JP2020063456A - Fluorine-containing ether composition, coating liquid and article - Google Patents

Abstract

To provide a fluorine-containing ether composition capable of forming a surface layer excellent in water drop slip property.SOLUTION: A fluorine-containing ether composition is a composition containing a fluorine-containing ether compound (A) and a fluorine-containing ether compound (B), in which the compound (A) and the compound (B) each has a poly(oxyperfluoroalkylene) chain, a perfluoroalkyl group bonded to one terminal thereof and a group represented by formula (I), in the combination of the compound (A) and the compound (B) contained in the composition, the carbon number of the perfluoroalkyl group of the compound (A) is smaller than the carbon number of the perfluoroalkyl group of the compound (B), and a content of the compound (A) is 30-95 mass% to the total of the compound (A) and the compound (B). In formula (I):SiRL, 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 0-2.SELECTED DRAWING: None

Description

  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 and the like. For example, when a surface layer is formed on the surface of a base material by the surface treatment agent, lubricity, water repellency and oil repellency are imparted, stains on the surface of the base material are easily wiped off, and stain removability is improved. Among the fluorine-containing compounds, a fluorine-containing ether compound having a poly (oxyperfluoroalkylene) chain having an ether bond (—O—) in the middle of the perfluoroalkyl chain is excellent in removing stains such as fats and oils.

  As a fluorine-containing ether compound, a compound having a hydrolyzable silyl group has been proposed. Such a fluorine-containing ether compound does not easily deteriorate the water and oil repellency even when repeatedly rubbed with a finger (rubbing resistance) and the ability to easily remove fingerprints adhering to the surface by wiping (fingerprint stain removability). Is used for a long period of time, for example, as a surface treatment agent for a member constituting a surface of a touch panel that is touched by a finger.

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

International Publication No. 2013/121984

However, the present inventor has found that the surface layer formed by the fluorine-containing ether compound, composition or mixture described in Patent Document 1 has insufficient water drop sliding property. The water drop sliding property is a property in which water drops easily slide on the inclined surface (the sliding angle is small or / and the sliding speed is fast).
An object of the present invention is to provide a fluorine-containing ether composition and a coating liquid capable of forming a surface layer having excellent water drop slip property, and an article having a surface layer having excellent water drop slip property.

The present invention provides a fluorinated ether composition, a coating liquid and an article having the following constitutions [1] to [15].
[1] A composition containing 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 a poly (oxyperfluoroalkylene) chain, a perfluoroalkyl group bonded to one end of the chain, and a formula (I) below. Has 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 the fluorine-containing ether compound. Less than the carbon number of the perfluoroalkyl group of (B),
The content of the fluorinated ether compound (A) is 30 to 95 mass% with respect to the total of the fluorinated ether compound (A) and the fluorinated ether compound (B). Ether composition.
_{-SiR n L 3-n ··· (} I)
However, L is a hydroxyl group or a hydrolyzable group,
R is a hydrogen atom or a monovalent hydrocarbon group,
n is an integer of 0 to 2,
When n is 0 or 1, (3-n) 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) in the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) may be the same or different.

[2] The fluorine-containing ether compound (A) has a perfluoroalkyl group having 1 to 19 carbon atoms, and the fluorine-containing ether compound (B) has a perfluoroalkyl group having 2 to 20 carbon atoms, [1] Fluorine-containing ether composition.
[3] The fluorine-containing ether compound (A) has a perfluoroalkyl group having 1 carbon atom, the fluorine-containing ether compound (B) has a perfluoroalkyl group having 2 or 3 carbon atoms, or the fluorine-containing ether compound The fluorine-containing ether composition of [1] or [2], wherein the perfluoroalkyl group of the compound (A) has 2 carbon atoms, and the perfluoroalkyl group of the fluorine-containing ether compound (B) has 3 carbon atoms.
[4] The fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) each have 1 to 3 groups represented by the formula (I), [1] to [3] The fluorine-containing ether composition according to any one of 1.
[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. 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), 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 of [1], which has less carbon atoms.
_{^{[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 group, and oxyfluoroalkylene constituting the group. The alkylene groups may all be the same or different,
R ^PF is a poly (oxyperfluoroalkylene) chain,
Z is a (r + s) -valent linking group,
—SiR _n L _3-n is a group represented by the above formula (I), and when s is 2 or more, s groups represented by the formula (I) are the same groups;
Each of r and s is 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 fluorinated ether composition according to [6] or [7], wherein s is 1 to 3.

[9] Containing the fluorinated ether compound (A1) represented by the following formula (A1) and the fluorinated ether compound (B1) represented by the following formula (B1), and containing the fluorinated ether compound (A1) The amount of the fluorine-containing ether compound (A1) and the fluorine-containing ether compound (B1) is 30 to 95% by mass, based on the total amount of the fluorine-containing ether compound (A1).
_{^{[R fa -O-Q 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, the carbon number of R ^fa is smaller than the carbon number of 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, and The constituent oxyfluoroalkylene groups 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 of 0 to 2,
n1 is 0 or (3-n1) in the case of 1-number of ^L a, (3-n) when n2 is 0 or 1 pieces of ^{L b} respectively, it may be the same or different and
When n1 is 2, n1 R ^a 's and when n2 is 2, n2 R ^b's may be the same or different, and
r1 and r2 are integers of 1 or more, and when r1 is 2 or more, r 1 R ^{fa s} , Q ^a and R ^PFa may be the same or different, and when r2 is 2 or more, r 2 R ^fb , Q ^b and R ^PFb in each may be the same or different,
s1 and s2 are integers greater than or equal to 1, s1 is s1 or when two or more ^{_{[-SiR a n1 L a 3-}} n1] may be different even in the same, s2 is 2 or more At this time, s2 [-SiR ^b _n2 L ^b _3-n2 ] may be the same or different.

[10] The fluorine-containing ether composition of [9], wherein when r1 in the formula (A1) is 2 or more, r1 ^Rfa's are the same.
[11] The fluorinated ether composition of [9] or [10], wherein when r2 in the formula (A2) is 2 or more, r 2 R ^fb's are the same.
[12] Any of [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-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). Is 2, and the fluorine-containing ether composition of any of [9] to [12], wherein R ^fb in the 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 according to 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 drop sliding property.
The article of the present invention has a surface layer having excellent water drop slipperiness.

In this specification, the compound represented by the formula (1) is referred to as a compound (1), and the group represented by the formula (I) is referred to as a group (I). The same applies to compounds or groups represented by other formulas.
Further, the chemical formula of the oxyperfluoroalkylene group is represented 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 (hereinafter, also referred to as “present composition”) of the present invention includes a fluorine-containing ether compound (A) (hereinafter, also referred to as “compound (A)”) and a fluorine-containing ether compound (B). ) (Hereinafter, also referred to as “compound (B)”). The composition does not contain a liquid medium as described below. The composition may be composed of the compound (A) and the compound (B), and 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.
Each of the compound (A) and the compound (B) has a poly (oxyperfluoroalkylene) chain (hereinafter, also referred to as “R ^PF chain”) and a perfluoroalkyl group bonded to one end thereof (hereinafter, “R ^f group”). ], 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 hydrolyzable group,
R is a hydrogen atom or a monovalent hydrocarbon group,
n is an integer of 0 to 2,
When n is 0 or 1, (3-n) L's may be the same or different,
When n is 2, n Rs may be the same or different.

