JP7243783B2 - FLUORINE-CONTAINING ETHER COMPOSITION, COATING LIQUID AND ARTICLE - Google Patents

Description

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

Fluorine-containing compounds are used as surface treatment agents and the like because they exhibit high lubricity, water and oil repellency, and the like. For example, when a surface layer is formed on the surface of a base material with the surface treatment agent, lubricity, water and oil repellency, etc. are imparted, making it easier to wipe off stains on the surface of the base material, thereby improving stain removability. Among fluorine-containing compounds, a fluorine-containing ether compound having a poly(oxyperfluoroalkylene) chain in which an ether bond (--O--) exists in the middle of the perfluoroalkyl chain is excellent in removing stains such as oils and fats.

As fluorine-containing ether compounds, those having a hydrolyzable silyl group have been proposed. Such a fluorine-containing ether compound has the property that the water and oil repellency does not deteriorate even when repeatedly rubbed with a finger (friction resistance), and the property that fingerprints adhering to the surface can be easily removed by wiping (fingerprint stain removability). is required to be maintained for a long period of time, for example, it is used as a surface treatment agent for members that constitute the surface touched by a finger of a touch panel.

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

JP 2014-65884 A

However, according to the inventors of the present invention, the surface layer formed from the fluorine-containing ether composition as described above tends to deteriorate in performance such as lubricity and water/oil repellency when repeatedly rubbed with a finger or the like. (durability is low). Therefore, it is difficult to achieve both lubricity and durability at high levels.

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

The present invention provides a fluorine-containing ether composition, a coating liquid and an article having the following constitutions [1] to [15].
[1] including a fluorine-containing ether compound (A) and a fluorine-containing ether compound (B),
The fluorine-containing ether compound (A) is a compound having a poly(oxyperfluoroalkylene) chain containing (CF ₂ O) units and a group represented by the following formula (I),
The fluorine-containing ether compound (B) is a compound having a poly(oxyperfluoroalkylene) chain containing no (CF ₂ O) unit and a group represented by the formula (I). Composition.
—SiR _n L _3-n (I)
provided that L is a hydroxyl group or a hydrolyzable group,
R is a hydrogen atom or a monovalent hydrocarbon group,
n is an integer from 0 to 2,
When n is 0 or 1, (3-n) L may be the same or different,
When n is 2, n R may be the same or different,
The groups represented by formula (I) in the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) may be the same or different.

[2] 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),
R ^f in the fluorine-containing ether compound (A) is a poly(oxyperfluoroalkylene) chain containing (CF ₂ O) units,
The fluorine-containing ether composition of [1], wherein R ^f in the fluorine-containing ether compound (B) is a poly(oxyperfluoroalkylene) chain containing no (CF ₂ O) unit.
[R ^f1 -OQR ^f -] _r Z [-SiR _n L _3-n ] _s (A/B)
provided that R ^f1 is a perfluoroalkyl group,
Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group in which 2 to 5 of the oxyfluoroalkylene groups are bonded, and the polyoxyfluoroalkylene group is The constituent oxyfluoroalkylene groups may all be the same or different,
R ^f is a poly(oxyperfluoroalkylene) chain,
Z is a (r+s)-valent linking group,
—SiR _n L _3-n is a group represented by formula (I) above,
when r is 2 or more, r pieces of [R ^f1 -OQR ^f -] are the same group;
When s is 2 or more, the s groups represented by formula (I) are the same group,
r and s are each an integer of 1 or more, and r+s is 3-8.

[3] The poly(oxyperfluoroalkylene) chain containing (CF ₂ O) units is a poly(oxyperfluoroalkylene) chain containing (CF ₂ O) units and (CF ₂ CF ₂ O) units, [ 1] or [2] fluorine-containing ether composition.
[4] The poly(oxyperfluoroalkylene) chain containing no (CF ₂ O) units comprises (CF ₂ CF ₂ O) units, (CF ₂ CF ₂ CF ₂ O) units and (CF ₂ CF ₂ CF ₂ CF ₂ O) The fluorine-containing ether composition of any one of [1] to [3], which is a poly(oxyperfluoroalkylene) chain containing at least one selected from units.
[5] The poly _{( oxyperfluoroalkylene} ) chain containing _no ( _CF2O ) units is a poly( _{oxyperfluoroalkylene} ) chain containing ( _{CF2CF2OCF2CF2CF2CF2O} ) _units . The fluorine-containing ether composition according to any one of [1] to [4].
[6] Any one of [1] to [5], wherein at least one of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) has three or more groups represented by the formula (I). A fluorine-containing ether composition.
[7] Any one of [1] to [5], wherein both the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) have two or more groups represented by the formula (I). fluorine-containing ether composition.
[8] Any one of [1] to [5], wherein both the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) have three or more groups represented by the formula (I). fluorine-containing ether composition.
[9] The fluorine-containing ether composition according to any one of [1] to [8], wherein the fluorine-containing ether compound (A) has a number average molecular weight of 2,000 to 20,000.
[10] The fluorine-containing ether composition according to any one of [1] to [9], wherein the fluorine-containing ether compound (B) has a number average molecular weight of 2,000 to 20,000.
[11] Any of [1] to [10], containing 10 to 80% by mass of the fluorine-containing ether compound (A) with respect to the total of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) A fluorine-containing ether composition.

