WO2018168497A1 - Fluorinated ether composition, coating liquid, and article - Google Patents

Abstract

Provided are a fluorinated ether composition and coating liquid which can form a surface layer having excellent lubricity and durability, and an article having a surface layer having excellent lubricity and durability. This fluorinated ether composition contains a fluorinated ether compound (A) and a fluorinated ether compound (B), wherein the fluorinated ether compound (A) has a poly(oxyperfluoroalkylene) chain containing a (CF₂O) unit, and a group represented by formula (I), and the fluorinated ether compound (B) has a poly(oxyperfluoroalkylene) chain not containing a (CF₂O) unit, and has a group represented by formula (I). Formula (I): -SiR_nL_3-n, wherein L represents a hydroxy group or a hydrolysable group, and R represents a hydrogen atom or a monovalent hydrocarbon group.

Description

Fluorine-containing ether composition, coating liquid and article

The present invention relates to a fluorine-containing ether composition, a coating liquid, and an article.

Fluorine-containing compounds exhibit high lubricity, water and oil repellency, etc., and are therefore used as surface treatment agents. For example, when a surface layer is formed on the surface of the base material by the surface treatment agent, lubricity, water and oil repellency, etc. are imparted, and it becomes easy to wipe off dirt on the surface of the base material, thereby improving dirt removal. Among fluorine-containing compounds, fluorine-containing ether compounds having a poly (oxyperfluoroalkylene) chain in which an ether bond (—O—) is present in the middle of the perfluoroalkyl chain are excellent in the removal of dirt such as fats and oils.

As a fluorine-containing ether compound, one having a hydrolyzable silyl group has been proposed. Such a fluorine-containing ether compound has a performance that prevents water and oil repellency from decreasing even when repeatedly rubbed with a finger (rubbing resistance) and a performance that can easily remove fingerprints attached to the surface by wiping (fingerprint stain removability) Is used for a surface treatment agent of a member constituting a surface touched by a finger of a touch panel, for example, which is required to be maintained for a long period of time.

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

JP 2014-65884 A

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

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

The present invention provides a fluorine-containing ether composition, a coating liquid, and an article having the following configurations [1] to [15].
[1] comprising 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 fluorinated ether compound (B) is a compound having a poly (oxyperfluoroalkylene) chain not containing a (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 hydrolysable group,
R is a hydrogen atom or a monovalent hydrocarbon group,
n is an integer from 0 to 2,
when n is 0 or 1, (3-n) L's may be the same or different;
when n is 2, n Rs may be the same or different;
The groups represented by the formula (I) which each of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) have may be the same or different.

[2] 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 fluorine-containing ether compound (A) is a poly (oxyperfluoroalkylene) chain containing a (CF ₂ O) unit,
The fluorine-containing ether composition according to [1], wherein R ^f in the fluorine-containing ether compound (B) is a poly (oxyperfluoroalkylene) chain not containing a (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 oxyfluoroalkylene groups constituting 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 formula (I),
When r is 2 or more, r [R ^f1 —OQR ^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 the (CF ₂ O) unit is a poly (oxyperfluoroalkylene) chain containing a (CF ₂ O) unit and a (CF ₂ CF ₂ O) unit. [1] or [2] fluorine-containing ether composition.
[4] The poly (oxyperfluoroalkylene) chain not containing the (CF ₂ O) unit is 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). poly (oxyperfluoroalkylene) chains containing at least one selected from _{2 O)} units, [1] or fluorinated ether composition to [3].
[5] The poly (oxyperfluoroalkylene) chain not containing the (CF ₂ O) unit is a poly (oxyperfluoroalkylene) chain containing a (CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) unit. [1] The fluorine-containing ether composition according to any one of [4].
[6] Any of [1] to [5], wherein at least one of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) has three or more groups represented by the formula (I) Such a fluorine-containing ether composition.
[7] Any of [1] to [5], wherein both the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) have two or more groups represented by the formula (I) 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 fluorine-containing ether composition according to any one of [1] to [8], wherein the fluorine-containing ether compound (A) has a number average molecular weight of 2,000 to 20,000.
[10] The fluorine-containing ether composition according to any one of [1] to [9], wherein the fluorine-containing ether compound (B) has a number average molecular weight of 2,000 to 20,000.
[11] Any of [1] to [10], containing 10 to 80% by mass of the fluorinated ether compound (A) based on the total of the fluorinated ether compound (A) and the fluorinated ether compound (B) Such a fluorine-containing ether composition.

[12] A fluorine-containing ether composition comprising the fluorine-containing ether compound (A1) represented by the following formula (A1) and the fluorine-containing ether compound (B1) represented by the following formula (B1).
_{^{[R f1a -O-Q a -R}} fa -] ra Z a [-SiR a na L a 3-na] sa ··· (A1)
_{^{[R f1b -O-Q b -R}} fb -] rb Z b [-SiR b nb L b 3-nb] sb ··· (B1)
^{However, R f1a} and ^{R f1b} is a perfluoroalkyl group,
Q ^a and Q ^b are a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 of the oxyfluoroalkylene groups, All of the oxyfluoroalkylene groups constituting the fluoroalkylene group may be the same or different,
R ^fa is a poly (oxyperfluoroalkylene) chain comprising _(CF 2 O) units,
R ^fb is a poly (oxyperfluoroalkylene) chain that does not contain (CF ₂ O) units;
Z ^a is a (ra + sa) -valent linking group,
Z ^b is a (rb + sb) -valent linking group,
L ^a and L ^b are a 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, respectively.
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 of 1 or more. When ra is 2 or more, ra [R ^f1a -OQ ^a -R ^fa- ] may be the same or different, and rb is 2 or when the rb pieces ^{[R f1b -O-Q b -R} fb -] may be the same or different and
sa and sb 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 Sometimes, the sb [-SiR ^b _nb L ^b _3-nb ] may be the same or different.
[13] The fluorine-containing ether composition according to [12], containing 10 to 80% by mass of the fluorine-containing ether compound (A1) with respect to the total of the fluorine-containing ether compound (A1) and the fluorine-containing ether compound (B1). .
[14] A coating liquid comprising the fluorine-containing ether composition according to any one of [1] to [13] and a liquid medium.
[15] An article having a surface layer formed from the fluorine-containing ether composition of any one of [1] to [13].

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

In the present 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 meanings of the following terms in this specification are as follows.
The “hydrolyzable silyl group” means a group that can form a silanol group (Si—OH) by a hydrolysis reaction. For example, L in the formula (I) is a group that is a hydrolyzable group.
The chemical formula of the oxyperfluoroalkylene group is expressed by describing the oxygen atom on the right side of the perfluoroalkylene group.
“Surface layer” means a layer formed on the surface of a substrate.
“Drying” by applying a coating solution refers to applying a coating solution to a substrate to form a coating film of the coating solution 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) comprises a fluorinated ether compound (A) (hereinafter also referred to as the compound (A)) and a fluorinated ether compound (B) (hereinafter referred to as the “compound”). Compound (B).). The composition does not contain a liquid medium as described later. The present composition may be composed of the compound (A) and the compound (B). As described later, other fluorine-containing ether compounds other than the compound (A) and the compound (B), the compound (A), the compound ( Impurities other than B) and other fluorine-containing ether compounds may be contained.
The compound (A) has a poly (oxyperfluoroalkylene) chain (hereinafter also referred to as A chain) containing a (CF ₂ O) unit, and a group (I).
The compound (B) has a poly (oxyperfluoroalkylene) chain (hereinafter also referred to as B chain) that does not contain a (CF ₂ O) unit, and a group (I). Compound (B) does not have an A chain.
-SiR _n L _3-n (I)
However, L is a hydroxyl group or a hydrolysable group,
R is a hydrogen atom or a monovalent hydrocarbon group,
n is an integer from 0 to 2,
when n is 0 or 1, (3-n) L's may be the same or different;
when n is 2, n Rs may be the same or different;
The groups (I) possessed by 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 compound (A) and compound (B) have group (II), group (II) which each has 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 of the oxyfluoroalkylene groups. All of 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)
However, 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 types of R ^f2 O having different carbon numbers.

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

(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 exist. (M1 + m2) is preferably an integer of 10 to 150, particularly preferably an integer of 20 to 100. If (m1 + m2) is not less than the lower limit of the above range, the lubricity of the surface layer is excellent. If (m1 + m2) is not more 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 is reduced, and durability is lowered.

The ratio of m1 to m2 (m1 / m2) is preferably 100/0 to 30/70, particularly preferably 90/10 to 40/60. There exists a tendency for the lubricity of a surface layer to be excellent, so that the ratio of m1 is high within the said range.