The carbon number of the R ^f group contained in the compound (A) is smaller than the carbon number of the R ^f group contained in the compound (B). That is, the present composition contains two kinds of fluorine-containing ether compounds having an R ^PF chain, an R ^f group, and a group (I), each having a different R ^f group carbon number. As a result, the water droplets of the surface layer are excellent in sliding property.
The R ^PF chain and the group (I) possessed by each of the compound (A) and the compound (B) may be the same or different.

(R ^f group)
The carbon number of the R ^f group is preferably from 1 to 20, more preferably from 1 to 10, further preferably from 1 to 6, and particularly preferably from 1 to 3 from the viewpoint that the surface layer is more excellent in lubricity and abrasion resistance.
Therefore, the compound (A) preferably has an R ^f group having 1 to 19 carbon atoms and the compound (B) has an R ^f group having 2 to 20 carbon atoms, and the compound (A) has an R ^f group. More preferably 1 to 9 carbon atoms, the compound (B) has an R ^f group having 2 to 10 carbon atoms, and the compound (A) has an R ^f group having 1 to 5 carbon atoms, a 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 Alternatively, it is particularly preferable that the R ^f group of the compound (A) has 2 carbon atoms and the R ^f group of the compound (B) has 3 carbon atoms.
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 — and CF ₃ CF ₂ — are particularly preferable.

The number of R ^f groups in the compound (A) 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 in the compound (B) 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) CF ₃ CF ₂ CF ₂ - are preferred combinations of, ^{R f} group is CF ₃ with compound (a) -, ^{R f} group compound (B) has the _CF 3 CF ₂ - combination of particularly preferred.

The R ^f group is typically attached to one end of the R ^PF chain via a linking group.
As the linking group, the group (II) is preferable. That is, it is preferable that the R ^f group is bound to one end of each R ^PF chain of the compound (A) and the compound (B) via the group (II). However, the left side of the group (II) is bonded to the R ^f group.
-O-Q -... (II)
However, Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by combining 2 to 5 (preferably 2 to 4) of the oxyfluoroalkylene group. 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) can be added to a liquid medium. Higher solubility. 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 be aggregated while being dried after being applied to the surface of the substrate. Further excellent appearance of the surface layer.
2-6 are preferable, as for carbon number of the oxyfluoroalkylene group in Q, 2-4 are more preferable, and 2 or 3 is especially preferable.
The number of hydrogen atoms in the oxyfluoroalkylene group is 1 or more, preferably 2 or more, and particularly preferably 3 or more, from the viewpoint of excellent appearance of the surface layer. The number of hydrogen atoms in the oxyfluoroalkylene group is preferably (carbon number of Q) × 2 or less, and particularly preferably (carbon number of Q) 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 that the wear resistance and lubricity of the surface layer are further excellent.
In the group formed by combining 2 to 5 oxyfluoroalkylene groups, 2 to 5 oxyfluoroalkylene groups may be the same or different.
As Q, 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 OCH ₂ CF ₂ O-, and _{-CF 2 CF 2 OCF 2 CH 2} OCH 2 CF 2 groups selected from the group consisting of 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)
However, R ^F is a perfluoroalkylene group,
m1 is an integer of 2 to 200,
(R ^F O) _m1 may be composed of two or more types of R ^F O having different carbon numbers.

The carbon number of R ^F is preferably 1 to 6, more preferably 1 to 4 from the viewpoint of further excellent abrasion resistance and fingerprint removability of the surface layer, and further excellent in lubricity of the surface layer. 1 to 2 is particularly preferable, and a perfluoroalkylene group having 3 to 4 carbon atoms is particularly preferable in terms of further excellent abrasion resistance of the surface layer.
R ^F may be branched or linear and is preferably linear because the surface layer is more excellent in abrasion resistance and lubricity.

  m1 is an integer of 2 to 200, preferably an integer of 5 to 150, and particularly preferably an integer of 10 to 80. When m1 is at least the lower limit value of the above range, the water / oil repellency of the surface layer is excellent. When m1 is equal to or less than the upper limit value of the above range, the abrasion resistance of the surface layer is excellent. That is, when the number average molecular weights of the compound (A) and the compound (B) are too large, the number of the group (I) existing per unit molecular weight is decreased and the abrasion resistance is lowered.

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

The (R ^F O) _m1 is {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 }, (CF ₂ CF ₂ ) from the viewpoint of further excellent abrasion resistance, fingerprint stain resistance and lubricity of the surface layer. _{O) m13, (CF 2 CF} 2 CF 2 O) m14, preferably _{(CF 2 CF 2 O-CF} 2 CF 2 CF 2 CF 2 O) m15, {(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 _, particularly preferably from _{(CF 2 CF 2 O-CF} 2 CF 2 CF 2 CF 2 O) m15.
However, 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) may each have one ^RPF chain or two or more ^RPF chains. From the viewpoint of abrasion resistance, 1 to 3 pieces are preferable, and 1 to 2 pieces are particularly preferable. When the number of R ^PF chains, and consequently the number of R ^f groups, is 1 or more, the surface layer is excellent in water drop slipperiness, water and oil repellency, durability, fingerprint stain removability, and lubricity. When the number of R ^PF chains is less than or equal to 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 the group (I), L is a hydroxyl group or a hydrolyzable group.
The hydrolyzable group is a group that becomes a hydroxyl group by a hydrolysis reaction. That is, when L is a hydrolyzable group, Si-L of the group (I) becomes a silanol group (Si-OH) by a hydrolysis reaction.
Examples of the hydrolyzable group include an alkoxy group, a halogen atom, an acyl group, an isocyanate group (-NCO) and the like. 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). A chlorine atom is particularly preferable as the halogen atom. L is preferably an alkoxy group having 1 to 4 carbon atoms, in that outgas at the time of coating is small and the storage stability of the compound (A) and the compound (B) is excellent, and that of the compound (A) and the compound (B) An ethoxy group is particularly preferable when long-term storage stability is required, and a methoxy group is particularly preferable when the reaction time after coating is short.

R is a hydrogen atom or a monovalent hydrocarbon group.
Examples of the monovalent hydrocarbon group include a saturated hydrocarbon group such as an alkyl group and a cycloalkyl group, an alkenyl group such as an allyl group, and the like, and a saturated hydrocarbon group is preferable.
The number of carbon atoms of the monovalent hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2 from the viewpoint of easy production of the compound (A) and the compound (B).

