are integers of 1 or more, and when sa is 2 or more, sa [-SiR ^a _na L ^a _3-na ] may be the same or different, and sb is 2 or more. When sb [-SiR ^b _nb L ^b _3-nb ] may be the same or different. The fluorine-containing ether composition according to claim 12, wherein the fluorine-containing ether compound (A1) is contained in an amount of 10 to 80% by mass based on the total of the fluorine-containing ether compound (A1) and the fluorine-containing ether compound (B1). A coating liquid comprising the fluorine-containing ether composition according to any one of claims 1 to 13 and a liquid medium. An article comprising a surface layer formed from the fluorine-containing ether composition according to any one of claims 1 to 13.