(CF ₂ O) _m1 (R ^f2 O) In _m2 , when m2 is 1 or more, that is, when two or more oxyperfluoroalkylene groups having different carbon numbers are present, each oxyperfluoroalkylene group (m1 CF ₂ The bonding order of O and m2 ^Rf2O ) is not limited. For example, each oxyperfluoroalkylene group may be arranged randomly, alternately, or in blocks. In particular, the (CF ₂ O) unit and the (R ^f2 O) unit are preferably arranged at random.
When m2 is 2 or more, (R ^f2 O) _m2 may be composed of two or more types of R ^f2 O having different carbon numbers. The binding order of m2 amino ^{R f2} O is not limited.

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

(B chain)
Examples of the B chain include a poly (oxyperfluoroalkylene) chain including at least one (R ^f3 O) unit represented by the following formula (b1).
(R ^f3 O) _m3 (b1)
However, R ^f3 is a perfluoroalkylene group having 2 or more carbon atoms,
m3 is an integer from 2 to 200,
(R ^f3 O) _m3 may be composed of two or more types of R ^f2 O having different carbon numbers,
(R ^f3 O) When _m3 is composed of two or more types 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 linear, and is preferably linear because the lubricity of the surface layer is further improved.
The number of carbon atoms in R ^f3 is preferably 2 to 6 because the durability and lubricity of the surface layer are further improved.

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 not less than the lower limit of the above range, the lubricity of the surface layer is excellent. When m3 is not more than the upper limit of the above range, the durability of the surface layer is excellent. That is, when the number average molecular weight of the compound (B) is too large, the number of groups (I) present per unit molecular weight is reduced, and durability is lowered.

(R ^f3 O) When _m3 is composed of two or more types 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 randomly, alternately, or in blocks.

(R ^f3 O) As the B chain when _m3 is composed of two or more types of R ^f2 O having different carbon numbers, those represented by the following formula (b2) are preferable.
{(CF ₂ CF ₂ O) _m4 (R ^f4 O) _m5 } (b2)
However, R ^f4 is a C ^3-6 perfluoroalkylene group,
m4 is an integer of 1 or more,
m5 is an integer of 1 or more,
(M4 + m5) is an integer of 2 to 200,
The bonding order of m4 CF ₂ CF ₂ O and m5 R ^f4 O is not limited.

R ^f4 is preferably CF ₂ CF ₂ CF ₂ CF ₂ .
The preferred range of (m4 + m5) is the same as m3.
The ratio of m4 to m5 (m4 / m5) is preferably 90/10 to 10/90, particularly preferably 70/30 to 30/70. The higher the ratio of m4 within the above range, the better the lubricity. The higher the ratio of m5 within the above range, 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. The poly (oxyperfluoroalkylene) chain is one or more units in which 1 to 3 units of (CF ₂ CF ₂ O) and 1 to 3 units of (R ^f3 O) are connected in series. It consists of A 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, it 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 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 ₂ O) unit. A chain is preferred. In particular, a poly (oxyperfluoroalkylene) chain containing a (CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) unit is preferable.
Specific examples of preferred B chain include the following (b3) to (b5).
(CF ₂ CF ₂ O) _m13 (b3)
(CF ₂ CF ₂ CF ₂ O) _m14 (b4)
(CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _m15 (b5)
However, m13 and m14 are each an integer of 2 to 200, and m15 is an integer of 1 to 100.
(B5) is a poly (oxyperfluoroalkylene) chain comprising (CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) units, and this poly (oxyperfluoroalkylene) chain is represented by (CF ₂ CF ₂ O ) Units and (CF ₂ CF ₂ CF ₂ CF ₂ O) units may be regarded as a poly (oxyperfluoroalkylene) chain formed by alternately bonding units.

(Group (I))
In 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 the hydrolysis reaction.
Examples of the hydrolyzable group include an alkoxy group, a halogen atom, an acyl group, an isocyanate group (—NCO) and the like. The number of carbon atoms of the alkoxy group is preferably 1 to 4. 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 preferable. L is preferably an alkoxy group having 1 to 4 carbon atoms from the viewpoint of little outgassing during coating and excellent storage stability of the compound (A), and when long-term storage stability of the compound (A) is required. Is particularly preferably an ethoxy group, and a methoxy group is particularly preferred 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, and an allyl group, and a saturated hydrocarbon group is preferable.
The number of carbon atoms of the monovalent hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2 in terms of easy production of the compound (A).

n is preferably 0 or 1, 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, (3-n) L may be the same or different. For example, a part of L may be a hydrolyzable group and the remaining L may be a hydroxyl group.

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

(Group (II))
In group (II), R ^f1 is a perfluoroalkyl group.
The number of carbon atoms of the perfluoroalkyl group in R ^f1 is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, and particularly preferably 1 to 3 from the viewpoint of further excellent lubricity and durability of the surface layer. preferable.
The perfluoroalkyl group may be branched or linear, 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 group. . In the polyoxyfluoroalkylene group, the plurality of oxyfluoroalkylene groups are usually bonded in series.
When Q is an oxyfluoroalkylene group containing a hydrogen atom or a polyoxyfluoroalkylene group formed by bonding 2 to 5 of the oxyfluoroalkylene groups, the compound (A) and the compound (B) can be dissolved in a liquid medium. Increases nature. Therefore, the compound (A) and the compound (B) are less likely to aggregate in the coating liquid, and the compound (A) and the compound (B) are less likely to aggregate during the drying process after being applied to the surface of the substrate. The appearance of the surface layer is even better.
The number of carbon atoms in the oxyfluoroalkylene group is preferably 1 to 6, more preferably 2 to 6, still more preferably 2 to 4, and particularly preferably 2 or 3.
The number of hydrogen atoms in the oxyfluoroalkylene group is 1 or more, preferably 2 or more, particularly preferably 3 or more, from the viewpoint of excellent appearance of the surface layer. The number of hydrogen atoms in the oxyfluoroalkylene group is preferably (Q carbon number) × 2 or less, particularly preferably (Q carbon number) or less, from the viewpoint of further excellent water and oil repellency of the surface layer.
The oxyfluoroalkylene group may be branched or linear, and is preferably linear because the lubricity of the surface layer is further improved.
In the polyoxyfluoroalkylene group, 2 to 5 oxyfluoroalkylene groups may all be the same or different.
Q is 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 is 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— (where the left side is bonded to R ^f1 —O). preferable.

The number of the A chain that the compound (A) has and the number of the B chain that the compound (B) has may be one each or two or more. One to three is preferable from the viewpoint of ease of production and handling.
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 group (I) possessed by each of the compound (A) and the compound (B) may be one or two or more. Two or more are preferable and three or more are particularly preferable from the viewpoint that the durability of the surface layer is further improved by increasing the bond with the substrate. 10 or less is preferable, 5 or less is more preferable, and 4 or less is particularly preferable from the viewpoint that the durability of the surface layer is further improved by increasing the density of molecules bonded to the substrate.
Therefore, the group (I) possessed by each of the compound (A) and the compound (B) is preferably 1 to 10, more preferably 2 to 5, and particularly preferably 3 to 4.
When compound (A) and compound (B) have two or more groups (I), each group (I) may be the same or different. In terms of ease of production of the compound (A) and the compound (B), it is preferred 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, it is preferable that the compound (A) 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. . If the number average molecular weights of the compound (A) and the compound (B) are not less than the lower limit of the above range, the lubricity of the surface layer is further improved. If the number average molecular weights of the compound (A) and the compound (B) are not less than the lower limit of the above range, the durability of the surface layer is further improved.
The number average molecular weight (Mn) is measured by the measuring method described in the examples described later.

The compound (A) and the compound (B) are not particularly limited as long as each has the A chain or the B chain and the group (I). For example, it can be appropriately selected from known fluorine-containing ether compounds described in the following documents.
JP 2013-91047 A, JP 2014-80473 A, International Publication No. 2013/042732, International Publication No. 2013/042733, International Publication No. 2013/121984, International Publication No. 2013/121985, International Publication No. 2013/121986, International Publication No. 2014/163004, International Publication No. 2014/175124, International Publication No. 2015/0887902, Japanese Unexamined Patent Publication No. 2013-227279, Japanese Unexamined Patent Publication No. 2013-241369, Japanese Unexamined Patent Publication No. 2013-2013. No. 256643, JP 2014-15609, JP 2014-37548, JP 2014-65884, JP 2014-210258, JP 2014-218639, JP 2015-2000884. Gazette, JP2015-2015 No. 21888, International Publication No. 2013/146112, International Publication No. 2013/187432, International Publication No. 2014/069592, International Publication No. 2015/099085, International Publication No. 2015/166760, Japanese Patent Application Laid-Open No. 2013-144726. Gazette, JP-A No. 2014-77836, JP-A No. 2013-1117012, JP-A No. 2014-214194, JP-A No. 2014-198822, JP-A No. 2015-129230, JP-A No. 2015-196723, JP-A-2015-13983, JP-A-2015-199915, JP-A-2015-199906, etc.

