WO2018151055A1 - Fluorine-containing ether composition, coating liquid, and article - Google Patents

Abstract

The present invention provides a fluorine-containing ether composition and a coating liquid with which it is possible to form a surface layer having excellent water droplet slip characteristics, and an article having a surface layer having excellent water droplet slip characteristics. Provided is a fluorine-containing ether composition containing a fluorine-containing ether compound (A) and a fluorine-containing ether compound (B), wherein each of the compound (A) and the compound (B) contains a poly(oxyperfluoroalkylene) chain, a perfluoroalkyl group bonded to one of termini thereof, and a group represented by formula (I), and wherein, in the combination of the compound (A) and the compound (B) contained in the composition, the number of carbon atoms in the perfluoroalkyl group included in the compound (A) is less than the number of carbon atoms in the perfluoroalkyl group included in the compound (B), and the contained amount of the compound (A) is 30-95% by mass relative to the total amount of the compound (A) and the compound (B). In -SiRnL3−n (I), L is a hydroxyl group or a hydrolyzable group, R is a hydrogen atom or a monovalent hydrocarbon group, and n is an integer of 0 to 2.

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.

As the fluorinated ether compound, for example, the following fluorinated ether compounds have been proposed.
1 to 3 groups (α) composed of at least one oxyperfluoroalkylene group having 1 to 2 carbon atoms and 1 to 3 groups (β) composed of at least one oxyperfluoroalkylene group having 3 to 6 carbon atoms Having a poly (oxyperfluoroalkylene) group having at least one terminal of the poly (oxyperfluoroalkylene) chain having a poly (oxyperfluoroalkylene) chain formed by linking two or more of the units A fluorine-containing ether compound having a hydrolyzable silyl group via a linking group (Patent Document 1).
Patent Document 1 discloses a composition containing 95% by mass or more of the fluorine-containing ether compound and a mixture containing two kinds of the fluorine-containing ether compound.

International Publication No. 2013/121984

However, according to the present inventor, it has been found that the surface layer formed by the fluorine-containing ether compound, composition or mixture described in Patent Document 1 has insufficient water droplet sliding properties. In addition, the water drop sliding property is a property in which water drops are likely to slide on an inclined surface (the sliding angle is small or / and the sliding speed is fast).
An object of this invention is to provide the fluorine-containing ether composition and coating liquid which can form the surface layer excellent in water-drop sliding property, and the article | item which has a surface layer excellent in water-drop sliding property.

The present invention provides a fluorine-containing ether composition, a coating liquid, and an article having the following configurations [1] to [15].
[1] A composition comprising a fluorinated ether compound (A) and a fluorinated ether compound (B),
The fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) are each represented by the following formula (I), a poly (oxyperfluoroalkylene) chain, a perfluoroalkyl group bonded to one end thereof, and And a group
In the combination of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) contained in the composition, the carbon number of the perfluoroalkyl group of the fluorine-containing ether compound (A) is Less than the carbon number of the perfluoroalkyl group (B) has,
The fluorine-containing ether compound (A) content is 30 to 95% by mass with respect to the total of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B). Ether 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 perfluoroalkyl group of the fluorine-containing ether compound (A) has 1 to 19 carbon atoms, and the perfluoroalkyl group of the fluorine-containing ether compound (B) has 2 to 20 carbon atoms. [1] A fluorine-containing ether composition.
[3] The perfluoroalkyl group of the fluorine-containing ether compound (A) has 1 carbon, the perfluoroalkyl group of the fluorine-containing ether compound (B) has 2 or 3, or the fluorine-containing ether The fluorinated ether composition according to [1] or [2], wherein the perfluoroalkyl group of the compound (A) has 2 carbon atoms and the fluorinated ether compound (B) has 3 carbon atoms.
[4] The number of the groups represented by the formula (I) that each of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) has is 1 to 3, [1] to [3] Any fluorine-containing ether composition of these.
[5] Any of [1] to [4], wherein each of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) has 1 to 3 poly (oxyperfluoroalkylene) chains. A fluorine-containing ether composition.

[6] 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), and the composition contains in combination with the fluorine-containing ether compound (a) and the fluorine-containing ether compound (B) contained, the carbon number of R ^f in the fluorine-containing ether compound (a), fluorine-containing ether compound in (B) of the R ^f The fluorine-containing ether composition according to [1], which has less carbon number.
_{^{[R f -O-Q-R}} PF -] r Z [-SiR n L 3-n] s ··· (A / B)
However, R ^f is a perfluoroalkyl group, and when r is 2 or more, r perfluoroalkyl groups are the same 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 alkylene groups may all be the same or different,
^RPF 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), and 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 8 or less.
[7] The fluorine-containing ether composition according to [6], wherein r is 1 to 3.
[8] The fluorine-containing ether composition of [6] or [7], wherein s is 1 to 3.

[9] Including 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), A fluorine-containing ether composition characterized in that the amount is 30 to 95% by mass with respect to the total of the fluorine-containing ether compound (A1) and the fluorine-containing ether compound (B1).
[R ^fa -OQ ^a -R ^PFa- ] _r1 Z ^a [-SiR ^a _n1 L ^a _3-n1 ] _s1 (A1)
_{^{[R fb -O-Q b -R}} PFb -] r2 Z b [-SiR b n2 L b 3-n2] s2 ··· (B1)
However, R ^fa and R ^fb are perfluoroalkyl groups, and the number of carbon atoms in R ^fa is less than the number of carbon atoms in R ^fb ,
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, The oxyfluoroalkylene groups constituting may all be the same or different,
R ^PFa and R ^PFb are poly ( ^{oxyperfluoroalkylene} ) chains;
Z ^a is a (r1 + s1) -valent linking group,
Z ^b is a (r2 + s2) -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,
n1 and n2 are integers from 0 to 2,
(3-n1) L ^a when n1 is 0 or 1 and (3-n) L ^b when n2 is 0 or 1 may be the same or different,
When n1 is 2, n1 R ^{a s} , and when n2 is 2, n2 R ^{b s} may be the same or different,
r1 and r2 are integers of 1 or more. When r1 is 2 or more, r1 R ^fa , Q ^a and R ^PFa may be the same or different, and r2 is 2 when r2 is 2 or more. Each of R ^fb , Q ^b and R ^PFb may be the same or different,
s1 and s2 are integers of 1 or more, and when s1 is 2 or more, s1 [-SiR ^a _n1 L ^a _3-n1 ] may be the same or different, and s2 is 2 or more Sometimes s2 [—SiR ^b _n2 L ^b _3-n2 ] may be the same or different.

[10] The fluorine-containing ether composition according to [9], wherein when r1 in the formula (A1) is 2 or more, r1 R ^fas are the same.
[11] The fluorine-containing ether composition according to [9] or [10], wherein when R2 in the formula (A2) is 2 or more, r2 ^Rfb's are the same.
[12] Any of [9] to [11], wherein R ^fa in formula (A1) has 1 to 19 carbon atoms, and R ^fb in formula (B1) has 2 to 20 carbon atoms Fluorine-containing ether composition.
[13] The carbon number of R ^fa in the formula (A1) is 1, the carbon number of R ^fb in the formula (B1) is 2 or 3, or the carbon number of R ^fa in the formula (A1) And the fluorine-containing ether composition according to any one of [9] to [12], wherein R ^fb in formula (B1) has 3 carbon atoms.