[12] A fluorine-containing ether composition comprising a fluorine-containing ether compound (A1) represented by the following formula (A1) and a fluorine-containing ether compound (B1) represented by the following formula (B1).
[R ^f1a —OQ ^a —R ^fa —] _ra Z ^a [—SiR ^a _na L ^a _3-na ] _sa (A1)
[R ^f1b —OQ ^b —R ^fb —] _rb Z ^b [—SiR ^b _nb L ^b _3-nb ] _sb (B1)
provided that R ^f1a and R ^f1b are perfluoroalkyl groups,
Q ^a and Q ^b are a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group in which 2 to 5 of the oxyfluoroalkylene groups are bonded, and the polyoxy All of the oxyfluoroalkylene groups constituting the fluoroalkylene group may be the same or different,
R ^fa is a poly(oxyperfluoroalkylene) chain containing (CF ₂ O) units,
R ^fb is a poly(oxyperfluoroalkylene) chain containing no (CF ₂ O) units;
Z ^a is a (ra + sa) valent linking group,
Z ^b is a (rb+sb)-valent linking group,
L ^a and L ^b are hydroxyl groups or hydrolyzable groups,
R ^a and R ^b are a hydrogen atom or a monovalent hydrocarbon group,
na and nb are integers from 0 to 2;
(3-na) L ^a when na is 0 or 1 and (3-nb) L ^b when nb is 0 or 1 may be the same or different,
When na is 2, na R ^a 's, and when nb is 2, nb R ^b 's may be the same or different,
ra and rb are integers of 1 or more, and when ra is 2 or more, ra [R ^f1a -OQ ^a -R ^fa -] may be the same or different, and rb is 2 In the above case, rb [R ^f1b -OQ ^b -R ^fb -] may be the same or different,
sa _and sb are ^an integer ^of 1 or _more ; The sb [-SiR ^b _nb L ^b _3-nb ] may be the same or different.
[13] The fluorine-containing ether composition of [12], containing 10 to 80% by mass of the fluorine-containing ether compound (A1) with respect to the total of the fluorine-containing ether compound (A1) and the fluorine-containing ether compound (B1). .
[14] A coating liquid comprising the fluorine-containing ether composition according to any one of [1] to [13] and a liquid medium.
[15] An article characterized by having a surface layer formed from the fluorine-containing ether composition according to any one of [1] to [13].

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

In this specification, the compound represented by formula (1) is referred to as compound (1). Compounds represented by other formulas are similarly described.
The following terms used herein have the following meanings.
“Hydrolyzable silyl group” means a group capable of forming a silanol group (Si—OH) by hydrolysis reaction. For example, L in formula (I) is a hydrolyzable group.
A chemical formula for an oxyperfluoroalkylene group shall be represented with the oxygen atom to the right of the perfluoroalkylene group.
A "surface layer" means a layer formed on the surface of a substrate.
Applying the coating liquid and "drying" refers to applying the coating liquid to a substrate to form a coating film of the coating liquid on the substrate, and then evaporating and removing the liquid medium from the coating film. .

[Fluorine-containing ether composition]
The fluorine-containing ether composition of the present invention (hereinafter also referred to as the present composition) comprises a fluorine-containing ether compound (A) (hereinafter also referred to as compound (A)) and a fluorine-containing ether compound (B) (hereinafter referred to as Also referred to as compound (B)). The composition does not contain a liquid medium, as described below. The present composition may consist of the compound (A) and the compound (B), and as described later, other fluorine-containing ether compounds other than the compound (A) and the compound (B), the compound (A), the compound ( It may contain impurities other than B) and other fluorine-containing ether compounds.
Compound (A) has a poly(oxyperfluoroalkylene) chain containing (CF ₂ O) units (hereinafter also referred to as chain A) and group (I).
Compound (B) has a poly(oxyperfluoroalkylene) chain (hereinafter also referred to as B chain) containing no (CF ₂ O) units, and group (I). Compound (B) does not have an A chain.
—SiR _n L _3-n (I)
provided that L is a hydroxyl group or a hydrolyzable group,
R is a hydrogen atom or a monovalent hydrocarbon group,
n is an integer from 0 to 2,
When n is 0 or 1, (3-n) L may be the same or different,
When n is 2, n R may be the same or different,
Group (I) possessed by compound (A) and compound (B) may be the same or different.

Compound (A) and compound (B) can each further have a group (II). When both compound (A) and compound (B) have group (II), the groups (II) each has may be the same or different.
R ^f1 -OQ- (II)
however,
R ^f1 is a perfluoroalkyl group,
Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 of the oxyfluoroalkylene groups. All of the oxyfluoroalkylene groups constituting the polyoxyfluoroalkylene group may be the same or different.

(A chain)
The A chain includes a poly(oxyperfluoroalkylene) chain containing (CF ₂ O) units and (R ^f2 O) units represented by the following formula (a1).
{(CF ₂ O) _m1 (R ^f2 O) _m2 } (a1)
provided that R ^f2 is a perfluoroalkylene group having 2 or more carbon atoms,
m1 is an integer of 1 or more, m2 is an integer of 0 or more, and (m1+m2) is an integer of 2 to 200,
When m2 is 1 or more, the bonding order of m1 CF ₂ O and m2 R ^f2 O is not limited,
When m2 is 2 or more (R ^f2 O) _m2 may consist of two or more kinds of R ^f2 O having different numbers of carbon atoms.

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

(m1+m2) is an integer from 2 to 200. Therefore, the minimum value of m2 is 1 when m1 is 1, and there is at least one (R ^f2 O). When m1 is 2 or more, the minimum value of m2 is 0, and (R ^f2 O) may or may not be present. (m1+m2) is preferably an integer of 10-150, particularly preferably an integer of 20-100. When (m1+m2) is at least the lower limit of the above range, the lubricity of the surface layer is excellent. When (m1+m2) is equal to or less than the upper limit of the above range, the durability of the surface layer is excellent. That is, when the number average molecular weight of compound (A) is too large, the number of groups (I) present per unit molecular weight decreases, resulting in a decrease in durability.

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

In (CF ₂ O) _m1 (R ^f2 O) _m2 , when m2 is 1 or more, that is, when there are two or more oxyperfluoroalkylene groups with different carbon numbers, each oxyperfluoroalkylene group (m1 CF ₂ The order of attachment of O and m2 R ^f2 O) is not limited. For example, each oxyperfluoroalkylene group may be arranged randomly, alternately, or in blocks. In particular, (CF ₂ O) units and (R ^f2 O) units are preferably arranged randomly.
When m2 is 2 or more, (R ^f2 O) _m2 may consist of two or more kinds of R ^f2 O having different carbon numbers. Also, the order of bonding of m2 R ^f2 O is not limited.

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

(B chain)
B chains include poly(oxyperfluoroalkylene) chains containing at least one (R ^f3 O) unit represented by the following formula (b1).
(R ^f3 O) _m3 (b1)
provided that R ^f3 is a perfluoroalkylene group having 2 or more carbon atoms,
m3 is an integer from 2 to 200,
(R ^f3 O) _m3 may consist of two or more R ^f2 O with different carbon numbers,
When (R ^f3 O) _m3 consists of two or more R ^f2 Os having different carbon numbers, the order of bonding of each R ^f2 O is not limited.