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

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

The number of the groups (I) contained in each of the compound (A) and the compound (B) may be one or two or more. From the viewpoint that the water drop of the surface layer is further excellent, 1 to 3 is preferable, and from the viewpoint that the abrasion resistance of the surface layer is further excellent, 2 or 3 is particularly preferable.
When the compound (A) and the compound (B) have two or more groups (I), all the groups (I) may or may not be the same group. From the viewpoint of easy production of the compound (A), it is preferable that all have 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 abrasion resistance is excellent.
The number average molecular weight (Mn) is measured by the measuring method described in Examples below.

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 one having a smaller molecular weight tends to evaporate first and be deposited on the substrate. The smaller the difference in the number average molecular weight (Mn), the less likely the uneven distribution of the compound (A) and the compound (B) will 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 the wet coating method, even if there is a difference between the number average molecular weight (Mn) of the compound (A) and the number average molecular weight (Mn) of the compound (B), the surface layer formed Since uneven distribution of the compound (A) and the compound (B) is unlikely to occur, 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 they have an R ^PF chain, an R ^f group and a group (I). For example, it can be appropriately selected from known fluorine-containing ether compounds such as fluorine-containing ether compounds described in the following documents and commercially available fluorine-containing ether compounds.
JP-A-2013-91047, JP-A-2014-80473, WO 2013/042732, WO 2013/042733, WO 2013/121984, WO 2013/121985, WO No. 2013/121986, International Publication No. 2014/163004, International Publication No. 2014/175124, International Publication No. 2015/087902, JP 2013-227279 A, JP 2013-241569 A, JP 2013-A. No. 256643, JP-A-2014-15609, JP-A-2014-37548, JP-A-2014-65884, JP-A-2014-210258, JP-A-2014-218639, and JP-A-2015-200884. Japanese Patent Laid-Open No. 2015-2015 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, JP2013-144726. JP, 2014-77836A, 2013-117012, 2013-214194, 2014-198822, 2015-129230, 2015-196723, JP-A-2015-13983, JP-A-2015-199915, JP-A-2015-199906 and the like.

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., KY-178, KY-185, KY-1900 and the like manufactured by K.K.
As an example of a fluorine-containing ether compound having an R ^PF chain, an R ^f group and a group (I), and the R ^f group is CF ₃ CF ₂ CF ₂ —, Daikin Industries' Optool DSX, AES, Toray Dow Examples include DOW CORNING (registered trademark) 2634 COATING manufactured by Corning, and KY-108 manufactured by Shin-Etsu Chemical Co., Ltd.
Among these, the 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). May be

In the 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, which 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 whose 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 is the same as a fluorine-containing ether compound which 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 group, and oxyfluoroalkylene constituting the group. The alkylene groups may all be the same or different,
R ^PF is a poly (oxyperfluoroalkylene) chain,
Z is a (r + s) -valent linking group,
—SiR _n L _3-n is a group represented by the above formula (I), and when s is 2 or more, s groups represented by the formula (I) are the same groups;
Each of r and s is an integer of 1 or more, and r + s is 8 or less.

The r represents the number of R ^PF chains, and thus the number of R ^f 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 abrasion resistance.
The s represents the number of the group (I), and as described above, 1 to 3 are preferable from the viewpoint that the surface layer is more excellent in the water drop sliding property, and 2 or 3 from the viewpoint that the surface layer is further excellent in the abrasion resistance. Is particularly preferable.
From the above-mentioned point, r + s is preferably 2-6, and particularly preferably 3-5.
The (r + s) number Z is a linking group, described later Z ^a, preferably the linking group represented by Z ^b, for example a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted carbon atoms of the hydrocarbon group - A group having a group or atom other than a hydrocarbon group between carbon atoms and / or at the terminal, an organopolysiloxane group and the like can be mentioned. Preferable Z is the same linking group as preferable Z ^a and Z ^b described later.

<Preferred embodiment>
In one preferable embodiment of the present composition, the compound (A) is a fluorine-containing ether compound (A1) represented by the following formula (A1) (hereinafter, also referred to as “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 the present embodiment contains 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 -O-Q 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 the carbon number of R ^fa is smaller than the carbon number of 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, and The constituent oxyfluoroalkylene groups 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 of 0 to 2,
n1 is 0 or (3-n1) in the case of 1-number of ^L a, (3-n) when n2 is 0 or 1 pieces of ^{L b} respectively, it may be the same or different and
When n1 is 2, n1 R ^a 's and when n2 is 2, n2 R ^b's may be the same or different, and
r1 and r2 are integers of 1 or more, and when r1 is 2 or more, r 1 R ^{fa s} , Q ^a and R ^PFa may be the same or different, and when r2 is 2 or more, r 2 R ^fb , Q ^b and R ^PFb in each 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. s2 amino ^{_{[-SiR b n2 L b 3-}} n2] can be different even in the same.

The R ^f group is the same as described above, and the preferred embodiments are also the same.
r1 is r1 amino R ^fa when 2 or more, it preferably has a carbon number of identical, in terms of ease of manufacture, the same group, that is, identical and chemical structure carbon atoms of the same group Is preferred. The groups having the same carbon number and the same chemical structure mean that when R1 is 2, for example, two R ^fa are CF ₃ CF ₂ CF ₂ — (two R ^fa are It is the same carbon atoms chemical structure is _{different, CF 3 CF 2 CF 2 -} , CF 3 CF (CF 3) - is not a combination of).
When r2 is 2 or more, it is preferable that the two R ^fb 's have the same carbon number, and from the viewpoint of ease of production, the same group, that is, the group having the same carbon number and the same chemical structure. Is preferred.
In this embodiment, from the viewpoint of further excellent lubricity and abrasion resistance of the surface ^layer is preferably the number of carbon atoms of ^{R fa} is 1 to 19 carbon atoms in ^{the R fb} is ^2-20, the number of carbon atoms in ^{R fa} Is more preferably 1 to 9 and R ^fb has 2 to 10 carbon atoms, R ^fa has 1 to 5 carbon atoms, and R ^fb has 2 to 6 carbon atoms, and R ^fa has 2 to 6 carbon atoms. It is particularly preferable that the carbon number is 1, the carbon number of R ^fb is 2 or 3, or the carbon number of R ^fa is 2 and the carbon number of R ^fb is 3.

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 the preferred embodiments are also the same.
R ^a and R ^b are the same as R in the group (I), and the preferred embodiments are also the same.
n1 and n2 are the same as n in the above-mentioned group (I), and preferred embodiments are also the same.
The preferred values of r1 and r2 are the same as the preferred number of R ^PF chains in the compound (A) and the compound (B). That is, r1 and r2 are preferably 1 to 3 and particularly preferably 1 to 2 from the viewpoint of abrasion resistance.
The preferred values of s1 and s2 are the same as the preferred numbers of the group (I) contained in the compound (A) and the compound (B). That is, s1 and s2 are preferably 1 to 3 and particularly preferably 2 to 3 from the viewpoint of excellent water-drop sliding property of the surface layer.

