JP2022069480A - Fluorine-containing ether composition, coating liquid and article - Google Patents

Abstract

PROBLEM TO BE SOLVED: 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):SiR_nL_3-n, 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

COPYRIGHT: (C)2022,JPO&INPIT

Description

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

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

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

As the fluorine-containing ether compound, for example, the following fluorine-containing ether compound has been proposed.
1-3 of a group (α) consisting of at least one oxyperfluoroalkylene group having 1 to 2 carbon atoms and 1 to 3 of a group (β) consisting of at least one oxyperfluoroalkylene group having 3 to 6 carbon atoms. It has a poly (oxyperfluoroalkylene) chain having a poly (oxyperfluoroalkylene) group having a pair as a unit, and two or more of the units are linked to each other, and at least one end of the poly (oxyperfluoroalkylene) chain. A fluoroether 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 the above two kinds of the above-mentioned 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 slipperiness. It should be noted that the water droplet sliding property is a property that the water droplet easily slides down on an inclined surface (the falling angle is small or / and the sliding speed is high).
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 droplet sliding property, and an article having a surface layer having excellent water droplet 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 containing a fluorine-containing ether compound (A) and a fluorine-containing ether compound (B).
The fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) are represented by a poly (oxyperfluoroalkylene) chain, a perfluoroalkyl group bonded to one end thereof, and the following formula (I), respectively. Has a base and
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 contained in the fluorine-containing ether compound (A) is the fluorine-containing ether compound. It has less carbon atoms than the perfluoroalkyl group of (B),
The content of the fluorine-containing ether compound (A) 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 hydrolyzable group, and is
R is a hydrogen atom or a monovalent hydrocarbon group,
n is an integer of 0 to 2 and
When n is 0 or 1, the (3-n) L's may be the same or different.
When n is 2, n Rs may be the same or different.
The groups represented by the formula (I) of each of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) may be the same or different.

[2] The fluorine-containing ether compound (A) has 1 to 19 carbon atoms, and the fluorine-containing ether compound (B) has 2 to 20 carbon atoms. [1] Fluorine-containing ether composition.
[3] The perfluoroalkyl group of the fluorine-containing ether compound (A) has 1 carbon atom, and the perfluoroalkyl group of the fluorine-containing ether compound (B) has 2 or 3 carbon atoms, or the fluorine-containing ether. The fluorine-containing ether composition according to [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 number of groups represented by the formula (I) of each of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) is 1 to 3, [1] to [3]. Fluorine-containing ether composition of any of the above.
[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] Both the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) are fluorine-containing ether compounds represented by the following formula (A / B), and are contained in the composition. In the combination of 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) is the same as that of R ^f in the fluorine-containing ether compound (B). The fluorine-containing ether composition of [1], which has less than the number of 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 having 2 to 5 bonds of the oxyfluoroalkylene group, and oxyfluoro constituting the group. All alkylene groups may be the same or different.
RPF is a poly ( ^{oxyperfluoroalkylene} ) chain and is
Z is a linking group of (r + s) valence,
-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 group.
r and s are integers of 1 or more, respectively, 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 according to [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) are contained, and the fluorine-containing ether compound (A1) is contained. 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 -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, and the carbon number of R ^fa is smaller than that 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 having 2 to 5 bonds of the oxyfluoroalkylene group. The constituent oxyfluoroalkylene groups may all be the same or different.
R ^PFa and R ^PFb are poly (oxyperfluoroalkylene) chains and are
Z ^a is a linking group having a (r1 + s1) valence.
Z ^b is a linking group having a (r2 + s2) valence.
^{La and L b are} hydroxyl groups or hydrolyzable groups,
R ^a and R ^b are hydrogen atoms or monovalent hydrocarbon groups.
n1 and n2 are integers from 0 to 2 and
The (3-n1) L a when n1 is 0 or 1 and the (3-n ^{) L b when} n2 is 0 or 1 may be the same or different, respectively.
When n1 is 2, n1 R as and when ^{n2 is 2, n2 R bs may} be the same or different.
r1 and r2 are integers of 1 or more, and r1 ^Rfa , ^{Qa and RPFa may} be the same or different when r1 is 2 or more, and r2 when r2 is 2 or more. R ^fb , Q ^b and R ^PF b may be the same or different, respectively.
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. When s2 [-SiR ^b _n2 L ^b _3-n2 ] may be the same or different.

[10] The fluorine-containing ether composition according to [9], wherein r1 ^Rfas are the same when r1 in the formula (A1) is 2 or more.
[11] The fluorine-containing ether composition according to [9] or [10], wherein r2 R ^fb are the same when r2 in the formula (A2) is 2 or more.
[12] Any of [9] to [11], wherein 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. 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. 2. The fluorine-containing ether composition according to any one 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 the above [1] to [13] and a liquid medium.
[15] An article having a surface layer formed from the fluorine-containing ether composition according to any one of the above [1] to [13].

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

In the present 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). Compounds or groups represented by other formulas are also described in the same manner.
Further, the chemical formula of the oxyperfluoroalkylene group shall be 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 of the present invention (hereinafter, also referred to as “the present composition”) includes a fluorine-containing ether compound (A) (hereinafter, also referred to as “compound (A)”) and a fluorine-containing ether compound (B). ) (Hereinafter, also referred to as “compound (B)”). This composition does not contain a liquid medium, as will be described later. The present composition may be composed of the compound (A) and the compound (B), and as described later, a fluorine-containing ether compound other than the compound (A) and the compound (B), the compound (A), and the compound ( It may contain impurities other than B) and other fluorine-containing ether compounds.
The compound (A) and the compound (B) are each a poly ( ^{oxyperfluoroalkylene} ) chain (hereinafter, also referred to as “RPF 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, and is
R is a hydrogen atom or a monovalent hydrocarbon group,
n is an integer of 0 to 2 and
When n is 0 or 1, the (3-n) L's may be the same or different.
When n is 2, n Rs may be the same or different.