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

m3 is an integer of 2-200, preferably an integer of 10-150, particularly preferably an integer of 15-100. When m3 is at least the lower limit of the above range, the lubricity of the surface layer is excellent. When m3 is equal to or less than the upper limit of the above range, the durability of the surface layer is excellent. That is, when the number average molecular weight of compound (B) is too large, the number of groups (I) present per unit molecular weight is reduced, resulting in deterioration of durability.

When (R ^f3 O) _m3 consists of two or more R ^f2 Os having different carbon numbers, the order of bonding of each R ^f3 O is not limited. For example, each R ^f3 O may be arranged randomly, alternately, or in blocks.

When (R ^f3 O) _m3 consists of two or more types of R ^f2 O having different carbon numbers, the B chain is preferably represented by the following formula (b2).
{( _CF2CF2O ) _m4 ( _Rf4O ) _m5 }...(b2 ⁾
provided that R ^f4 is a perfluoroalkylene group having 3 to 6 carbon atoms,
m4 is an integer of 1 or more,
m5 is an integer of 1 or more,
(m4+m5) is an integer from 2 to 200,
The binding order of m4 CF ₂ CF ₂ O and m5 R ^f4 O is not limited.

R ^f4 is preferably CF ₂ CF ₂ CF ₂ CF ₂ .
The preferred range for (m4+m5) is the same as for m3.
The ratio of m4 to m5 (m4/m5) is preferably 90/10 to 10/90, particularly preferably 70/30 to 30/70. Within the above range, the higher the ratio of m4, the better the lubricity tends to be. Within the above range, the higher the ratio of m5, the more excellent the durability tends to be.

A preferred embodiment of {(CF ₂ CF ₂ O) _m4 (R ^f4 O) _m5 } is {(CF ₂ CF ₂ O) _m41 -(R ^f4 O) _m51 } _m6 . However, m41 is an integer of 1-3, m51 is an integer of 1-3, m6 is an integer of 1 or more, and (m41+m51)×m6 is an integer of 2-200. The poly(oxyperfluoroalkylene) chain is one or more units in which a unit consisting of 1 to 3 units of (CF ₂ CF ₂ O) and a unit consisting of 1 to 3 units of (R ^f3 O) are connected in series. It consists of A preferred range of (m41+m51)×m6 is the same as (m4+m5). Preferably, m41 and m51 are each 1.
Note that {(CF ₂ CF ₂ O) _m41 - (R ^f4 O) _m51 } _m6 is a poly(oxyperfluoroalkylene) chain having {(CF ₂ CF ₂ O) _m41 - (R ^f4 O) _m51 } as a unit. and a poly(oxyperfluoroalkylene) chain in which (CF ₂ CF ₂ O) _m41 units and (R ^f4 O) _m51 units are alternately arranged.

B chain is poly _{( oxyperfluoroalkylene )} containing at _least one selected from ( _CF2CF2O ) units, ( _CF2CF2CF2O ) units and _{( CF2CF2CF2CF2O} ) _units Chains are preferred. _Particularly preferred _{are poly} ( _{oxyperfluoroalkylene} ) chains _containing ( _{CF2CF2OCF2CF2CF2CF2O} ) units.
Preferred specific embodiments of the B chain include the following (b3) to (b5).
(CF ₂ CF ₂ O) _m13 (b3)
(CF ₂ CF ₂ CF ₂ O) _m14 (b4)
(CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _m15 (b5)
However, m13 and m14 are each an integer of 2-200, and m15 is an integer of 1-100.
(b5) is a poly( _{oxyperfluoroalkylene} ) _{chain comprising} ( _{CF2CF2OCF2CF2CF2CF2O )} units, and _the poly( _{oxyperfluoroalkylene} ) chain is ( _CF2CF2O ) units and (CF ₂ CF ₂ CF ₂ CF ₂ O) units alternately bonded to form a poly(oxyperfluoroalkylene) chain.

(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 through a hydrolysis reaction. That is, when L is a hydrolyzable group, Si--L of the group (I) becomes a silanol group (Si--OH) by a hydrolysis reaction.
Hydrolyzable groups include alkoxy groups, halogen atoms, acyl groups, isocyanate groups (--NCO) and the like. The number of carbon atoms in the alkoxy group is preferably 1-4. The acyl group preferably has 2 to 5 carbon atoms.

L is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom from the viewpoint of ease of production of compound (A). A chlorine atom is particularly preferred as the halogen atom. L is preferably an alkoxy group having 1 to 4 carbon atoms from the viewpoint of less outgassing during coating and excellent storage stability of compound (A), and when long-term storage stability of compound (A) is required. is particularly preferably an ethoxy group, and is particularly preferably a methoxy group when the reaction time after coating is to be shortened.

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

n is preferably 0 or 1, particularly preferably 0. By having a plurality of L's in one group (I), the adhesiveness to the substrate becomes stronger and the durability of the surface layer is further improved.
When n is 0 or 1, (3-n) L's may be the same or different. For example, some L may be hydrolyzable groups and the remaining L may be hydroxyl groups.

Preferred groups (I) are Si( _OCH3 ) ₃ , _SiCH3 ( _OCH3 ) ₂ , Si( _{OCH2CH3 ) 3} , _SiCl3 , Si( _OCOCH3 ) ₃ and Si(NCO) ₃ . Si(OCH ₃ ) ₃ is particularly preferred from the viewpoint of ease of handling in industrial production.

(Group (II))
In group (II), R ^f1 is a perfluoroalkyl group.
The number of carbon atoms in the perfluoroalkyl group in R ^f1 is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 6, and particularly 1 to 3, from the viewpoint of further improving the lubricity and durability of the surface layer. preferable.
The perfluoroalkyl group may be branched or linear, preferably linear. Linear perfluoroalkyl groups include, for example, CF ₃ —, CF ₃ CF ₂ —, CF ₃ CF ₂ CF ₂ — and the like.

Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 (preferably 2 to 4) of the oxyfluoroalkylene groups. . A plurality of oxyfluoroalkylene groups in the polyoxyfluoroalkylene group are usually bonded in series.
When Q is an oxyfluoroalkylene group containing a hydrogen atom or a polyoxyfluoroalkylene group in which 2 to 5 of the oxyfluoroalkylene groups are bonded, compound (A) and compound (B) are dissolved in a liquid medium. become more sexual. Therefore, the compound (A) and the compound (B) are less likely to aggregate in the coating liquid, and the compound (A) and the compound (B) are less likely to aggregate during drying after coating on the surface of the substrate. The appearance of the surface layer is even better.
The number of carbon atoms in the oxyfluoroalkylene group is preferably 1-6, more preferably 2-6, still more preferably 2-4, 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 (number of carbon atoms in Q)×2 or less, particularly preferably (number of carbon atoms in Q), from the viewpoint of further improving the water and oil repellency of the surface layer.
The oxyfluoroalkylene group may be branched or straight-chain, and a straight-chain is preferred from the viewpoint of further improving the lubricity of the surface layer.
In the polyoxyfluoroalkylene group, 2 to 5 oxyfluoroalkylene groups may all be the same or different.
Q is a single bond, or -CHFCF ₂ OCH ₂ CF ₂ O-, -CF ₂ CHFCF ₂ OCH ₂ CF ₂ O-, from the viewpoint of ease of production of compound (A) and compound (B). _{, -CF2CF2CHFCF2OCH2CF2O- , -CF2CF2OCHFCF2OCH2CF2O- , -CF2CF2OCF2CF2OCHFCF2OCH2CF2O- , -CF2 _ _ _ _ _ _ _ _ _ _} A group selected from the group consisting of CH ₂ OCH ₂ CF ₂ O— and —CF ₂ CF ₂ OCF ₂ CH ₂ OCH ₂ CF ₂ O— (with the proviso that the left side is bonded to R ^f1 —O). preferable.

The number of A chains possessed by compound (A) and the number of B chains possessed by compound (B) may each be 1 or 2 or more. 1 to 3 are preferable from the viewpoint of ease of manufacture and ease of handling.
When compound (A) has two or more A chains, each A chain may be the same or different. When compound (B) has two or more B chains, each B chain may be the same or different.

Each of the compound (A) and the compound (B) may have one group (I) or two or more groups. The number is preferably 2 or more, and particularly preferably 3 or more, from the viewpoint that the durability of the surface layer is improved by increasing the number of bonds with the base material. The number is preferably 10 or less, more preferably 5 or less, and particularly preferably 4 or less, from the viewpoint of improving the durability of the surface layer by increasing the density of molecules that bond to the substrate.
Therefore, the number of groups (I) possessed by compound (A) and compound (B) is preferably 1 to 10, more preferably 2 to 5, and particularly preferably 3 to 4.
When compound (A) and compound (B) have two or more groups (I), each group (I) may be the same or different. From the viewpoint of ease of production of compound (A) and compound (B), it is preferred that all of them are the same group.

Group (II) is preferably bound to one end of the A chain and B chain. That is, compound (A) preferably further has group (II) bonded to one end of the A chain. Compound (B) preferably further has a group (II) attached to one end of the B chain. Thereby, the lubricity of the surface layer is further improved.

The number average molecular weight (Mn) of compound (A) and compound (B) is preferably 2,000 to 20,000, more preferably 3,000 to 15,000, and particularly preferably 4,000 to 12,000. . When the number average molecular weights of compound (A) and compound (B) are at least the lower limit of the above range, the lubricity of the surface layer is further improved. When the number average molecular weights of compound (A) and compound (B) are at least the lower limit of the above range, durability of the surface layer is further improved.
The number average molecular weight (Mn) is measured by the measuring method described in Examples below.

Compound (A) and compound (B) are not particularly limited as long as they each have an A chain or B chain and group (I). For example, it can be appropriately selected from known fluorine-containing ether compounds as described in the following documents.
JP 2013-91047, JP 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. 2015/087902, JP 2013-227279, JP 2013-241569, JP 2013- 256643, JP 2014-15609, JP 2014-37548, JP 2014-65884, JP 2014-210258, JP 2014-218639, JP 2015-200884 Publications, JP 2015-221888, WO 2013/146112, WO 2013/187432, WO 2014/069592, WO 2015/099085, WO 2015/166760, JP 2013-144726, JP 2014-77836, JP 2013-117012, JP 2014-214194, JP 2014-198822, JP 2015-129230, JP 2015-196723, JP 2015-13983, JP 2015-199915, JP 2015-199906 and the like.

In the present composition, the compound (A) may be a single compound consisting of one compound (A), or a mixture consisting of two or more compounds (A).
In the present specification, fluorine-containing ether compounds which are the same group of compounds except for having a distribution in the number of repeating oxyperfluoroalkylene groups in the poly(oxyperfluoroalkylene) chain are regarded as a single compound. For example, in the case of compound (A) whose poly(oxyperfluoroalkylene) chain is (CF ₂ O) _m1 (R ^f2 O) _m2 , a group of compounds that are identical except that they have a distribution in m1 and m2 are single compounds. A fluorine-containing ether compound is used.

(Preferred combination of compound (A) and compound (B))
In a preferred embodiment of the present composition, at least one of compound (A) and compound (B) has 3 or more groups (I), more preferably 3 to 5 groups. If at least one has 3 or more groups (I), the durability of the surface layer will be more excellent.
When only one has 3 or more groups (I), the other has 1 or 2 groups (I), preferably 2 from the viewpoint of durability.

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

When the surface layer is formed by a dry coating method, it is preferable that the difference between the number average molecular weight (Mn) of compound (A) and the number average molecular weight (Mn) of compound (B) is small. In the case of the dry coating method, there is a tendency that the smaller the molecular weight, the earlier it evaporates and deposits on the substrate. The smaller the difference in number average molecular weight (Mn), the less uneven the distribution of the compound (A) and the compound (B) in the formed surface layer.
The difference between the number average molecular weight (Mn) of compound (A) and the number average molecular weight (Mn) of compound (B) is preferably 3,000 or less, particularly preferably 2,000 or less.
When forming the surface layer by a wet coating method, even if there is a difference between the number average molecular weight (Mn) of the compound (A) and the number average molecular weight (Mn) of the compound (B), the formed surface layer Since unevenness in the distribution of the compound (A) and the compound (B) is unlikely to occur, the difference between them is not particularly limited.

