JPWO2018168497A1 - Fluorinated ether composition, coating liquid and article - Google Patents

Abstract

Provided are a fluorine-containing ether composition and a coating liquid capable of forming a surface layer having excellent lubricity and durability, and an article having a surface layer having excellent lubricity and durability. It contains a fluorinated ether compound (A) and a fluorinated ether compound (B), and the fluorinated ether compound (A) is represented by the following formula (I) and a poly (oxyperfluoroalkylene) chain containing a (CF2O) unit. Wherein the fluorinated ether compound (B) is a compound having a poly (oxyperfluoroalkylene) chain containing no (CF2O) unit and a group represented by the formula (I). Fluorine ether composition. -SiRnL3-n (I); wherein L is a hydroxyl group or a hydrolyzable group, and R is a hydrogen atom or a monovalent hydrocarbon group.

Description

  The present invention relates to a fluorinated ether composition, a coating liquid, and an article.

  Fluorine-containing compounds are used for surface treatment agents and the like because they exhibit high lubricity, water repellency and oil repellency. For example, when a surface layer is formed on the surface of the substrate by the surface treatment agent, lubricity, water repellency, oil repellency, and the like are imparted, and dirt on the surface of the substrate is easily wiped off, thereby improving dirt removal. Among the fluorinated compounds, a fluorinated ether compound having a poly (oxyperfluoroalkylene) chain having an ether bond (—O—) 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 such a property that the water / oil repellency is hardly reduced even when repeatedly rubbed with a finger (rubbing resistance) and a property that a fingerprint attached to the surface can be easily removed by wiping (fingerprint stain removing property). Is required to be maintained for a long time, for example, a surface treatment agent for a member constituting a surface of a touch panel that is touched by a finger.

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

JP 2014-65884 A

  However, according to the present inventor, the surface layer formed by the above-mentioned fluorine-containing ether composition, when friction with a finger or the like is repeated, lubricity, water repellency, oil repellency and the like are likely to deteriorate. (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 having excellent lubricity and durability, and an article having a surface layer having excellent lubrication and durability.

The present invention provides a fluorine-containing ether composition, a coating liquid and an article having the following constitutions [1] to [15].
[1] including a fluorinated ether compound (A) and a fluorinated 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,
R is a hydrogen atom or a monovalent hydrocarbon group,
n is an integer of 0 to 2,
When n is 0 or 1, (3-n) Ls 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) in the fluorinated ether compound (A) and the fluorinated ether compound (B) may be the same or different.

[2] Both the fluorinated ether compound (A) and the fluorinated ether compound (B) are fluorinated ether compounds represented by the following formula (A / B),
R ^f in the fluorinated ether compound (A) is a poly (oxyperfluoroalkylene) chain containing a (CF ₂ O) unit;
The fluorinated ether composition according to [1], wherein R ^f in the fluorinated 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,
Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 of the oxyfluoroalkylene groups; The constituent oxyfluoroalkylene groups may all be the same or different,
R ^f is a poly (oxyperfluoroalkylene) chain;
Z is a (r + s) -valent linking group,
—SiR _n L _3-n is a group represented by the above formula (I),
If r is 2 or more, r pieces of ^{[R f1 -O-Q-R} f -] are the same group,
When s is 2 or more, s groups represented by the formula (I) are the same group,
r and s are each an integer of 1 or more, and r + s is 3 to 8.

[3] The poly (oxyperfluoroalkylene) chain containing (CF ₂ O) units is a poly (oxyperfluoroalkylene) chain containing (CF ₂ O) units and (CF ₂ CF ₂ O) units. 1] or the fluorine-containing ether composition of [2].
[4] The poly (oxyperfluoroalkylene) chain not containing the (CF ₂ O) unit has a (CF ₂ CF ₂ O) unit, a (CF ₂ CF ₂ CF ₂ O) unit and a (CF ₂ CF ₂ CF ₂ CF) unit. ₂ ) 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 poly (oxyperfluoroalkylene) chain containing no (CF ₂ O) unit is a poly (oxyperfluoroalkylene) chain containing (CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) unit. The fluorinated ether composition according to any one of [1] to [4].
[6] Any of [1] to [5], wherein at least one of the fluorinated ether compound (A) and the fluorinated ether compound (B) has three or more groups represented by the formula (I). The fluorinated ether composition.
[7] Any of [1] to [5], wherein both the fluorinated ether compound (A) and the fluorinated ether compound (B) have two or more groups represented by the formula (I). A fluorine-containing ether composition.
[8] Any of [1] to [5], wherein both the fluorinated ether compound (A) and the fluorinated ether compound (B) have three or more groups represented by the formula (I). A fluorine-containing ether composition.
[9] The fluorinated ether composition according to any one of [1] to [8], wherein the fluorinated ether compound (A) has a number average molecular weight of 2,000 to 20,000.
[10] The fluorinated ether composition according to any one of [1] to [9], wherein the fluorinated ether compound (B) has a number average molecular weight of 2,000 to 20,000.
[11] Any of [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). The fluorinated ether composition.

[12] A fluorinated ether composition comprising the fluorinated ether compound (A1) represented by the following formula (A1) and the 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 is a single bond, one or more oxy-fluoroalkylene group containing a hydrogen atom or a polyoxyalkylene fluoroalkylene group 2-5 is formed by bonding of said oxy fluoroalkylene group, the polyoxy All oxyfluoroalkylene groups constituting the fluoroalkylene group may be the same or different,
R ^fa is a poly (oxyperfluoroalkylene) chain containing (CF ₂ O) units,
R ^fb is a poly (oxyperfluoroalkylene) chain containing no (CF ₂ O) unit;
Z ^a is a (ra + sa) -valent linking group,
Z ^b is a (rb + sb) -valent linking group,
L ^a and ^{L b} are hydroxyl group or a hydrolyzable group,
R ^a and R ^b are a hydrogen atom or a monovalent hydrocarbon group,
na and nb are integers of 0 to 2,
(3-na) L ^a when na is 0 or 1 and (3-nb) L ^b when nb is 0 or 1 may be the same or different;
When na is 2, na R ^a , and when nb is 2, nb R ^b may be the same or different,
ra and rb are integers greater than or equal to 1, ra is the ra number when two or more ^{[R f1a -O-Q a -R} fa -] may be different even in the same, rb 2 or when the rb pieces ^{[R f1b -O-Q b -R} fb -] may be the same or different and
sa and sb is an integer of 1 or more, sa is sa number when two or more ^{_{[-SiR a na L a 3-}} na] may be different even in the same, sb 2 or more when sb pieces ^{_{[-SiR b nb L b 3-}} nb] may be be the same or different.
[13] The fluorinated ether composition according to [12], comprising 10 to 80% by mass of the fluorinated ether compound (A1) based on the total of the fluorinated ether compound (A1) and the fluorinated ether compound (B1). .
[14] A coating liquid comprising the fluorinated ether composition according to any one of [1] to [13] and a liquid medium.
[15] An article having a surface layer formed from the fluorinated ether composition of any one of [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 this specification, a compound represented by the formula (1) is referred to as a compound (1). The same applies to compounds represented by other formulas.
The meaning of the following terms in this specification is as follows.
The “hydrolyzable silyl group” means a group capable of forming a silanol group (Si—OH) by a hydrolysis reaction. For example, L in the formula (I) is a group that is a hydrolyzable group.
In the chemical formula of the oxyperfluoroalkylene group, its oxygen atom is described and described on the right side of the perfluoroalkylene group.
“Surface layer” means a layer formed on the surface of a substrate.
Applying the coating liquid and "drying" refers to applying the coating liquid to a substrate to form a coating film of the coating liquid on the substrate, and then evaporating and removing the liquid medium from the coating film. .

(Fluorine-containing ether composition)
The fluorinated ether composition of the present invention (hereinafter, also referred to as the present composition) includes a fluorinated ether compound (A) (hereinafter, also referred to as compound (A)) and a fluorinated ether compound (B) (hereinafter, referred to as compound (A)). Compound (B).). The composition does not include a liquid medium, as described below. The present composition may be composed of the compound (A) and the compound (B), and as described later, other fluorinated ether compounds other than the compound (A) and the compound (B), the compound (A), the compound ( It may contain impurities other than B) and other fluorine-containing ether compounds.
The compound (A) has a poly (oxyperfluoroalkylene) chain containing (CF ₂ O) units (hereinafter also referred to as A chain), and a group (I).
The compound (B) has a poly (oxyperfluoroalkylene) chain containing no (CF ₂ O) unit (hereinafter, also referred to as a B chain), and a group (I). Compound (B) has no A chain.
—SiR _n L _3-n (I)
However, L is a hydroxyl group or a hydrolyzable group,
R is a hydrogen atom or a monovalent hydrocarbon group,
n is an integer of 0 to 2,
When n is 0 or 1, (3-n) Ls may be the same or different,
When n is 2, n Rs may be the same or different;
The group (I) of each of the compound (A) and the compound (B) may be the same or different.

Each of the compound (A) and the compound (B) can further have a group (II). When both the compound (A) and the compound (B) have the group (II), the groups (II) possessed by each may be the same or different.
R ^f1 -OQ- (II)
However,
R ^f1 is a perfluoroalkyl group,
Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 oxyfluoroalkylene groups. All 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 represented by the following formula (a1) and containing (CF ₂ O) units and (R ^f2 O) units.
{(CF ₂ O) _m1 (R ^f2 O) _m2 } (a1)
Here, R ^f2 is a perfluoroalkylene group having 2 or more carbon atoms,
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 bonding 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 be composed of two or more kinds of R ^f2 O having different carbon numbers.