As Z ^a , for example, a (r1 + s1) -valent substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group having a group or atom other than the hydrocarbon group between the carbon-carbon atoms or / and at the terminal. Examples thereof include a (r1 + s1) -valent group and a (r1 + s1) -valent organopolysiloxane group.
Examples of Z ^b include the same as Z ^a except that the valence is (r2 + s2).

The unsubstituted hydrocarbon group may be, for example, a linear or branched saturated hydrocarbon group or an aromatic hydrocarbon cyclic group (for example, (a + b) hydrogens from an aromatic hydrocarbon ring such as a benzene ring or a naphthalene ring). A group excluding atoms), a group consisting of a combination of a linear or branched saturated hydrocarbon group and an aromatic hydrocarbon cyclic group (for example, an alkyl group as a substituent bonded to the aromatic hydrocarbon cyclic group). Group, a group having an arylene group such as a phenylene group at a carbon atom or / and a terminal of the saturated hydrocarbon group), a group formed of a combination of two or more aromatic hydrocarbon cyclic groups, and the like. Of these, a linear or branched saturated hydrocarbon group is preferable.
The substituted hydrocarbon group is a group in which a 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 having a carbon-carbon atom or / and a terminal of the hydrocarbon group include, for example, an etheric oxygen atom (—O—), a thioetheric sulfur atom (—S—), and a nitrogen atom ( -N <), silicon atoms (> Si <), carbon atoms ^{(> C <), - N} (R 15) -, - C (O) N (R 15) -, - OC (O) N (R 15 )-, -Si (R ¹⁶ ) (R ¹⁷ )-, an organopolysiloxane group, -C (O)-, -C (O) -O-, -C (O) -S- and the like. However, R ¹⁵ is a hydrogen atom, an alkyl group or a phenyl group, and R ^{16 to} R ¹⁷ are 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 preferable because it is more excellent in the abrasion resistance of the surface layer and the 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 are as defined above,
Q ^32a is a fluoroalkylene group or a group having an etheric oxygen atom between the carbon and carbon atoms of the 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 represents a single bond, an alkylene group, terminal alkylene groups _{^{(wherein, C [-R 35a -SiR a n1}} L a 3-n1] 3 binding to the side end and.) In a group having an etheric oxygen atom, carbon of 2 or more alkylene groups having a carbon - terminal alkylene group group or having two or more carbons, having an etheric oxygen atom between carbon atoms (provided _{^{that, C [-R 35a -SiR a n1}} L a 3-n1] ₃ is a group having an ethereal oxygen atom between a carbon atom and a terminal end on the side of bonding with ₃ ),
R ^35a is an alkylene group, a group having an etheric oxygen atom at the end of the alkylene group (excluding the end on the side 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,
Three _{^{[-R 35a -SiR a n1 L a}} 3-n1] may or may not be the same.

The compound (A11) is the above formula (A1), wherein r1 is 1, s1 is 3, and Z is -Q ^32a- [C (O) N (R ^33a )] _{p 1} -R ^34a -C [. It is a compound of ^-R35a- ] ₃ .

In Q ^32a , the fluoroalkylene group is preferably a perfluoroalkylene group or a fluoroalkylene group containing one or more hydrogen atoms. Therefore, as Q ^32a , a perfluoroalkylene group, a fluoroalkylene group containing one or more hydrogen atoms, a group having an etheric oxygen atom between the carbon and carbon atoms of a perfluoroalkylene group having 2 or more carbon atoms, or one or more The group having an etheric oxygen atom between the carbon-carbon atoms of the fluoroalkylene group having 2 or more carbon atoms including the hydrogen atom is preferable.

When p1 is 0, Q ^32a is preferably a perfluoroalkylene group, and the perfluoroalkylene group preferably does not have a branched structure. When Q ^32a is a perfluoroalkylene group having no branched structure, the surface layer is more excellent in abrasion resistance and lubricity.
When p1 is 0, Q ^32a is typically a carbon when R ^PFa is {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 } or (CF ₂ CF ₂ O) _m13. When it is a perfluoroalkylene group of the formula 1, 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) is when an _m15 is typically a perfluoroalkylene group linear 3 carbon atoms.

When p1 is 1, Q ^32a includes the groups below.
(I) Perfluoroalkylene group.
(Ii) -R ^F CH ₂ O- (provided that R ^F is a perfluoroalkylene group.) ^Is present on the side where R ^PFa is bonded and has a fluoroalkylene group containing one or more hydrogen atoms (carbon-carbon). A group having an etheric oxygen atom between the atoms) on the side bonded to C (O) N (R ³³ ).

As Q ^{32a in} (ii), the following groups are preferable from the viewpoint of easy production of the compound (A11).
_{^{-R F CH 2 OCF 2 CHFOCF 2}} CF 2 CF 2 -, - R F CH 2 OCF 2 CHFCF 2 OCF 2 CF 2 -, - R F CH 2 OCF 2 CHFCF 2 OCF 2 CF 2 CF _{^{2 -, - R F CH 2}} OCF 2 CHFOCF 2 CF 2 CF 2 OCF 2 CF 2 -.
When the compound (A11) in which Q ^32a has no branched structure, a surface layer having excellent durability and lubricity can be formed.

[C (O) N (R ^33a )] When _p1 in the _p1 group is 0 and 1, the properties of the fluorine-containing ether compound are almost the same. When p is 1, it has an amide bond, but at least one fluorine atom is bonded to the terminal carbon atom of Q ^32a on the side bonded to [C (O) N (R ^33a )], The polarity of the amide bond becomes small, and the water / oil repellency of the surface layer does not easily deteriorate. Whether p1 is 0 or 1 can be selected from the viewpoint of ease of manufacturing.
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 may be a single bond, —CH ₂ O—, —CH ₂ OCH ₂ —, or —CH ₂ OCH ₂ CH ₂ O— from the viewpoint of easy production of the compound (A11). and _{-CH 2 OCH 2 CH 2 OCH 2} - selected from the group consisting of the groups (. However, the left side is bonded to ^{Q 32a)} are 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 is —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ OCH ₂ CH ₂ CH ₂ —, or —OCH ₂ CH, from the viewpoint of easy production of the compound (A11). ₂ CH ₂ - group selected from the group consisting of (. However, the right side is attached to the Si) are preferred.
As R ^35a , those having no etheric oxygen atom are particularly preferable from the viewpoint of excellent light resistance of the surface layer. In a touch panel for outdoor use (a vending machine, a digital signage such as a guide plate), an in-vehicle touch panel, etc., the water and oil repellent layer is required to have light resistance.
The three R ^35a in the compound (A11) may be the same or different.