In the present composition, the compound (A) may be a single compound composed of one kind of compound (A) or a mixture composed of two or more kinds of compounds (A).
In the present specification, fluorine-containing ether compounds that are the same compound group except that they have a distribution in the number of repeating oxyperfluoroalkylene groups in the poly (oxyperfluoroalkylene) chain are 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 is a single compound except that it has a distribution in m1 and m2. Let it be a fluorine-containing ether compound.

(Preferable 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 3 or more, more preferably 3 to 5, groups (I). If at least one has three or more groups (I), the durability of the surface layer is more excellent.
When only any one has three or more groups (I), the number of the groups (I) which the other has is 1 or 2, and 2 is preferable from the viewpoint of durability.

In another preferred embodiment of the present composition, both of the compound (A) and the compound (B) have 2 or more, more preferably 3 or more, and further preferably 3 to 5 groups (I). . If both have two or more groups (I), the durability of the surface layer is more excellent.

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

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

Both the compound (A) and the compound (B) are preferably fluorine-containing ether compounds represented by the following formula (A / B). In the following formula (A / B), R ^f of the compound (A) is a poly (oxyperfluoroalkylene) chain containing a (CF ₂ O) unit, and R ^f of the compound (B) is (CF ₂ O) 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 formula (A / B), R ^f1 is the R ^f1 , Q is the Q, and —SiR _n L _3-n is a group represented by the 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 compound (A) and the compound (B).
From the number of poly (oxyperfluoroalkylene) chains and the number of groups (I), r + s is preferably 2 to 13, more preferably 3 to 8, and particularly preferably 4 to 7. 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 [R ^f1 —OQR ^f —] are preferably the same group, and when s is 2 or more, s formula (I) Are preferably the same group.

(Preferred embodiment)
As a preferred embodiment of the present composition, the compound (A) is a fluorinated ether compound (A1) represented by the following formula (A1) (hereinafter also referred to as the compound (A1)), and the compound (B) is represented by the formula: Examples include a fluorine-containing ether compound (B1) represented by (B1) (hereinafter also referred to as compound (B1)). That is, the composition of this aspect contains a compound (A1) and a compound (B1).
_{^{[R f1a -O-Q a -R}} fa -] ra Z a [-SiR a na L a 3-na] sa ··· (A1)
_{^{[R f1b -O-Q b -R}} fb -] rb Z b [-SiR b nb L b 3-nb] sb ··· (B1)
^{However, R f1a} and ^{R f1b} is a perfluoroalkyl group,
Q ^a and Q ^b are a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 of the oxyfluoroalkylene groups, All of the oxyfluoroalkylene groups constituting the fluoroalkylene group may be the same or different,
R ^fa is the A chain;
R ^fb is the 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 a 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, respectively.
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 of 1 or more. When ra is 2 or more, ra [R ^f1a -OQ ^a -R ^fa- ] may be the same or different, and rb is 2 or when the rb pieces ^{[R f1b -O-Q b -R} fb -] may be the same or different and
sa and sb 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 Sometimes, the sb [-SiR ^b _nb L ^b _3-nb ] may be the same or different.

R ^f1a and ^{R f1b} is the same as ^{R f1} of each of said in group (II), preferable embodiments thereof are also the same.
When ra is 2 or more, the ra R ^f1a preferably have the same carbon number, and from the viewpoint of ease of production, are the same group, that is, the group having the same carbon number and the same chemical structure. Is preferred. The 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 — (of two R ^fa (It is not a combination of CF ₃ CF ₂ CF ₂ — and CF ₃ CF (CF ₃ ) —, which have the same carbon number but different chemical structures.)
When rb is 2 or more, it is preferable that rb R ^f1b have the same carbon number, and from the viewpoint of ease of production, the same group, that is, 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), and preferred embodiments are also the same.
The A chain of R ^fa and the B chain of R ^fb are the same as described above, and the preferred embodiments are also the same.
L ^a and L ^b are the same as L in the group (I), and preferred embodiments 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 the same as the preferred numbers of the A chain of the compound (A) and the B chain of the compound (B), respectively. That is, ra and rb are each preferably an integer of 1 to 3.
The preferred values of s1 and s2 are the same as the preferred number of groups (I) that each of the compound (A) and the compound (B) has. That is, each of s1 and s2 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.

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 And (ra + sa) -valent groups, (ra + sa) -valent organopolysiloxane groups, and the like.
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, an aromatic hydrocarbon cyclic group (for example, (ra + sa) from an aromatic hydrocarbon ring such as a benzene ring or a naphthalene ring, or ( rb + sb) a group excluding hydrogen atoms), a group comprising 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 alkyl group bonded thereto, a group having an arylene group such as a phenylene group at or between the carbon atoms of the saturated hydrocarbon group, or a group comprising 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 number of carbon atoms of the unsubstituted hydrocarbon group is preferably 20 or less.
The substituted hydrocarbon group is a group in which part or all of the hydrogen atoms of the hydrocarbon group are substituted with a substituent. Examples of the substituent include a hydroxyl group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and 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 the carbon-carbon atoms and / or the terminal of the hydrocarbon group include an etheric oxygen atom (—O—), a thioetheric sulfur atom (—S—), a nitrogen atom ( —N <), silicon atom (> Si <), carbon atom (> C <), —N (R ¹⁵ ) —, —C (O) N (R ¹⁵ ) —, —OC (O) N (R ¹⁵ )-, -Si (R ¹⁶ ) (R ¹⁷ )-, organopolysiloxane groups, -C (O)-, -C (O) -O-, -C (O) -S- and the like. However, R ¹⁵ is a hydrogen atom, an alkyl group or a phenyl group, and R ¹⁶ to R ¹⁷ are 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 Form 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 used because the surface layer is further excellent in friction resistance and fingerprint stain removability. preferable.

“Compound (A11)”
The compound (A11) is represented by the following formula (A11).
R ^f1a -O-Q ^a -R ^fa -Q ^32a- [C (O) N (R ^33a )] _pa -R ^34a -C [-R ^35a -SiR ^a _na L ^a _3-na ] _3. A11)
^{However, R f1a, Q a, R} fa, R a, L a and na have the same meanings as defined above,
Q ^32a represents 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 (however, one end is bonded to the etheric oxygen atom). Except for 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 end of the alkylene group (provided that the end 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 on the side bonded to ₃ )) and a group having an etheric oxygen atom between carbon-carbon atoms,
R ^35a represents 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 carbon-carbon atoms of
The three [—R ^34a —SiR _na L _3-na ] may be the same or different.

In the compound (A11), in the above formula (A1), ra is 1, sa is 3, and Z ^a is —Q ^32a — [C (O) N (R ^33a )] _pa —R ^34a —C [—R ^35a −] ₃
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 , the fluoroalkylene group having 1 to 20 carbon atoms is preferably a perfluoroalkylene group or a fluoroalkylene group containing one or more hydrogen atoms. The fluoroalkylene group is preferably linear from the viewpoint of friction resistance and lubricity of the surface layer.
Examples of the group having an etheric oxygen atom between the carbon-carbon atoms of the fluoroalkylene group having 2 to 20 carbon atoms include the group (ii) described later.
Q ^32a includes a perfluoroalkylene group having 1 to 20 carbon atoms, a fluoroalkylene group having 1 to 20 carbon atoms containing one or more hydrogen atoms, and a fluoro having 2 to 20 carbon atoms containing one or more hydrogen atoms. 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, examples of Q ^32a include the following groups.
(I) a perfluoroalkylene group.
(Ii) a fluoroalkylene group having R ^F CH ₂ O (wherein R ^F is a C 1-6 perfluoroalkylene group) on the side bonded to R ^fa and containing one or more hydrogen atoms A group having (may have an etheric oxygen atom between carbon-carbon atoms) on the side bonded to C (O) N (R ^33a ).

As Q ^32a of (ii), the following groups are preferred from the viewpoint of durability and lubricity of the surface layer and ease of production of the compound (A11).
-R ^F CH ₂ O-CF ₂ CHFOCF ₂ CF ₂ CF _2- , -R ^F CH ₂ O-CF ₂ CHFCF ₂ OCF ₂ CF _2- , -R ^F CH ₂ O-CF ₂ CHFCF ₂ OCF ₂ CF ₂ CF ₂ —, —R ^F CH ₂ O—CF ₂ CHFOCF ₂ CF ₂ CF ₂ OCF ₂ CF ₂ —.

[C (O) N (R ^33a )] When _pa in the _pa group is 0 and 1, the characteristics of the fluorine-containing ether compound are hardly changed. When pa is 1, it has an amide bond, but at least one fluorine atom is bonded to the carbon atom of the terminal on the side bonded to [C (O) N (R ^33a )] of Q ^32a. The polarity of the amide bond becomes small, and the water / oil repellency of the surface layer is hardly lowered. Whether pa is 0 or 1 can be selected from the viewpoint of ease of production.
The ^{[C (O) N (R} 33a)] R 33a in _pa group, from the standpoint of ease of preparation of the compound (A11), a hydrogen atom is preferable.
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 represents a single bond, —CH ₂ O—, —CH ₂ OCH ₂ —, —CH ₂ OCH ₂ CH ₂ O— from the viewpoint of ease of production of the compound (A11). And a group selected from the group consisting of —CH ₂ OCH ₂ CH ₂ OCH ₂ — (wherein the left side is bonded to Q ³² ) is preferable.
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 easy production of the compound (A11).