R ^f2 may be branched or straight-chain, and is preferably straight-chain from the viewpoint of further improving the lubricity of the surface layer.
The carbon number of R ^f2 is preferably from 2 to 6, more preferably from 2 to 4, from the viewpoint of further improving the durability and lubricity of the surface layer, and particularly preferably 2 from the viewpoint of further improving the 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, particularly preferably an integer of 20 to 100. When (m1 + m2) is equal to or more than the lower limit of the above range, the surface layer is excellent in lubricity. When (m1 + m2) is equal to or less than the upper limit of the above range, the durability of the surface layer is excellent. That is, when the number average molecular weight of the compound (A) is too large, the number of groups (I) present per unit molecular weight decreases, and the durability decreases.

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

In ^{_{(CF 2 O) m1 (R}} f2 O) m2, m2 when one or more, that is, when there are two or more oxyperfluoroalkylene groups having different numbers of carbon atoms, each of oxyperfluoroalkylene groups (m1 amino CF ₂ The bonding order of O and m2 R ^f2 O) is not limited. For example, each oxyperfluoroalkylene group may be arranged randomly, alternately, or in blocks. 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 numbers. Further, the bonding 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)
Here, 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 (m1 + m2).
The ratio of m11 and m12 (m11 / m12) is preferably from 99/1 to 30/70, and particularly preferably from 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 (A3) above is particularly preferred.

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

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

  m3 is an integer of 2 to 200, preferably an integer of 10 to 150, particularly preferably an integer of 15 to 100. If m3 is equal to or more than the lower limit of the above range, the surface layer is excellent in lubricity. When m3 is equal to or less 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 the 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 is composed of two or more kinds of R ^f2 O having different carbon numbers, the bonding order of each R ^f3 O is not limited. For example, each R ^f3 O may be arranged in any of random, alternating, and block.

(R ^f3 O) When _{m3 comprises} two or more kinds of R ^f2 O having different numbers of carbon atoms, the B chain 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;
binding order of m4 amino _CF 2 CF ₂ O and m5 one ^{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 m3.
The ratio between m4 and m5 (m4 / m5) is preferably 90/10 to 10/90, and particularly preferably 70/30 to 30/70. Within the above range, the higher the ratio of m4, the better the lubricity tends to be. Within the above range, the higher the ratio of m5, the better the durability.

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 has at least one unit of a unit 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). m41 and m51 are each preferably 1.
_{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)
Here, m13 and m14 are each an integer of 2 to 200, 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 can be regarded as a poly (oxyperfluoroalkylene) chain in which units are alternately bonded.

(Group (I))
In the group (I), L is a hydroxyl group or a hydrolyzable group.
The hydrolyzable group is a group that becomes a hydroxyl group by a hydrolysis reaction. That is, when L is a hydrolyzable group, Si-L of the group (I) becomes a silanol group (Si-OH) by a 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 easy production of the compound (A). As the halogen atom, a chlorine atom is particularly preferred. L is preferably an alkoxy group having 1 to 4 carbon atoms from the viewpoint of low outgassing at the time of coating and excellent storage stability of the compound (A), and is required when long-term storage stability of the compound (A) is required. Is particularly preferably an ethoxy group, and particularly preferably a methoxy group 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 from 1 to 6, more preferably from 1 to 3, and particularly preferably from 1 to 2 in that the compound (A) is easily produced.

n is preferably 0 or 1, and particularly preferably 0. By the presence of a plurality of L in one group (I), the adhesion to the substrate becomes stronger, and the durability of the surface layer is further improved.
When n is 0 or 1, the (3-n) Ls may be the same or different. For example, some 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 preferred from the viewpoint of easy handling in industrial production.

(Group (II))
In the group (II), R ^f1 is a perfluoroalkyl group.
The carbon number of the perfluoroalkyl group in R ^f1 is preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 3, from the viewpoint of further improving the lubricity and durability of the surface layer. preferable.
The perfluoroalkyl group may be branched or linear, and is 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 formed by bonding 2 to 5 (preferably 2 to 4) of the oxyfluoroalkylene groups. . In the polyoxyfluoroalkylene group, a plurality of oxyfluoroalkylene groups are usually connected 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, dissolution of the compound (A) and the compound (B) in a liquid medium The nature becomes high. Therefore, the compound (A) and the compound (B) hardly aggregate in the coating liquid, and the compound (A) and the compound (B) hardly aggregate during the drying after being applied to the surface of the base material. The appearance of the surface layer is even better.
The carbon number of the oxyfluoroalkylene group is preferably from 1 to 6, more preferably from 2 to 6, still more preferably from 2 to 4, and particularly preferably 2 or 3.
The number of hydrogen atoms in the oxyfluoroalkylene group is one or more, preferably two or more, and particularly preferably three or more from the viewpoint of excellent surface layer appearance. The number of hydrogen atoms in the oxyfluoroalkylene group is preferably (Q carbon number) x 2 or less, particularly preferably (Q carbon number) or less, from the viewpoint of further improving the water / oil repellency of the surface layer.
The oxyfluoroalkylene group may be branched or straight-chain, and is preferably straight-chain from the viewpoint of further improving the lubricity of the surface layer.
In the polyoxyfluoroalkylene group, the 2 to 5 oxyfluoroalkylene groups may be all the same or different.
Q represents a single bond or —CHFCF ₂ OCH ₂ CF ₂ O— or —CF ₂ CHFCF ₂ OCH ₂ CF ₂ O— from the viewpoint of ease of production of the compound (A) and the compound (B). _{, -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 It may be 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 bonded to R ^f1 —O). preferable.

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

The compound (A) and the compound (B) each may have one group (I) or two or more groups. From the viewpoint that the durability of the surface layer is more excellent due to an increase in bonding with the substrate, two or more are preferable, and three or more are particularly preferable. The number is preferably 10 or less, more preferably 5 or less, and particularly preferably 4 or less, from the viewpoint that the durability of the surface layer is further improved by increasing the molecular density bonded to the substrate.
Therefore, the number of groups (I) in each of compound (A) and 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. From the viewpoint of ease of production of the compound (A) and the compound (B), it is preferable that all are 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, the compound (A) preferably further has a group (II) bonded to one end of the A chain. The compound (B) preferably further has a group (II) bonded to one end of the B chain. Thereby, the lubricity of the surface layer is further improved.

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 weight of the compound (A) or the compound (B) is at least the lower limit of the above range, the lubricity of the surface layer will be more excellent. When the number average molecular weight of the compound (A) and the compound (B) is at least the lower limit of the above range, the durability of the surface layer will be more excellent.
The number average molecular weight (Mn) is measured by a measurement method described in Examples described later.

The compound (A) and the compound (B) are not particularly limited as long as they have the A chain or the B chain and the group (I). For example, it can be appropriately selected from known fluorine-containing ether compounds as described in the following documents.
JP 2013-91047 A, JP 2014-80473 A, WO 2013/042732, WO 2013/042733, WO 2013/121984, WO 2013/121985, WO 2013/121986, International Publication No. 2014/163004, International Publication No. 2014/175124, International Publication No. 2015/087902, JP-A-2013-227279, JP-A-2013-241569, JP-A-2013-2013 No. 256643, JP-A-2014-15609, JP-A-2014-37548, JP-A-2014-65884, JP-A-2014-210258, JP-A-2014-218639, JP-A-2015-200884 Gazette, JP-A-2015 WO 21888, WO 2013/146112, WO 2013/187432, WO 2014/069592, WO 2015/099905, WO 2015/166760, JP 2013-144726. JP, JP-A-2014-77836, JP-A-2013-117012, JP-A-2014-214194, JP-A-2014-198822, JP-A-2015-129230, JP-A-2015-196723, JP-A-2015-13983, JP-A-2015-199915, JP-A-2015-199906, and the like.

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 fluorinated ether compound which is the same compound group except that it has a distribution in the number of repeating oxyperfluoroalkylene groups in a poly (oxyperfluoroalkylene) chain is regarded as a single compound. For example, in the case of the compound (A) in which the poly (oxyperfluoroalkylene) chain is (CF ₂ O) _m1 (R ^f2 O) _m2 , the same compound group except for having distribution in m1 and m2 is a single compound. It is a fluorinated ether compound.

(Preferred combination of compound (A) and compound (B))
In a preferred embodiment of the present composition, at least one of the compound (A) and the compound (B) has three or more groups (I), more preferably 3 to 5 groups. When at least one has three or more groups (I), the durability of the surface layer is more excellent.
When only one of the groups has three or more groups (I), the other has one or two groups (I), and preferably two in terms of durability.