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

However, W in these ^{formulas, R fa -O-Q a -R} PFa - a. The preferred form of W will be a combination of the preferred R ^fa , Q ^a and R ^PFa described above. The 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 42a -R 43a -N [-R 44a -SiR a n1 L a 3-n1] 2 ··· (A12)
However, R ^fa , Q ^a , R ^PFa , R ^a , L ^a, and n1 are 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 on the side bonded to N), a carbon atom of an alkylene group having 2 or more carbon atoms. -Etheric group having a 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 a carbon-carbon atom. 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 be the same or different.

Compound (A12) is, in the above formula (A1), r1 is 1, s1 is 2, Z is ^{-R 42a -R 43a -N [-R 44a} -] a _second compound.

R ^42a is preferably a perfluoroalkylene group having no branched structure. When R ^42a is a perfluoroalkylene group having no branched structure, the surface layer is more excellent in abrasion resistance and lubricity.
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 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 linear perfluoroalkylene group having 3 carbon atoms.

As R ^43a , from the viewpoint of ease of production of the compound (A12), —CH ₂ —, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ OCH ₂ CH ₂ —, and — A group selected from the group consisting of CH ₂ NHCH ₂ CH ₂ — (provided that the left side is bonded to R ^42a ) is preferable.
Since R ^43a has a high polarity and does not have an ester bond having insufficient chemical resistance and light resistance, R ^43a is excellent in 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 — (provided that the right side is bonded to Si, from the viewpoint of easy production of the compound (A12). ) Is preferred.
Since ^R44a has high polarity and does not have an ester bond having insufficient chemical resistance and light resistance, R44a is excellent in initial water repellency, chemical resistance and light resistance of the surface layer.
As R ^44a , those not having an etheric oxygen atom are particularly preferable 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 may not be the same group.

  Examples of compound (A12) include compounds of the following formulae. The compound is preferable because it is industrially easy to produce, easy to handle, and more excellent in water repellency, oil repellency, abrasion resistance, fingerprint stain removability, lubricity, chemical resistance, and light resistance.

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

"Compound (A13)"
The compound (A13) is represented by the following formula (A13).
^{[R fa -O-Q 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 are 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 at least one etheric oxygen atom between the carbon atom and the carbon atom of the hydrocarbon group,
R ^53a is an alkylene group,
e1 is an integer of 1 or more,
f1 is an integer of 1 or more,
(E1 + f1) is 3 or more,
When e1 is 2 or more, e1 R ^fa's are all the same group, and e1's Q ^a , R ^PFa , R ^51a and R ^52a may be the same or different,
f1 is f1 or when two or more _{^{[-O-R 53 -SiR n L}} 3-n] may be be the same or different.

The compound (A13) is the above formula (A1), wherein 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 is typically, _-CF 2 CF ₂ - a ^{and, R PFa} is _{(CF 2 CF 2 O-CF} 2 CF 2 CF 2 CF 2 _O) when it is _{m15 typically,} -CF _{2 CF} 2 _CF 2 - is.
When R ^51a is a linear compound (A13), a surface layer having excellent abrasion resistance and lubricity can be formed.

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

^{R fa -O-Q a -R PFa} -R 51a - The group, water and oil repellency, the durability of the surface layer, the fingerprint stain removal properties, lubricity, further further excellent terms and compounds in the appearance of (A13) 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 to 200, m21 amino CF the order of linking ₂ O and m22 amino _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 groups of the following formulae. As Z ^3a , a residue obtained by removing a hydroxyl group from a polyhydric alcohol having a primary hydroxyl group is preferable from the viewpoint of excellent reactivity of the hydroxyl group, and from the viewpoint of easy availability of raw materials, a group (Z-1), a group (Z-2) or the group (Z-3) is particularly preferable. However, R ⁴ is an alkyl group, and preferably a methyl group or an ethyl group.

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

  The preferred values of e1 and f1 are similar to the preferred values of r1 and r2, respectively.

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

However, W in these ^{formulas, R fa -O-Q a -R} PFa - a. The preferred form of W will be a combination of the preferred R ^fa , Q ^a and R ^PFa described above. The preferable 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 compounds (B11), compound (B12) and compound (B13), from the viewpoint of further excellent abrasion resistance of the surface layer 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 have the same ^meanings as described above,
Q ^32b is a fluoroalkylene group or a group having an etheric oxygen atom between the carbon and carbon atoms of the 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 represents a single bond, an alkylene group, terminal alkylene groups _{^{(wherein, C [-R 35b -SiR b n2}} L b 3-n2] 3 binding to the side end and.) In a group having an etheric oxygen atom, carbon of 2 or more alkylene groups having a carbon - terminal alkylene group group or having two or more carbons, having an etheric oxygen atom between carbon atoms (provided _{^{that, C [-R 35b -SiR b n2}} L b 3-n2] ₃ is a group having an ethereal oxygen atom between a carbon atom and a terminal end on the side of bonding with ₃ ),
R ^35b is an alkylene group, a group having an ethereal oxygen atom at the end of the alkylene group (excluding the end on the side bonded to Si), or an ether between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms. A group having a reactive oxygen atom,
Three _{^{[-R 35b -SiR b n2 L b}} 3-n2] may or may not be the same.

Compound (B11), in the above formula (B1), r2 is 1, s2 is 3, ^{Z b} is _{^{-Q 32b - [C (O)}} N (R 33b)] p2 -R 34b -C It is a compound of [ ^-R35b- ] ₃ .

Q ^32b , R ^33b , p2, R ^34b , and R ^35b are the same as Q ^32a , R ^33a , p1, R ^34a , and R ^35a in the formula (A11), respectively, and the 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 have the same ^meanings as described above,
R ^42b is a perfluoroalkylene group,
R ^43b is a single bond, an alkylene group, a group having an etheric oxygen atom or -NH- at the terminal of the alkylene group (excluding the terminal on the side bonded to N), carbon of an alkylene group having 2 or more carbon atoms. -Etheric group having a 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 a carbon-carbon atom. 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] it 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 have the same ^meanings as described above,
R ^51b is a linear perfluoroalkylene group,
R ^52b is an alkylene group,
Z ^3b is a (e2 + f2) -valent hydrocarbon group, or a group having 2 or more carbon atoms and a (e2 + f2) -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,
e2 is an integer of 1 or more,
f2 is an integer of 1 or more,
(E2 + f2) is 3 or more,
When e2 is 2 or more, e2 R ^fb's are all the same group, and e2's Q ^b , R ^PFb , R ^51b and R ^52b may be the same or different,
f2 is f2 or when two or more _{^{[-O-R 53b -SiR b n2}} L b 3-n2] can be different even in the same.

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 - ] It is a compound of _f2 .

R ^51b , R ^52b , Z ^3b , R ^53b , e2 and f2 are the same as R ^51a , R ^52a , Z ^3a , R ^53a , e1 and f1 in the formula (A13), respectively, and preferred embodiments are also the same. .