R ^35a represents —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ OCH ₂ CH ₂ CH ₂ —, —OCH ₂ CH from the viewpoint of ease of production of the compound (A11). _A group selected from the group consisting of ₂ CH ₂ — (where the right side is bonded to Si) is preferred.
As R ^35a , one having no etheric oxygen atom is particularly preferred from the viewpoint of excellent light resistance of the surface layer. In outdoor touch panels (digital signage such as vending machines and guide plates), in-vehicle touch panels, and the like, the water and oil repellent layers are required to have light resistance.
Three R ^35a in the compound (A11) may be the same or different.

Examples of the compound (A11) include compounds of the following formula. The compound is preferable because it is easy to produce industrially, is easy to handle, and is excellent in water / oil repellency, friction resistance, fingerprint stain removability, lubricity and appearance of the surface layer.

However, W in these formulas is R ^f1a —OQ ^a —R ^fa —. A preferable form of W is a combination of the above-described preferable R ^f1a , Q ^a and R ^fa . A preferable range of Q ^32a is as described above.

“Compound (A12)”
The compound (A12) is represented by the following formula (A12).
R ^f1a -OQ ^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 the terminal of the alkylene group (excluding the terminal bonded to N), A group having an etheric oxygen atom or —NH— between carbon and carbon atoms of an alkylene group of 2 to 6 or 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, the carbon of the alkylene group or an alkylene group having 2 to 6 carbon atoms, having 1 to 6 carbon atoms - a group having an -NH- or etheric oxygen atom between carbon atoms,
Two _{^{[-R 44a -SiR na L 3-}} na] may also be the same or different.

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

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

R ^43a is —CH ₂ —, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ OCH ₂ CH ₂ — and — from the viewpoint of ease of production of the compound (A12). A group selected from the group consisting of CH ₂ NHCH ₂ CH ₂ — (wherein the left side is bonded to R ^42a ) is preferred.
Since R ^43a has a high polarity and does not have an ester bond having insufficient chemical resistance and light resistance, it is excellent in the initial water repellency, chemical resistance and light resistance of the surface layer.

R ^44a is —CH ₂ CH ₂ CH ₂ — and —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ — (provided that the right side is bonded to Si from the viewpoint of ease of production of the compound (A12)). ) Is preferred.
Since R ^44a has a high polarity and does not have an ester bond having insufficient chemical resistance and light resistance, it has excellent initial water repellency, chemical resistance and light resistance of the surface layer.
As R ^44a , one having no etheric oxygen atom is particularly preferred from the viewpoint of excellent light resistance of the surface layer.
Two R ^44a in the compound (A12) may be the same or different.

Examples of the compound (A12) include compounds of the following formula. The compound is preferred because it is easy to produce industrially, is easy to handle, and is further excellent in water / oil repellency, friction resistance, fingerprint stain removability, lubricity, chemical resistance and light resistance.

However, W in these formulas is R ^f1a —OQ ^a —R ^fa —. A preferable form of W is a combination of the above-described preferable R ^f1a , Q ^a and R ^fa . A preferred range for R ^42a is as described above.

“Compound (A13)”
Compound (A13) is represented by the following formula (A13).
[R ^f1a -OQ ^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 group having 2 or more carbon atoms and a (ea + fa) -valent group having one or more etheric oxygen atoms between carbon atoms of the hydrocarbon group,
R ^53a is an alkylene group having 1 to 20 carbon atoms,
ea is an integer greater than or equal to 1,
fa is an integer of 1 or more,
(Ea + fa) is 3 or more,
When ea is 2 or more, ea [R ^f1a -OQ ^a -R ^fa -R ^51a -R ^52a -O-] may be the same 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.

In the compound (A13), in the above formula (A1), ra is ea, sa is fa, Z ^a is [—R ^51a —R ^52a —O—] _ea Z ^3a [—O—R ^53a — It is a compound of _fa .

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. If R ^51a is a straight-chain compound (A13), a surface layer that is superior in friction resistance and lubricity can be formed.

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

R ^f1a —O—Q ^a —R ^fa —R ^51a — is a group having excellent water and oil repellency, durability, fingerprint stain removability, lubricity, and appearance as well as the compound (A13). From the viewpoint of ease of production, the group (R ^f -1) and the group (R ^f -2) are preferable.
_{^{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 ~ 200, m21 amino CF The bonding order of ₂ O and m22 CF ₂ CF ₂ O is not limited.

Z ^3a includes a residue obtained by removing a hydroxyl group from a polyhydric alcohol having (ea + fa) hydroxyl groups.
Specific examples of Z ^3a include a group of the following formula. Z ^3a is preferably a residue obtained by removing a hydroxyl group from a polyhydric alcohol having a primary hydroxyl group from the viewpoint of excellent hydroxyl reactivity. From the viewpoint of easy availability of the raw material, (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.

R ^53a is preferably an alkylene group having 3 to 14 carbon atoms from the viewpoint of easy production of the compound (A13). Furthermore, a by-product in which part or all of the allyl group (—CH ₂ CH═CH ₂ ) is isomerized to the inner olefin (—CH═CHCH ₃ ) during hydrosilylation in the production of the compound (A13) described later is obtained. An alkylene group having 4 to 10 carbon atoms is particularly preferred because it is difficult to form.

Examples of the compound (A13) include compounds (A13-1) to (A13-6) represented by the following formulas. The compound is preferable because it is easy to produce industrially, is easy to handle, and is excellent in water / oil repellency, friction resistance, fingerprint stain removability, lubricity and appearance of the surface layer.

However, W in these formulas is R ^f1a —OQ ^a —R ^fa —. A preferable form of W is a combination of the above-described preferable R ^f1a , Q ^a and R ^fa . A preferred form of R ^51a is as described above.

<Preferred Form of Compound (B1)>
As the compound (B1), the following compound (B11), compound (B12) and compound (B13) are preferable from the viewpoint of further excellent friction resistance and fingerprint stain removability of the surface layer.

“Compound (B11)”
The compound (B11) is represented by the following formula (B11).
^{R f1b -O-Q b -R fb} -Q 32b - [C (O) N (R 33b)] pb -R 34b -C [-R 35b -SiR nb L 3-nb] 3 ··· (B11)
However, R ^f1b , Q ^b , R ^fb , R ^b , L ^b and nb are each as defined above,
Q ^32b represents 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 (however, one end is bonded to the etheric oxygen atom). Except that the fluoroalkylene group whose other end is 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 etheric oxygen at the terminal of the alkylene group (however, the terminal of the side bonded to C [—R ^34b —SiR _nb L _3-nb ] 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 ^34b —SiR _nb L _3-nb ] ₃ and the terminal having a etheric oxygen atom between carbon-carbon atoms.
R ^35b represents 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 carbon-carbon atoms of
The three [—R ^34b —SiR _nb L _3-nb ] may 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 [—R ^35b —] ₃

The group having an etheric oxygen atom between the carbon-carbon atoms of the fluoroalkylene group and the fluoroalkylene group in Q ^32b is respectively the carbon-carbon atom of the fluoroalkylene group and the fluoroalkylene group in Q ^32a in the formula (A11) The same as the group having an etheric oxygen atom.
The number of (CF ₂ O) in Q ^32b is preferably 0 to 3.
Q ^32b is typically a C 1 perfluoroalkylene group when p 1 is 0 and R ^fb is (CF ₂ CF ₂ O) _m 13. When p1 is 0 and R ^fb is (CF ₂ CF ₂ CF ₂ O) _m14, it is typically a _C 2 perfluoroalkylene group. When p1 is 0 and R ^fb is (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _m15, it is typically a linear perfluoroalkylene group having 3 carbon atoms.
R ^33b , pb, R ^34b and R ^35b are the same as R ^33a , pa, R ^34a and R ^35a in the formula (A11), respectively, and preferred embodiments are also the same.

“Compound (B12)”
The compound (B12) is represented by the following formula (B12).
R ^f1b -OQ ^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 the terminal of the alkylene group (excluding the terminal bonded to N), A group having an etheric oxygen atom or —NH— between carbon and carbon atoms of an alkylene group of 2 to 6 or 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, the carbon of the alkylene group or an alkylene group having 2 to 6 carbon atoms, having 1 to 6 carbon atoms - a group having an -NH- or etheric oxygen atom between carbon atoms,
Two [—R ⁴⁴ —SiR _n L _3-n ] may be the same or different.