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

When the surface layer is formed by a 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, a material having a smaller molecular weight tends to evaporate first and be deposited on a substrate. As the difference in the number average molecular weight (Mn) is smaller, the distribution of the compound (A) and the compound (B) is less likely to be uneven 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, particularly preferably 2,000 or less.
When the surface layer is formed by the wet coating method, 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), the formed surface layer Since the distribution unevenness of the compound (A) and the compound (B) hardly occurs, their difference 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: Combination of compound (A) having one A chain and three groups (I) and compound (B) having one B chain and three groups (I).
Combination example 2: Combination of compound (A) having two A chains and four groups (I) and compound (B) having two B chains and four groups (I).
Combination example 3: Combination of compound (A) having one A chain and five groups (I) and compound (B) having one B chain and five groups (I).
In each of these combinations, the compound (A) preferably has a group (II) bonded 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 fluorinated ether compounds represented by the following formula (A / B). In the following formula (A / B), R ^f of compound (A) is a poly (oxyperfluoroalkylene) chain containing a (CF ₂ O) unit, and R ^f of compound (B) is (CF ₂ O) It is a poly (oxyperfluoroalkylene) chain containing no units.
_{^{[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 above R ^f1 , Q is the above Q, and -SiR _n L _3-n is a group represented by the above formula (I). Z is a (r + s) -valent linking group. r is an integer of 1 or more, and is a number corresponding to the number of poly (oxyperfluoroalkylene) chains in the compounds (A) and (B). s is an integer of 1 or more, and is a number corresponding to the number of groups (I) in the compounds (A) and (B).
From the number of the poly (oxyperfluoroalkylene) chains and the number of the groups (I), r + s is preferably 2 to 13, more preferably 3 to 8, and particularly preferably 4 to 7. As Z is a linking group (r + s) value, below the ^Z a, include groups represented by ^{Z b.}
Furthermore, when r is 2 or more, r pieces of ^{[R f1 -O-Q-R} f -] is preferably the same group, when s is 2 or more, s pieces of the formula (I) The groups represented by are preferably the same groups.

(Preferred embodiment)
In a preferred embodiment of the composition, the compound (A) is a fluorinated ether compound (A1) represented by the following formula (A1) (hereinafter, also referred to as compound (A1)), and the compound (B) is represented by the formula (A1). An embodiment is 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 is a single bond, one or more oxy-fluoroalkylene group containing a hydrogen atom or a polyoxyalkylene fluoroalkylene group 2-5 is formed by bonding of said oxy fluoroalkylene group, the polyoxy All oxyfluoroalkylene groups constituting the fluoroalkylene group may be the same or different,
R ^fa is the A chain;
R ^fb is a B chain,
Z ^a is a (ra + sa) -valent linking group,
Z ^b is a (rb + sb) -valent linking group,
L ^a and ^{L b} are hydroxyl group or a hydrolyzable group,
R ^a and R ^b are a hydrogen atom or a monovalent hydrocarbon group,
na and nb are integers of 0 to 2,
(3-na) L ^a when na is 0 or 1 and (3-nb) L ^b when nb is 0 or 1 may be the same or different;
When na is 2, na R ^a , and when nb is 2, nb R ^b may be the same or different,
ra and rb are integers greater than or equal to 1, ra is the ra number when two or more ^{[R f1a -O-Q a -R} fa -] may be different even in the same, rb 2 or when the rb pieces ^{[R f1b -O-Q b -R} fb -] may be the same or different and
sa and sb is an integer of 1 or more, sa is sa number when two or more ^{_{[-SiR a na L a 3-}} na] may be different even in the same, sb 2 or more when sb pieces ^{_{[-SiR b nb L b 3-}} nb] may be 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 easiness of production, the same group, that is, a group having the same carbon number and the same chemical structure Is preferred. A group having the same carbon number and the same chemical structure means that, for example, when ra is 2, two R ^f1a are CF ₃ CF ₂ CF ₂ — (the two R ^fa It is the same carbon atoms chemical structure is _{different, CF 3 CF 2 CF 2 -} , CF 3 CF (CF 3) - is not a combination of).
When rb is 2 or more, rb R ^f1b preferably have the same carbon number, and from the viewpoint of ease of production, are the same group, that is, a group having the same carbon number and the same chemical structure. Is preferred.

Q ^a and ^{Q b} are the same as Q in the group (II), preferable embodiments thereof are also the same.
The A chain of R ^fa and the B chain of R ^fb are the same as described above, and 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 preferred embodiments are also the same.
na and nb are the same as n in the group (I), and preferred embodiments are also the same.
Preferred values of ra and rb are respectively the same as the preferred numbers of the A chain of the compound (A) and the B chain of the compound (B). That is, each of ra and rb is preferably an integer of 1 to 3.
Preferred values of s1 and s2 are the same as the preferred number of groups (I) in each of compound (A) and compound (B). That is, s1 and s2 are each preferably an integer of 1 to 10, more preferably an integer of 2 to 5, and particularly preferably an integer of 3 to 4.

The Z ^a, for example, (ra + sa) valent substituted or unsubstituted hydrocarbon group, the carbon of a substituted or unsubstituted hydrocarbon group - between carbon atoms and / or the terminal, the group or atom other than a hydrocarbon group (Ra + sa) -valent groups and organopolysiloxane groups having (ra + sa) -valent values.
The Z ^b, except that the valency (rb + sb) titer include the same ^{Z a.}

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

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

<Preferred embodiment of compound (A1)>
As the compound (A1), at least one selected from the group consisting of the following compound (A11), compound (A12) and compound (A13) is more preferable in that the surface layer has more excellent rub resistance and fingerprint stain removal properties. preferable.

"Compound (A11)"
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 fluoroalkylene group having 1 to 20 carbon atoms or a group having an etheric oxygen atom between carbon-carbon atoms of a fluoroalkylene group having 2 to 20 carbon atoms (provided that one end is bonded to the etheric oxygen atom Excluding the case where the other end of 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,
R ^34a is a single bond, an alkylene group having 1 to 6 carbon atoms, and an etheric oxygen at the terminal of the alkylene group (provided that the terminal is bonded to C [-R ^34a -SiR _na L _3-na ] ₃ ). A group having an atom, a group having an etheric oxygen atom between carbon-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 (provided that C [-R ^34a -SiR _na L _3-na ] ₃ ) and a group having an etheric oxygen atom between the carbon-carbon atoms;
R ^35a is an alkylene group having 1 to 6 carbon atoms, a group having an etheric oxygen atom at the terminal of the alkylene group (excluding the terminal bonded to Si), or an alkylene group having 2 to 6 carbon atoms. A group having an etheric oxygen atom between the carbon-carbon atoms of
3 _{^{[-R 34a -SiR na L 3-}} na] may be be the same or different.

Compound (A11) is, in the above formula (A1), ra is 1, sa is 3, ^{Z a} is _{^{-Q 32a - [C (O)}} N (R 33a)] pa -R 34a -C ^[-R 35a _-] is ₃ compound.
However, the number of (CF ₂ O) in R ^fa is preferably 4 or more, and the number of (CF ₂ O) in Q ^32a is preferably 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 view of the friction resistance and lubricity of the surface layer.
Examples of the group having an etheric oxygen atom between the carbon atoms of the fluoroalkylene group having 2 to 20 carbon atoms include the group (ii) described below.
Q ^32a includes a perfluoroalkylene group having 1 to 20 carbon atoms, a fluoroalkylene group having 1 to 20 carbon atoms containing at least one hydrogen atom, and a fluoroalkylene having 2 to 20 carbon atoms containing at least one hydrogen atom. A group having an etheric oxygen atom between carbon-carbon atoms of the alkylene group is preferred.

When pa is 0 and R ^fa is {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 }, Q ^32a is typically a _C 1 perfluoroalkylene group.
When pa is 1, Q ^32a includes the following groups.
(I) a 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 (which may have an etheric oxygen atom between carbon-carbon atoms) on the side bonded to C (O) N (R ^33a ).

As Q ^{32a in} (ii), the following groups are preferred from the viewpoints of durability and lubricity of the surface layer and ease of production of 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 )] The characteristics of the fluorinated ether compound hardly change when pa in the _pa group is 0 or 1. When pa is 1, it has an amide bond, but at least one fluorine atom is bonded to the terminal carbon atom on the side of Q ^32a bonded to [C (O) N (R ^33a )]. In addition, the polarity of the amide bond becomes small, and the water / oil repellency of the surface layer is hardly reduced. Whether pa is 0 or 1 can be selected from the viewpoint of ease of manufacture.
[C (O) N (R ^33a )] As the R ^33a in the _pa group, a hydrogen atom is preferable from the viewpoint of easy 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 may be a single bond, —CH ₂ O—, —CH ₂ OCH ₂ —, or —CH ₂ OCH ₂ CH ₂ O— from the viewpoint of easy 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, R ^34a is preferably a group selected from the group consisting of a single bond, —CH ₂ — and —CH ₂ CH ₂ — from the viewpoint of ease of production of compound (A11).

As R ^35a , from the viewpoint of easy production of the 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 — (however, the right side is bonded to Si) is preferable.
As R ^35a , a compound having no etheric oxygen atom is particularly preferable from the viewpoint of excellent light resistance of the surface layer. In outdoor touch panels (digital signage such as vending machines and guide boards) and in-vehicle touch panels, the water and oil repellent layers are required to have light resistance.
The three R ^35a in the compound (A11) may be the same or different.

  Examples of the compound (A11) include a compound represented by the following formula. The compound is preferred because it is easily manufactured industrially, is easy to handle, and is further excellent in water / oil repellency, friction resistance, fingerprint stain removal property, lubricity, and appearance of the surface layer.

However, W in these ^{formulas, R f1a -O-Q a -R} fa - a. A preferred form of W is a combination of the preferred R ^f1a , Q ^a and R ^fa described above. The preferred range of ^Q32a is as described above.

"Compound (A12)"
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 C 1-6 perfluoroalkylene group,
R ^43a is a single bond, an alkylene group having 1 to 6 carbon atoms, a group having an etheric oxygen atom or -NH- at a terminal of the alkylene group (excluding a terminal bonded to N), A group having an etheric oxygen atom or -NH- between carbon-carbon atoms of an alkylene group of 2 to 6, or a terminal of an alkylene group having 2 to 6 carbon atoms (excluding the terminal on the side bonded to N) And a group having an etheric oxygen atom or -NH- between carbon-carbon atoms,
R ^44a is an alkylene group having 1 to 6 carbon atoms or a group having an etheric oxygen atom or -NH- between carbon-carbon atoms of the alkylene group having 2 to 6 carbon atoms;
Two _{^{[-R 44a -SiR na L 3-}} na] may also be the same or different.