[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 the coating liquid of the present invention, it is possible to form a surface layer having excellent water droplet sliding properties.
The article of the present invention has a surface layer that is excellent in water slidability.

In the present specification, a compound represented by the formula (1) is referred to as a compound (1), and a group represented by the formula (I) is referred to as a group (I). The same applies to compounds or groups represented by other formulas.
In addition, 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.

[Fluorine-containing ether composition]
The fluorine-containing ether composition of the present invention (hereinafter also referred to as “the present composition”) comprises a fluorine-containing ether compound (A) (hereinafter also referred to as “compound (A)”) and a fluorine-containing ether compound (B). (Hereinafter also referred to as “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.
Compound (A) and Compound (B) are each a poly (oxyperfluoroalkylene) chain (hereinafter also referred to as “ ^RPF chain”) and a perfluoroalkyl group (hereinafter referred to as “R ^f group”) bonded to one end thereof. And a group represented by the following formula (I) (hereinafter also referred to as “group (I)”).

-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 R may be the same or different.

The number of carbon atoms in the R ^f group that the compound (A) has is less than the number of carbon atoms in the R ^f group that the compound (B) has. That is, this composition contains 2 types from which carbon number of ^Rf group differs as a fluorine-containing ether compound which has ^RPF chain ^| strand, ^Rf group, and group (I). Thereby, the water droplet sliding property of a surface layer is excellent.
The ^RPF chain and group (I) possessed by each of the compound (A) and the compound (B) may be the same or different.

(R ^f group)
The number of carbon atoms in the R ^f group 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 improving the lubricity and friction resistance of the surface layer.
Thus, compound (A) ^{R f} carbon atoms 1 to 19 groups having preferably a carbon number of ^{the R f} group to the compound (B) has is 2 ~ 20, ^{the R f} group having compound (A) carbon atoms 1-9, more preferably carbon number of ^{the R f} group is 2 to 10 compound (B) has, compound the carbon number of ^{the R f} group (a) has 1 to 5, compound ( more preferably carbon number of ^the R ^f group is 2 to 6 B) has, compound (number of carbon atoms in ^the R ^f group is 1 a) has a carbon number of ^the R ^f group to the compound (B) has 2 It is particularly preferable that the number of carbon atoms in the R ^f group of the compound (A) is 2, and the number of carbon atoms of the R ^f group in the compound (B) is 3.
The R ^f group may be branched or linear, and is preferably linear. Examples of the R ^f group include CF ₃ —, CF ₃ CF ₂ —, CF ₃ CF ₂ CF ₂ — and the like, and CF ₃ —, CF ₃ CF ₂ — are particularly preferable.

The number of R ^f groups that the compound (A) has is the same as the number of R ^PF chains. If the compound (A) has two or more R ^f group may be all the ^the R ^f group has optionally substituted by one or more identical radicals, preferably identical radicals.
Similarly, the number of R ^f groups that compound (B) has is the same as the number of R ^PF chains. When the compound (B) has two or more R ^f group may be all the ^the R ^f group has optionally substituted by one or more identical radicals, preferably identical radicals.
However, the number of carbon atoms of the most common ^the R ^f group with the carbon number of ^the R ^f group to compound (A) is, than the number of carbon atoms in the least ^the R ^f group with the carbon number of ^the R ^f group to the compound (B) has Few.

Examples of the combination of ^the R ^f group, compound (A) having ^{the R f} group is CF ₃ -, the compound (B) ^{the R f} group having there is _CF 3 CF ₂ - a combination of the ^{the R f} group to compound (A) CF ₃ -, the compound (B) ^{the R f} group having there is _CF 3 _CF 2 CF ₂ - a combination of the compound (a) ^{the R f} group having there is _CF 3 CF ₂ -, is ^{the R f} group having compound (B) A combination of CF ₃ CF ₂ CF ₂ — is preferable, and a combination of CF ₃ — as the R ^f group of the compound (A) and CF ₃ CF ₂ — as the R ^f group of the compound (B) is particularly preferable.

The ^Rf group is typically attached to one end of the ^RPF chain via a linking group.
As the linking group, group (II) is preferred. That is, it is preferable that the R ^f group is bonded to one end of each ^RPF chain of each of the compound (A) and the compound (B) via the group (II). However, the left side of the group (II) is bonded to the ^Rf group.
-OQ- (II)
Q represents a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 (preferably 2 to 4) of the oxyfluoroalkylene groups. It is. All of the oxyfluoroalkylene groups constituting the group may be the same or different.

When Q is an oxyfluoroalkylene group having a hydrogen atom or a polyoxyfluoroalkylene group formed by bonding 2 to 5 of the oxyfluoroalkylene groups, the compound (A) and the compound (B) into the liquid medium Solubility increases. 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 of the oxyfluoroalkylene group in Q is preferably 2 to 6, 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 an oxyfluoroalkylene group having no branched structure or an oxyfluoroalkylene group having a branched structure. An oxyfluoroalkylene group having no branched structure is preferable from the viewpoint of further excellent wear resistance and lubricity of the surface layer.
In a group formed by bonding 2 to 5 oxyfluoroalkylene groups, 2 to 5 oxyfluoroalkylene groups may be the same or different.
Q is a single bond or —CHFCF ₂ OCH ₂ CF ₂ O—, —CF ₂ CHFCF ₂ OCH ₂ CF ₂ O—, — 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 CH ₂ A group selected from the group consisting of 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 O) is preferred.

(R ^PF chain)
The R ^PF chain, for example, the ^{R PF} chain represented by the following formula (1).
(R ^F O) _m1 (1)
Where R ^F is a perfluoroalkylene group,
m1 is an integer from 2 to 200,
(R ^F O) _m1 may be composed of two or more R ^F Os having different carbon numbers.

The number of carbon atoms in R ^F is, from the viewpoint of further excellent abrasion resistance and fingerprint removal of the surface layer is preferably 1 to 6, more preferably 1 to 4, from the viewpoint of further excellent lubricity of the surface layer, One to two is particularly preferred, and a perfluoroalkylene group having 3 to 4 carbon atoms is particularly preferred from the viewpoint of further improving the friction resistance of the surface layer.
R ^F may be branched or linear, and is preferably linear because the surface layer is further excellent in friction resistance and lubricity.

M1 is an integer of 2 to 200, preferably an integer of 5 to 150, particularly preferably an integer of 10 to 80. If m1 is not less than the lower limit of the above range, the water and oil repellency of the surface layer is excellent. If m1 is not more than the upper limit of the above range, the surface layer has excellent friction resistance. That is, when the number average molecular weights of the compound (A) and the compound (B) are too large, the number of groups (I) present per unit molecular weight is reduced, and the friction resistance is lowered.

(R ^F O) In _m1 , when two or more types of R ^F O having different carbon numbers exist, the bonding order of each R ^F O is not limited. For example, if the two R ^{F O} are present, the two R ^{F O} is random, alternating, or may be arranged in blocks.