The number of carbon atoms of the R ^{f group of the compound (A) is smaller than the number of carbon atoms of the R f group} of the compound (B). That is, this composition contains two kinds of fluorine-containing ether compounds having an ^RPF chain, an ^Rf group and a group (I) having different carbon atoms of the ^Rf group. As a result, the surface layer has excellent slipperiness of water droplets.
^{The RPF} chain and the group (I) of each of the compound (A) and the compound (B) may be the same or different.

(R ^f group)
The carbon number of the ^Rf group is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 6, and particularly preferably 1 to 3 from the viewpoint of further excellent lubricity and friction resistance of the surface layer.
Therefore, it is preferable that the R ^f group of the compound (A) has 1 to 19 carbon atoms and the R ^f group of the compound (B) has 2 to 20 carbon atoms, and the R ^f group of the compound (A) has. It is more preferable that the carbon number of the R f group of the compound (B) is 1 to 9 and the carbon number of the R ^f group of the compound (B) is 2 to 10, and the carbon number of the R ^f group of the compound (A) is 1 to 5 and the compound ( It is more preferable that the R ^f group of B) has 2 to 6 carbon atoms, the R ^f group of the compound (A) has 1 carbon atom, and the R ^f group of the compound (B) has 2 carbon atoms. Alternatively, it is particularly preferable that the number of carbon atoms of the R ^f group of the compound (A) is 2, and the number of carbon atoms of the R ^f group of the compound (B) is 3.
The ^Rf group may be branched or linear, and linear is preferable. Examples of the ^Rf group include CF _3- , CF ₃ CF _2- , CF ₃ CF ₂ CF _2- , and the like, with CF _3- and CF ₃ CF _2- particularly preferred.

The number of R ^f groups contained in compound (A) is the same as the number of ^RPF chains. When compound (A) has two or more R ^f groups, all R ^f groups may be the same group or different groups, and are preferably the same group.
Similarly, the number of R ^f groups of compound (B) is the same as the number of ^RPF chains. When compound (B) has two or more R ^f groups, all R ^f groups may be the same group or different groups, and are preferably the same group.
However, the carbon number of the ^Rf group having the largest number of carbon atoms among the ^Rf groups possessed by the compound (A) is higher than the carbon number of the ^Rf group having the smallest carbon number among the ^Rf groups possessed by the compound (B). few.

As the combination of R ^f groups, the R ^{f group of the compound (A) is CF 3-, the R f group of the compound (B) is CF 3 CF 2-, and the R f} _group ^of _{the compound} ⁽ A) is The combination of CF _3- , the R ^f group of the compound (B) is CF ₃ CF ₂ CF _2- , the R ^f group of the compound (A) is CF ₃ CF _2- , and the R ^f group of the compound (B) is The combination of CF ₃ CF ₂ CF ₂ -is preferable, and the combination of the R ^f group of the compound (A) is CF ₃ − and the R ^f group of the compound (B) is CF ₃ CF _2- is particularly preferable.

The ^Rf group typically attaches to one end of the ^RPF chain via a linking group.
As the linking group, the group (II) is preferable. That is, it is preferable that the ^Rf group is bonded to one end of the ^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 attached to the R ^f group.
-OQ -... (II)
However, Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group to which 2 to 5 (preferably 2 to 4) of the oxyfluoroalkylene groups are bonded. Is. The oxyfluoroalkylene groups constituting the group may be all the same or different.

When Q is an oxyfluoroalkylene group having a hydrogen atom or a polyoxyfluoroalkylene group in which 2 to 5 of the oxyfluoroalkylene groups are bonded, the compound (A) and the compound (B) can be added to a liquid medium. Highly soluble. Therefore, the compound (A) and the compound (B) are difficult to aggregate in the coating liquid, and the compound (A) and the compound (B) are difficult to aggregate during drying after being applied to the surface of the base material. The appearance of the surface layer is even better.
The carbon number 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, and particularly preferably 3 or more, from the viewpoint of excellent appearance of the surface layer. The number of hydrogen atoms in the oxyfluoroalkylene group is preferably (Q carbon number) x 2 or less, and particularly preferably (Q carbon number) or less, from the viewpoint of further excellent water and oil repellency of the surface layer.
The oxyfluoroalkylene group may be 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 consisting of 2 to 5 oxyfluoroalkylene groups bonded, the 2 to 5 oxyfluoroalkylene groups may be the same or different.
As Q, from the viewpoint of ease of production of the compound (A) and the compound (B), a single bond or -CHFCF ₂ OCH ₂ CF ₂ O-, -CF ₂ CHFCF ₂ OCH ₂ CF ₂ O-,- CF ₂ CF ₂ CHFCF ₂ OCH ₂ CF ₂ O-, -CF ₂ CF ₂ OCHFCF ₂ OCH ₂ CF ₂ O-, -CF ₂ CF ₂ OCF ₂ CF ₂ OCHFCF ₂ OCH ₂ CF ₂ O-, -CF ₂ 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 binds to O) is preferred.

(R ^PF chain)
Examples of the R ^PF chain include an R ^PF chain represented by the following formula (1).
( ^RFO ) _m1 ... (1)
However, ^RF is a perfluoroalkylene group and is a perfluoroalkylene group.
m1 is an integer from 2 to 200,
( ^RFO ) _m1 may be composed of two or more types of ^RFO having different carbon atoms.

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

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 of the above range, the surface layer is excellent in water repellency and oil repellency. When m1 is not more than the upper limit of the above range, the friction resistance of the surface layer is excellent. That is, if 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 decreases, and the friction resistance decreases.

( ^RFO ) When two or more kinds of ^RFOs having different carbon atoms are present in _m1 , the bonding order of each ^RFO is not limited. For example, when two types of ^RFOs are present, the two types of ^RFOs may be randomly, alternately, or arranged in blocks.

( _RFO ) _m1 is {(CF ₂ O) _m11 (CF ₂ CF ₂ O) ^m12 }, (CF ₂ CF ₂ ) because it is more excellent in abrasion resistance, fingerprint stain resistance, and lubricity of the surface layer. 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 is preferable, {(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 preferable, and (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _m15 is particularly preferable.
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 binding order of m11 CF ₂ O and m12 CF ₂ CF ₂ O. Is not limited. m13 and m14 are integers of 2 to 200, respectively, and m15 is an integer of 1 to 100, respectively. m15 is preferably an integer of 2 to 100.