Compound (A12) is, in the above formula (A1), ra is 1, sa is 2, ^{Z a} is ^{-R 42a -R 43a -N [-R 44a} -] a _second compound.

R ^42a is preferably a linear perfluoroalkylene group. When ^R42 is a linear perfluoroalkylene group, the friction resistance and lubricity of the surface layer are further excellent.
When R ^fa is {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 }, R ^42a is typically a _C 1 perfluoroalkylene group.

The R ^43a, in terms of the compound (A12) ease of manufacture _{of, -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 — (however, the left side is bonded to R ^42a ) is preferable.
^R43a has a high polarity and does not have an ester bond with insufficient chemical resistance and light resistance, and thus has excellent initial water repellency, chemical resistance and light resistance of the surface layer.

The R ^44a, from the viewpoint of ease of preparation of the compound _{(A12), -CH 2 CH 2} CH 2 - and _{-CH 2 CH 2 OCH 2 CH 2} CH 2 - ( where the right side is attached to the Si. Is preferred.
Since ^R44a has a high polarity and does not have an ester bond with insufficient chemical resistance and light resistance, the surface layer has excellent initial water repellency, chemical resistance and light resistance.
The R ^44a, from the viewpoint of excellent in light resistance of the surface layer, is particularly preferable not to have an etheric oxygen atom.
Two R ^44a in the compound (A12) may be the same or different.

  Examples of the compound (A12) include a compound represented by the following formula. The compound is preferable because it is easily manufactured industrially, is easy to handle, and is more excellent in water / oil repellency, friction resistance, fingerprint stain removal property, lubricity, chemical resistance, and light resistance.

However, W in these ^{formulas, R f1a -O-Q a -R} fa - a. A 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)"
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 C 1-6 perfluoroalkylene group,
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 at least one etheric oxygen atom between carbon atoms of the hydrocarbon group;
R ^53a is an alkylene group having 1 to 20 carbon atoms,
ea is an integer of 1 or more;
fa is an integer of 1 or more;
(Ea + fa) is 3 or more;
^{ea [-O- R f1a -O-Q} a -R fa -R 51a -R 52a] of ea number is 2 or more, which may be identical or different,
fa is fa number when two or more _{^{[-O-R 53a -SiR a na}} L a 3-na] may be 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 - ] _{Fa is} a compound.

  ea is preferably an integer of 1 to 3. 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 — when, for example, R ^fa is {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 }.
R ^51a is preferably linear. When R ^51a is a linear compound (A13), a surface layer having more excellent friction resistance and lubricity can be formed.

As R ^52a , an alkylene group having 1 to 4 carbon atoms is preferable, and -CH ₂ -is particularly preferable, from the viewpoint of easy production of the compound (A13).

^{R f1a -O-Q a -R fa} -R 51a - The group, water and oil repellency, the durability of the surface layer, the fingerprint stain removal properties, lubricity, further further excellent terms and compounds in the appearance of (A13) The group (R ^f -1) and the group (R ^f -2) are preferred 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 bonding order of ₂ O and m22 CF ₂ CF ₂ O is not limited.

Examples of Z ^3a include a residue obtained by removing a hydroxyl group from a polyhydric alcohol having (ea + fa) hydroxyl groups.
Specific examples of Z ^3a include, for example, groups of the following formula. As Z ^3a , a residue obtained by removing a hydroxyl group from a polyhydric alcohol having a primary hydroxyl group is preferable from the viewpoint of excellent reactivity of a hydroxyl group, and from the viewpoint of availability of raw materials, a group (Z-1) or a group (Z-2) and the group (Z-3) are particularly preferred. However, R ⁴ is an alkyl group, and is 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 easy production of the compound (A13). Further, during hydrosilylation in the production of the compound (A13) described later, a by-product in which part or all of the allyl group (—CH ₂ CH ＝ CH ₂ ) isomerized to an inner olefin (—CH ＝ CHCH ₃ ) is formed. An alkylene group having 4 to 10 carbon atoms is particularly preferable because it is difficult to form.

  The compound (A13) includes, for example, compounds (A13-1) to (A13-6) of the following formulas. The compound is preferred because it is easily manufactured industrially, is easy to handle, and is further excellent in water / oil repellency, friction resistance, fingerprint stain removal property, lubricity, and appearance of the surface layer.

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

<Preferred embodiment of compound (B1)>
As the compound (B1), the following compounds (B11), (B12) and (B13) are preferable from the viewpoint that the surface layer is more excellent in friction resistance and fingerprint stain removal properties.

"Compound (B11)"
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 are each as defined above,
Q ^32b is a fluoroalkylene group having 1 to 20 carbon atoms or a group having an etheric oxygen atom between the carbon-carbon atoms of the fluoroalkylene group having 2 to 20 carbon atoms (provided that one end is bonded to the etheric oxygen atom The other end of which is not the case where 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,
R ^34b is a single bond, an alkylene group having 1 to 6 carbon atoms, and an end of the alkylene group (provided that C [-R ^34b -SiR _nb L _3-nb ] ₃ is bonded to an etheric oxygen terminal). A group having an atom, a group having an etheric oxygen atom between carbon-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 (provided that C [-R ^34b -SiR _nb L _3-nb ] ₃ ) and a group having an etheric oxygen atom between the carbon-carbon atoms;
R ^35b is an alkylene group having 1 to 6 carbon atoms, a group having an etheric oxygen atom at the terminal of the alkylene group (excluding the terminal bonded to Si), or an alkylene group having 2 to 6 carbon atoms. A group having an etheric oxygen atom between the carbon-carbon atoms of
Three _{^{[-R 34b -SiR nb L 3-}} nb] may be be the same or different.

Compound (B11), in the above formula (B1), rb is 1, sb is 3, ^{Z b} is _{^{-Q 32b - [C (O)}} N (R 33b)] pb -R 34b -C [ ^-R35b- ] ₃ .

The fluoroalkylene group in Q ^{32b and} the group having an etheric oxygen atom between the carbon-carbon atoms of the fluoroalkylene group are the same as the carbon-carbon atoms of the fluoroalkylene group and fluoroalkylene group in Q ^32a in the formula (A11), respectively. Is the same as the group having an etheric oxygen atom.
The number of (CF ₂ O) in Q ^32b is preferably 0 to 3.
When p1 is 0 and R ^fb is (CF ₂ CF ₂ O) _m13 , Q ^32b is typically a C 1 perfluoroalkylene group. When p1 is 0 and R ^fb is (CF ₂ CF ₂ CF ₂ O) _m14, it is typically a _C 2 perfluoroalkylene group. In p1 is ^0, when ^{R fb} is _{(CF 2 CF 2 O-CF} 2 CF 2 CF 2 CF 2 O) m15, typically a perfluoroalkylene group linear 3 carbon atoms.
R ^33b , pb, R ^34b , and R ^35b are respectively the same as R ^33a , pa, R ^34a , and R ^35a in Formula (A11), and the preferred embodiments are also the same.

"Compound (B12)"
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 are each as defined above,
R ^42a is a C 1-6 perfluoroalkylene group,
R ^43a is a single bond, an alkylene group having 1 to 6 carbon atoms, a group having an etheric oxygen atom or -NH- at a terminal of the alkylene group (excluding a terminal bonded to N), A group having an etheric oxygen atom or -NH- between carbon-carbon atoms of an alkylene group of 2 to 6, or a terminal of an alkylene group having 2 to 6 carbon atoms (excluding the terminal on the side bonded to N) And a group having an etheric oxygen atom or -NH- between carbon-carbon atoms,
R ^44a is an alkylene group having 1 to 6 carbon atoms or a group having an etheric oxygen atom or -NH- between carbon-carbon atoms of the alkylene group having 2 to 6 carbon atoms;
Two _{^{[-R 44 -SiR n L 3-}} n] may be be the same or different.

Compound (B12), in the above formula (B1), rb is 1, sb is 2, ^{Z b} is ^{-R 42b -R 43b -N [-R 44b} -] a _second compound.

R ^42b , R ^43b and R ^44b are respectively the same as R ^42a , R ^43a and R ^44a in the formula (A12).
However, when R ^fb is (CF ₂ CF ₂ O) _m13 , R ^42b is typically a C 1 perfluoroalkylene group. When R ^fb is (CF ₂ CF ₂ CF ₂ O) _m14, it is typically a _C 2 perfluoroalkylene group. If R ^fb is _{(CF 2 CF 2 O-CF} 2 CF 2 CF 2 CF 2 O) m15, typically a perfluoroalkylene group linear 3 carbon atoms.

"Compound (B13)"
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 are each as defined above,
R ^51b is a C 1-6 perfluoroalkylene group,
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 at least one etheric oxygen atom between carbon atoms of the hydrocarbon group;
R ^53b is an alkylene group having 1 to 20 carbon atoms,
eb is an integer of 1 or more;
fb is an integer of 1 or more;
(Eb + fb) is 3 or more;
When eb is 2 or more, eb [R ^{f1b -OQR fb} -R ^51b -R ^52b -O-] may be the same or different;
fb is fb number when two or more _{^{[-O-R 53b -SiR b nb}} L b 3-nb] may be be the same or different.