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

R ^42b , R ^43b and R ^44b are the same as R ^42a , R ^43a and R ^44a in the formula (A12), respectively.
However, R ^42b is typically a C 1 perfluoroalkylene group when R ^fb is (CF ₂ CF ₂ O) _m 13. When R ^fb is (CF ₂ CF ₂ CF ₂ O) _m14, it is typically a _C 2 perfluoroalkylene group. When R ^fb is (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _m15, it is typically a linear perfluoroalkylene group having 3 carbon atoms.

“Compound (B13)”
The compound (B13) is represented by the following formula (B13).
[R ^f1b -OQ ^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 an (eb + fb) -valent hydrocarbon group or a group having 2 or more carbon atoms and an (eb + fb) -valent group having at least one etheric oxygen atom between the carbon atom and the carbon atom of the hydrocarbon group,
R ^53b is an alkylene group having 1 to 20 carbon atoms,
eb is an integer greater than or equal to 1,
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,
When fb is 2 or more, fb [—O—R ^53b —SiR ^b _nb L ^b _3−nb ] may 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 - It is a compound of _fb .

R ^51b , R ^52b , Z ^3b , R ^53b , eb, and fb are the same as R ^51a , R ^52a , Z ^3a , R ^53a , ea, and fa in the formula (A13), respectively.
The R ^f1b —O—Q ^b —R ^fb —R ^51b —R ^52b — group includes a compound and a compound that are superior in terms of water / oil repellency, durability, fingerprint stain removability, lubricity, and appearance of the surface layer ( From the viewpoint of ease of production of B13), the group (R ^f -3) is preferred.
R ^f11 O (CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) _m25 CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ − (R ^f −3)
^{However, R f11} is a linear perfluoroalkyl group with 1 to 20 carbon atoms; m25 is an integer of 1 to 100.

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

Examples of the compound (C) include the compound (C1).
A ³¹ —O—Q ⁵¹ — (R ^F3 O) _m30 — [Q ⁵² —O] _p3 —A ³² ... (C1)
Provided that A ³¹ and A ³² are each independently a perfluoroalkyl group having 1 to 20 carbon atoms; Q ⁵¹ is a single bond having 1 to 6 carbon atoms that does not have a branched structure containing one or more hydrogen atoms. An etheric oxygen atom at the terminal of a fluoroalkylene group having 1 to 6 carbon atoms not having a branched structure containing one or more hydrogen atoms (excluding the terminal on the side bonded to A ³¹ —O) A group having 1 or more, a group having an etheric oxygen atom between carbon-carbon atoms of a C 2-6 fluoroalkylene group not having a branched structure containing one or more hydrogen atoms, or one or more hydrogen atoms A group having an etheric oxygen atom between the terminal of a fluoroalkylene group having 2 to 6 carbon atoms not having a branched structure (excluding the terminal on the side bonded to A ³¹ —O) and the carbon-carbon atom (Provided that the oxygen number is 10 or less); Q ⁵² represents a fluoroalkylene group having 1 to 20 carbon atoms which does not have a branched structure containing one or more hydrogen atoms, or one or more hydrogen atoms. A group having an etheric oxygen atom between carbon-carbon atoms of a fluoroalkylene group having 2 to 6 carbon atoms not having a branched structure (provided that the oxygen number is 10 or less); R ^F3 is a branched structure 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), one produced by a known production method may be used, or a commercially available product may be used. For example, commercial products of compound (C1) in which Q ⁵¹ is a single bond and p3 is 0 include FOMBLIN (registered trademark) M, FOMBLIN (registered trademark) Y, FOMBLIN (registered trademark) Z (above, Solvaiso Lexis), Krytox (registered trademark) (manufactured by DuPont), and Demnam (registered trademark) (manufactured by Daikin Industries).

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

(Composition of this composition)
In the present composition, the content of the compound (A) relative to the total of the compound (A) and the compound (B) (mass ratio of the compound (A) / [compound (A) + 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) within 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) relative 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 the compound (A) and the compound (B) is preferably 50% by mass or more, particularly preferably 80% by mass or more based on the total mass of the present composition. An upper limit is not specifically limited, 100 mass% may be sufficient.

[Coating solution]
The coating liquid of the present invention (hereinafter also referred to as the present coating liquid) includes the present composition and a liquid medium. The coating liquid may be liquid, may be a solution, or may be a dispersion.
This coating liquid should just contain this composition, and may contain impurities, such as a by-product produced | generated by manufacturing processes, such as a compound (A) and a compound (B).
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 liquid. Particularly preferred.

As the liquid medium, an organic solvent is preferable. The organic solvent may be a fluorinated organic solvent, a non-fluorinated 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 Glass Co., Ltd., Asahi Culin (registered trademark) AC-2000), C ₆ F ₁₃ C ₂ H ₅ (Asahi Glass Co., Ltd., Asahi Clin (registered trademark) AC-6000). C ₂ F ₅ CHFCHFCF ₃ (manufactured by Chemers, Bertrell (registered trademark) XF), and the like.
Examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis (trifluoromethyl) benzene.
As the fluoroalkyl ether, a compound having 4 to 12 carbon atoms is preferable. Examples of commercially available products include CF ₃ CH ₂ OCF ₂ CF ₂ H (Asahi Glass Co., Ltd., Asahi Clin (registered trademark) AE-3000), 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), etc. .
Examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
Examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol and the like.
As the non-fluorine-based organic solvent, a compound consisting only of a hydrogen atom and a carbon atom and a compound consisting only of a hydrogen atom, a carbon atom and an oxygen atom are preferable, a hydrocarbon-based organic solvent, an alcohol-based organic solvent, a ketone-based organic solvent, Examples include ether organic solvents and ester organic solvents.
The coating liquid preferably contains 50 to 99.999% by mass of a liquid medium, more preferably 70 to 99.5% by mass, further preferably 90 to 99.5% by mass, and more preferably 99 to 99.99% by mass. It is particularly preferable to contain 9% by mass.

In addition to the present composition and medium, the present coating liquid may contain other components 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 hydrolysis and condensation reaction of the hydrolyzable silyl group.
The content of other components in the coating solution is preferably 10% by mass or less, and particularly preferably 1% by mass or less.

The solid content concentration of the present coating liquid is preferably 0.001 to 50% by mass, more preferably 0.05 to 30%, further preferably 0.05 to 10% by mass, and particularly preferably 0.01 to 1% by mass.
The solid content concentration of the coating liquid is a value calculated from the mass of the coating liquid before heating and the mass after heating 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 and solvent.

[Goods]
The article of the present invention has a surface layer formed from the composition on the surface of the 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 silanol group (Si— OH) is formed, and the silanol group reacts between molecules to form a Si—O—Si bond, or the silanol group chemically reacts with a hydroxyl group (substrate—OH) on the surface of the substrate. A bond (substrate-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 groups (I) of the compound (A) and the compound (B) are hydrolyzed. When L in the group (I) is a hydroxyl group, the above reaction proceeds without undergoing a hydrolysis reaction.

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

(Base material)
The base material in the present invention is not particularly limited as long as it is required to impart lubricity and water / oil repellency. Examples of the material for the substrate include metals, resins, glass, sapphire, ceramics, stones, and composite materials thereof. The glass may be chemically strengthened. A base film such as a SiO ₂ film may be formed on the surface of the substrate.
As a base material, the base material for touchscreens, the base material for displays, and a spectacles lens are suitable, and the base material for touchscreens is especially suitable. The base material for touch panels has translucency. “Having translucency” means that a normal incidence visible light transmittance in accordance with JIS R3106: 1998 (ISO 9050: 1990) is 25% or more. As a material of the base material for touch panels, glass and transparent resin are preferable.

(Product manufacturing method)
The article of the present invention can be manufactured, for example, by the following method.
-The method of obtaining the article | item of this invention by processing the surface of a base material by the dry-coating method using this composition.
A method of obtaining the article of the present invention by applying the coating liquid on the surface of the substrate by a wet coating method and drying it.

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

The temperature during vacuum deposition is preferably 20 to 300 ° C, particularly preferably 30 to 200 ° C.
The pressure during 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. Examples thereof include a coating method.

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

[Function and effect]
Since the present composition and the present coating liquid contain the compound (A) and the compound (B), a surface layer excellent in lubricity and durability can be formed. That is, by forming a surface layer on the surface of the substrate using the present composition or the present coating liquid, excellent initial lubricity, water and oil repellency, and the like are imparted, and the surface is repeatedly formed. Even when rubbed, excellent durability is obtained in which the characteristics are not easily lowered. Further, even if the surface is repeatedly rubbed, the water / oil repellency is unlikely to be lowered, so that the performance of removing fingerprint stains on the surface of the substrate (fingerprint stain removability) can be obtained.
Since the compound (A) contains a (CF ₂ O) unit in the A chain, it has excellent lubricity. On the other hand, it is inferior in durability compared with 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 is excellent in durability. On the other hand, it is inferior in lubricity compared with the case where a (CF ₂ O) unit is included. When these are combined, each excellent characteristic is sufficiently maintained, and both excellent lubricity and durability can be achieved. The reason for this is considered that the durability of the highly durable component (compound (B)) is further enhanced by dispersing the force applied to wear with the highly lubricious component (compound (A)).