As (R ^F O) _m1 , {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 }, (CF ₂ CF ₂ ) from the point that the surface layer is further excellent in friction resistance, fingerprint stain resistance, and lubricity. O) _m13 , (CF ₂ CF ₂ CF ₂ O) _m14 , (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _m15 are preferred, and {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 }, (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _m15 is more preferred, and (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _m15 is particularly preferred.
Here, m11 is an integer of 1 or more, m12 is an integer of 1 or more, (m11 + m12) is an integer of 2 to 200, and the bonding order of m11 CF ₂ O and m12 CF ₂ CF ₂ O Is not limited. m13 and m14 are each an integer of 2 to 200, and m15 is an integer of 1 to 100. m15 is preferably an integer of 2 to 100.

The compound (A) and the compound (B) each may have one ^RPF chain or two or more ^RPF chains. From the viewpoint of friction resistance, 1 to 3 is preferable, and 1 to 2 is particularly preferable. When the number of ^RPF chains, and thus the number of ^Rf groups, is 1 or more, the surface layer is excellent in water droplet sliding property, water / oil repellency, durability, fingerprint stain removability, and lubricity. If the number of ^RPF chains is not more than the upper limit of the above range, the appearance of the surface layer is excellent.
Compound (A), compound (B) may have two or more R ^PF chain, each R ^PF chain may be the same or different.

(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. As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable.

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) and the compound (B). 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 that the outgassing during coating is small and the storage stability of the compound (A) and the compound (B) is excellent, and the compound (A) and the compound (B) An ethoxy group is particularly preferred when long-term storage stability is required, 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 monovalent hydrocarbon groups include saturated hydrocarbon groups such as alkyl groups and cycloalkyl groups, alkenyl groups such as allyl groups, and the like, and saturated hydrocarbon groups are preferred.
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) and the compound (B).

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.

The group (I) possessed by each of the compound (A) and the compound (B) may be one or two or more. One to three is preferable from the viewpoint of further excellent water droplet sliding property of the surface layer, and two or three is particularly preferable from the viewpoint of further excellent friction resistance of the surface layer.
When the compound (A) and the compound (B) have two or more groups (I), all of the groups (I) may or may not be the same group. In terms of ease of production of the compound (A), it is preferred that all are the same group.

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 2,500 to 15,000, and particularly preferably 3,000 to 10,000. . When the number average molecular weight is within the above range, the friction resistance is excellent.
The number average molecular weight (Mn) is measured by the measuring method described in the examples described later.

When the surface layer is formed by a dry coating method, it is preferable that the difference between the number average molecular weight (Mn) of the compound (A) and the number average molecular weight (Mn) of the compound (B) is small. In the case of the dry coating method, 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 2,000 or less, and particularly preferably 1,000 or less.
When the surface layer is formed by a 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.
The dry coating method and the wet coating method will be described in detail later.

The compound (A) and the compound (B) are not particularly limited as long as each has an ^RPF chain, an ^Rf group and a group (I). For example, it can be appropriately selected from known fluorine-containing ether compounds such as fluorine-containing ether compounds and commercially available 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.

R ^PF chain has ^{the R f} group and a group (I), ^{the R f} group is CF ₃ - Examples of the fluorine-containing ether compound is is manufactured by Daikin Industries, Ltd. of Optool (registered trademark) UD509, manufactured by Shin-Etsu Chemical Co., Examples thereof include KY-178, KY-185, and KY-1900 manufactured by the same company.
Examples of fluorine-containing ether compounds having an ^RPF chain, an R ^f group and a group (I), and the R ^f group is CF ₃ CF ₂ CF ₂ — include OPTOOL DSX, AES and Toray Dow manufactured by Daikin Industries, Ltd. Examples include DOW CORNING (registered trademark) 2634 COATING manufactured by Corning, and KY-108 manufactured by Shin-Etsu Chemical Co., Ltd.
Among these, this composition contains a fluorine-containing ether compound which is CF _3- as the compound (A) and a fluorine-containing ether compound whose R ^f group is CF ₃ CF ₂ CF _2- as the compound (B). It may be.

In the present composition, each of the compound (A) and the compound (B) may be a single compound composed of one kind of compound or a mixture composed of two or more kinds of compounds.
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 a compound in which the R ^PF chain is {(CF ₂ O) _m11 (R ^f2 O) _m12 }, the same compound group except that it has a distribution in m11 and m12 includes a fluorine-containing ether compound that is a single compound. To do.

As the compound (A) and the compound (B), a fluorine-containing ether compound represented by the following formula (A / B) is preferable.
R ^f in the following formula (A / B) represents the R ^f group, and in the combination of the compound (A) and the compound (B) contained in the present composition, the carbon of R ^f in the compound (A) The number is smaller than the carbon number of R ^f in the compound (B). R ^PF represents the R ^PF chain, and Q and SiR _n L _3-n are the same as those described above.
_{^{[R f -O-Q-R}} PF -] r Z [-SiR n L 3-n] s ··· (A / B)
However, R ^f is a perfluoroalkyl group, and when r is 2 or more, r perfluoroalkyl groups are the same 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 alkylene groups may all be the same or different,
^RPF 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), and 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 8 or less.

The r represents the number of ^RPF chains, and thus the number of ^Rf groups, and is an integer of 1 or more. As described above, r is preferably 1 to 3, and particularly preferably 1 to 2, from the viewpoint of friction resistance.
The above s represents the number of groups (I), and as described above, 1 to 3 is preferable from the viewpoint of further excellent water droplet sliding properties of the surface layer, and 2 or 3 from the viewpoint of further excellent friction resistance of the surface layer. Is particularly preferred.
In view of the above, r + s is preferably 2 to 6, and particularly preferably 3 to 5.
Z as the (r + s) -valent linking group is preferably a linking group represented by Z ^a or Z ^b described later, for example, a carbon atom of a substituted or unsubstituted hydrocarbon group or a substituted or unsubstituted hydrocarbon group. A group having a group or atom other than a hydrocarbon group, or an organopolysiloxane group between carbon atoms or / and at the terminal may be mentioned. Preferred Z is the same linking group as preferred ^{Z a} and ^{Z b} below.

<Preferred embodiment>
In 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 “compound (A1)”), and the compound (B) Is a fluorine-containing ether compound (B1) represented by the following formula (B1) (hereinafter also referred to as “compound (B1)”). That is, the composition of this embodiment includes the compound (A1) and the compound (B1), and the content of the compound (A1) is 30 to 95 mass with respect to the total of the compound (A1) and the compound (B1). %.