Compound (B13), in the above formula (B1), rb is eb, sb is fb, ^{Z b} is _{^{[-R 51b -R 52b -O-] eb}} Z 3b [-O-R 53b - _Fb .

R ^51b , R ^52b , Z ^3b , R ^53b , eb and fb are respectively the same as R ^51a , R ^52a , Z ^3a , R ^53a , ea and fa in the formula (A13).
^{R f1b -O-Q b -R fb} -R 51b -R 52b - The group, repellent surface layer, durability, fingerprint stain removal properties, lubricity, further further excellent terms and compounds in appearance ( The group (R ^f -3) is preferred from the viewpoint of ease of production of 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 fluorinated 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).
As another fluorine-containing ether compound, for example, a fluorine-containing ether compound having a poly (oxyperfluoroalkylene) chain and having no group (I) (hereinafter, also referred to as compound (C)) may be mentioned. The poly (oxyperfluoroalkylene) chain may be an A chain or a B chain.

Compound (C) includes, for example, 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 each independently a perfluoroalkyl group having 1 to 20 carbon atoms; Q ⁵¹ is a single bond, 1 to 6 carbon atoms having no branched structure containing one or more hydrogen atoms. An etheric oxygen atom is added to the terminal of the fluoroalkylene group having 1 to 6 carbon atoms and not having a branched structure containing at least one hydrogen atom (excluding the terminal bonded to A ³¹ -O). A group having an etheric oxygen atom between the carbon-carbon atoms of a C2-C6 fluoroalkylene group having no branched structure containing at least one hydrogen atom, or containing at least one hydrogen atom A group having an etheric oxygen atom between the terminal of a C 2-6 fluoroalkylene group having no branched structure (excluding the terminal on the side bonded to A ³¹ -O) and a carbon-carbon atom (Provided that the number of oxygen atoms is 10 or less); Q ⁵² is a fluoroalkylene group having 1 to 20 carbon atoms and having no branched structure containing one or more hydrogen atoms, or one or more hydrogen atoms. including carbon fluoroalkylene group having 2 to 6 carbon atoms having no branched structure - a group having an etheric oxygen atom between carbon atoms (. However, the number of oxygen is 10 or less); R ^F3 is a branched structure Is a C 1-6 perfluoroalkylene group having no; m30 is an integer of 2 to 200; (R ^F3 O) _m30 is _composed of two or more types of R ^F3 O having different carbon numbers. at best; ^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, as a commercially available compound (C1) in which Q ⁵¹ is a single bond and p3 is 0, FOMBLIN (registered trademark) M, FOMBLIN (registered trademark) Y, FOMBLIN (registered trademark) Z (hereinafter referred to as Solbeiso Lexis), Krytox (registered trademark) (manufactured by DuPont), Demnum (registered trademark) (manufactured by Daikin Industries, Ltd.) and the like.

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

(Composition of the present composition)
In the present composition, the content of compound (A) (the mass ratio of compound (A) / [compound (A) + compound (B)]) to the total of compound (A) and compound (B) is 10 to 80. % By mass is preferable, and 20 to 50% by mass is particularly preferable. The higher the content of the compound (A) in the above range, the more excellent 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 more excellent the durability of the surface layer.

  In the present composition, the total amount of compound (A) and compound (B) is preferably at least 50% by mass, particularly preferably at least 80% by mass, 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) contains the present composition and a liquid medium. The present coating liquid may be a liquid, may be a solution, or may be a dispersion.
The present coating liquid only needs to include the present composition, and may include impurities such as by-products generated in the production process of the compound (A), the compound (B), and the like.
The concentration of the present composition is preferably 0.001 to 50% by mass, more preferably 0.05 to 30%, still more preferably 0.05 to 10% by mass, and 0.1 to 1% by mass in the present coating solution. Particularly preferred.

  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 include both solvents.

Examples of the fluorinated organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.
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 Klin (registered trademark) AC-2000, manufactured by Asahi Glass Co., Ltd.) and C ₆ F ₁₃ C ₂ H ₅ (Asahi Klin (registered trademark) AC-6000, manufactured by Asahi Glass Co., Ltd.) , C ₂ F ₅ CHFCHFCF ₃ (Bertrel (registered trademark) XF, manufactured by Kemers) 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. Commercially available products include, for example, CF ₃ CH ₂ OCF ₂ CF ₂ H (Asahiclean (registered trademark) AE-3000, manufactured by Asahi Glass Co., Ltd.), C ₄ F ₉ OCH ₃ (manufactured by 3M, Novec (registered trademark) 7100), C ₄ F ₉ OC ₂ H ₅ (manufactured by 3M, Novec (registered trademark) 7200), C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ (manufactured by 3M, Novec (registered trademark) 7300) and the like. .
Examples of the fluorinated alkylamine include perfluorotripropylamine, perfluorotributylamine and the like.
Examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol and the like.
As the non-fluorinated organic solvent, a compound consisting of only a hydrogen atom and a carbon atom, and a compound consisting of only 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, Ether organic solvents and ester organic solvents are exemplified.
This coating liquid preferably contains 50 to 99.999% by mass of the liquid medium, more preferably 70 to 99.5% by mass, further preferably 90 to 99.5% by mass, and more preferably 99 to 99.5% by mass. It is particularly preferred to contain 9% by mass.

The present coating liquid may contain other components in addition to the present composition and the medium as long as the effects of the present invention are not impaired.
Examples of the 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 the present coating liquid is preferably 10% by mass or less, particularly preferably 1% by mass or less.

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

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

(Surface layer)
In the present composition, when L in the group (I) in the compound (A) and the compound (B) is a hydrolyzable group, the group (I) undergoes a hydrolysis reaction to form a silanol group (Si- 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 form a chemical. A bond (base-O-Si) is formed. Therefore, the surface layer contains the compound (A) and the compound (B) in a state where a part or all of the group (I) of each of the compound (A) and the compound (B) is hydrolyzed. When L in the group (I) is a hydroxyl group, the above reaction proceeds without a hydrolysis reaction.

  The thickness of the surface layer is preferably from 1 to 100 nm, particularly preferably from 1 to 50 nm. When the thickness of the surface layer is equal to or more than 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 equal to or less than the upper limit of the above range, utilization efficiency is high. The thickness of the surface layer is determined by obtaining an interference pattern of reflected X-rays by an X-ray reflectivity method using an X-ray diffractometer for thin film analysis (manufactured by RIGAKU, ATX-G), and obtaining a vibration cycle of the interference pattern. Can be calculated.

(Base material)
The substrate in the present invention is not particularly limited as long as it is a substrate required to impart lubricity and water / oil repellency. Examples of the material of the substrate 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 substrate, a substrate for a touch panel, a substrate for a display, and an eyeglass lens are preferable, and a substrate for a touch panel is particularly preferable. The substrate for a touch panel has translucency. The phrase “having translucency” means that the vertical incidence type visible light transmittance according to JIS R3106: 1998 (ISO 9050: 1990) is 25% or more. As a material of the substrate for a touch panel, glass and a transparent resin are preferable.

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

<Dry coating method>
The present composition can be used as it is in a dry coating method. The present 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 evaporation method, a CVD method, and a sputtering method. From the viewpoint of suppressing the decomposition of the compound (A) and the compound (B) and the simplicity of the apparatus, the vacuum deposition method is particularly preferable. At the time of vacuum deposition, a pellet-like substance obtained by impregnating a porous metal such as iron or steel with the present composition or the present coating solution may be used.

The temperature at the time of vacuum deposition is preferably from 20 to 300 ° C, particularly preferably from 30 to 200 ° C.
The pressure at the time of vacuum deposition is preferably 1 × 10 ⁻¹ Pa or less, particularly preferably 1 × 10 ⁻² Pa or less.

<Wet coating method>
Wet coating methods include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, ink jet, flow coating, roll coating, casting, Langmuir-Blodgett, and gravure. Coating method and the like can be mentioned.

<Post-processing>
In order to improve the friction resistance of the surface layer, an operation for accelerating the reaction between the compound (A) and the compound (B) and the substrate may be performed, if necessary. The operation includes heating, humidification, light irradiation and the like.
For example, a substrate on which a surface layer is formed is heated in an atmosphere having moisture to undergo a hydrolysis reaction of a hydrolyzable silyl group to a silanol group, a reaction between a hydroxyl group or the like of a substrate surface and a silanol group, a silanol Reactions such as formation of a siloxane bond by a group condensation reaction can be promoted.
After the surface treatment, the compounds in the surface layer that are not chemically bonded to other compounds or the substrate may be removed as necessary. Specific examples of the method include a method in which a solvent is applied to the surface layer, a method in which the solvent is wiped with a cloth impregnated with the solvent, and the like.

(Effects)
Since the present composition and the present coating solution 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 a substrate using the present composition or the present coating liquid, excellent initial lubricity, properties such as water and oil repellency are imparted, and the surface is repeatedly formed. Excellent durability in which their properties are hardly deteriorated even when rubbed is obtained. In addition, since the water / oil repellency is unlikely to be reduced even if the surface is repeatedly rubbed, a performance (fingerprint stain removal property) of easily removing fingerprint stains on the surface of the substrate can be obtained.
Compound (A) is excellent in lubricity because it contains (CF ₂ O) units in the A chain. On the other hand, the durability is inferior to the case where no (CF ₂ O) unit is included. Since the compound (B) does not contain a (CF ₂ O) unit in the B chain, it has excellent durability. On the other hand, the lubricating properties are inferior to those containing (CF ₂ O) units. When these are combined, the respective excellent properties are sufficiently maintained, and both excellent lubricity and durability can be achieved. It is considered that the reason for this is that a component having high lubricity (compound (A)) disperses the force applied to abrasion, and the durability of the component having high durability (compound (B)) is further increased.