[Use]
Therefore, the base material having a surface layer obtained in this manner is suitable as a member constituting the 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 moisture-proof coats for electronic devices, heat exchangers, batteries, etc. Antifouling coating, antifouling coating for toiletries; coating on materials that require liquid repellency while conducting; water repellency / waterproof / sliding coating for heat exchangers; vibration screens, low friction surface coatings inside cylinders, etc. be able to.
More specific examples of use include a front protective plate of a display, an antireflection plate, a polarizing plate, an antiglare plate, or an antireflection coating on the surface thereof, a touch panel of a device such as a mobile phone or a portable information terminal. Various devices with display input devices that operate on the screen with human fingers or palms such as sheets and touch panel displays, decorative building materials around water such as toilets, baths, washrooms, and kitchens, waterproof coating heat exchangers for wiring boards Water / water-proof coating, water-repellent coating for solar cells, waterproof / water-repellent coating for printed wiring boards, waterproof / water-repellent coating for electronic equipment casings and electronic parts, insulation improvement coating for power transmission lines, various filters Water repellent coat, waterproof coat of radio wave absorber and sound absorbing material, bath, kitchen equipment, antifouling coat for toiletries, water repellent / waterproof / slidable 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.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. 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. Examples 6, 12, 18, 24, 30 to 41 , 50 to 51, 60, and 66 to 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 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 greater the water contact angle, the better the water repellency.

(Lubricity)
The dynamic friction coefficient of the surface layer with respect to the artificial skin (Idemitsu Techno Fine Co., Ltd., PBZ13001) was measured using a load variation type frictional wear test system (Shinto Kagaku Co., Ltd., HHS2000), contact area: 3 cm × 3 cm, load: 0.98 N It measured on condition of this. The smaller the dynamic friction coefficient, the better the lubricity.

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

(Durability 2 (difficult to reduce dynamic friction coefficient))
The steel wool bon tester was reciprocated 3,000 times under the condition <Durability 1>, and then the dynamic friction coefficient was measured under the same condition as the <Lubricity>. The smaller the change in the dynamic friction coefficient, the less the outermost surface is damaged by friction and the better the durability.

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

(B-1): Compound (B-1) obtained in Production Example B-1 described later.
(B-2): Composition (B-2) obtained in Production Example B-2 described later.
(B-3): Compound (B-3) obtained in Production Example B-3 described later.
(B-4): Compound (B-4) obtained in Production Example B-4 described later.
(B-5): Compound (B-5) obtained in Production Example B-5 described later.
(B-6): The solvent of “2634 coating” manufactured by Toray Dow Corning was used after being distilled off. _{CF 3 CF 2 CF 2 O (} CF 2 CF 2 CF 2 O) 21 CF 2 CF 2 CH 2 OCH 2 CH 2 CH 2 Si (OCH 3) 3.

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

(A-1) to (A-5), (B-1) to (B-5), (C-1) having a repeating unit of poly (oxyperfluoroalkylene) chain, poly (oxyperfluoroalkylene) chain Table 1 shows the number (hereinafter also referred to as PEPE number), the number of groups (I), and the number average molecular weight (Mn).
Note that the repeating unit “(CF ₂ O) (CF ₂ CF ₂ O)” in (A-1) to (A-5) and (C-1) is a (CF ₂ O) unit and a (CF ₂ CF ₂ ) unit. O) represents 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% KOH aqueous solution, 33 g of tert-butyl alcohol, and 220 g of compound (1) (Solveisolexis, FLUOROLINK (registered trademark) D4000), and CF ₃ CF 29.4 g of ₂ CF ₂ —O—CF═CF ₂ (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere. The organic phase was recovered once by washing with dilute hydrochloric acid aqueous solution and concentrated by an evaporator to obtain 233 g of a crude product. The crude product was separated by development on silica gel column chromatography. As developing solvents, C ₆ F ₁₃ CH ₂ CH ₃ (Asahi Glass Co., Ltd., AC-6000), AC-6000 / CF ₃ CH ₂ OCF ₂ CF ₂ H (Asahi Glass Co., Ltd., AE-3000) = 1/2 ( Mass ratio) and AE-3000 / ethyl acetate = 9/1 (mass ratio) were used in this order. For each fraction, the average value of the structure of the terminal group and the number of structural units (x1, x2) 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 value 21 of unit number x1, average value 20 of unit number x2, number average molecular weight 4,150.
Compound (3): average value 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 (Asahi Glass Co., Ltd., AK-225) were placed, and CF ₃ CF ₂ CF ₂ OCF ( 3.5 g of CF ₃ ) COF was added. The mixture was stirred at 50 ° C. for 24 hours under a nitrogen atmosphere. After removing the sodium fluoride powder with a pressure filter, excess CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COF and AK-225 were distilled off under reduced pressure. The obtained crude product was diluted with C ₆ F ₁₃ H (Asahi Glass Co., Ltd., AC-2000), passed through a silica gel column, and the recovered solution was concentrated with an evaporator to obtain 31.8 g (yield) of compound (4). 98.8%).
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 value 21 of unit number x1, average value 20 of unit number x2, number average molecular weight 4,460.

At the gas outlet of the 1 L nickel autoclave, a cooler kept at 20 ° C., a NaF pellet packed bed and a cooler kept at 0 ° C. were installed in series. A liquid return line for returning the liquid aggregated from the cooler maintained at 0 ° C. to the autoclave was installed.
750 g of ClCF ₂ CFClCF ₂ OCF ₂ CF ₂ Cl (hereinafter also referred to as CFE-419) was placed in the autoclave and stirred while maintaining at 25 ° C. After nitrogen gas was blown into the autoclave at 25 ° C. for 1 hour, 20% fluorine gas was blown in at 25 ° C. and a flow rate of 2.0 L / hour for 1 hour. While blowing 20% fluorine gas at the same flow rate, a solution of 31.0 g of compound (4) dissolved in 124 g of CFE-419 was injected into the autoclave over 4.3 hours. While blowing 20% fluorine gas at the same flow rate, the internal pressure of the autoclave was increased to 0.15 MPa (gauge pressure). 4 mL of a benzene solution containing 0.05 g / mL benzene in CFE-419 was injected into the autoclave while heating from 25 ° C. to 40 ° C., and the benzene solution inlet of the autoclave was closed. After stirring for 15 minutes, 4 mL of the benzene solution was injected again while maintaining 40 ° C., and the injection port was closed. The same operation was repeated three more times. The total amount of benzene injected was 0.17 g. Stirring was continued for 1 hour while blowing 20% fluorine gas at the same flow rate. The pressure in the autoclave was set to atmospheric pressure, and nitrogen gas was blown for 1 hour. The content of the autoclave was 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 value 21 of unit number x1, average value 20 of unit number x2, number average molecular weight 4,550.

In a round bottom flask made of a tetrafluoroethylene-perfluoro (alkoxy vinyl ether) copolymer (hereinafter also referred to as PFA), 30.0 g of compound (5) and 60 g of AK-225 were placed. The mixture was stirred while being cooled in an ice bath, and 2.0 g of methanol was slowly dropped from the 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 value 21 of unit number x1, average value 20 of unit number x2, number average molecular weight 4,230.

In a 100 mL three-necked eggplant flask, 0.18 g of lithium chloride was dissolved in 18.3 g of ethanol. To this was added 25.0 g of compound (6), and while cooling with an ice bath, a solution of 0.75 g of sodium borohydride dissolved in 22.5 g of ethanol was slowly added dropwise. The ice bath was removed and stirring was continued while slowly warming to room temperature. After stirring at room temperature for 12 hours, an aqueous hydrochloric acid solution was added dropwise until the liquid became acidic. 20 mL of AC-2000 was added, washed once with water and once with saturated brine, 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 ( ₂ ) 7)
Compound (7): average value 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 compound (7), 0.21 g of tetrabutylammonium hydrogen sulfate, 1.76 g of BrCH ₂ CH═CH ₂ and 2.6 g of 30% aqueous sodium hydroxide solution were added. In addition, the mixture was stirred at 60 ° C. for 8 hours. After completion of the reaction, 20 g of AC-2000 was added and washed once with dilute hydrochloric acid aqueous solution, and the organic phase was recovered. 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 (yield 98.2%) of compound (8).
CF ₃ CF ₂ CF ₂ —O— (CF ₂ CF ₂ O) (CF ₂ CF ₂ O) {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } —CF ₂ —CH ₂ OCH ₂ CH═CH ₂ ... (8)
Compound (8): average value 21 of unit number x1, average value 20 of unit number x2, number average molecular weight 4,250.