[R ^fa -OQ ^a -R ^PFa- ] _r1 Z ^a [-SiR ^a _n1 L ^a _3-n1 ] _s1 (A1)
_{^{[R fb -O-Q b -R}} PFb -] r2 Z b [-SiR b n2 L b 3-n2] s2 ··· (B1)
However, R ^fa and R ^fb are R ^f groups, and R ^fa has fewer carbon atoms than R ^fb ,
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, The oxyfluoroalkylene groups constituting may all be the same or different,
R ^PFa and R ^PFb are R ^PF chains;
Z ^a is a (r1 + s1) -valent linking group,
Z ^b is a (r2 + s2) -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,
n1 and n2 are integers from 0 to 2,
(3-n1) L ^a when n1 is 0 or 1 and (3-n) L ^b when n2 is 0 or 1 may be the same or different,
When n1 is 2, n1 R ^{a s} , and when n2 is 2, n2 R ^{b s} may be the same or different,
r1 and r2 are integers of 1 or more. When r1 is 2 or more, r1 R ^fa , Q ^a and R ^PFa may be the same or different, and r2 is 2 when r2 is 2 or more. Each of R ^fb , Q ^b and R ^PFb may be the same or different,
s1 and s2 are integers of 1 or more, and when s1 is 2 or more, s1 [-SiR ^a _n1 L ^a _3-n1 ] may be the same or different, and when s2 is 2 or more The s2 [—SiR ^b _n2 L ^b _3-n2 ] may be the same or different.

The R ^f group is the same as described above, and the preferred embodiment is also the same.
When r1 is 2 or more, it is preferable that r1 R ^fas have the same carbon number, and from the viewpoint of ease of production, they are the same group, that is, 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 r1 is 2, two R ^fa are CF ₃ CF ₂ CF ₂ — (the two R ^fa are (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 r2 is 2 or more, it is preferable that r2 R ^fb have the same carbon number, and from the viewpoint of ease of production, it is the same group, that is, a group having the same carbon number and the same chemical structure. Is preferred.
In this embodiment, from the viewpoint of further improving the lubricity and friction resistance of the surface layer, R ^fa preferably has 1 to 19 carbon atoms and R ^fb has 2 to 20 carbon atoms, and R ^{fa has} a carbon number of Is more preferably 1 to 9, and R ^fb has 2 to 10 carbon atoms, R ^fa has 1 to 5 carbon atoms, R ^fb has 2 to 6 carbon atoms, and R ^fa has 2 to 6 carbon atoms. It is particularly preferred that the carbon number is 1, R ^fb has 2 or 3 carbon atoms, or R ^fa has 2 carbon atoms and R ^fb has 3 carbon atoms.

Q ^a and Q ^b are the same as Q in the group (II), and preferred embodiments are also the same.
The R ^PF chains of R ^PFa and R ^PFb 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.
n1 and n2 are the same as n in the group (I), and preferred embodiments are also the same.
The preferable values of r1 and r2 are the same as the preferable number of ^RPF chains that the compound (A) and the compound (B) have. That is, r1 and r2 are preferably 1 to 3 and particularly preferably 1 to 2 from the viewpoint of friction resistance.
The preferred values of s1 and s2 are the same as the preferred number of groups (I) that compound (A) and compound (B) have. That is, s1 and s2 are preferably from 1 to 3, and particularly preferably from 2 to 3, from the viewpoint of excellent water droplet sliding property of the surface layer.

The Z ^a, for example, (r1 + s1) valent substituted or unsubstituted hydrocarbon group, the carbon of a substituted or unsubstituted hydrocarbon group - between carbon atoms and / or at the end, with a group or atom other than a hydrocarbon group (R1 + s1) -valent group, (r1 + s1) -valent organopolysiloxane group, and the like.
Z ^b may be the same as Z ^a except that the valence is (r2 + s2).

Examples of the unsubstituted hydrocarbon group include a linear or branched saturated hydrocarbon group, an aromatic hydrocarbon cyclic group (for example, (a + b) hydrogen atoms from an aromatic hydrocarbon ring such as a benzene ring or a naphthalene ring). A group excluding an atom), a group composed of a combination of a linear or branched saturated hydrocarbon group and an aromatic hydrocarbon cyclic group (for example, an alkyl group bonded to the aromatic hydrocarbon cyclic group as a substituent) And groups having an arylene group such as a phenylene group between and / or at the terminal of the saturated hydrocarbon group), and a group formed of a combination of two or more aromatic hydrocarbon cyclic groups. Among these, a linear or branched saturated hydrocarbon group is preferable.
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 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 fa -O-Q a -R PFa} -Q 32a - [C (O) N (R 33a)] p1 -R 34a -C [-R 35a -SiR a n1 L a 3-n1] 3 ··· ( A11)
^{However, R fa, Q a, R} PFa, R a, L a and n1 have the same meanings as defined above,
Q ^32a is a fluoroalkylene group or a group having an etheric oxygen atom between carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms,
R ^33a is a hydrogen atom or an alkyl group,
p1 is 0 or 1,
R ^34a is a single bond, an alkylene group, or a group having an etheric oxygen atom at the end of the alkylene group (provided that C [—R ^35a —SiR ^a _n1 L ^a _3-n1 ] ₃ is bonded to the end); A group having an etheric oxygen atom between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or a terminal of an alkylene group having 2 or more carbon atoms (provided that C [—R ^35a -SiR ^a _n1 L ^a _3-n1 ] ₃ ) and a group having an etheric oxygen atom between carbon-carbon atoms,
R ^35a is an alkylene group, a group having an etheric oxygen atom at the terminal of the alkylene group (excluding the terminal bonded to Si), or an ether between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms. A group having a reactive oxygen atom,
The three [—R ^35a —SiR ^a _n1 L ^a _3-n1 ] may be the same or different.

In the compound (A11), in the above formula (A1), r1 is 1, s1 is 3, and Z is —Q ^32a — [C (O) N (R ^33a )] _p1 —R ^34a —C [ -R ^35a- ] ₃ .

In Q ^32a , the fluoroalkylene group is preferably a perfluoroalkylene group or a fluoroalkylene group containing one or more hydrogen atoms. Accordingly, as Q ^32a , a perfluoroalkylene group, a fluoroalkylene group containing one or more hydrogen atoms, a group having an etheric oxygen atom between carbon-carbon atoms of a perfluoroalkylene group having 2 or more carbon atoms, or one or more Of these, a group having an etheric oxygen atom between carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms containing a hydrogen atom is preferred.

If p1 is 0, the Q ^32a, preferably a perfluoroalkylene group, perfluoroalkylene group preferably has no branched structure. If Q ^32a is a perfluoroalkylene group having no branched structure, the friction resistance and lubricity of the surface layer are further improved.
When p1 is 0, Q ^32a is typically carbon when R ^PFa is {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 } or (CF ₂ CF ₂ O) _m13. When the number 1 is a perfluoroalkylene group and R ^PFa is (CF ₂ CF ₂ CF ₂ O) _m14 , it is typically a C 2 perfluoroalkylene group, and R ^PFa is (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _m15 is typically a straight-chain perfluoroalkylene group having 3 carbon atoms.

When p1 is 1, examples of Q ^32a include the following groups.
(I) a perfluoroalkylene group.
(Ii) a fluoroalkylene group (carbon-carbon having —R ^F CH ₂ O— (wherein R ^F is a perfluoroalkylene group) on the side bonded to R ^PFa and containing one or more hydrogen atoms; A group having an etheric oxygen atom between atoms) on the side bonded to C (O) N (R ³³ ).