(Other fluorinated ether compounds)
The composition may further contain a fluorine-containing ether compound other than the compound (A) and the compound (B).
Examples of the other fluorine-containing ether compound include a fluorine-containing ether compound 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)
However, A ³¹ and A ³² are each independently a perfluoroalkyl group having 1 to 20 carbon atoms; Q ⁵¹ is a single bond, a fluoroalkylene group having no branched structure containing one or more hydrogen atoms, and 1 A group having an etheric oxygen atom at the end (excluding the end on the side bonded to A ³¹ -O) of a fluoroalkylene group having no branched structure containing the above hydrogen atom, and containing one or more hydrogen atoms A group having an etheric oxygen atom between carbon and carbon atoms of a fluoroalkylene group having 2 or more carbon atoms having no branched structure, or a fluoroalkylene group having 2 or more carbon atoms having no branched structure containing one or more hydrogen atoms. Is a group having an etheric oxygen atom between the terminal (excluding the terminal on the side bonded to A ³¹ —O) and the carbon-carbon atom (provided that the oxygen number is 10). Q ⁵² is a fluoroalkylene group having no branched structure containing one or more hydrogen atoms, or a fluoroalkylene group having two or more carbon atoms having no branched structure containing one or more hydrogen atoms. A group having an etheric oxygen atom between carbon and carbon atoms (provided that the number of oxygen is 10 or less); R ^F3 is a perfluoroalkylene group having no branched structure; m30 is 2 to 200 Is an integer; (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 It is 1 in cases other than a single bond.

As the compound (C1), those produced by a known production method may be used, or commercially available products may be used. For example, as a commercially available product of compound (C1) in which Q ⁵¹ is a single bond and p3 is 0, FOMBLIN (registered trademark) M, FOMBLIN (registered trademark) Y, FOMBLIN (registered trademark) Z (above, solveiso) Examples include Lexis), Krytox (registered trademark) (Dupont), and Demnum (registered trademark) (Daikin Industries).

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

(Composition of this composition)
In the composition, the content of the compound (A) and the compound (B) having a smaller number of carbon atoms in the R ^f group is 30 to 95 mass with respect to the total amount of the compound (A) and the compound (B). %, 40 to 90 mass% is preferable, and 40 to 80 mass% is particularly preferable. When the content of the R ^f group having the smaller number of carbon atoms is within the above range, the surface layer has excellent water drop slipperiness.

  In the present composition, the total amount of the compound (A) and the compound (B) is preferably 10% by mass or more, and particularly preferably 20% by mass or more, based on the total mass of the composition. The upper limit is not particularly limited and may be 100% by mass.

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

  The liquid medium is preferably an organic solvent. The organic solvent may be a fluorine-based organic solvent, a non-fluorine-based organic solvent, or may include both solvents.

Examples of the fluorinated organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines and fluoroalcohols.
As the fluorinated alkane, a compound having 4 to 8 carbon atoms is preferable. Commercially available products include, for example, C ₆ F ₁₃ H (Asahi Glass Co., Ltd., Asahi Clin (registered trademark) AC-2000), C ₆ F ₁₃ C ₂ H ₅ (Asahi Glass Co., Ltd., Asahi Culin (registered trademark) AC-6000). , C ₂ F ₅ CHFCHFCF ₃ (manufactured by Chemmers, Bertrel (registered trademark) XF) and the like.
Examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, bis (trifluoromethyl) benzene and the like.
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 Klin (registered trademark) AE-3000, manufactured by Asahi Glass Co., Ltd.), C ₄ F ₉ OCH ₃ (3M, Novec (registered trademark) 7100), C ₄ F ₉ OC ₂ H ₅ (manufactured by 3M, Novec (registered trademark) 7200), C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ (manufactured by 3M, Novec (registered trademark) 7300) and the like can be mentioned. .
Examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
Examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol and hexafluoroisopropanol.
The non-fluorine-based organic solvent is preferably a compound consisting of only hydrogen atoms and carbon atoms, and a hydrogen atom, a compound consisting of only carbon atoms and oxygen atoms, hydrocarbon-based organic solvents, alcohol-based organic solvents, ketone-based organic solvents, Examples include ether type organic solvents and ester type organic solvents.
The coating liquid preferably contains the liquid medium in an amount of 50 to 99.999% by mass, more preferably 70 to 99.5% by mass, further preferably 90 to 99.5% by mass, and 99 to 99. It is particularly preferable to contain 9% by mass.

The present coating liquid may contain, in addition to the present composition and a liquid medium, other components as long as the effects of the present invention are not impaired.
Other components include, for example, known additives such as acid catalysts and basic catalysts that accelerate the hydrolysis and condensation reaction of the hydrolyzable silyl group.
The content of other components in the present coating liquid is preferably 10% by mass or less, 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%, further 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, the solvent and the like.

[Article]
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 intermolecularly to form a Si-O-Si bond, or the silanol group chemically reacts with a hydroxyl group (base material-OH) on the surface of the base material. 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. When the thickness of the surface layer is at least the lower limit value of the above range, the effect of the surface treatment is likely to be sufficiently obtained. If the thickness of the surface layer is not more than the upper limit value of the above range, the utilization efficiency is high. The thickness of the surface layer is obtained by obtaining an interference pattern of reflected X-rays by an X-ray reflectance method using an X-ray diffractometer for thin film analysis (RIGAKU, ATX-G), and from the vibration cycle of the interference pattern. Can be calculated.

(Base material)
The substrate in the present invention is not particularly limited as long as it is a substrate required to have lubricity and water / oil repellency. Examples of the material of the base material include metal, resin, glass, sapphire, ceramic, stone, 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 base material.
As the base material, a base material for a touch panel, a base material for a display, a base material for an eyeglass lens is suitable, and a base material for a touch panel is particularly suitable. The touch panel substrate has a light-transmitting property. "Has translucency" means that the vertical incident type visible light transmittance according to JIS R3106: 1998 (ISO 9050: 1990) is 25% or more. As a material for the touch panel substrate, glass or transparent resin is preferable.

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

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

20-300 degreeC is preferable and, as for the temperature at the time of vacuum evaporation, 30-200 degreeC is especially preferable.
The pressure at the time of vacuum vapor deposition is preferably 1 × 10 ⁻¹ Pa or less, and particularly preferably 1 × 10 ⁻² Pa or less.

<Wet coating method>
Wet coating methods include spin coating method, wipe coating method, spray coating method, squeegee coating method, dip coating method, die coating method, inkjet method, flow coating method, roll coating method, casting method, Langmuir-Blodgett method, gravure method. Examples include a coating method.

<Post-processing>
In order to improve the abrasion resistance of the surface layer, an operation for promoting the reaction between the compound (A) and the compound (B) and the base material may be carried out, if necessary. Examples of the operation include heating, humidification, light irradiation and the like.
For example, by heating a substrate on which a surface layer is formed in an atmosphere having water, a hydrolysis reaction of a hydrolyzable silyl group into a silanol group, a reaction between a hydroxyl group on the surface of the substrate and a silanol group, silanol, etc. It is possible to promote reactions such as the formation of siloxane bonds due to the condensation reaction of groups.
After the surface treatment, compounds in the surface layer which are not chemically bonded to other compounds or the base material may be removed as necessary. Specific methods include, for example, a method of pouring a solvent on the surface layer, a method of wiping with a cloth soaked with a solvent, and the like.