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

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

As L, an alkoxy group or a halogen atom having 1 to 4 carbon atoms is preferable from the viewpoint of ease of producing the compound (A) and the compound (B). As the halogen atom, a chlorine atom is particularly preferable. As L, an alkoxy group having 1 to 4 carbon atoms is preferable, and the compound (A) and the compound (B) have a low angstrom during coating and are excellent in storage stability 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 a saturated hydrocarbon group is preferable.
The number of carbon atoms of the monovalent hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2 in that the compound (A) and the compound (B) can be easily produced.

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

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

Each of the compound (A) and the compound (B) may have one group (I) or two or more groups (I). From the viewpoint of further excellent water droplet sliding property of the surface layer, 1 to 3 pieces are preferable, and from the viewpoint of further excellent friction resistance of the surface layer, 2 or 3 pieces are particularly preferable.
When the compound (A) and the compound (B) have two or more groups (I), each group (I) may or may not be the same group. In terms of ease of production of compound (A), it is preferable that all of them 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 Examples described later.

When the surface layer is formed by the dry coating method, it is preferable that the difference between the number average molecular weight (Mn) of the compound (A) and the number average molecular weight (Mn) of the compound (B) is small. In the case of the dry coating method, the smaller the molecular weight, the more likely it is to evaporate first and deposit on the substrate. The smaller the difference in the number average molecular weight (Mn), the less uneven the distribution of the compound (A) and the compound (B) occurs in the formed surface layer.
The difference between the number average molecular weight (Mn) of the compound (A) and the number average molecular weight (Mn) of the compound (B) is preferably 2,000 or less, and particularly preferably 1,000 or less.
When the surface layer is formed by the wet coating method, the surface layer is formed even if there is a difference between the number average molecular weight (Mn) of the compound (A) and the number average molecular weight (Mn) of the compound (B). Since uneven distribution of the compound (A) and the compound (B) is unlikely to occur, the difference between them is not particularly limited.
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 ^RPF chain, an ^Rf group and a group (I), respectively. For example, it can be appropriately selected from known fluorine-containing ether compounds such as the fluorine-containing ether compounds described in the following documents and commercially available fluorine-containing ether compounds.
Japanese Unexamined Patent Publication No. 2013-91047, Japanese Unexamined Patent Publication No. 2014-80473, International Publication No. 2013/042732, International Publication No. 2013/042733, International Publication No. 2013/121984, International Publication No. 2013/121985, International Publication No. 2013/121986, International Publication No. 2014/163004, International Publication No. 2014/175124, International Publication No. 2015/08792, Japanese Patent Application Laid-Open No. 2013-227279, Japanese Patent Application Laid-Open No. 2013-241569, Japanese Patent Application Laid-Open No. 2013- 256643, 2014-15609, 2014-37548, 2014-65884, 2014-21258, 2014-218639, 2015-208844. Gazette, JP-A-2015-221888, International Publication No. 2013/146112, International Publication No. 2013/187432, International Publication No. 2014/065922, International Publication No. 2015/099805, International Publication No. 2015/1667660, JP-A-2013-144726, JP-A-2014-77736, JP-A-2013-117012, JP-A-2014-214194, JP-A-2014-198822, JP-A-2015-129230, JP-A. 2015-196723A, 2015-13983A, 2015-199915A, 2015-199906A, etc.

As an example of a fluorine-containing ether compound having an RPF chain, an ^Rf group and a group (I), and the ^Rf group is CF _3- , ^Optool (registered trademark) UD509 manufactured by Daikin Industries, Ltd., Shin-Etsu Chemical Co., Ltd. KY-178, KY-185, KY-1900 and the like manufactured by KY-1900 and the like.
^Optool DSX, AES, Toray Dow manufactured by Daikin Industries, Ltd. as an example of a fluoroether compound having an RPF chain, an ^Rf group and a group (I) and having an ^Rf group of CF ₃ CF ₂ CF _2- . Examples thereof include DOWN CORNING (registered trademark) 2634 COATING manufactured by Corning Co., Ltd., KY-108 manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
Among these, the present composition contains a fluorine-containing ether compound having CF ₃ − as compound (A) and a fluorine-containing ether compound having an ^Rf group of CF ₃ CF ₂ CF _2- as compound (B). May be.

In the present composition, the compound (A) and the compound (B) may each 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, a fluorine-containing ether compound which is the same compound group except that it has a distribution in the number of repetitions of an oxyperfluoroalkylene group in a poly (oxyperfluoroalkylene) chain is regarded as a single compound. For example, in the case of a compound in which the _RPF chain is {(CF ₂ O) _m11 (R ^f2 O) ^m12 }, the same compound group except that the compounds have distributions in m11 and m12 is the same as the fluorine-containing ether compound which is a single compound. 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 less than the number of carbon atoms of R ^f in compound (B). Further, 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 having 2 to 5 bonds of the oxyfluoroalkylene group, and oxyfluoro constituting the group. All alkylene groups may be the same or different.
RPF is a poly ( ^{oxyperfluoroalkylene} ) chain and is
Z is a linking group of (r + s) valence,
-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 group.
r and s are integers of 1 or more, respectively, and r + s is 8 or less.

The r represents the number of the ^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 abrasion resistance.
The 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 property of the surface layer, and 2 or 3 from the point of further excellent friction resistance of the surface layer. Is particularly preferable.
Further, from the above points, r + s is preferably 2 to 6, and particularly preferably 3 to 5.
As the Z which is a (r + s) -valent linking group, a linking group represented by Z ^a and Z ^b described later is preferable, and for example, a substituted or unsubstituted hydrocarbon group and a substituted or unsubstituted hydrocarbon group carbon-. Examples thereof include a group having a group or atom other than a hydrocarbon group, an organopolysiloxane group and the like between carbon atoms and / or at the terminal thereof. Preferred Z is the same linking group as preferred Z ^a and Z ^b described later.