As Q ^32a of (ii), the following groups are preferable from the viewpoint of easy 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 —.
According to the compound (A11) in which Q ^32a does not have a branched structure, a surface layer excellent in durability and lubricity can be formed.

[C (O) N (R ^33a )] When _p1 in the _p1 group is 0 and 1, the characteristics of the fluorine-containing ether compound are hardly changed. When p is 1, it has an amide bond, but at least one fluorine atom is bonded to the terminal carbon atom bonded to [C (O) N (R ^33a )] of Q ^32a . The polarity of the amide bond becomes small, and the water and oil repellency of the surface layer is unlikely to decrease. Whether p1 is 0 or 1 can be selected from the viewpoint of ease of manufacture.
The ^{[C (O) N (R} 33a)] R 33a in _p1 groups, from the viewpoint 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 p1 is 0, R ^34a is preferably 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 — (the left side is bonded to Q ^32a ) is preferred.
When p1 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 ^fa —O—Q ^a —R ^PFa —. A preferable form of W is a combination of the above-mentioned preferable R ^fa , Q ^a and R ^PFa . A preferable range of Q ^32a is as described above.

“Compound (A12)”
The compound (A12) is represented by the following formula (A12).
R ^fa —O—Q ^a —R ^PFa —R ^{42 a} —R ^{43 a} —N [—R ^{44 a} —SiR ^a _n1 L ^a _3-n1 ] ₂ ... (A12)
^{However, R fa, Q a, R} PFa, R a, L a and n1 have the same meanings as defined above,
R ^42a is a perfluoroalkylene group,
R ^43a is a single bond, an alkylene group, a group having an etheric oxygen atom or —NH— at the end of the alkylene group (excluding the end bonded to N), or a carbon of an alkylene group having 2 or more carbon atoms. A group having an etheric oxygen atom or —NH— between carbon atoms, or an alkylene group having 2 or more carbon atoms (excluding the terminal on the side bonded to N) and an etheric group between carbon and carbon atoms A group having an oxygen atom or -NH-,
R ^44a is an alkylene group or a group having an etheric oxygen atom or —NH— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms;
Two [—R ^44a —SiR ^a _n1 L ^a _3-n1 ] may be the same or different.

The compound (A12) is a compound in which, in the above formula (A1), r1 is 1, s1 is 2, and Z is —R ^42a —R ^43a —N [—R ^44a —] ₂ .

R ^42a is preferably a perfluoroalkylene group having no branched structure. If R ^42a is a perfluoroalkylene group having no branched structure, the friction resistance and lubricity of the surface layer are further improved.
R ^42a is ^typically a C 1 perfluoroalkylene group when R ^PFa is {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 } or (CF ₂ CF ₂ O) _m13. When R ^PFa is (CF ₂ CF ₂ CF ₂ O) _m14 , it is typically a perfluoroalkylene group having 2 carbon atoms, and R ^PFa is (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF _{2 O)} is when an _m15 is typically a perfluoroalkylene group linear 3 carbon atoms.

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 — or —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ — (where 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.
The two R ^44a in the compound (A12) may be the same group or not the same group.

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 ^fa —O—Q ^a —R ^PFa —. A preferable form of W is a combination of the above-mentioned preferable R ^fa , Q ^a and R ^PFa . A preferred range for R ^42a is as described above.

“Compound (A13)”
Compound (A13) is represented by the following formula (A13).
[R ^fa -OQ ^a -R ^PFa -R ^51a -R ^52a -O-] _e1 Z ^3a [-O-R ^53a -SiR ^a _n1 L ^a _3-n1 ] _f1 (A13)
^{However, R fa, Q a, R} PFa, R a, L a and n1 have the same meanings as defined above,
R ^51a is a linear perfluoroalkylene group,
R ^52a is an alkylene group;
Z ^3a is a (e1 + f1) -valent hydrocarbon group, or a group having 2 or more carbon atoms and a (e1 + f1) -valent group having one or more etheric oxygen atoms between carbon atoms of the hydrocarbon group,
R ^53a is an alkylene group;
e1 is an integer of 1 or more,
f1 is an integer greater than or equal to 1,
(E1 + f1) is 3 or more,
e1 is e1 amino ^{R fa} when 2 or more, all of the same group, e1 amino ^{Q a,} R ^PFa, each ^{R 51a} and ^{R 52a,} which may be the same or different and
When f1 is 2 or more, f1 [—O—R ⁵³ —SiR _n L _3-n ] may be the same or different.

In the compound (A13), in the above formula (A1), r1 is e1, s1 is f1, and Z is [—R ^51a —R ^52a —O—] _e1 Z ^3a [—O—R ^53a —] It is a compound of _f1 .

R ^51a is typically —CF ₂ —, for example when R ^PFa is {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 } or (CF ₂ CF ₂ O) _m13 , When R ^PFa is (CF ₂ CF ₂ CF ₂ O) _m14 , it is typically —CF ₂ CF ₂ —, and R ^PFa is (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) When it is _m15 , it is typically —CF ₂ CF ₂ CF ₂ —.
If R ^51a is a straight-chain compound (A13), a surface layer having excellent 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).

The R ^fa —O—Q ^a —R ^PFa —R ^51a — group includes the point that the surface layer is further excellent in water and oil repellency, durability, fingerprint stain removability, lubricity, and appearance, and the compound (A13). From the viewpoint of ease of production, the group (R ^f -1), the group (R ^f -2), or the group (R ^f -3) is 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)
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; m21 and m22 are each an integer of 1 or more, m21 + m22 is an integer of 2 ~ 200, m21 amino CF _The order of bonding of ₂ O and m22 CF ₂ CF ₂ O is not limited; m25 is an integer of 1 to 100.

^Examples of Z ^3a include a residue obtained by removing a hydroxyl group from a polyhydric alcohol having (e1 + f1) 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) or group (Z-3) is particularly preferred. However, R ⁴ is an alkyl group, 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.

The preferable values of e1 and f1 are the same as the preferable values of r1 and r2, respectively.

Examples of the compound (A13) include compounds (1-1) to (1-6) shown below. 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 ^fa —O—Q ^a —R ^PFa —. A preferable form of W is a combination of the above-mentioned preferable R ^fa , Q ^a and R ^PFa . A preferred form of R ^51a is as described above.

<Preferred Form of Compound (B1)>
As the compound (B1), at least one selected from the group consisting of the following compound (B11), compound (B12) and compound (B13) is used because the surface layer is further excellent in friction resistance and fingerprint stain removability. preferable.

“Compound (B11)”
The compound (B11) is represented by the following formula (B11).
^{R fb -O-Q b -R PFb} -Q 32b - [C (O) N (R 33b)] p2 -R 34b -C [-R 35b -SiR b n2 L b 3-n2] 3 ··· ( B11)
However, R ^fa , Q ^b , R ^PFb , R ^b , L ^b and n2 are as defined above,
Q ^32b is a fluoroalkylene group or a group having an etheric oxygen atom between carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms,
R ^33b is a hydrogen atom or an alkyl group,
p2 is 0 or 1,
R ^34b is a single bond, an alkylene group, or a group having an etheric oxygen atom at the end of the alkylene group (provided that C [—R ^35b —SiR ^b _n2 L ^b _3-n2 ] ₃ is bonded to the end); A group having an etheric oxygen atom between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or a terminal of an alkylene group having 2 or more carbon atoms (provided that C [—R ^35b —SiR ^b _n2 L ^b _3-n2 ] ₃ ) and a group having an etheric oxygen atom between carbon-carbon atoms,
R ^35b represents an alkylene group, a group having an etheric oxygen atom at the terminal of the alkylene group (excluding the terminal bonded to Si), or an ether between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms. A group having a reactive oxygen atom,
The three [—R ^35b —SiR ^b _n2 L ^b _3-n2 ] may be the same or different.