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

Both compound (A) and compound (B) are preferably fluorine-containing ether compounds represented by the following formula (A/B). In the following formula (A/B), R ^f of compound (A) is a poly(oxyperfluoroalkylene) chain containing (CF ₂ O) units, and R ^f of compound (B) is (CF ₂ O) It is a poly(oxyperfluoroalkylene) chain containing no units.
[R ^f1 -OQR ^f -] _r Z [-SiR _n L _3-n ] _s (A/B)
In formula (A/B) above, R ^f1 is R ^f1 above, Q is Q above, and —SiR _n L _3-n is a group represented by formula (I) above. Z is a (r+s)-valent linking group. r is an integer of 1 or more, and is a number corresponding to the number of poly(oxyperfluoroalkylene) chains in the compound (A) and compound (B). s is an integer of 1 or more and is a number corresponding to the number of groups (I) in the compound (A) and compound (B).
Based on the number of poly(oxyperfluoroalkylene) chains and the number of groups (I), r+s is preferably 2 to 13, more preferably 3 to 8, and particularly preferably 4 to 7. Examples of the (r+s)-valent linking group Z include groups represented by Z ^a and Z ^b described later.
Furthermore, when r is 2 or more, r ^f1 -OQR ^f -] are preferably the same group, and when s is 2 or more, s of formula (I) The groups represented by are preferably the same group.

(preferred embodiment)
In a preferred embodiment of the present composition, compound (A) is a fluorine-containing ether compound (A1) represented by the following formula (A1) (hereinafter also referred to as compound (A1)), and compound (B) is represented by the formula An embodiment that is a fluorine-containing ether compound (B1) represented by (B1) (hereinafter also referred to as compound (B1)) is exemplified. That is, the composition of this embodiment contains compound (A1) and compound (B1).
[R ^f1a —OQ ^a —R ^fa —] _ra Z ^a [—SiR ^a _na L ^a _3-na ] _sa (A1)
[R ^f1b —OQ ^b —R ^fb —] _rb Z ^b [—SiR ^b _nb L ^b _3-nb ] _sb (B1)
provided that R ^f1a and R ^f1b are perfluoroalkyl groups,
Q ^a and Q ^b are a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group in which 2 to 5 of the oxyfluoroalkylene groups are bonded, and the polyoxy All of the oxyfluoroalkylene groups constituting the fluoroalkylene group may be the same or different,
R ^fa is the A chain;
R ^fb is the B chain;
Z ^a is a (ra + sa) valent linking group,
Z ^b is a (rb+sb)-valent linking group,
L ^a and L ^b are hydroxyl groups or hydrolyzable groups,
R ^a and R ^b are a hydrogen atom or a monovalent hydrocarbon group,
na and nb are integers from 0 to 2;
(3-na) L ^a when na is 0 or 1 and (3-nb) L ^b when nb is 0 or 1 may be the same or different,
When na is 2, na R ^a 's, and when nb is 2, nb R ^b 's may be the same or different,
ra and rb are integers of 1 or more, and when ra is 2 or more, ra [R ^f1a -OQ ^a -R ^fa -] may be the same or different, and rb is 2 In the above case, rb [R ^f1b -OQ ^b -R ^fb -] may be the same or different,
sa _and sb are ^an integer ^of 1 or _more ; The sb [-SiR ^b _nb L ^b _3-nb ] may be the same or different.

R ^f1a and R ^f1b are the same as R ^f1 in the group (II), and preferred embodiments are also the same.
When ra is 2 or more, ra R ^f1a preferably have the same number of carbon atoms, and from the viewpoint of ease of production, they are the same group, that is, a group with the same number of carbon atoms and the same chemical structure. is preferred. A group having the same number of carbon atoms and the same chemical structure means that, for example, when ra is 2, two R ^f1a are CF ₃ CF ₂ CF ₂ — (two R ^fa It is not a combination of CF ₃ CF ₂ CF ₂ — and CF ₃ CF(CF ₃ )—, which have the same number of carbon atoms but different chemical structures.).
When rb is 2 or more, rb R ^f1b preferably have the same number of carbon atoms. is preferred.

^Qa and ^Qb are the same as Q in the above group (II), and preferred embodiments are also the same.
The A chain of R ^fa and the B chain of R ^fb are the same as described above, and preferred embodiments are also the same.
L ^a and L ^b are the same as L in the group (I), and preferred embodiments are also the same.
R ^a and R ^b are the same as R in the group (I), and preferred embodiments are also the same.
na and nb are the same as n in the above group (I), and preferred embodiments are also the same.
Preferred values of ra and rb are the same as the preferred numbers of A chain in compound (A) and B chain in compound (B). That is, each of ra and rb is preferably an integer of 1-3.
Preferred values of sa and sb are the same as the preferred numbers of groups (I) possessed by compound (A) and compound (B), respectively. That is, each of sa and sb is preferably an integer of 1-10, more preferably an integer of 2-5, and particularly preferably an integer of 3-4.

Z ^a is, for example, a (ra+sa) valent substituted or unsubstituted hydrocarbon group, a group or atom other than a hydrocarbon group between the carbon-carbon atoms of the substituted or unsubstituted hydrocarbon group or/and at the end. (ra+sa)-valent group, (ra+sa)-valent organopolysiloxane group, and the like.
Examples of ^Zb include those similar to ^Za except that the valence is (rb+sb).

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

Groups or atoms other than the hydrocarbon group between the carbon-carbon atoms of the hydrocarbon group and/or at the end include, for example, an etheric oxygen atom (-O-), a thioetheric sulfur atom (-S-), a nitrogen atom ( -N<), silicon atom (>Si<), carbon atom (>C<), -N(R ¹⁵ )-, -C(O)N(R ¹⁵ )-, -OC(O)N(R ¹⁵ )-, -Si(R ¹⁶ )(R ¹⁷ )-, organopolysiloxane group, -C(O)-, -C(O)-O-, -C(O)-S- and the like. However, R ¹⁵ is a hydrogen atom, an alkyl group or a phenyl group, and R ¹⁶ to R ¹⁷ are each independently an alkyl group or a phenyl group. The number of carbon atoms in the alkyl group is preferably 1-6.
The organopolysiloxane group may be linear, branched, or cyclic.

<Preferred Form of Compound (A1)>
As the compound (A1), at least one selected from the group consisting of the following compound (A11), compound (A12) and compound (A13) is used from the viewpoint of further excellent rub resistance and fingerprint stain removability of the surface layer. preferable.