<Preferable aspect>
As a preferred embodiment of the present composition, the compound (A) is a fluorine-containing ether compound (A1) represented by the following formula (A1) (hereinafter, also referred to as “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 contains the compound (A1) and the compound (B1), and the content of the compound (A1) is 30 to 95% by 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 having 2 to 5 bonds of the oxyfluoroalkylene group. The constituent oxyfluoroalkylene groups may all be the same or different.
R ^PFa and R ^PFb are R ^PF chains and are R PF chains.
Z ^a is a linking group having a (r1 + s1) valence.
Z ^b is a linking group having a (r2 + s2) valence.
^{La and L b are} hydroxyl groups or hydrolyzable groups,
R ^a and R ^b are hydrogen atoms or monovalent hydrocarbon groups.
n1 and n2 are integers from 0 to 2 and
The (3-n1) L a when n1 is 0 or 1 and the (3-n ^{) L b when} n2 is 0 or 1 may be the same or different, respectively.
When n1 is 2, n1 R as and when ^{n2 is 2, n2 R bs may} be the same or different.
r1 and r2 are integers of 1 or more, and r1 ^Rfa , ^{Qa and RPFa may} be the same or different when r1 is 2 or more, and r2 when r2 is 2 or more. R ^fb , Q ^b and R ^PF b may be the same or different, respectively.
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 ^Rf 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 manufacture, they have the same group, that is, the same group having the same carbon number and the same chemical structure. Is preferable. A group having the same number of carbon atoms and the same chemical structure means that, for example, when r1 is 2, the two R ^fas are CF ₃ CF ₂ CF _2- (of two R ^fas ). It is not a combination of CF ₃ CF ₂ CF _2- and CF ₃ CF (CF ₃ )-that have the same number of carbon atoms but different chemical structures.)
When r2 is 2 or more, it is preferable that the r2 R ^fbs have the same carbon number, and from the viewpoint of ease of manufacture, the same group, that is, the group having the same carbon number and the same chemical structure. Is preferable.
In this embodiment, the carbon number of R ^fa is preferably 1 to 19 and the carbon number of R ^fb is 2 to 20 from the viewpoint of further excellent lubricity and abrasion resistance of the surface layer, and the carbon number of R ^fa is preferably 2 to 20. Is 1 to 9, the carbon number of R ^fb is more preferably 2 to 10, the carbon number of R ^fa is 1 to 5, and the carbon number of R ^fb is more preferably 2 to 6 ^. It is particularly preferable that the number of carbon atoms is 1, the number of carbon atoms of R ^fb is 2 or 3, or the number of carbon atoms of R ^fa is 2 and the number of carbon atoms of R ^fb is 3.

^Qa and ^Qb are the same as Q in the group (II), and preferred embodiments are also the same.
The ^RPF chains of ^RPFa and ^RPFb are the same as described above, and the preferred embodiments are also the same.
^{La and L b are} the same as L in the group (I), and the preferred embodiment is also the same.
R ^a and R ^b are the same as R in the group (I), and the preferred embodiment is also the same.
n1 and n2 are the same as n in the group (I), and the preferred embodiment is also the same.
The preferred values of r1 and r2 are the same as the preferred number of ^RPF chains of compound (A) and 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 number 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 sliding property of water droplets on the surface layer.

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

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

Examples of the group or atom other than the carbon dioxide group having between carbon atoms of the hydrocarbon group and / and the terminal include an ethereal oxygen atom (—O—), a thioetherulfurous sulfur atom (—S—), and 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 group, -C (O)-, -C (O) -O-, -C (O) -S- and the like. However, R ¹⁵ is a hydrogen atom, an alkyl group or a phenyl group, and R ¹⁶ to R ¹⁷ are independently alkyl groups or phenyl groups, respectively.
The organopolysiloxane group may be linear, branched or cyclic, or cyclic.

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

"Compound (A11)"
The compound (A11) is represented by the following formula (A11).
R ^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 , ^La and n1 have the same meanings as described above.
Q ^32a is a fluoroalkylene group or a group having an ethereal oxygen atom between 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 and is
R ^34a is ^a group having an ethereal oxygen atom at the terminal of a single bond, an alkylene group, or an alkylene group (however, the terminal on the side bonded to C [-R ^35a -SiR ann1 L ^a _{3-n1 ] 3} ). A group having an ethereal oxygen atom between 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 (however, C [-R ^35a -SiR ^a _n1 L ^a _3-n1 ]] ₃ ) and a group having an etheric oxygen atom between carbon atoms.
R ^35a 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 atoms of an alkylene group having 2 or more carbon atoms. A group with a sex oxygen atom
The three [-R ^35a -SiR ^a _n1 ^La _3-n1 ] may be the same or different.

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

In Q ^32a , as the fluoroalkylene group, a perfluoroalkylene group or a fluoroalkylene group containing one or more hydrogen atoms is preferable. Therefore, as Q ^32a , a perfluoroalkylene group, a fluoroalkylene group containing one or more hydrogen atoms, a group having an ethereal oxygen atom between carbon atoms of a perfluoroalkylene group having two or more carbon atoms, or one or more groups. A group having an ethereal oxygen atom between carbon atoms of a fluoroalkylene group having 2 or more carbon atoms including a hydrogen atom is preferable.

When p1 is 0, the Q ^32a is preferably a perfluoroalkylene group, and the perfluoroalkylene group preferably does not have a branched structure. If Q ^32a is a perfluoroalkylene group having no branched structure, the friction resistance and lubricity of the surface layer are further excellent.
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 it is a perfluoroalkylene group of number 1 and 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) When it is _m15 , it is typically a linear perfluoroalkylene group having 3 carbon atoms.

When p1 is 1, examples of Q ^32a include the following groups.
(I) Perfluoroalkylene group.
(Ii) ^-RF CH ₂ O- (where ^{RF is a perfluoroalkylene group) is on the side to be bonded to RPFa ,} and a fluoroalkylene group (carbon-carbon) containing one or more hydrogen atoms. A group having an ethereal oxygen atom between the atoms on the side to be bonded to C (O) N (R ³³ ).