In the compound (B11), in the above formula (B1), r2 is 1, s2 is 3, and Z ^b is —Q ^32b — [C (O) N (R ^33b )] _p2 —R ^34b —C [—R ^35b —] ₃

Q ^32b , R ^33b , p 2, R ^34b , and R ^35b are the same as Q ^32a , R ^33a , p 1, 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 ^fb -O-Q ^b -R ^PFb -R ^42b -R ^43b -N [-R ^44b -SiR _n2 L _3-n2 ] ₂ (B12)
However, R ^fa , Q ^b , R ^PFb , R ^b , L ^b and n2 are as defined above,
R ^42b is a perfluoroalkylene group,
R ^43b represents a single bond, an alkylene group, a group having an etheric oxygen atom or —NH— at the end of the alkylene group (excluding the end bonded to N), or a carbon of an alkylene group having 2 or more carbon atoms. A group having an etheric oxygen atom or —NH— between carbon atoms, or an alkylene group having 2 or more carbon atoms (excluding the terminal on the side bonded to N) and an etheric group between carbon and carbon atoms A group having an oxygen atom or -NH-,
R ^44b is an alkylene group or a group having an etheric oxygen atom or —NH— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms;
Two [—R ^44b —SiR ^b _n2 L ^b _3-n2 ] may not be the same group.

Compound (B12), in the above formula (B1), r2 is 1, s2 is 2, ^{Z b} is ^{-R 42b -R 43b -N [-R 44b} -] a _second compound.

R ^42b , R ^43b and R ^44b are the same as R ^42a , R ^43a and R ^44a in the formula (A12), respectively, and the preferred embodiments are also the same.

“Compound (B13)”
The compound (B13) is represented by the following formula (B13).
[R ^fb -O-Q ^b -R ^PFb -R ^51b -R ^52b -O-] _e2 Z ^3b [-O-R ^53b -SiR ^b _n2 L ^b _3-n2 ] _f2 (B13)
However, R ^fa , Q ^b , R ^PFb , R ^b , L ^b and n2 are as defined above,
R ^51b is a linear perfluoroalkylene group,
R ^52b is an alkylene group;
Z ^3b is an (e2 + f2) -valent hydrocarbon group or a group having 2 or more carbon atoms and an (e2 + f2) -valent group having one or more etheric oxygen atoms between carbon atoms of the hydrocarbon group,
R ^53b is an alkylene group;
e2 is an integer of 1 or more,
f2 is an integer greater than or equal to 1,
(E2 + f2) is 3 or more,
When e2 is 2 or more, all of e2 R ^fb are the same group, and e2 Q ^b , R ^PFb , R ^51b and R ^52b may be the same or different, respectively.
When f2 is 2 or more, f2 [—O—R ^53b —SiR ^b _n2 L ^b _3-n2 ] may be the same or different.

Compound (B13), in the above formula (B1), r2 is e2, s2 is f2, ^{Z b} is _{^{[-R 51b -R 52b -O-] e2}} Z 3b [-O-R 53b - ] A compound of _f2 .

R ^51b , R ^52b , Z ^3b , R ^53b , e 2 and f 2 are the same as R ^51a , R ^52a , Z ^3a , R ^53a , e1 and f1 in the formula (A13), respectively, and the preferred embodiments are also the same. .

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

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 each independently represent a perfluoroalkyl group having 1 to 20 carbon atoms; Q ⁵¹ represents a single bond, a fluoroalkylene group having no branched structure containing one or more hydrogen atoms, one A group having an etheric oxygen atom at the end of a fluoroalkylene group having no branched structure containing the above hydrogen atoms (excluding the end on the side bonded to A ³¹ —O), containing one or more hydrogen atoms A group having an etheric oxygen atom between carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms that does not have a branched structure, or a fluoroalkylene group having 2 or more carbon atoms that does not have a branched structure containing one or more hydrogen atoms end (except the ends of the side that binds to a ^{31 -O.)} and carbon - is a group having an etheric oxygen atom between carbon atoms (provided that the number of oxygen atoms 10 Q ⁵² is a fluoroalkylene group having no branched structure containing one or more hydrogen atoms, or a fluoroalkylene group having 2 or more carbon atoms not having a branched structure containing one or more hydrogen atoms. A group having an etheric oxygen atom between carbon-carbon atoms (however, the oxygen number is 10 or less); R ^F3 is a perfluoroalkylene group having no branched structure; (R ^F3 O) _m30 may be composed of two or more types of R ^F3 O having different carbon numbers; p3 is 0 when Q ⁵¹ is a single bond, and Q ⁵¹ is 1 for cases other than single bonds.

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 having the smaller number of carbon atoms in the R ^f group among the compound (A) and the compound (B) is 30 to 95 mass with ^respect to the total of the compound (A) and the compound (B). %, Preferably 40 to 90% by mass, particularly preferably 40 to 80% by mass. ^If the content of the ^Rf group having a smaller number of carbon atoms is within the above range, the surface layer will have excellent water droplet sliding properties.

In the present composition, the total amount of the compound (A) and the compound (B) is preferably 10% by mass or more, particularly preferably 20% 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 and particularly preferably 0.1 to 1% by mass in the present coating liquid. .

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 the liquid 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 coating liquid is preferably 0.001 to 50% by mass, more preferably 0.05 to 30, still more preferably 0.05 to 10, 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 touch panels, the base material for displays, and the base material for eyeglass lenses are suitable, and the base material for touch panels 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 or transparent resin is 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]
The present composition and the present coating liquid contain the compound (A) and the compound (B), and the content of the compound (A) having a small number of carbon atoms in the R ^f group is the compound (A) and the compound (B). Since it is 30 to 95% by mass with respect to the total of (B), a surface layer excellent in water droplet sliding property can be formed.
Each compound (A) and compound (B), by ^the R ^f group to one end of the R ^PF chain is attached, the other end side based on the R ^PF chain (I) is present. According to the compound (A) and the compound (B) having such a structure, when the surface layer is formed on the substrate, the R ^f group of each compound is easily oriented on the side opposite to the substrate side. When the ^Rf group is oriented on the side opposite to the substrate side, the surface energy of the formed surface layer is lowered.
In addition, by compounds (A) and (B) the number of carbon atoms of each of ^the R ^f group is different, different ^the R ^f group carbon numbers are distributed in a specific ratio on the surface of the surface layer, It is considered that a physical or physical fine uneven structure is formed. Thereby, it is considered that the water repellency of the surface of the surface layer is further increased, and the contact angle and the falling angle of the water droplet are reduced, and excellent water droplet sliding property is exhibited.