"Compound (A11)"
Compound (A11) is represented by the following formula (A11).
R ^f1a —O—Q ^a —R ^fa —Q ^32a —[C(O)N(R ^33a )] _pa —R ^34a —C[—R ^35a —SiR ^a _na L ^a _3-na ] ₃ ( A11)
provided that R ^f1a , Q ^a , R ^fa , R ^{a ,} La and na are the same as defined above,
Q ^32a is a fluoroalkylene group having 1 to 20 carbon atoms, or a group having an etheric oxygen atom between the carbon-carbon atoms of a fluoroalkylene group having 2 to 20 carbon atoms (provided that one end is bonded to an etheric oxygen atom Except when the fluoroalkylene group whose other end is bonded to R ^fa is a perfluoroalkylene group),
R ^33a is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
pa is 0 or 1,
R ^34a is a single bond, an alkylene group having 1 to 6 carbon atoms, or an etheric oxygen at the terminal of the alkylene group (provided that the terminal on the side bonding to C[-R ^34a -SiR _na L _3-na ] ₃ ) atom, a group having an etheric oxygen atom between the carbon-carbon atoms of an alkylene group having 2 to 6 carbon atoms, or a terminal of an alkylene group having 2 to 6 carbon atoms (with the proviso that C[-R ^34a -SiR _na L _3-na ] _3. ) and an etheric oxygen atom between carbon atoms,
R ^35a is an alkylene group having 1 to 6 carbon atoms, a group having an etheric oxygen atom at the terminal of the alkylene group (excluding the terminal on the side bonding to Si), or an alkylene group having 2 to 6 carbon atoms. is a group having an etheric oxygen atom between the carbon-carbon atoms of
Three [-R ^34a -SiR _na L _3-na ] may be the same or different.

Compound (A11) is represented by formula (A1) above, wherein ra is 1, sa is 3, and Z ^a is —Q ^32a —[C(O)N(R ^33a )] _pa —R ^34a —C It is a compound of [-R ^35a -] ₃ .
However, it is preferable that the number of (CF ₂ O) in R ^fa is 4 or more and the number of (CF ₂ O) in Q ^32a is 0 to 3.

In Q ^32a , the fluoroalkylene group having 1 to 20 carbon atoms is preferably a perfluoroalkylene group and a fluoroalkylene group containing one or more hydrogen atoms. The fluoroalkylene group is preferably linear in terms of friction resistance and lubricity of the surface layer.
Examples of the group having an etheric oxygen atom between the carbon atoms of the fluoroalkylene group having 2 to 20 carbon atoms include groups (ii) described later.
Q ^32a is a perfluoroalkylene group having 1 to 20 carbon atoms, a fluoroalkylene group having 1 to 20 carbon atoms containing one or more hydrogen atoms, and a fluoro alkylene group having 1 to 20 carbon atoms containing one or more hydrogen atoms. Groups having an etheric oxygen atom between the carbon-carbon atoms of the alkylene group are preferred.

When pa is 0 and R ^fa is {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 }, Q ^32a is typically a C 1 perfluoroalkylene group.
When pa is 1, Q ^32a includes the following groups.
(i) a perfluoroalkylene group;
(ii) a fluoroalkylene group having R ^F CH ₂ O (where R ^F is a perfluoroalkylene group having 1 to 6 carbon atoms) on the side bonded to R ^fa and containing one or more hydrogen atoms; A group having (optionally having an etheric oxygen atom between carbon atoms) on the side to which C(O)N(R ^33a ) is bonded.

As ^Q32a of (ii), the following groups are preferable from the viewpoint of the durability and lubricity of the surface layer and the ease of production of compound (A11).
^-RF _{CH2O - CF2CHFOCF2CF2CF2- , -RF} ^CH2O _{- CF2CHFCF2OCF2CF2- , -RF} ^CH2O _{- CF2CHFCF2OCF2CF2CF _ _ _ _ 2-} , -R ^F CH ₂ O-CF ₂ CHFOCF ₂ CF ₂ CF ₂ OCF ₂ CF ₂ -.

When pa in the [C(O)N(R ^33a )] _pa group is 0 or 1, the properties of the fluorine-containing ether compound are almost the same. When pa is 1, it has an amide bond, and at least one fluorine atom is bonded to the terminal carbon atom on the side of Q ^32a that bonds to [C(O)N(R ^33a )]. , the polarity of the amide bond is reduced, and the water and oil repellency of the surface layer is less likely to deteriorate. Whether pa is 0 or 1 can be selected from the viewpoint of ease of manufacture.
[C(O)N(R ^33a )] R ^33a in _{the pa} group is preferably a hydrogen atom from the viewpoint of ease of production of compound (A11).
When R ^33a is an alkyl group, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms.

When pa is 0, R ^34a is 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 - (where the left side is bonded to Q ³² ) is preferred.
When pa is 1, R ^34a is preferably a group selected from the group consisting of a single bond, —CH ₂ — and —CH ₂ CH ₂ — from the viewpoint of facilitating production of compound (A11).

As R ^35a , —CH ₂ CH ₂ —, —CH _{2 CH 2 CH 2 —, —CH 2 OCH 2 CH 2 CH 2 —, —OCH 2 CH , from the viewpoint of ease} of production of compound (A11) A group selected from the group consisting of ₂ CH ₂ — (where the right side is bonded to Si) is preferred.
As R ^35a , one having no etheric oxygen atom is particularly 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) and in-vehicle touch panels, the water- and oil-repellent layer is required to have light resistance.
Three R ^35a in compound (A11) may be the same or different.

Compound (A11) includes, for example, compounds of the following formula. This compound is preferable because it is easy to industrially produce and handle, and the surface layer is more excellent in water and oil repellency, abrasion resistance, fingerprint stain removability, lubricity, and appearance.

However, W in these formulas is R ^f1a -OQ ^a -R ^fa -. A preferred form of W is a combination of the preferred R ^f1a , Q ^a and R ^fa described above. Preferred ranges for ^Q32a are as described above.