As Q ^32a of (ii), the following groups are preferable from the viewpoint of ease of production of the compound (A11).
^-RF CH ₂ O-CF ₂ CHFOCF ₂ CF ₂ ^CF 2-, ^-RF CH ₂ O-CF ₂ CHFCF ₂ OCF ₂ CF ₂ -,-RF CH ₂ O _- CF ₂ CHFCF ₂ OCF ₂ CF ₂ CF _2- , ^-RF 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 having excellent 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 almost the same. When p is 1, it has an amide bond, but at least one fluorine atom is bonded to the carbon atom at the end of Q ^32a that is bonded to [C (O) N (R ^33a )]. The polarity of the amide bond becomes small, and the water and oil repellency of the surface layer does not easily decrease. Whether p1 is 0 or 1 can be selected from the viewpoint of ease of manufacture.
[C (O) N (R ^33a )] As the R ^33a in the _p1 group, a hydrogen atom is preferable from the viewpoint of ease of production of the compound (A11).
When R ^33a is an alkyl group, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms.

When p1 is 0, R ^34a has a single bond, -CH ₂ O-, -CH ₂ OCH _2- , -CH ₂ OCH ₂ CH ₂ O- from the viewpoint of ease of production of compound (A11). And -CH ₂ OCH ₂ CH ₂ OCH ₂ -A group selected from the group (where the left side binds 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 ease of production of the compound (A11).

As R ^35a , from the viewpoint of ease of production of compound (A11), -CH ₂ CH _2- , -CH ₂ CH ₂ CH _2- , -CH ₂ OCH ₂ CH ₂ CH _2- , -OCH ₂ CH A group selected from the group consisting of ₂ CH _2- (where the right side binds to Si) is preferable.
As R ^35a , those having no ethereal oxygen atom are particularly preferable from the viewpoint of excellent light resistance of the surface layer. In touch panels for outdoor use (digital signage such as vending machines and information boards), in-vehicle touch panels, etc., the water- and oil-repellent layer is required to have light resistance.
The three ^R35a in compound (A11) may be the same or different.

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

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

"Compound (A12)"
The compound (A12) is represented by the following formula (A12).
R ^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 , ^La and n1 have the same meanings as described above.
R ^42a is a perfluoroalkylene group and is a perfluoroalkylene group.
R ^43a is a single bond, an alkylene group, a group having an ethereal oxygen atom or -NH- at the end of the alkylene group (excluding the end on the side bonded to N), and carbon of an alkylene group having 2 or more carbon atoms. -Etheres between carbon atoms A group having an oxygen atom or -NH-, or an alkylene group having 2 or more carbon atoms (excluding the end on the side bonded to N) and an ethereal property between carbon and carbon atoms. A group having an oxygen atom or -NH-
R ^44a is an alkylene group or a group having an ethereal oxygen atom or -NH- between carbon atoms of an alkylene group having 2 or more carbon atoms.
The two [-R ^44a -SiR ^a _n1 L ^a _3-n1 ] may be the same or different.

The compound (A12) is a compound having r1 of 1, s1 of 2, and Z of —R ^42a −R ^43a −N [ ^−R44a −] ₂ in the above formula (A1).

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 excellent.
R ^42a is typically a perfluoroalkylene group having 1 carbon atom when R ^PFa is {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 } or (CF ₂ CF ₂ O) _m13 . Yes, when R ^PFa is (CF ₂ CF ₂ CF ₂ O) _m14 , it is typically a perfluoroalkylene group with 2 carbon atoms 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 a linear perfluoroalkylene group having 3 carbon atoms.

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

As R ^44a , -CH ₂ CH ₂ CH _2- or -CH ₂ CH ₂ OCH ₂ CH ₂ CH _2- (however, the right side is bound to Si) from the viewpoint of ease of production of the compound (A12). ) Is preferable.
Since R ^44a has high polarity and does not have an ester bond having insufficient chemical resistance and light resistance, it is excellent in initial water repellency, chemical resistance and light resistance of the surface layer.
As R ^44a , one having no ethereal oxygen atom is particularly preferable from the viewpoint of excellent light resistance of the surface layer.
The two R ^44a in compound (A12) may or may not be the same group.

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

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

"Compound (A13)"
The compound (A13) is represented by the following formula (A13).
[R ^fa -O-Q ^a -R ^PFa -R ^51a -R ^52a -O-] _e1 Z ^3a [-OR ^53a -SiR ^a _n1 L ^a _3-n1 ] _f1 ... (A13)
However, R ^fa , Q ^a , R ^PFa , R ^a , ^La and n1 have the same meanings as described above.
R ^51a is a linear perfluoroalkylene group.
R ^52a is an alkylene group and is an alkylene group.
Z ^3a is a (e1 + f1) -valent hydrocarbon group or a (e1 + f1) -valent group having 2 or more carbon atoms and having one or more ethereal oxygen atoms between carbon atoms of the hydrocarbon group.
R ^53a is an alkylene group and 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, all e1 R ^{fas are the same group, and e1 Qa, R PFa , R 51a} and R ^52a may be the same or different, respectively.
When f1 is 2 or more, f1 [-OR 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- when, for example, R ^{P Fa} 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 ^{P Fa} 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 linear compound (A13), a surface layer having excellent abrasion resistance and lubricity can be formed.

As R ^52a , an alkylene group having 1 to 4 carbon atoms is preferable, and _—CH2 − is particularly preferable, from the viewpoint of ease of production of the compound (A13).

R ^fa -O-Q ^a -R ^PFa -R ^51a -As a group, the surface layer has water and oil repellency, durability, fingerprint stain removal, lubricity, and is more excellent in appearance and compound (A13). From the viewpoint of ease of manufacture, a group (R ^f -1), a group (R ^f -2), or a 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 having 1 to 20 carbon atoms; m21 and ^m22 are integers of 1 or more, respectively, and m21 + m22 is an integer of 2 to 200, and m21 CFs. The binding order of ₂ O and m2 2 CF ₂ CF ₂ O is not limited; m25 is an integer from 1 to 100.