[Use]
Applications of the present composition, the present coating liquid and the article are not particularly limited. For example, display input devices such as touch panels; surface protective coats made of transparent glass or transparent plastic (acrylic, polycarbonate, etc.) members, antifouling coats for kitchens; water and moisture repellent 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 coat, solar cell water-repellent coat, printed circuit board waterproof / water-repellent coat, waterproof / water-repellent coat for electronic equipment casings and electronic parts, transmission line insulation improvement coat, various filter waterproof / 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 sieve 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.

Because of the above effects, the present composition, the present coating liquid, and the article are suitably used for applications that require water drop slidability. Such applications include, for example, kitchen antifouling coatings; heat exchanger water and moisture repellent and antifouling coatings and toiletry antifouling coatings; coatings for materials that require liquid repellency while conducting electrical conduction; A waterproof / sliding coat can be used.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. Hereinafter, “%” is “% by mass” unless otherwise specified.
Of Examples 1 to 10, Examples 3 to 9 are examples, and Examples 1 to 2 and 10 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, the group (I) or the ^Rf group.

(Water drop falling angle)
After 50 μL of water droplets were dropped on the surface (surface layer) of the article held horizontally, the article was gradually tilted, and the angle (falling angle) between the article and the horizontal plane when the water drop began to fall was measured.

(Water drop sliding speed)
The angle (inclination angle) between the surface of the article and the horizontal plane was set to 40 °, 50 μL of water droplets were dropped on the surface (surface layer) of the article, and the time when the water drops moved 50 mm was measured. This moving time is defined as the sliding speed.

[Synthesis Example 1]
The compound (14I-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 -C (O) OCH 3 ··· (14I- 1)
Compound (14I-1): average number of units × 3, number average molecular weight 4,700

In a 50 mL eggplant flask, 9.0 g of compound (14I-1) and 0.45 g of H ₂ N—CH ₂ —C (CH ₂ CH═CH ₂ ) ₃ were added and stirred for 12 hours. From NMR, it was confirmed that all of the compound (14I-1) was converted to the compound (17I-1). In addition, by-product methanol was generated. The resulting solution was diluted with 9.0 g of CF ₃ CH ₂ OCF ₂ CF ₂ H (Asahi Glass Co., Ltd., AE-3000), purified by silica gel column chromatography (developing solvent: AE-3000), and compound (17I- 7.6 g (yield 84%) of 1) was obtained.
CF ₃ —O— (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _x3 (CF ₂ CF ₂ O) —CF ₂ CF ₂ CF ₂ —C (O) NH—CH ₂ —C (CH ₂ CH = CH ₂ ) ₃ (17I-1)
Compound (17I-1): average number of units × 3, number average molecular weight 4,800

In a 10 mL PFA sample tube, 6.0 g of the compound (17I-1) and a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2% ), 0.08 g of HSi (OCH ₃ ) ₃ , 0.02 g of dimethyl sulfoxide, and 0.49 g of 1,3-bis (trifluoromethyl) benzene (manufactured by Tokyo Chemical Industry Co., Ltd.) Stir at 0 ° C. 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 1.0 μm to obtain 6.7 g (yield 100%) of the compound (A-1).
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 ... (A-1)

NMR spectrum of compound (A-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.8 (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), -119.4 (2F), -125.4 (52F), -126.2 (2F).
Average value of number of units × 3: 13, number average molecular weight of compound (A-1): 5,100.

[Synthesis Example 2]
The compound (14I-2) was obtained according to the method described in Example 2 of International Publication No. 2013/121984.
CF ₃ CF ₂ —O— (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _x4 (CF ₂ CF ₂ O) —CF ₂ CF ₂ CF ₂ —C (O) OCH _3. 14I-2)
Compound (141-2): average number of units × 4, number average molecular weight 4,800.

8.4 g (yield 93%) of compound (17I-2) was obtained in the same manner as Example 1-2 except that compound (14I-2) was used instead of compound (14I-1).
CF ₃ CF ₂ —O— (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _x4 (CF ₂ CF ₂ O) —CF ₂ CF ₂ CF ₂ —C (O) NH—CH ₂ —C (CH ₂ CH═CH ₂ ) ₃ (17I-2)
Compound (17I-2): unit number × 4 average value 13, number average molecular weight 4,900

6.7 g (yield 100%) of compound (B-1) was obtained in the same manner as in Example 1-3, except that compound (17I-2) was used instead of compound (17I-1).
CF ₃ CF ₂ —O— (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _x4 (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-1)

NMR spectrum of compound (B-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.8 (6H), 1.3 to 1.6 (12H), 3.4 (2H), 3. 7 (27H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −84.0 (54F), −88.2 (3F), −89.2 (58F), −119 .7 (2F), -126.5 (54F).
Average number of units × 4: 13, number average molecular weight of compound (B-1): 5,200.

[Examples 1 to 10]
The compound (A-1) and the compound (B-1) were used and mixed at a mass ratio shown in Table 1 to prepare a composition, which was subjected to the following evaluation. However, only compound (A-1) was used in Example 1, and only compound (B-1) was used in Example 2.

(Evaluation)
Using each compound or composition obtained in Examples 1 to 10, surface treatment of the substrate was performed to obtain an article having a surface layer on the surface of the substrate. As the surface treatment method, the following dry coating method and wet coating method were used for each example. Chemically tempered glass (Dragon Trail) was used as the substrate. The obtained article was evaluated for water contact angle and water drop sliding speed. The results are shown in Table 1.

<Dry coating method>
Dry coating was performed using a vacuum deposition apparatus (VTR-350M, manufactured by ULVAC) (vacuum deposition method). 0.5 g of each compound or composition obtained in Examples 1 to 10 was filled in a molybdenum boat in a vacuum deposition apparatus, and the inside of the vacuum deposition apparatus was evacuated to 1 × 10 ⁻³ Pa or less. The boat on which the composition was placed was heated at a rate of temperature rise of 10 ° C./min or less, and when the deposition rate by the quartz oscillation type film thickness meter exceeded 1 nm / second, the shutter was opened and the surface of the substrate was formed. The membrane was started. When the film thickness reached about 50 nm, the shutter was closed to finish the film formation on the surface of the substrate. The substrate on which the composition was deposited was heat-treated at 120 ° C. for 30 minutes and washed with AK-225 to obtain an article having a surface layer on the surface of the substrate.

<Wet coating method>
Each compound or composition obtained in Examples 1 to 10 and C ₄ F ₉ OC ₂ H ₅ (manufactured by 3M, Novec (registered trademark) 7200) as a liquid medium were mixed to obtain a solid content concentration of 0.05. % 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 coating film was dried at 120 ° C. for 30 minutes and washed with AK-225 to obtain an article having a surface layer on the surface of the substrate.

The compositions of Examples 3 to 9 containing the compound (A-1) and the compound (B-1), and the content of the compound (A-1) is 30 to 95% by mass based on the total of them. Compared to Examples 1 and 2 where each of the compound (A-1) and the compound (B-1) was used alone, the sliding angle was low, the sliding speed was high, and the surface layer was excellent in water droplet sliding ability.
The water droplet sliding property of the surface layer in Example 10 in which the content of the compound (A-1) was less than 30% by mass relative to the total of them was the same as Example 1.