[Application]
Therefore, the thus obtained substrate having a surface layer is suitable as a member constituting a touch panel.
However, the use of the present composition, the present coating liquid and the article is not limited to the touch panel. For example, display input devices other than touch panels; surface protective coats made of 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. And antifouling coats, antifouling coats for toiletries; coatings on members that require liquid repellency while conducting; water-repellent, waterproof, water-sliding coats for heat exchangers; be able to.
More specific examples of use include a front protective plate of a display, an anti-reflection plate, a polarizing plate, an anti-glare plate, or an anti-reflection coating on those surfaces, and a touch panel of a device such as a mobile phone or a portable information terminal. Various devices having display input devices such as sheets and touch panel displays that perform operations on the screen with human fingers or palms, decorative building materials around water in toilets, baths, washrooms, kitchens, etc., waterproof coatings for wiring boards, repelling heat exchangers Water / water-repellent coat, water-repellent coat for solar cells, waterproof / water-repellent coat for printed wiring boards, waterproof / water-repellent coat for electronic equipment housings and electronic parts, insulation-improving coat for transmission lines, waterproofing for various filters Water repellent coat, waterproof coat of radio wave absorbing material and sound absorbing material, bath, kitchen equipment, antifouling coat for toiletries, water repellent / waterproof / sliding coat of heat exchanger, vibration Low surface friction coating Rui and the cylinder interior and the like, mechanical parts, vacuum equipment parts, bearing parts, automobile parts, surface protection coating such as a tool and the like.

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

[Physical properties and evaluation]
(Number average molecular weight)
The number average molecular weight of the fluorinated ether compound was calculated by determining the number (average value) of the oxyperfluoroalkylene groups based on the terminal groups by ¹ H-NMR and ¹⁹ F-NMR. The terminal group is, for example, group (I) or 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 Interface Science Co., Ltd.). Measurement was performed at five different locations on the surface of the surface layer, and the average value was calculated. The 2θ method was used to calculate the contact angle. The larger the water contact angle, the better the water repellency.

(Lubricity)
The dynamic friction coefficient of the surface layer with respect to the artificial skin (PBZ13001, manufactured by Idemitsu Technofine Co., Ltd.) was determined using a load-varying friction and wear test system (HHS2000, manufactured by Shinto Kagaku), contact area: 3 cm × 3 cm, load: 0.98 N It measured on condition of. The smaller the coefficient of kinetic friction, the better the lubricity.

(Durability 1 (the number of times the contact angle is maintained at 100 ° or more))
For the surface layer, a steel wool bon tester (バ ー ス 0000) was used at a pressure of 98.07 kPa using a reciprocating traverse tester (manufactured by KNT Corporation) in accordance with JIS L0849: 2013 (ISO 105-X12: 2001) at a pressure of 98.07 kPa and at a speed of: It was reciprocated at 320 cm / min. The water contact angle was measured each time it was reciprocated 1,000 times, and the upper limit number of times that the water contact angle was maintained at 100 ° or more (the number of times the contact angle was maintained at 100 ° or more) was determined. The greater the number of times, the less the surface layer is damaged by friction, and the more excellent the durability.

(Durability 2 (the difficulty of lowering the dynamic friction coefficient))
After the steel wool bond tester was reciprocated 3,000 times under the condition of <Durability 1>, the dynamic friction coefficient was measured under the same conditions as <Lubricity>. The smaller the change in the dynamic friction coefficient, the less the outermost surface is damaged by friction, and the more excellent the durability.

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

(B-1): Compound (B-1) obtained in Production Example B-1 described below.
(B-2): Composition (B-2) obtained in Production Example B-2 described below.
(B-3): Compound (B-3) obtained in Production Example B-3 described below.
(B-4): Compound (B-4) obtained in Production Example B-4 described below.
(B-5): Compound (B-5) obtained in Production Example B-5 described below.
(B-6): The solvent of "2634 coating" manufactured by Dow Corning Toray Co., Ltd. was distilled 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): CF 3} O {(CF 2 O) r1 (CF 2 CF 2 O) r2} fluorine-containing ether compound represented by _{CF 3 (r1 / r2 = 20} /21) ( Solvay Solexis "FOMBLIN M03").

(A-1) to (A-5), (B-1) to (B-5), and a repeating unit of a poly (oxyperfluoroalkylene) chain contained in (C-1), a poly (oxyperfluoroalkylene) chain (Hereinafter also referred to as PEPE number), the number of groups (I) and the number average molecular weight (Mn) are shown in Table 1.
The repeating unit “(CF ₂ O) (CF ₂ CF ₂ O)” in (A-1) to (A-5) and (C-1) includes a (CF ₂ O) unit and a (CF ₂ CF ₂ ) unit. O) means that the unit is a poly (oxyperfluoroalkylene) chain randomly arranged.

[Production Example A-1]
A 300 mL three-necked flask was charged with 24.4 g of a 24% aqueous KOH solution, 33 g of tert-butyl alcohol, and 220 g of compound (1) (FLUOROLINK (registered trademark) D4000, manufactured by Solvay Solexis), and CF ₃ CF was added to 19.4g of _{2 CF 2 -O-CF = CF} 2 ( manufactured by Tokyo Kasei Kogyo Co., Ltd.). The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere. After washing once with a dilute hydrochloric acid aqueous solution, the organic phase was collected and concentrated by an evaporator to obtain 233 g of a crude product. The crude product was fractionated by developing on silica gel column chromatography. 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 Company, 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 constitutional unit was determined from the integrated values of 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): average number 21 of unit number x1, average value 20 of unit number x2, number average molecular weight 4,150.
Compound (3): average number 21 of unit number x1, average value 20 of unit number x2, number average molecular weight 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 ( 3.5 g of CF ₃ ) COF were added. The mixture was stirred at 50 ° C for 24 hours under a nitrogen atmosphere. After removal of sodium fluoride powder in a pressure filter, the excess of _{CF 3 CF 2 CF 2 OCF (} CF 3) COF and AK-225 was 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 collected solution was concentrated with an evaporator to obtain 31.8 g of the compound (4) (yield). 98.8%).
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): average number 21 of unit number x1, average value 20 of unit number x2, number average molecular weight 4,460.

At the gas outlet of a 1-L nickel autoclave, a cooler maintained at 20 ° C, a packed bed of NaF pellets, and a cooler maintained at 0 ° C were installed in series. A liquid return line was provided for returning the condensed liquid from the cooler maintained at 0 ° C. to the autoclave.
Autoclave _{ClCF 2 CFClCF 2 OCF 2 CF 2} Cl ( hereinafter also referred to. As CFE-419) 750 g was placed and stirred while maintaining the 25 ° C.. After nitrogen gas was blown into the autoclave at 25 ° C. for 1 hour, 20% fluorine gas was blown at 25 ° C. at a flow rate of 2.0 L / hour for 1 hour. While blowing 20% fluorine gas at the same flow rate, a solution in which 31.0 g of compound (4) was dissolved in 124 g of CFE-419 was injected into the autoclave over 4.3 hours. The internal pressure of the autoclave was increased to 0.15 MPa (gauge pressure) while blowing 20% fluorine gas at the same flow rate. Into the autoclave, 4 mL of a benzene solution containing 0.05 g / mL of benzene in CFE-419 was injected 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 again injected while maintaining the temperature at 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. The stirring was continued for 1 hour while blowing 20% fluorine gas at the same flow rate. The pressure in the autoclave was adjusted to the atmospheric pressure, and nitrogen gas was blown for one hour. The contents of the autoclave were concentrated with 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): average number 21 of unit number x1, average value 20 of unit number x2, number average molecular weight 4,550.

A round bottom flask made of a tetrafluoroethylene-perfluoro (alkoxy vinyl ether) copolymer (hereinafter also referred to as PFA) was charged with 30.0 g of the compound (5) and 60 g of AK-225. The mixture was stirred while being cooled in an ice bath, and 2.0 g of methanol was slowly added dropwise from a dropping funnel under a nitrogen atmosphere. The mixture was stirred for 12 hours while bubbling with nitrogen. The reaction mixture was concentrated with 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 -COOCH 3 ··· (6 )
Compound (6): average number 21 of unit number x1, average value 20 of unit number x2, number average molecular weight 4,230.

In a 100 mL three-neck eggplant flask, 0.18 g of lithium chloride was dissolved in 18.3 g of ethanol. A solution of 0.75 g of sodium borohydride in 22.5 g of ethanol was slowly added dropwise thereto while adding 25.0 g of the compound (6) and cooling with an ice bath. 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 solution became acidic. 20 mL of AC-2000 was added, and the mixture was washed once with water and once with saturated saline, and the organic phase was recovered. The collected 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): average number 21 of unit number x1, average value 20 of unit number x2, number average molecular weight 4,200.