Examples of Z ^3a include residues obtained by removing hydroxyl groups from a polyhydric alcohol having (e1 + f1) hydroxyl groups.
As a specific example of Z ^3a , for example, the group of the following formula can be mentioned. As Z ^3a , a residue obtained by removing the hydroxyl group from a polyhydric alcohol having a primary hydroxyl group is preferable from the viewpoint of excellent reactivity of the hydroxyl group, and a group (Z-1) or a group is preferable from the viewpoint of easy availability of a raw material. (Z-2) or group (Z-3) is particularly preferred. However, R ⁴ is an alkyl group, preferably a methyl group or an ethyl group.

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

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

Examples of the compound (A13) include the 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 is further excellent in water and oil repellency, abrasion resistance, fingerprint stain removing property, lubricity, and appearance of the surface layer.

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

<Preferable 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) is selected from the viewpoint of further excellent abrasion resistance and fingerprint stain removing property of the surface layer. 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 ^PF b, R ^b , L ^b and n 2 have the same meanings as described above.
Q ^32b is a fluoroalkylene group or a group having an ethereal oxygen atom between 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 and is
R ^34b is a group having an ethereal oxygen atom at the end of a single bond, an alkylene group, or an alkylene group (where C [-R ^35b -SiR ^b _n2 L ^b _3-n2 ] ₃ is bonded to C [-R 35b-SiR b n2 L b 3-n2] 3). A group having an ethereal oxygen atom between 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 (however, C [-R ^35b -SiR ^b _n2 L ^b _3-n2 ]] It is a group having an ethereal oxygen atom between carbon atoms and the end on the side that bonds 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 atoms of an alkylene group having 2 or more carbon atoms. A group with a sex oxygen atom
The three [-R ^35b -SiR ^b _n2 L ^b _3-n2 ] may be the same or different.

In the above formula (B1), the compound (B11) has r2 of 1, s2 of 3, and ^{Zb of −Q 32b- [} C (O) N (R ^33b )] _p2 -R ^34b -C. [-R ^35b- ] It is a compound of 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 above formula (A11), respectively, and the preferred embodiments are also the same.

"Compound (B12)"
The compound (B12) is represented by the following formula (B12).
R ^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 ^PF b, R ^b , L ^b and n 2 have the same meanings as described above.
R ^42b is a perfluoroalkylene group and
R ^43b is a single bond, an alkylene group, a group having an ethereal oxygen atom or -NH- at the end of the alkylene group (excluding the end on the side bonded to N), and carbon of an alkylene group having 2 or more carbon atoms. -Etheres between carbon atoms A group having an oxygen atom or -NH-, or an alkylene group having 2 or more carbon atoms (excluding the end on the side bonded to N) and an ethereal property between carbon and carbon atoms. A group having an oxygen atom or -NH-
R ^44b is an alkylene group or a group having an ethereal oxygen atom or -NH- between carbon atoms of an alkylene group having 2 or more carbon atoms.
The two [-R ^44b -SiR ^b _n2 L ^b _3-n2 ] do not have to be the same group.

The compound (B12) is a compound having r2 of 1, s2 of 2, and ^Zb of -R ^42b -R ^43b -N [-R ^44b- ] ₂ in the above formula (B1).

R ^42b , R ^43b , and R ^44b are the same as R ^42a , R ^43a , and R ^44a in the above formula (A12), respectively, 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 [-OR ^53b -SiR ^b _n2 L ^b _3-n2 ] _f2 ... (B13)
However, R ^fa , Q ^b , R ^PF b, R ^b , L ^b and n 2 have the same meanings as described above.
R ^51b is a linear perfluoroalkylene group.
R ^52b is an alkylene group and has an alkylene group.
Z ^3b is a (e2 + f2) valent hydrocarbon group, or a (e2 + f2) valent group having 2 or more carbon atoms and having one or more ethereal oxygen atoms between carbon atoms of the hydrocarbon group.
R ^53b is an alkylene group and 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, all e2 R fbs are the same group, and e2 Q ^b , R ^PFb , R ^51b and R ^{52 b} may be the same or different, respectively.
When f2 is 2 or more, the f2 [-OR ^53b -SiR ^b _n2 L ^b _3-n2 ] may be the same or different.

In the compound (B13), in the above formula (B1), r2 is e2, s2 is f2, and 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 above 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 a fluorine-containing ether compound having a poly (oxyperfluoroalkylene) chain and no group (I) (hereinafter, also referred to as compound (C)).

Examples of the compound (C) include the compound (C1).
A ³¹ -O-Q _{51- (RF3 O) m30-} ^{[Q 52 - O} ] _p3 -A ³² ... (C1)
However, A ³¹ and A ³² are independently perfluoroalkyl groups having 1 to 20 carbon atoms; Q ⁵¹ is a single bond, a fluoroalkylene group having no branched structure containing one or more hydrogen atoms, and one. A group having an ethereal oxygen atom at the end of a fluoroalkylene group having no branched structure containing the above hydrogen atom (excluding the end on the side bonded to ^A31 -O) and containing one or more hydrogen atoms. A group having an ethereal oxygen atom between 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. It is a group having an ethereal oxygen atom between the end of A31-O (excluding the end on the side bonded to ^A31 -O) and the carbon-carbon atom (however, the number of oxygen is 10 or less); ^Q52 . Is ethereal between carbon-carbon atoms of 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. It is a group having an oxygen atom (however, the number of oxygen is 10 or less); RF3 is a perfluoroalkylene group having no branched structure; ^m30 is an integer of 2 to 200; ( ^RF3 O). ) M30 may consist of two or more _RF3Os with different carbon atoms; ^p3 is 0 if Q ⁵¹ is a single bond and 1 if Q ⁵¹ is not a single bond. be.