[Action effect]
The present composition and the present coating liquid contain the compound (A) and the compound (B), and the content of the compound (A) in which the R ^f group has a small number of carbon atoms is the compound (A) and the compound (B). Since it is 30 to 95 mass% with respect to the total of (B), it is possible to form a surface layer having excellent water drop sliding property.
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 side of the substrate. By orienting the R ^f group on the side opposite to the base material side, the surface energy of the formed surface layer becomes low.
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 concavo-convex structure is formed. It is considered that the water repellency of the surface of the surface layer is further enhanced by this, and the contact angle and the falling angle of the water droplet are reduced, and the excellent water droplet sliding property is exhibited.

[Use]
The use of the present composition, the present coating liquid and the article is not particularly limited. For example, a display input device such as a touch panel; a surface protective coat of a transparent glass or transparent plastic (acrylic, polycarbonate, etc.) member, an antifouling coat for kitchen; a water-repellent and moisture-proof coat of electronic devices, heat exchangers, batteries, etc. Antifouling coat, antifouling coat for toiletries; Coat on members that require liquid repellency while conducting; Water repellent / waterproof / sliding coat for heat exchangers; Used for vibration sifter and surface low friction coat such as cylinder interior be able to. More specific examples of use include a front protective plate for a display, an antireflection plate, a polarizing plate, an antiglare plate, or those whose surface is subjected to an antireflection film treatment, and a touch panel for devices such as mobile phones and personal digital assistants. Various equipment such as seats and touch panel displays that have a display input device that operates on the screen with human fingers or palms, decorative building materials around water such as toilets, baths, washrooms, kitchens, etc. Water / waterproof coat, solar cell water-repellent coat, printed wiring board waterproof / water-repellent coat, electronic device housing / electronic component waterproof / water-repellent coat, power line insulation improving coat, various filter waterproof / Water repellent coat, waterproof coating of radio wave absorber and sound absorbing material, antifouling coat for bath, kitchen equipment, toiletries, water repellent / waterproof / sliding coat of heat exchanger, shaking 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 requiring water drop slipperiness. Such applications include, for example, antifouling coats for kitchens; water repellent and antifouling coats for heat exchangers, antifouling coats for toiletries; coats for members that require liquid repellency while conducting; water repellency for heat exchangers Examples include waterproof / sliding coats.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. Hereinafter, “%” is “mass%” unless otherwise specified.
Among Examples 1-10, Examples 3-9 are Examples, and Examples 1-2, 10 are Comparative Examples.

[Physical properties and evaluation]
(Number average molecular weight)
The number average molecular weight of the fluorine-containing ether compound was calculated by ¹ H-NMR and ¹⁹ F-NMR to determine the number (average value) of oxyperfluoroalkylene groups based on the terminal group. The terminal group is, for example, the group (I) or the R ^f group.

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

(Sliding speed of water drop)
The angle (tilt angle) between the surface of the article and the horizontal plane was set to 40 °, 50 μL of water droplet was dropped on the surface (surface layer) of the article, and the time when the water droplet moved 50 mm was measured. This moving time is the sliding speed.

[Synthesis Example 1]
The compound (14I-1) was obtained according to the method described in Example 6 of WO 2013/121984.
_{CF 3 -O- (CF 2 CF 2} O-CF 2 CF 2 CF 2 CF 2 O) x3 (CF 2 CF 2 O) -CF 2 CF 2 CF 2 -C (O) OCH 3 ··· (14I- 1)
Compound (14I-1): average number 13 of unit number x3, number average molecular weight 4,700.

Eggplant flask 50 mL, placed 9.0g and _{H 2 N-CH 2 -C (} CH 2 CH = CH 2) 3 of 0.45g of the compound (14I-1), and stirred for 12 hours. From NMR, it was confirmed that all the compound (14I-1) was converted to the compound (17I-1). In addition, methanol, which is a by-product, was produced. The resulting solution was diluted with 9.0 g of CF ₃ CH ₂ OCF ₂ CF ₂ H (AE-3000 manufactured by Asahi Glass Co., Ltd.) and purified by silica gel column chromatography (developing solvent: AE-3000) to obtain the 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 13 of unit number x3, 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% ), 0.78 g of HSi (OCH ₃ ) ₃ , 0.02 g of dimethylsulfoxide, and 0.49 g of 1,3-bis (trifluoromethyl) benzene (manufactured by Tokyo Chemical Industry Co., Ltd.), 40 The mixture was stirred 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 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 , reference: 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 number of units x3: 13, number average molecular weight of compound (A-1): 5,100.

[Synthesis example 2]
Compound (14I-2) was obtained according to the method described in Example 2 of WO 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 (14I-2): average number 13 of unit number x4, number average molecular weight 4,800.

8.4 g (yield 93%) of compound (17I-2) was obtained in the same manner as in 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): average number 13 of unit number x4, number average molecular weight 4,900.

6.7 g (yield 100%) of compound (B-1) was obtained like Example 1-3 except having used compound (17I-2) 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 , reference: 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): -84.0 (54F), -88.2 (3F), -89.2 (58F), -119. .7 (2F), -126.5 (54F).
The average number of units x4: 13, the number average molecular weight of the 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 the compound (A-1) was used in Example 1, and only the compound (B-1) was used in Example 2.

(Evaluation)
Using each of the compounds or compositions obtained in Examples 1 to 10, the surface treatment of the base material was performed to obtain an article having a surface layer on the surface of the base material. As the surface treatment method, the following dry coating method and wet coating method were used for each example. As the base material, chemically strengthened glass (Dragon Trail) was used. With respect to the obtained article, the water contact angle and the water drop sliding speed were evaluated. The results are shown in Table 1.

<Dry coating method>
The dry coating was performed using a vacuum vapor deposition device (VTR-350M manufactured by ULVAC) (vacuum vapor deposition method). 0.5 g of each compound or composition obtained in Examples 1 to 10 was filled in a molybdenum boat inside the vacuum vapor deposition apparatus, and the inside of the vacuum vapor deposition apparatus was evacuated to 1 × 10 ⁻³ Pa or less. The boat on which the composition is placed is heated at a temperature rising rate of 10 ° C./min or less, and when the vapor deposition rate by the crystal oscillation type film thickness meter exceeds 1 nm / sec, the shutter is opened to form the composition on the surface of the substrate. The membrane was started. When the film thickness reached about 50 nm, the shutter was closed to complete the film formation on the surface of the base material. 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 was mixed with C ₄ F ₉ OC ₂ H ₅ (3M, Novec (registered trademark) 7200) as a liquid medium to give a solid content concentration of 0.05. % Coating solution was prepared. The substrate was dipped in the coating liquid, left for 30 minutes, and then pulled up (dip coating method). The coating film was dried at 120 ° C. for 30 minutes and washed with AK-225 to obtain an article having a surface layer on the surface of the base material.