"Compound (A12)"
Compound (A12) is represented by the following formula (A12).
R ^f1a -OQ ^a -R ^fa -R ^42a -R ^43a -N [-R ^44a -SiR ^a _na L ^a _3-na ] ₂ (A12)
provided that R ^f1a , Q ^a , R ^fa , R ^{a ,} La and na are the same as defined above,
R ^42a is a perfluoroalkylene group having 1 to 6 carbon atoms,
R ^43a is a single bond, an alkylene group having 1 to 6 carbon atoms, a group having an etheric oxygen atom or —NH— at the terminal of the alkylene group (excluding the terminal on the side that bonds to N), and the number of carbon atoms A group having an etheric oxygen atom or —NH— between the carbon-carbon atoms of an alkylene group of 2 to 6 carbon atoms, or the terminal of an alkylene group of 2 to 6 carbon atoms (excluding the terminal on the N-bonded side) and a group having an etheric oxygen atom or -NH- between carbon-carbon atoms,
R ^44a is an alkylene group having 1 to 6 carbon atoms, or a group having an etheric oxygen atom or —NH— between carbon atoms of an alkylene group having 2 to 6 carbon atoms,
Two [-R ^44a -SiR _na L _3-na ] may be the same or different.

Compound (A12) is a compound of formula (A1) above wherein ra is 1, sa is 2, and Z ^a is —R ^42a —R ^43a —N[—R ^44a —] ₂ .

R ^42a is preferably a linear perfluoroalkylene group. If R ^42a is a straight-chain perfluoroalkylene group, the surface layer has even better abrasion resistance and lubricity.
R ^42a is typically a C 1 perfluoroalkylene group when R ^fa is {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 }.

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

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

Compound (A12) includes, for example, compounds of the following formula. This compound is preferable because it is easy to industrially produce, easy to handle, and further excellent in water and oil repellency, abrasion resistance, fingerprint stain removability, lubricity, chemical resistance and light resistance.

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

"Compound (A13)"
Compound (A13) is represented by the following formula (A13).
[R ^f1a -OQ ^a -R ^fa -R ^51a -R ^52a -O-] _ea Z ^3a [-OR ^53a -SiR ^a _na L _3-na ] _fa (A13)
provided that R ^f1a , Q ^a , R ^fa , R ^{a ,} La and na are the same as defined above,
R ^51a is a perfluoroalkylene group having 1 to 6 carbon atoms,
R ^52a is an alkylene group having 1 to 6 carbon atoms,
Z ^3a is a (ea+fa)-valent hydrocarbon group or a (ea+fa)-valent group having 2 or more carbon atoms and having one or more etheric oxygen atoms between the carbon atoms of the hydrocarbon group;
R ^53a is an alkylene group having 1 to 20 carbon atoms,
ea is an integer of 1 or more,
fa is an integer of 1 or more,
(ea+fa) is 3 or more,
when ea is 2 or more, ea [R ^f1a -OQ ^a -R ^fa -R ^51a -R ^52a -O-] may be the same or different,
When fa is 2 or more, fa [-OR ^53a -SiR ^a _na L ^a _3-na ] may be the same or different.

Compound (A13) has the formula (A1) above wherein ra is ea, sa is fa, and Z ^a is [-R ^51a -R ^52a -O-] _ea Z ^3a [-OR ^53a - ] is a compound of _fa .

ea is preferably an integer of 1-3. Fa is preferably an integer of 1-10, more preferably an integer of 2-5, and particularly preferably an integer of 3-4.

R ^51a is _-CF 2 -, for example, when R ^fa is {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 }.
R ^51a is preferably linear. A compound (A13) in which R ^51a is linear can form a surface layer that is more excellent in friction resistance and lubricity.

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

The R ^f1a -OQ ^a -R ^fa -R ^51a - group is excellent in water and oil repellency, durability, fingerprint stain removability, lubricity, and appearance of the surface layer, and compound (A13). Groups (R ^f -1) and (R ^f -2) are preferred from the standpoint of ease of production.
R ^f11 O {(CF ₂ O) _m21 (CF ₂ CF ₂ O) _m22 } CF ₂ − (R ^f −1)
R ^f11 OCHFCF ₂ OCH ₂ CF ₂ O {(CF ₂ O) _m21 (CF ₂ CF ₂ O) _m22 } CF ₂ − (R ^f −2)
provided that R ^f11 is a linear perfluoroalkyl group having 1 to 20 carbon atoms; m21 and m22 are each an integer of 1 or more; m21+m22 is an integer of 2 to 200; The binding order of ₂ O and m22 CF ₂ CF ₂ O is not limited.

Examples of Z ^3a include residues obtained by removing hydroxyl groups from polyhydric alcohols having (ea+fa) hydroxyl groups.
Specific examples of Z ^3a include groups of the following formulae. Z ^3a is preferably a residue obtained by removing the hydroxyl group from a polyhydric alcohol having a primary hydroxyl group from the viewpoint of excellent reactivity of the hydroxyl group, and from the viewpoint of the availability of raw materials, the group (Z-1), the group (Z-2) and group (Z-3) are particularly preferred. However, R ⁴ is an alkyl group, preferably a methyl group or an ethyl group.

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

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

However, W in these formulas is R ^f1a -OQ ^a -R ^fa -. A preferred form of W is a combination of the preferred R ^f1a , Q ^a and R ^fa described above. Preferred forms of ^R51a are as described above.

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

"Compound (B11)"
Compound (B11) is represented by the following formula (B11).
R ^f1b —O—Q ^b —R ^fb —Q ^32b —[C(O)N(R ^33b )] _pb —R ^34b —C[—R ^35b —SiR _nb L _3-nb ] ₃ (B11)
provided that R ^f1b , Q ^b , R ^fb , R ^b , L ^b and nb are as defined above,
Q ^32b is a fluoroalkylene group having 1 to 20 carbon atoms, or a group having an etheric oxygen atom between the carbon-carbon atoms of a fluoroalkylene group having 2 to 20 carbon atoms (provided that one end is bonded to an etheric oxygen atom Except when the fluoroalkylene group bonded to R ^fb at the other end is a perfluoroalkylene group),
R ^33b is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
pb is 0 or 1;
R ^34b is a single bond, an alkylene group having 1 to 6 carbon atoms, or an etheric oxygen at the terminal of the alkylene group (provided that the terminal on the side bonding to C[-R ^34b -SiR _nb L _3-nb ] ₃ ) atom, a group having an etheric oxygen atom between the carbon-carbon atoms of an alkylene group having 2 to 6 carbon atoms, or a terminal of an alkylene group having 2 to 6 carbon atoms (with the proviso that C[-R ^34b -SiR _nb L _3-nb ] _3. ) and an etheric oxygen atom between carbon atoms,
R ^35b is an alkylene group having 1 to 6 carbon atoms, a group having an etheric oxygen atom at the terminal of the alkylene group (excluding the terminal on the side bonding to Si), or an alkylene group having 2 to 6 carbon atoms. is a group having an etheric oxygen atom between the carbon-carbon atoms of
The three [-R ^34b -SiR _nb L _3-nb ] may be the same or different.