In a 100 mL two-necked eggplant flask, 20.0 g of the 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 were placed. 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 hydrochloric acid aqueous solution to recover an organic phase. The collected organic phase was passed through a silica gel column, and the collected solution was concentrated with an evaporator to obtain 19.8 g of Compound (8) (yield 98.2%).
_{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): average number 21 of unit number x1, average value 20 of unit number x2, number average molecular weight 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%) were added. 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 Chemical Industry Co., Ltd.) were added, and the mixture was heated at 40 ° C. Stir for 4 hours. After completion of the reaction, the solvent and the like were distilled off under reduced pressure, and the residue was filtered through a membrane filter having a pore size of 0.2 μm. One of the compound (9) in which one allyl group of the compound (8) was hydrosilylated and one of the compound (8) As a result, 4.9 g (yield: 95%) of a composition (A-1) consisting of a by-product in which the allyl group of was isomerized into an inner olefin (—CH ＝ CHCH ₃ ) was obtained. The conversion 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 H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.7 (6H), 1.7 (6H), 3.6 (11H), 3.8 (2H) .
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: 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 and the average value of the number of units x2, 20, the number average molecular weight of the compound (9): 4,370.

[Production 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 1.01 g of ₃ SO ₂ Cl (manufactured by Wako Pure Chemical Industries) and 1.00 g of triethylamine were added, and the mixture was stirred under a nitrogen atmosphere at room temperature for 4 hours. After the reaction was completed, 15 g of AK-225 was added, and the mixture was washed once with water and a saturated saline solution, and the organic phase was recovered. The collected 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): average value 21 of the number of units x1, average value 20 of the number of units x2, number average molecular weight 4,340.

In a 50 mL eggplant-shaped flask, 15.0 g of the compound (10), 15.0 g of 1,3-bis (trifluoromethyl) benzene (manufactured by Tokyo Chemical Industry Co., Ltd.), and HN (CH ₂ CH = CH ₂ ) ₂ ( 2.27 g of 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 a saturated saline solution, and the organic phase was recovered. Then, the organic phase was mixed with 1.5 g of silica gel, and the organic phase was recovered by filtration with a filter. The collected 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): average value of unit number x1, average value of unit number x2, 20, number average molecular weight 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%) were added. 0.03 g, 1.3 g of HSi (OCH ₃ ) ₃ , 0.01 g of dimethylsulfoxide and 0.5 g of 1,3-bis (trifluoromethyl) benzene (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was heated at 40 ° C. Stirred for 10 hours. After the completion of the reaction, the solvent and the like were distilled off under reduced pressure, and the residue was filtered with a membrane filter having a pore size of 0.2 μm. The compound (12) and the compound (11) in which two allyl groups of the compound (11) were hydrosilylated were obtained. 11.9 g (yield: 92%) of a composition (A-2) composed of a by-product formed by cyclization of the allyl group in the molecule. The conversion 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 H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: 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 , standard: 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 was 21, the average value of the number of units x2 was 20, and the number average molecular weight of the compound (12) was 4,530.

[Production Example A-3]
5.0 g of the 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 in a 50-mL eggplant flask, and stirred for 12 hours. did. From NMR, it was confirmed that all of the compound (6) was converted to the compound (13). Further, methanol as 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): average value 21 of the number of units x1, average value 20 of the number of units x2, number average molecular weight 4,360.

In a 10 mL sample tube made of PFA, 4 g of compound (13) and 0.1 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%). 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 Chemical Industry Co., Ltd.) were added, and the mixture was added at 40 ° C. for 10 hours. Stirred. After completion of the reaction, the solvent and the like were distilled off under reduced pressure, and the residue was filtered with 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);
^{2. 1} H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.75 (6H), 1.3 to 1.6 (12H), 3.4 (2H), 7 (27H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −52.4 to −55.8 (42F), −82.2 (3F), −89.4 to -91.1 (92F), -130.8 (2F).
Average value of the number of units x1, 21; average value of the number of units x2: 20, number average molecular weight of compound (A-3): 4,720.

[Production Example A-4]
In a 300 mL three-necked flask, 15.0 g of dipentaerythritol (manufactured by ACROS), 29.5 g of a 48% aqueous NaOH 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. After washing once with a dilute hydrochloric acid aqueous 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 collect 5.3 g of the compound (14) and 6.0 g of the compound (15).

1.0 g of the compound (14), 0.4 g of 2,6-lutidine, and 5 g of AE-3000 were placed in a 50 mL two-necked eggplant flask. The mixture was stirred while being cooled 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 hydrochloric acid aqueous solution, and the organic phase was recovered. The recovered solution was concentrated by an evaporator to obtain a crude product. The crude product was expanded to silica gel column chromatography, HO- compound (14) _CF 3 SO ₃ - was fractionated 1.2g of the converted compound (16).

In a 50 mL eggplant-shaped flask, 1.0 g of the compound (16), 6.6 g of the compound (17) obtained by the method described in Production Example 6 of WO2015 / 087902, 2.7 g of cesium carbonate, Then, 6.6 g of 2,3-bis (trifluoromethyl) benzene was added, and the mixture was stirred at 80 ° C. under reflux for 4 hours. AE-3000 (10 g) was added, and the mixture was washed once with a dilute hydrochloric acid aqueous solution to recover an organic phase. The recovered solution was concentrated by 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 the compound (18) converted to _2- O- was collected.
_{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%) were added. 0.03 g, 1.2 g of trimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.01 g of dimethyl sulfoxide and 0.9 g of 1,3-bis (trifluoromethyl) benzene were added, and the mixture was stirred at 40 ° C. for 4 hours. did. The solvent and the like were distilled off under reduced pressure, and the residue was filtered with a membrane filter having a pore size of 0.2 μm to obtain 6.4 g of Compound (A-4) in which five allyl groups of Compound (18) were hydrosilylated. The conversion of the hydrosilylation was 100%, and the 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).

[Production Example A-5]
In the same manner as in Production Example A-4 except that the compound (15) obtained in Production Example A-4 was used instead of the compound (14), all of the two HO— of the compound (15) were CF ₃ SO Compound (19) converted to _3- was obtained. Next, in the same manner as in Production Example A-4 (3) except that the compound (19) was used instead of the compound (16), all of the two CF ₃ SO ₃ — of the compound (19) were 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, in the same manner as in Production Example A-4 except that compound (20) was used instead of compound (18), compound (A-5) in which four allyl groups of compound (20) were hydrosilylated was used. 6.4 g were 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).

[Production Example B-1]
According to the method described in Example 6 of WO 2013/121984, compound (B-1) 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 -CONHCH 2 CH 2 CH 2 -Si (OCH 3) ₃ ... (B-1)
Compound (B-1): average number of units × 3, number average molecular weight 4,870.

[Production Example B-2]
Compound (21) was obtained according to the method described in Example 7 of WO 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): average number of units × 3, number average molecular weight 4,700.

Production Example A-2 except that the compound (7) was changed to the 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 number of units x 3 13, number average molecular weight 4,830.

Compound (10) was replaced with compound (22) in the same manner as in Production Example A-2 except that 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. Thus, 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 number of units × 3 13, 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. The compound (24) in which two allyl groups of (23) are hydrosilylated and the composition (B-2) comprising by-products formed by cyclization of two allyl groups in a compound (23) in a molecule. 11.8 g (94% yield) was obtained. The conversion 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 H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: 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 , standard: 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.

[Production Example B-3]
According to the method described in Example 6 of WO 2013/121984, compound (25) 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) OCH 3 ··· (25)
Compound (25): average number of units × 3 = 13, 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. Thus, 7.6 g (yield 84%) of the compound (26) 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 = CH ₂ ) ₃ (25)
Compound (26): average number of units × 3 13, number average molecular weight 4,800.

Compound (13) was added to 6.0 g of compound (26), the amount of the platinum complex solution was set to 0.07 g, the amount of HSi (OCH ₃ ) ₃ was set to 0.78 g, and the amount of dimethyl sulfoxide was set to 0.02 g. 6.7 g of compound (B-3) was prepared in the same manner as in Production Example A-3 except that the amount of 1,3-bis (trifluoromethyl) benzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was changed to 0.49 g. Yield 100%).
_{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 H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: 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 , standard: 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).
Average value of the number of units x3: 13, number average molecular weight of compound (B-3): 5,400.

[Production Example B-4]
Instead of the compound (17), a compound (27) (average value of m25: 13, number average molecular weight: 4,700) obtained by the method described in Example 7 of WO 2013/121984 was used. Except for the above, the compound (16) was prepared in the same manner as in Production Example A-4 except that CF ₃ SO ₃ — was 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. Compound (28) converted to CF ₂ —CH ₂ —O— was obtained. Next, in the same manner as in Production Example A-4 except that compound (28) was used instead of compound (18), compound (B-4) in which five allyl groups of compound (28) were hydrosilylated was used. 6.3 g were 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).

[Production Example B-5]
In the same manner as in Production Example A-5 except that the compound (27) was used instead of the compound (17), all of the two CF ₃ SO ₃ — of the compound (19) were CF ₃ CF ₂ CF ₂ OＣＦ ( obtain _{CF 2 O) m21 (CF 2} CF 2 O) m22} CF 2 -CH 2 -O- in the converted compound (29). Next, in the same manner as in Production Example A-4 except that compound (29) was used instead of compound (18), compound (B-5) in which four allyl groups of compound (29) were hydrosilylated was used. 6.1 g were 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 substrate was performed by the following dry coating method to obtain the article of Example 1. Chemically strengthened glass was used as a substrate. The resulting articles were evaluated for durability 1 (the number of times that the contact angle was maintained at 100 ° or more), lubricity, and durability 2 (the dynamic friction coefficient was not easily reduced). The results are shown in Tables 3 to 5.