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 amount thereof. Compared to Examples 1 and 2 in which 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 water-drop sliding property of the surface layer was excellent.
The water drop slipperiness of the surface layer in Example 10 in which the content of the compound (A-1) was less than 30% by mass based on the total amount thereof was equivalent to that in Example 1.

(Examples 11 to 20)
A commercially available compound represented by CF ₃ O {(CF ₂ CF ₂ O) _m (CF ₂ O) _n } CF ₂ CH ₂ OH (average value of m is 20, average value of n is 21) is used, The following compound (A-2) was obtained according to the method described in Synthesis Examples 11 to 15 of 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, the following compound (B-2) was obtained according to the method described in Example 1 of WO2017 / 038830.
_{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)
The above-mentioned compound (A-2) and compound (B-2) were used to dry-coat a substrate in the same manner as in Examples 1 to 10, and the obtained article was evaluated for the falling angle and the falling speed. The results are shown in Table 2.

The compositions of Examples 13 to 19 containing the compound (A-2) and the compound (B-2), and the content of the compound (A-2) is 30 to 90 mass% with respect to the total thereof, Compared to Examples 11 and 12 in which each of the compound (A-2) and the compound (B-2) was used alone, the sliding angle was low, the sliding speed was high, and the water droplet sliding property of the surface layer was excellent.
The water drop slipperiness of the surface layer in Example 20 in which the content of the compound (A-2) was less than 30% by mass based on the total amount thereof was equivalent to that in Example 11.

The present composition and the present coating liquid can be used in various applications where lubricity and water / oil repellency are required. For example, a display input device such as a touch panel; a surface protective coat of transparent glass or a transparent plastic member, an antifouling coat for kitchens; a water-repellent and antifouling coat for electronic devices, heat exchangers, batteries, etc., for toiletries It can be used as an antifouling coat; a coat for a member that requires liquid repellency while conducting; a water-repellent / waterproof / sliding coat for a heat exchanger; a low-friction coat for the surface of a vibrating sieve or a cylinder.
Note that the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2017-024879 filed on February 14, 2017 are cited herein and incorporated as the disclosure of the specification of the present invention. Is.

Claims (15)

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 a poly (oxyperfluoroalkylene) chain, a perfluoroalkyl group bonded to one end of the chain, and a formula (I) below. Has 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 the fluorine-containing ether compound. Less than the carbon number of the perfluoroalkyl group of (B),
The content of the fluorinated ether compound (A) is 30 to 95 mass% with respect to the total of the fluorinated ether compound (A) and the fluorinated ether compound (B). Ether composition.
_{-SiR n L 3-n ··· (} I)
However, L is a hydroxyl group or a hydrolyzable group,
R is a hydrogen atom or a monovalent hydrocarbon group,
n is an integer of 0 to 2,
When n is 0 or 1, (3-n) 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) in the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) may be the same or different.   The carbon number of the perfluoroalkyl group which the said fluorine-containing ether compound (A) has is 1 to 19, and the carbon number of the perfluoroalkyl group which the said fluorine-containing ether compound (B) has is 2 to 20. Fluorine-containing ether composition.   The fluorine-containing ether compound (A) has a perfluoroalkyl group having 1 carbon atom, the fluorine-containing ether compound (B) has 2 or 3 carbon atoms, or the fluorine-containing ether compound (A 3. The fluorine-containing ether composition according to claim 1 or 2, wherein the perfluoroalkyl group contained in) has 2 carbon atoms, and the perfluoroalkyl group contained in the fluorine-containing ether compound (B) has 3 carbon atoms.   4. The number of groups represented by the formula (I) in each of the fluorinated ether compound (A) and the fluorinated ether compound (B) is 1 to 3, 4. The fluorine-containing ether composition described in 1.   The number of poly (oxyperfluoroalkylene) chains that each of the fluorinated ether compound (A) and the fluorinated ether compound (B) has is from 1 to 3, and the number of poly (oxyperfluoroalkylene) chains is from 1 to 4. Fluorine-containing ether composition. 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 larger than that of R ^{f in} the fluorinated ether compound (B). The fluorine-containing ether composition according to claim 1, which is also less.
_{^{[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 group, and oxyfluoroalkylene constituting the group. The alkylene groups may all be the same or different,
R ^PF is a poly (oxyperfluoroalkylene) chain,
Z is a (r + s) -valent linking group,
—SiR _n L _3-n is a group represented by the above formula (I), and when s is 2 or more, s groups represented by the formula (I) are the same groups;
Each of r and s is an integer of 1 or more, and r + s is 8 or less.   The fluorinated ether composition according to claim 6, wherein the r is 1 to 3.   The fluorinated ether composition according to claim 6 or 7, wherein the s is 1 to 3. 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) are contained, and the content of the fluorine-containing ether compound (A1) is 30-95 mass% with respect to the total of the said fluorine-containing ether compound (A1) and the said fluorine-containing ether compound (B1), The fluorine-containing ether composition characterized by the above-mentioned.
_{^{[R fa -O-Q 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, the carbon number of R ^fa is smaller than the carbon number of 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, and The constituent oxyfluoroalkylene groups 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 of 0 to 2,
n1 is 0 or (3-n1) in the case of 1-number of ^L a, (3-n) when n2 is 0 or 1 pieces of ^{L b} respectively, it may be the same or different and
When n1 is 2, n1 R ^a 's and when n2 is 2, n2 R ^b's may be the same or different, and
r1 and r2 are integers of 1 or more, and when r1 is 2 or more, r 1 R ^{fa s} , Q ^a and R ^PFa may be the same or different, and when r2 is 2 or more, r 2 R ^fb , Q ^b and R ^PFb in each may be the same or different,
s1 and s2 are integers greater than or equal to 1, s1 is s1 or when two or more ^{_{[-SiR a n1 L a 3-}} n1] may be different even in the same, s2 is 2 or more At this time, s2 [-SiR ^b _n2 L ^b _3-n2 ] may be the same or different. The fluorinated ether composition according to claim 9, wherein when r1 in the formula (A1) is 2 or more, r1 ^Rfa's are the same. The fluorinated ether composition according to claim 9 or 10, wherein when r2 in the formula (A2) is 2 or more, r 2 R ^{fb s} are the same. The carbon number of R ^fa in the formula (A1) is 1 to 19, and the carbon number of R ^fb in the formula (B1) is 2 to 20. The inclusion according to any one of claims 9 to 11. Fluorine ether composition. 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.   A coating liquid comprising the fluorine-containing ether composition according to any one of claims 1 to 13 and a liquid medium.   An article having a surface layer formed from the fluorine-containing ether composition according to any one of claims 1 to 13.