As the compound (C1), a compound produced by a known production method may be used, or a commercially available product may be used. For example, as commercially available products of the compound (C1) in which Q51 is a single bond and p3 is 0, FOMBLIN (registered trademark) M, FOMBLIN (registered trademark) Y, and FOMBLIN (registered trademark) Z (hereinafter, ^sorbiso ) are available. Lexis), Krytox (registered trademark) (DuPont), Demnam (registered trademark) (Daikin Industries, Ltd.) and the like.

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

(Composition of this composition)
In the present composition, the content of the compound (A) and the compound (B) having the smaller number of carbon atoms of the R ^f group is 30 to 95 mass by mass with respect to the total of the compound (A) and the compound (B). %, Preferably 40 to 90% by mass, and particularly preferably 40 to 80% by mass. When the content of the ^Rf group having a smaller number of carbon atoms is within the above range, the surface layer has excellent water droplet sliding property.

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. The upper limit is not particularly limited and may be 100% by mass.

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

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

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

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

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

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

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

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

(Base material)
The base material in the present invention is not particularly limited as long as it is a base material that is required to be imparted with lubricity and water / oil repellency. Examples of the material of the base material include metal, resin, glass, sapphire, ceramic, stone, and 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, and a base material for a spectacle lens are suitable, and a base material for a touch panel is particularly suitable. The base material for the touch panel has translucency. "Having translucency" means that the vertically incident type visible light transmittance according to JIS R3106: 1998 (ISO 9050: 1990) is 25% or more. As the material of the base material for the touch panel, glass or a transparent resin is preferable.

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

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

The temperature at the time of vacuum 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, and particularly preferably 1 × 10 ^-2 Pa or less.

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

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

[Action effect]
In the present composition and the present coating liquid, the content of the compound (A) containing the compound (A) and the compound (B) and having a small number of carbon atoms in the ^Rf group among them is the compound (A) and the compound. Since it is 30 to 95% by mass with respect to the total of (B), a surface layer having excellent water droplet sliding property can be formed.
In each of the compound (A) and the compound (B), the group (I) is present on the other end side of the R ^PF chain because the R ^f group is bonded to one end of the R ^PF chain. According to the compound (A) and the compound (B) having such a structure, when the surface layer is formed on the base material, the ^Rf group of each compound tends to be oriented on the side opposite to the base material side. By orienting the ^Rf group on the side opposite to the base material side, the surface energy of the formed surface layer is lowered.
In addition to this, the R ^f groups of the compound (A) and the compound (B) have different carbon numbers, so that the R ^f groups having different carbon numbers are dispersed and arranged on the surface of the surface layer at a specific ratio. It is considered that a fine uneven structure of physical or physical properties is formed. It is considered that this further enhances the water repellency of the surface of the surface layer, reduces the contact angle and the falling angle of the water droplet, and exhibits excellent water droplet sliding property.

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

Since the above effects are obtained, the present composition, the present coating liquid and the article are suitably used for applications in which water droplet slipperiness is required. Such applications include, for example, antifouling coats for kitchens; water- and moisture-proof coats and antifouling coats for heat exchangers, antifouling coats for toiletries; coats for members that require liquid repellency while conducting; water-repellent coatings for heat exchangers. Examples include waterproof and water-sliding coats.

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto. Hereinafter, "%" is "mass%" unless otherwise specified.
Of Examples 1 to 10, Examples 3 to 9 are Examples, and Examples 1 to 2 and 10 are Comparative Examples.

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

(Falling angle of water droplets)
After dropping 50 μL of water droplets 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 droplets began to fall was measured.

(Sliding speed of water droplets)
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 droplets moved by 50 mm was measured. This travel time is defined as the sliding speed.

[Synthesis Example 1]
Compound (14I-1) was obtained according to the method described in Example 6 of International Publication No. 2013/121984.
CF ₃ -O- (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _x3 (CF ₂ CF ₂ O) -CF ₂ CF ₂ CF ₂ -C (O) OCH ₃ ... (14I-) 1)
Compound (14I-1): average value 13 of unit number x 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 placed 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 obtained solution was diluted with 9.0 g of CF ₃ CH ₂ OCF ₂ CF ₂ H (manufactured by Asahi Glass Co., Ltd., AE-3000), purified by silica gel column chromatography (developing solvent: AE-3000), and compounded (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 value 13 of unit number x 3, number average molecular weight 4,800.

In a 10 mL PFA sample tube, 6.0 g of compound (17I-1) and a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%). ) 0.07 g, HSi (OCH ₃ ) ₃ 0.78 g, dimethyl sulfoxide 0.02 g, 1,3-bis (trifluoromethyl) benzene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 0.49 g, 40 The mixture was stirred at ° 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 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). Mean value of unit number 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 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 (14I-2): mean number 13 of unit number x 4, 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): mean number 13 of units x 4, 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 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).
Mean value of unit number x4: 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 mixed at the mass ratios shown in Table 1 to prepare a composition, which was subjected to the following evaluation. However, in Example 1, only compound (A-1) was used, and in Example 2, only compound (B-1) was used.

(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. Chemically tempered glass (Dragontrail) was used as the base material. For the obtained article, the water contact angle and the sliding speed of water droplets were evaluated. The results are shown in Table 1.

<Dry coating method>
Dry coating was performed using a vacuum vapor deposition apparatus (VTR-350M, manufactured by ULVAC, Inc.) (vacuum vapor 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 vapor deposition apparatus, and the inside of the vacuum vapor deposition apparatus was exhausted to 1 × 10 ^-3 Pa or less. The boat on which the composition is placed is heated at a heating 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 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 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 is mixed with C ₄ F ₉ OC ₂ H ₅ (3M, Novek® 7200) as a liquid medium, and the solid content concentration is 0.05. % Coating solution was prepared. The base material was dipped in the coating liquid, left for 30 minutes, and then the base material was pulled up (dip 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, which include compound (A-1) and compound (B-1) and have a content of compound (A-1) of 30 to 95% by mass based on the total content thereof, are: Compared with Examples 1 and 2 in which the compound (A-1) and the compound (B-1) were used alone, the rolling angle was low, the sliding speed was high, and the water droplet sliding property of the surface layer was excellent.
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 with respect to the total of them was equivalent to that in Example 1.