(Dry coating method)
Dry coating was performed using a vacuum evaporation apparatus (manufactured by Showa Vacuum Co., SGC-22WA) (vacuum evaporation method). 35 mg of the composition was charged into a molybdenum boat in a vacuum evaporation apparatus, and the inside of the vacuum evaporation apparatus was evacuated to 5 × 10 ⁻³ Pa or less. The boat on which the composition was placed was heated to deposit the composition on the surface of the substrate, thereby forming a vapor-deposited film on the surface of the substrate. The substrate on which the deposited film was formed was left overnight at a temperature of 25 ° C. and a humidity of 40% to obtain an article having a surface layer on the surface of the substrate.

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

Durability 1 (maintenance times of contact angle 100 ° or more)

Lubricity (dynamic friction coefficient)

Durability 2 (hard to decrease dynamic friction coefficient)

  The compositions of Examples 1 to 5, 7 to 11, 13 to 17, 19 to 23, and 25 to 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 which the compound (C-1) was combined, the durability and the lubricity were excellent. Further, the lubricating property was superior to those of Examples 31 to 35 using compound (B) alone. In addition, as the number of groups (I) in each of the compound (A) and the compound (B) increases, the durability tends to be improved.

(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 a substrate was prepared by the dry coating method. An article was obtained by forming a surface layer of the above, and the obtained article was evaluated. Table 6 shows the results.
In addition, each composition was subjected to surface treatment of a substrate by the following wet coating method to obtain an article. Chemically strengthened glass was used as a substrate. The obtained article was evaluated for durability 1 and lubricity. Table 7 shows the results.

(Wet coating method)
Each composition obtained in Examples 41 to 50 was mixed with C ₄ F ₉ OC ₂ H ₅ (manufactured by 3M, Novec (registered trademark) 7200) as a liquid medium to give a solid content of 0.05%. A coating solution was prepared. The substrate was dipped in the coating liquid, left for 30 minutes, and then pulled up (dip coating 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 a substrate was prepared by the dry coating method. An article was obtained by forming a surface layer of the above, and the obtained article was evaluated. Table 8 shows the results.

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

The present composition and the present coating liquid can be used for various applications in which imparting lubricity or water / oil repellency is required. For example, display input devices such as touch panels; surface protection coats made of transparent glass or transparent plastic members, antifouling coats for kitchens; water repellent and moistureproof coats and antifouling coats for electronic equipment, heat exchangers, batteries, etc., and toiletries Antifouling coat; Coating for members requiring liquid repellency while conducting; Water repellent / waterproof / sliding coat of heat exchanger; Vibration sieve, Low friction surface coat inside cylinder, etc.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2017-050558 filed on Mar. 15, 2017 are incorporated herein by reference as the disclosure of the specification of the present invention. It is.

(Group (II))
In the group (II), R ^f1 is a perfluoroalkyl group.
The number of carbon atoms of the perfluoroalkyl group definitive in R ^f1, from the viewpoint of superior lubricity and durability of the surface layer is more preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 6, 1-3 Particularly preferred.
The perfluoroalkyl group may be branched or linear, and is preferably linear. Examples of the linear perfluoroalkyl group include CF ₃ —, CF ₃ CF ₂ —, CF ₃ CF ₂ CF ₂ —, and the like.

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

Q ^a and ^{Q b} are the same as Q in the group (II), preferable embodiments thereof are also the same.
The A chain of R ^fa and the B chain of R ^fb are the same as described above, and 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 preferred embodiments are also the same.
na and nb are the same as n in the group (I), and preferred embodiments are also the same.
Preferred values of ra and rb are respectively the same as the preferred numbers of the A chain of the compound (A) and the B chain of the compound (B). That is, each of ra and rb is preferably an integer of 1 to 3.
Preferred values of s a and s b may compound (A), is similar to the preferred number of compounds (B) groups each having (I). That is, each s a and s b, 1 to 10 integer, more preferably from 2 to 5 integer 3-4 integer are particularly preferred.

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.
When R ^fa is {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 }, R ^42a is typically a _C 1 perfluoroalkylene group.

[Coating liquid]
The coating liquid of the present invention (hereinafter also referred to as the present coating liquid) contains the present composition and a liquid medium. The present coating liquid may be a liquid, may be a solution, or may be a dispersion.
The present coating liquid only needs to include the present composition, and may include impurities such as by-products generated in the production process of the compound (A), the compound (B), and the like.
The concentration of the present 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 present coating solution. % Is particularly preferred.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. Hereinafter, “%” is “% by mass” unless otherwise specified.
Examples 8 to 11, 14 to 17, 20 to 23, 26 to 29, 42 to 49, 52 to 59, 61 to 65 are Examples, and Examples 1 to 5, 7, 13 , 19 , and 25 are Reference Examples. Yes , Examples 6 , 12 , 18 , 24 , 30-41 , 50-51 , 60 , 66-67 are comparative examples.

Claims (15)

Including a fluorinated ether compound (A) and a fluorinated 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,
R is a hydrogen atom or a monovalent hydrocarbon group,
n is an integer of 0 to 2,
When n is 0 or 1, (3-n) Ls 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) in the fluorinated ether compound (A) and the fluorinated ether compound (B) may be the same or different. The fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) are both fluorine-containing ether compounds represented by the following formula (A / B),
R ^f in the fluorinated ether compound (A) is a poly (oxyperfluoroalkylene) chain containing a (CF ₂ O) unit;
The fluorinated ether compound (B) in R ^f is a (CF 2 _O) units does not include the poly (oxyperfluoroalkylene) chains, fluorinated ether composition of claim 1.
_{^{[R f1 -O-Q-R}} f -] r Z [-SiR n L 3-n] s ··· (A / B)
However, R ^f1 is a perfluoroalkyl group,
Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 of the oxyfluoroalkylene groups; The constituent oxyfluoroalkylene groups may all be the same or different,
R ^f is a poly (oxyperfluoroalkylene) chain;
Z is a (r + s) -valent linking group,
—SiR _n L _3-n is a group represented by the above formula (I),
If r is 2 or more, r pieces of ^{[R f1 -O-Q-R} f -] are the same group,
When s is 2 or more, s groups represented by the formula (I) are the same group,
r and s are each an integer of 1 or more, and r + s is 3 to 8. The poly (oxyperfluoroalkylene) chain containing (CF ₂ O) units is a poly (oxyperfluoroalkylene) chain containing (CF ₂ O) units and (CF ₂ CF ₂ O) units. 3. The fluorinated ether composition according to 2. The poly (oxyperfluoroalkylene) chain which does not contain the (CF ₂ O) unit has (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 fluorinated ether composition according to any one of claims 1 to 3, which is a poly (oxyperfluoroalkylene) chain containing at least one selected from 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 fluorinated ether composition according to any one of claims 1 to 4.   6. The method according to claim 1, wherein at least one of the fluorinated ether compound (A) and the fluorinated ether compound (B) has three or more groups represented by the formula (I). 7. A fluorine-containing ether composition.   The method according to any one of claims 1 to 5, wherein both the fluorinated ether compound (A) and the fluorinated ether compound (B) have two or more groups represented by the formula (I). Fluorinated ether composition.   6. The method according to claim 1, wherein both the fluorinated ether compound (A) and the fluorinated ether compound (B) have three or more groups represented by the formula (I). 7. Fluorinated ether composition.   The fluorinated ether composition according to any one of claims 1 to 8, wherein the fluorinated ether compound (A) has a number average molecular weight of 2,000 to 20,000.   The fluorinated ether composition according to any one of claims 1 to 9, wherein the fluorinated ether compound (B) has a number average molecular weight of 2,000 to 20,000.   The fluorinated ether compound (A) is contained in an amount of 10 to 80% by mass based on the total amount of the fluorinated ether compound (A) and the fluorinated ether compound (B). A fluorine-containing ether composition. 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 is a single bond, one or more oxy-fluoroalkylene group containing a hydrogen atom or a polyoxyalkylene fluoroalkylene group 2-5 is formed by bonding of said oxy fluoroalkylene group, the polyoxy All oxyfluoroalkylene groups constituting the fluoroalkylene group may be the same or different,
R ^fa is a poly (oxyperfluoroalkylene) chain containing (CF ₂ O) units,
R ^fb is a poly (oxyperfluoroalkylene) chain containing no (CF ₂ O) unit;
Z ^a is a (ra + sa) -valent linking group,
Z ^b is a (rb + sb) -valent linking group,
L ^a and ^{L b} are hydroxyl group or a hydrolyzable group,
R ^a and R ^b are a hydrogen atom or a monovalent hydrocarbon group,
na and nb are integers of 0 to 2,
(3-na) L ^a when na is 0 or 1 and (3-nb) L ^b when nb is 0 or 1 may be the same or different;
When na is 2, na R ^a , and when nb is 2, nb R ^b may be the same or different,
ra and rb are integers greater than or equal to 1, ra is the ra number when two or more ^{[R f1a -O-Q a -R} fa -] may be different even in the same, rb 2 or when the rb pieces ^{[R f1b -O-Q b -R} fb -] may be the same or different and
sa and sb is an integer of 1 or more, sa is sa number when two or more ^{_{[-SiR a na L a 3-}} na] may be different even in the same, sb 2 or more when sb pieces ^{_{[-SiR b nb L b 3-}} nb] may be be the same or different.   The fluorinated ether composition according to claim 12, comprising 10 to 80% by mass of the fluorinated ether compound (A1) based on the total of the fluorinated ether compound (A1) and the fluorinated ether compound (B1).   A coating liquid comprising the fluorinated ether composition according to any one of claims 1 to 13 and a liquid medium.   An article having a surface layer formed from the fluorinated ether composition according to any one of claims 1 to 13.