In a 100 mL eggplant flask made of PFA, 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. Add 0.005 g, 0.25 g of HSi (OCH ₃ ) ₃ , 0.005 g of dimethyl sulfoxide and 0.20 g of 1,3-bis (trifluoromethyl) benzene (Tokyo Chemical Industry Co., Ltd.) at 40 ° C. Stir for 4 hours. After completion of the reaction, the solvent and the like were distilled off under reduced pressure and filtered through a membrane filter having a pore size of 0.2 μm, and one of compound (9) and compound (8) in which one allyl group of compound (8) was hydrosilylated. 4.9 g (yield 95%) of a composition (A-1) consisting of a by-product in which the allyl group was isomerized to an inner olefin (—CH═CHCH ₃ ) was obtained. The conversion rate of hydrosilylation was 100%, and the compound (8) did not remain. The hydrosilylation selectivity 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).
Average value of unit number x1: 21, Average value of unit number x2: 20, Number average molecular weight of 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 ₃ SO ₂ Cl (manufactured by Wako Pure Chemical Industries, Ltd.) 1.01 g and triethylamine 1.00 g were added, and the mixture was stirred at room temperature for 4 hours in a nitrogen atmosphere. After completion of the reaction, 15 g of AK-225 was added and washed once each with water and saturated brine to recover the organic phase. The collected organic phase was concentrated with 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 unit number x1, average value 20 of unit number x2, number average molecular weight 4,340.

In a 50 mL eggplant flask, 15.0 g of compound (10), 15.0 g of 1,3-bis (trifluoromethyl) benzene (manufactured by Tokyo Chemical Industry Co., Ltd.), HN (CH ₂ CH═CH ₂ ) ₂ ( 2.27 g of Tokyo Chemical Industry Co., Ltd.) and 0.68 g of triethylamine were added and stirred at 90 ° C. for 24 hours under a nitrogen atmosphere. After completion of the reaction, 15 g of AK-225 was added, washed once each with water and saturated brine, and the organic phase was recovered, mixed with 1.5 g of silica gel, and the organic phase was recovered by filter filtration. The recovered organic phase was concentrated with 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 21 of unit number x1, average value 20 of unit number x2, number average molecular weight 4,280.

In a 100 mL eggplant flask made of PFA, 12.0 g of the compound (11) and a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%) 0.03 g, 1.3 g of HSi (OCH ₃ ) ₃ , 0.01 g of dimethyl sulfoxide and 0.5 g of 1,3-bis (trifluoromethyl) benzene (manufactured by Tokyo Chemical Industry Co., Ltd.) were added at 40 ° C. Stir for 10 hours. After completion of the reaction, the solvent and the like were distilled off under reduced pressure and filtered through a membrane filter having a pore size of 0.2 μm, and two compounds (12) and two compounds (11) in which two allyl groups of compound (11) were hydrosilylated As a result, 11.9 g (yield 92%) of a composition (A-2) comprising a by-product produced by cyclization of the allyl group in the molecule was obtained. The conversion rate of hydrosilylation was 100%, and the compound (11) did not remain. The hydrosilylation selectivity 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 , reference: CFCl ₃ ) δ (ppm): −52.4 to −55.7 (42F), −74.4 (1F), −76.6 ( 1F), -82.2 (3F), -89.4 to -91.1 (90F), -130.5 (2F).
Average value of unit number x1: 21, Average value of unit number x2: 20, Number average molecular weight of compound (12): 4,530.

[Production Example A-3]
In a 50 mL eggplant flask, 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 added and stirred for 12 hours. did. From NMR, it was confirmed that all of the compound (6) was converted to the compound (13). In addition, by-product methanol was generated. 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 unit number x1, average value 20 of unit number x2, number average molecular weight 4,360.

To a 10 mL PFA sample tube, 0.4 g of a compound (13) xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%) was added. 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 10 hours at 40 ° C. Stir. After completion of the reaction, the solvent and the like were distilled off under reduced pressure and filtered through a membrane filter having a pore size of 1.0 μm to obtain 4.3 g (yield 100%) of compound (A-3).
CF ₃ CF ₂ CF ₂ —O— (CF ₂ CF ₂ O) (CF ₂ CF ₂ O) {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } —CF ₂ —C (O) NH—CH ₂ -C [CH ₂ CH ₂ CH ₂ -Si (OCH ₃ ) ₃ ] ₃ (A-3)

NMR spectrum of compound (A-3);
¹ 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 unit number x1: 21; average value of unit number 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 48% NaOH aqueous solution, and 150 g of dimethyl sulfoxide were placed. The mixture was heated to 40 ° C., 39.5 g of 5-bromo-1-pentene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred for 4 hours. 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 collected solution was concentrated by an evaporator to obtain 29.4 g of a crude product. The crude product was developed on silica gel column chromatography to fractionate 5.3 g of compound (14) and 6.0 g of compound (15).

In a 50 mL two-necked eggplant flask, 1.0 g of compound (14), 0.4 g of 2,6-lutidine, and 5 g of AE-3000 were placed. The mixture was stirred while cooling in an ice bath, and 0.5 g of trifluoromethanesulfonic anhydride was slowly added dropwise under a nitrogen atmosphere. The mixture was further stirred for 1 hour and washed once with a dilute hydrochloric acid aqueous solution to recover the organic phase. The collected solution was concentrated with 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 flask, 1.0 g of compound (16), 6.6 g of compound (17) obtained by the method described in Production Example 6 of International Publication No. 2015/088702, 2.7 g of cesium carbonate, 1 , 3-bis (trifluoromethyl) benzene (6.6 g) was added, and the mixture was stirred at 80 ° C. under reflux for 4 hours. 10 g of AE-3000 was added and washed once with a dilute hydrochloric acid aqueous solution to recover the organic phase. The collected solution was concentrated with an evaporator to obtain a crude product. The crude product was expanded to silica gel column chromatography, _CF 3 SO ₃ compound (16) - is _{CF 3 CF 2 CF 2 O {} (CF 2 O) m21 (CF 2 CF 2 O) m22} CF 2 -CH 6.6 g of compound (18) converted to ₂ -O- was 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 eggplant flask made of PFA, 6.0 g of the compound (18) and a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%) 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 stirred at 40 ° C. for 4 hours. did. The solvent and the like were distilled off under reduced pressure and filtered through 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 rate of 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 -in 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 Compound (15) obtained in Production Example A-4 was used in place of Compound (14), the two HO— in Compound (15) were all CF ₃ SO _{3. The} 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), the two CF ₃ SO ₃ — in the compound (19) were all CF ₃ CF to give _{2 CF 2 O {(CF 2} O) m21 (CF 2 CF 2 O) m22} CF 2 -CH 2 -O- in the converted compound (20). Next, 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 was obtained.
Here, the compound (A-5) is a compound in which WR ^51a -in the compound (A13-4) is a group represented by the formula (R ^f -1).

[Production Example B-1]
The compound (B-1) was obtained according to the method described in Example 6 of WO2013 / 121984.
CF ₃ —O— (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _x3 (CF ₂ CF ₂ O) —CF ₂ CF ₂ CF ₂ —CONHCH ₂ CH ₂ CH ₂ —Si (OCH ₃ ) ₃ ... (B-1)
Compound (B-1): average number of units × 3, number average molecular weight 4,870

[Production Example B-2]
The compound (21) was obtained according to the method described in Example 7 of International Publication No. 2013/121984.
CF ₃ —O— (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _{× 3} (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.

Except that Compound (7) was changed to Compound (21), the amount of CF ₃ SO ₂ Cl (manufactured by Wako Pure Chemical Industries, Ltd.) was changed to 0.86 g, and the amount of triethylamine was changed to 1.02 g, Production Example A-2 and 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) _{× 3} (CF ₂ CF ₂ O) —CF ₂ CF ₂ CF ₂ —CH ₂ OSO ₂ CF ₃ (22)
Compound (22): average number of units × 3, number average molecular weight 4,830.

The same procedure as in Production Example A-2 except that Compound (10) was changed to Compound (22), the amount of HN (CH ₂ CH═CH ₂ ) ₂ was changed to 2.08 g, and the amount of triethylamine was changed to 0.63 g. 14.6 g (98% yield) of the 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, number average molecular weight 4,780

The compound (11) was changed to the compound (23), the amount of the platinum complex solution was changed to 0.029 g, and the amount of HSi (OCH ₃ ) ₃ was changed to 1.2 g. A compound (24) in which two allyl groups of (23) are hydrosilylated and a by-product formed by cyclization of two allyl groups of compound (23) in the molecule (B-2) 11.8 g (yield 94%) was obtained. The conversion rate of hydrosilylation was 100%, and the 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).
Average value of number of units × 3: 13, number average molecular weight of compound (24): 5,020.

[Production Example B-3]
The compound (25) was obtained according to the method described in Example 6 of International Publication No. 2013/121984.
CF ₃ —O— (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _x3 (CF ₂ CF ₂ O) —CF ₂ CF ₂ CF ₂ —C (O) OCH ₃ (25)
Compound (25): average number of units × 3, number average molecular weight 4,700.