(Examples 11 to 20)
Using a commercially available compound represented by CF ₃ O {(CF ₂ CF ₂ O) _m (CF ₂ O) _n } CF ₂ CH ₂ OH (mean value of m is 20, mean value of n is 21), The following compound (A-2) was obtained according to the methods described in Synthesis Examples 11 to 15 of Japanese Patent No. 5676305.
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 International Publication No. 2017/038830.
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)
Using the above compound (A-2) and compound (B-2), the substrate was dry-coated in the same manner as in Examples 1 to 10, and the falling angle and falling speed of the obtained article were evaluated. The results are shown in Table 2.

The compositions of Examples 13-19 comprising compound (A-2) and compound (B-2) and having a content of compound (A-2) of 30 to 90% by mass based on the total content thereof are available. Compared with Examples 11 and 12, in which the compound (A-2) and the compound (B-2) were used alone, the rolling angle was low, the sliding speed was high, and the water droplet sliding property of the surface layer was excellent.
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 with respect to the total of them was equivalent to that in Example 11.

The present composition and the present coating liquid can be used for various applications in which lubricity and water repellency and oil repellency are required. For example, display input devices such as touch panels; surface protective coats made of transparent glass or transparent plastic materials, antifouling coats for kitchens; water- and moisture-repellent coats for electronic devices, heat exchangers, batteries, etc., antifouling coats, and toiletries. Antifouling coat; Coat for members that require liquid repellency while conducting; Water repellent / waterproof / water-sliding coat for heat exchangers; Can be used for vibration sieves, surface low friction coats such as inside cylinders, and the like.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2017-024879 filed on February 14, 2017 are cited here and incorporated as disclosure of the specification of the present invention. Is.

Claims (15)

A composition containing a fluorine-containing ether compound (A) and a fluorine-containing ether compound (B).
The fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) are represented by a poly (oxyperfluoroalkylene) chain, a perfluoroalkyl group bonded to one end thereof, and the following formula (I), respectively. Has a base and
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 contained in the fluorine-containing ether compound (A) is the fluorine-containing ether compound. It has less carbon atoms than the perfluoroalkyl group of (B),
The content of the fluorine-containing ether compound (A) 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 hydrolyzable group, and is
R is a hydrogen atom or a monovalent hydrocarbon group,
n is an integer of 0 to 2 and
When n is 0 or 1, the (3-n) L's may be the same or different.
When n is 2, n Rs may be the same or different.
The groups represented by the formula (I) of each of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) may be the same or different. The first aspect of claim 1, wherein the fluorine-containing ether compound (A) has 1 to 19 carbon atoms and the fluorine-containing ether compound (B) has 2 to 20 carbon atoms. Fluorine-containing ether composition. The perfluoroalkyl group of the fluorine-containing ether compound (A) has 1 carbon atom, and the perfluoroalkyl group of the fluorine-containing ether compound (B) has 2 or 3 carbon atoms, or the fluorine-containing ether compound (A). The fluorine-containing ether composition according to claim 1 or 2, wherein the perfluoroalkyl group of the above-mentioned compound (B) has 2 carbon atoms and the perfluoroalkyl group of the fluorine-containing ether compound (B) has 3 carbon atoms. One of claims 1 to 3, wherein each of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) has 1 to 3 groups represented by the formula (I). Fluorine-containing ether composition according to. The invention according to any one of claims 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. Both the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) are the fluorine-containing ether compounds represented by the following formula (A / B), and are contained in the composition. In the combination of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B), the carbon number of R ^f in the fluorine-containing ether compound (A) is higher than the carbon number of R ^f in the fluorine-containing ether compound (B). The fluorine-containing ether composition according to claim 1, which is 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 having 2 to 5 bonds of the oxyfluoroalkylene group, and oxyfluoro constituting the group. All alkylene groups may be the same or different.
RPF is a poly ( ^{oxyperfluoroalkylene} ) chain and is
Z is a linking group of (r + s) valence,
-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 group.
r and s are integers of 1 or more, respectively, and r + s is 8 or less. The fluorine-containing ether composition according to claim 6, wherein r is 1 to 3. The fluorine-containing ether composition according to claim 6 or 7, wherein the s is 1 to 3. It contains a fluorine-containing ether compound (A1) represented by the following formula (A1) and a fluorine-containing ether compound (B1) represented by the following formula (B1), and the content of the fluorine-containing ether compound (A1) is A fluorine-containing ether composition, which is 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 -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, and the carbon number of R ^fa is smaller than that 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 having 2 to 5 bonds of the oxyfluoroalkylene group. The constituent oxyfluoroalkylene groups may all be the same or different.
R ^PFa and R ^PFb are poly (oxyperfluoroalkylene) chains and are
Z ^a is a linking group having a (r1 + s1) valence.
Z ^b is a linking group having a (r2 + s2) valence.
^{La and L b are} hydroxyl groups or hydrolyzable groups,
R ^a and R ^b are hydrogen atoms or monovalent hydrocarbon groups.
n1 and n2 are integers from 0 to 2 and
The (3-n1) L a when n1 is 0 or 1 and the (3-n ^{) L b when} n2 is 0 or 1 may be the same or different, respectively.
When n1 is 2, n1 R as and when ^{n2 is 2, n2 R bs may} be the same or different.
r1 and r2 are integers of 1 or more, and r1 ^Rfa , ^{Qa and RPFa may} be the same or different when r1 is 2 or more, and r2 when r2 is 2 or more. R ^fb , Q ^b and R ^PF b may be the same or different, respectively.
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. When s2 [-SiR ^b _n2 L ^b _3-n2 ] may be the same or different. The fluorine-containing ether composition according to claim 9, wherein when r1 in the formula (A1) is 2 or more, r1 ^Rfas are the same. The fluorine-containing ether composition according to claim 9 or 10, wherein when r2 in the formula (A2) is 2 or more, r2 R ^fbs are the same. The inclusion according to any one of claims 9 to 11, wherein 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. 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 comprising a surface layer formed from the fluorine-containing ether composition according to any one of claims 1 to 13.