(Examples 11 to 20)
Using commercially available _{CF 3 O {(CF 2 CF} 2 O) m (CF 2 O) n} CF 2 CH 2 a compound represented by OH (average value of the average value of 20, n m is 21), The following compound (A-2) was obtained according to the method described in Synthetic Examples 11 to 15 in Japanese Patent No. 5761305.
CF ₃ —O — {(CF ₂ CF ₂ O) ₂₀ — (CF ₂ O) ₂₁ } —CF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ —Si [CH ₂ CH ₂ CH ₂ —Si (OCH ₃ ) ₃ ] ₃ ... (A-2)
Further, according to the method described in Example 1 of International Publication No. 2017/038830, the following compound (B-2) was obtained.
CF ₃ CF ₂ CF ₂ —O— (CF ₂ CF ₂ O) ₂ {(CF ₂ O) ₂₁ (CF ₂ CF ₂ O) ₂₀ } —CF ₂ —CH ₂ OCH ₂ —C [CH ₂ OCH ₂ CH ₂ CH ₂ —Si (OCH ₃ ) ₃ ] ₃ ... (B-2)
Using the compound (A-2) and the compound (B-2), the substrate was dry coated in the same manner as in Examples 1 to 10, and the falling angle and the falling speed of the obtained article were evaluated. The results are shown in Table 2.

The compositions of Examples 13 to 19 including the compound (A-2) and the compound (B-2), and the content of the compound (A-2) is 30 to 90% by mass based on the total of them. Compared to Examples 11 and 12 in which the compound (A-2) and the compound (B-2) were each used alone, the sliding angle was low, the sliding speed was high, and the surface layer was excellent in water droplet sliding properties.
The water droplet sliding property of the surface layer in Example 20 in which the content of the compound (A-2) was less than 30% by mass relative to the total of them was the same as in Example 11.

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. 2017-024879 filed on Feb. 14, 2017 are incorporated herein as the disclosure of the specification of the present invention. It is.

Claims (15)

1. A composition comprising a fluorinated ether compound (A) and a fluorinated ether compound (B),
   The fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) are each represented by the following formula (I), a poly (oxyperfluoroalkylene) chain, a perfluoroalkyl group bonded to one end thereof, and And a group
   In the combination of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) contained in the composition, the carbon number of the perfluoroalkyl group of the fluorine-containing ether compound (A) is Less than the carbon number of the perfluoroalkyl group (B) has,
   The fluorine-containing ether compound (A) content is 30 to 95% by mass with respect to the total of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B). Ether 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 perfluoroalkyl group of the fluorinated ether compound (A) has 1 to 19 carbon atoms, and the perfluoroalkyl group of the fluorinated ether compound (B) has 2 to 20 carbon atoms. Fluorine-containing ether composition.
3. The perfluoroalkyl group of the fluorinated ether compound (A) has 1 carbon, the perfluoroalkyl group of the fluorinated ether compound (B) has 2 or 3 carbon atoms, or the fluorinated ether compound (A The fluorine-containing ether composition of Claim 1 or 2 whose carbon number of the perfluoroalkyl group which (2) has is 2, and carbon number of the perfluoroalkyl group which the said fluorine-containing ether compound (B) has is 3.
4. The number of groups represented by the formula (I) in each of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) is 1 to 3, The fluorine-containing ether composition described in 1.
5. The number of poly (oxyperfluoroalkylene) chains that each of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) has is 1 to 3, according to any one of claims 1 to 4. Fluorine-containing ether composition.
6. 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), and are contained in the composition In the combination of the fluorinated ether compound (A) and the fluorinated ether compound (B), the carbon number of R ^{f in} the fluorinated ether compound (A) is greater than the carbon number of R ^{f in} the fluorinated ether compound (B). The fluorine-containing ether composition according to claim 1, wherein
   _{^{[R f -O-Q-R}} PF -] r Z [-SiR n L 3-n] s ··· (A / B)
   However, R ^f is a perfluoroalkyl group, and when r is 2 or more, r perfluoroalkyl groups are the same 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 alkylene groups may all be the same or different,
   ^RPF 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), and 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 8 or less.
7. The fluorine-containing ether composition according to claim 6, wherein r is 1 to 3.
8. The fluorine-containing ether composition according to claim 6 or 7, wherein the s is 1 to 3.
9. 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), wherein the content of the fluorine-containing ether compound (A1) is A fluorine-containing ether composition characterized by being 30 to 95% by mass based on the total of the fluorine-containing ether compound (A1) and the fluorine-containing ether compound (B1).
   [R ^fa -OQ ^a -R ^PFa- ] _r1 Z ^a [-SiR ^a _n1 L ^a _3-n1 ] _s1 (A1)
   _{^{[R fb -O-Q b -R}} PFb -] r2 Z b [-SiR b n2 L b 3-n2] s2 ··· (B1)
   However, R ^fa and R ^fb are perfluoroalkyl groups, and the number of carbon atoms in R ^fa is less than the number of carbon atoms in R ^fb ,
   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, The oxyfluoroalkylene groups constituting may all be the same or different,
   R ^PFa and R ^PFb are poly ( ^{oxyperfluoroalkylene} ) chains;
   Z ^a is a (r1 + s1) -valent linking group,
   Z ^b is a (r2 + s2) -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,
   n1 and n2 are integers from 0 to 2,
   (3-n1) L ^a when n1 is 0 or 1 and (3-n) L ^b when n2 is 0 or 1 may be the same or different,
   When n1 is 2, n1 R ^{a s} , and when n2 is 2, n2 R ^{b s} may be the same or different,
   r1 and r2 are integers of 1 or more. When r1 is 2 or more, r1 R ^fa , Q ^a and R ^PFa may be the same or different, and r2 is 2 when r2 is 2 or more. Each of R ^fb , Q ^b and R ^PFb may be the same or different,
   s1 and s2 are integers of 1 or more, and when s1 is 2 or more, s1 [-SiR ^a _n1 L ^a _3-n1 ] may be the same or different, and s2 is 2 or more Sometimes s2 [—SiR ^b _n2 L ^b _3-n2 ] may be the same or different.
10. The fluorine-containing ether composition according to claim 9, wherein r1 R ^fa are the same when r1 in the formula (A1) is 2 or more.
11. The fluorine-containing ether composition according to claim 9 or 10, wherein r2 ^Rfb is the same when r2 in the formula (A2) is 2 or more.
12. The inclusion according to any one of claims 9 to 11, wherein R ^fa in the formula (A1) has 1 to 19 carbon atoms and R ^fb in the formula (B1) has 2 to 20 carbon atoms. Fluorine ether composition.
13. The carbon number of R ^fa in the formula (A1) is 1, the carbon number of R ^fb in the formula (B1) is 2 or 3, or the carbon number of R ^fa in the formula (A1) is 2, The fluorine-containing ether composition according to any one of claims 9 to 12, wherein R ^fb in the formula (B1) has 3 carbon atoms.
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.