Same as Production Example A-3, except that Compound (6) was changed to 9.0 g of Compound (25) and the amount of H ₂ N—CH ₂ —C (CH ₂ CH═CH ₂ ) ₃ was changed to 0.45 g. 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, number average molecular weight 4,800.

Compound (13) is 6.0 g of Compound (26), the amount of platinum complex solution is 0.07 g, the amount of HSi (OCH ₃ ) ₃ is 0.78 g, the amount of dimethyl sulfoxide is 0.02 g, 6.7 g of compound (B-3) was obtained in the same manner as in Production Example A-3 except that the amount of 1,3-bis (trifluoromethyl) benzene (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 , reference: CFCl ₃ ) δ (ppm): −55.2 (3F), −82.1 (54F), −88.1 (54F), −90 .2 (2F), -119.6 (2F), -125.4 (52F), -126.2 (2F).
Average value of number of units × 3: 13, number average molecular weight of compound (B-3): 5,400.

[Production Example B-4]
Instead of the compound (17), the compound (27) (average value of m25: 13, number average molecular weight: 4,700) obtained by the method described in Example 7 of International Publication No. 2013/121984 was used. Except for the above, in the same manner as in Production Example A-4, CF ₃ SO ₃ — of the compound (16) is CF ₃ O (CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) _m25 CF ₂ CF ₂ OCF ₂ CF ₂ The compound (28) converted into 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 was obtained.
CF ₃ O (CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) _m25 CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ —CH ₂ —OH (27)
Here, the compound (B-4) is a compound in which WR ^51a -of the compound (A13-3) is a group represented by the formula (R ^f -3).

[Production Example B-5]
Except that the compound (27) was used instead of the compound (17), in the same manner as in Production Example A-5, the two CF ₃ SO ₃ — in the compound (19) were all CF ₃ CF ₂ CF ₂ O {( obtain _{CF 2 O) m21 (CF 2} CF 2 O) m22} CF 2 -CH 2 -O- in the converted compound (29). Next, in the same manner as in Production Example A-4 except that compound (29) was used in place of compound (18), compound (B-5) in which four allyl groups of compound (29) were hydrosilylated was used. 6.1 g was obtained.
Here, the compound (B-5) is a compound in which WR ^51a -in 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 tempered glass was used as the substrate. The obtained article was evaluated for durability 1 (the number of times the contact angle was maintained at 100 ° or more), lubricity and durability 2 (hardness to decrease the dynamic friction coefficient). The results are shown in Tables 3-5.

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

[Examples 2 to 40]
Except having changed the kind and combination of the compound to be used as shown in Table 2, the composition was prepared in the same manner as in Example 1, the surface layer was formed to obtain the article, and the obtained article was evaluated. It was. In the example in which two compounds are combined, the mass ratio of each compound is 50:50. The results are shown in Tables 3-5.

Durability 1 (Number of maintenance with a contact angle of 100 ° or more)

Lubricity (dynamic friction coefficient)

Durability 2 (difficult to reduce 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 to the compositions of Examples 36 to 40 combined with the compound (C-1), the durability and lubricity were excellent. Further, it was superior in lubricity as compared with Examples 31 to 35 in which the compound (B) was used alone. Moreover, the tendency for durability to improve was seen as the number of group (I) which each of a compound (A) and a compound (B) has increased.

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

(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, and the solid content concentration was 0.05%. A coating solution was prepared. The substrate was dipped in the coating solution, and after standing for 30 minutes, the substrate was pulled up (dip coating method). The coated film was dried at 120 ° C. for 30 minutes and washed with AK-225 to obtain an article having a surface treatment layer on the surface of the substrate.

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

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

The present composition and the present coating liquid can be used in various applications that require lubricity and water / oil repellency. For example, display input devices such as touch panels; surface protective coats made of transparent glass or transparent plastic parts, antifouling coats for kitchens; water and water repellent and antifouling coats for electronic devices, heat exchangers, batteries, etc. Antifouling coating; coating on a member that requires liquid repellency while conducting; water-repellent / waterproof / sliding coat of heat exchanger; surface sieve such as vibrating screen or 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 hereby incorporated by reference as the disclosure of the specification of the present invention. It is.

Claims (15)

1. A fluorine-containing ether compound (A) and a fluorine-containing ether compound (B),
   The fluorine-containing ether compound (A) is a compound having a poly (oxyperfluoroalkylene) chain containing a (CF ₂ O) unit and a group represented by the following formula (I):
   The fluorinated ether compound (B) is a compound having a poly (oxyperfluoroalkylene) chain not containing a (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 hydrolysable group,
   R is a hydrogen atom or a monovalent hydrocarbon group,
   n is an integer from 0 to 2,
   when n is 0 or 1, (3-n) L's may be the same or different;
   when n is 2, n Rs may be the same or different;
   The groups represented by the formula (I) which each of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) have may be the same or different.
2. 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 fluorine-containing ether compound (A) is a poly (oxyperfluoroalkylene) chain containing a (CF ₂ O) unit,
   The fluorine-containing ether composition according to claim 1, wherein R ^f in the fluorine-containing ether compound (B) is a poly (oxyperfluoroalkylene) chain not containing a (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 oxyfluoroalkylene groups constituting 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 formula (I),
   When r is 2 or more, r [R ^f1 —OQR ^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 the (CF ₂ O) unit is a poly (oxyperfluoroalkylene) chain containing a (CF ₂ O) unit and a (CF ₂ CF ₂ O) unit. 2. The fluorine-containing ether composition according to 2.
4. The poly (oxyperfluoroalkylene) chain not containing the (CF ₂ O) unit is 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 ₂ O). The fluorine-containing ether composition according to any one of claims 1 to 3, which is a poly (oxyperfluoroalkylene) chain containing at least one selected from units.
5. The poly (oxyperfluoroalkylene) chain that does not include the (CF ₂ O) unit is a poly (oxyperfluoroalkylene) chain that includes a (CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) unit. 5. The fluorine-containing ether composition according to any one of 1 to 4.
6. 6. At least one of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) has three or more groups represented by the formula (I), according to any one of claims 1 to 5. A fluorine-containing ether composition.
7. The fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) both have two or more groups represented by the formula (I) according to any one of claims 1 to 5. Fluorine-containing ether composition.
8. The fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) both have three or more groups represented by the formula (I) according to any one of claims 1 to 5. Fluorine-containing ether composition.
9. The fluorine-containing ether composition according to any one of claims 1 to 8, wherein the fluorine-containing ether compound (A) has a number average molecular weight of 2,000 to 20,000.
10. The fluorine-containing ether composition according to any one of claims 1 to 9, wherein the fluorine-containing ether compound (B) has a number average molecular weight of 2,000 to 20,000.
11. The fluorinated ether compound (A) is contained in an amount of 10 to 80% by mass based on the total of the fluorinated ether compound (A) and the fluorinated ether compound (B). A fluorine-containing ether composition.
12. A fluorine-containing ether composition comprising a fluorine-containing ether compound (A1) represented by the following formula (A1) and a fluorine-containing ether compound (B1) represented by the following formula (B1).
    _{^{[R f1a -O-Q a -R}} fa -] ra Z a [-SiR a na L a 3-na] sa ··· (A1)
    _{^{[R f1b -O-Q b -R}} fb -] rb Z b [-SiR b nb L b 3-nb] sb ··· (B1)
    ^{However, R f1a} and ^{R f1b} is a perfluoroalkyl group,
    Q ^a and Q ^b are a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 of the oxyfluoroalkylene groups, All of the oxyfluoroalkylene groups constituting the fluoroalkylene group may be the same or different,
    R ^fa is a poly (oxyperfluoroalkylene) chain comprising _(CF 2 O) units,
    R ^fb is a poly (oxyperfluoroalkylene) chain that does not contain (CF ₂ O) units;
    Z ^a is a (ra + sa) -valent linking group,
    Z ^b is a (rb + sb) -valent linking group,
    L ^a and L ^b are a 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, respectively.
    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 of 1 or more. When ra is 2 or more, ra [R ^f1a -OQ ^a -R ^fa- ] may be the same or different, and rb is 2 or when the rb pieces ^{[R f1b -O-Q b -R} fb -] may be the same or different and
    sa and sb 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 Sometimes, the sb [-SiR ^b _nb L ^b _3-nb ] may be the same or different.
13. The fluorine-containing ether composition according to claim 12, comprising 10 to 80% by mass of the fluorine-containing ether compound (A1) with respect to the total of the fluorine-containing ether compound (A1) and the fluorine-containing ether compound (B1).
14. A coating liquid comprising the fluorinated ether composition according to any one of claims 1 to 13 and a liquid medium.
15. An article having a surface layer formed from the fluorine-containing ether composition according to any one of claims 1 to 13.