Compound (B11) is represented by formula (B1) above, wherein rb is 1, sb is 3, and Z ^b is —Q ^32b —[C(O)N(R ^33b )] _pb —R ^34b —C It is a compound of [-R ^35b -] ₃ .

The fluoroalkylene group in Q ^32b and the group having an etheric oxygen atom between the carbon-carbon atoms of the fluoroalkylene group are the fluoroalkylene group in Q ^32a in the above formula (A11) and the carbon-carbon atoms of the fluoroalkylene group, respectively. is the same as a group having an etheric oxygen atom in
The number of (CF ₂ O) in Q ^32b is preferably 0-3.
Q ^32b is typically a C 1 perfluoroalkylene group when p1 is 0 and R ^fb is (CF ₂ CF ₂ O) _m13 . When p1 is 0 and R ^fb is (CF ₂ CF ₂ CF ₂ O) _m14 , it is typically a perfluoroalkylene group having 2 carbon atoms. When p1 is 0 and R ^fb is (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _m15 , it is typically a linear perfluoroalkylene group having 3 carbon atoms.
R ^33b , pb, R ^34b and R ^35b are respectively the same as R ^33a , pa, R ^34a and R ^35a in formula (A11) above, and preferred embodiments are also the same.

"Compound (B12)"
Compound (B12) is represented by the following formula (B12).
R ^f1b —O—Q ^b —R ^fb —R ^42b —R ^43b —N[—R ^44b —SiR _nb L _3-nb ] ₂ (B12)
provided that R ^f1b , Q ^b , R ^fb , R ^b , L ^b and nb are as defined above,
R ^42a is a perfluoroalkylene group having 1 to 6 carbon atoms,
R ^43a is a single bond, an alkylene group having 1 to 6 carbon atoms, a group having an etheric oxygen atom or —NH— at the terminal of the alkylene group (excluding the terminal on the side that bonds to N), and the number of carbon atoms A group having an etheric oxygen atom or —NH— between the carbon-carbon atoms of an alkylene group of 2 to 6 carbon atoms, or the terminal of an alkylene group of 2 to 6 carbon atoms (excluding the terminal on the N-bonded side) and a group having an etheric oxygen atom or -NH- between carbon-carbon atoms,
R ^44a is an alkylene group having 1 to 6 carbon atoms, or a group having an etheric oxygen atom or —NH— between carbon atoms of an alkylene group having 2 to 6 carbon atoms,
Two [-R ⁴⁴ -SiR _n L _3-n ] may be the same or different.

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

R ^42b , R ^43b and R ^44b are respectively the same as R ^42a , R ^43a and R ^44a in formula (A12).
However, when R ^fb is (CF ₂ CF ₂ O) _m13 , R ^42b is typically a C 1 perfluoroalkylene group. When R ^fb is (CF ₂ CF ₂ CF ₂ O) _m14 , it is typically a perfluoroalkylene group having 2 carbon atoms. When R ^fb is (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _m15 , it is typically a linear perfluoroalkylene group having 3 carbon atoms.

"Compound (B13)"
Compound (B13) is represented by the following formula (B13).
[R ^f1b -O-Q ^b -R ^fb -R ^51b -R ^52b -O-] _eb Z ^3b [-OR ^53b -SiR ^b _nb L ^b _3-nb ] _f (B13)
provided that R ^f1b , Q ^b , R ^fb , R ^b , L ^b and nb are as defined above,
R ^51b is a perfluoroalkylene group having 1 to 6 carbon atoms,
R ^52b is an alkylene group having 1 to 6 carbon atoms,
Z ^3b is a (eb+fb)-valent hydrocarbon group or a (eb+fb)-valent group having 2 or more carbon atoms and having one or more etheric oxygen atoms between the carbon atoms of the hydrocarbon group;
R ^53b is an alkylene group having 1 to 20 carbon atoms,
eb is an integer of 1 or more,
fb is an integer of 1 or more,
(eb + fb) is 3 or more,
when eb is 2 or more, eb [R ^f1b -OQR ^fb -R ^51b -R ^52b -O-] may be the same or different,
When fb is 2 or more, fb [-OR ^53b -SiR ^b _nb L ^b _3-nb ] may be the same or different.

Compound (B13) has the formula (B1) above wherein rb is eb, sb is fb, and Z ^b is [-R ^51b -R ^52b -O-] _eb Z ^3b [-OR ^53b - ] is a compound of _fb .

R ^51b , R ^52b , Z ^3b , R ^53b , eb and fb are respectively the same as defined for R ^51a , R ^52a , Z ^3a , R ^53a , ea and fa in formula (A13).
The R ^f1b —O—Q ^b —R ^fb —R ^51b —R ^52b — group is a compound ( The group (R ^f -3) is preferred from the standpoint of ease of production of B13).
R ^f11 O (CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) _m25 CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ − (R ^f −3)
provided that R ^f11 is a linear perfluoroalkyl group having 1 to 20 carbon atoms; m25 is an integer of 1 to 100;

(Other fluorine-containing ether compounds)
The composition may consist of compound (A) and compound (B), or may further contain a fluorine-containing ether compound other than compound (A) and compound (B).
Other fluorine-containing ether compounds include, for example, a fluorine-containing ether compound having a poly(oxyperfluoroalkylene) chain and not having group (I) (hereinafter also referred to as compound (C)). The poly(oxyperfluoroalkylene) chain may be an A chain or a B chain.

Compound (C) includes, for example, compound (C1).
A ³¹ -O-Q ⁵¹ -(R ^F3 O) _m30 -[Q ⁵² -O] _p3 -A ³² (C1)
with the proviso that A ³¹ and A ³² are each independently a perfluoroalkyl group ^having 1 to 20 carbon atoms; An etheric oxygen atom at the end of a fluoroalkylene group or a fluoroalkylene group having 1 to 6 carbon atoms that does not have a branched structure containing one or more hydrogen atoms (excluding the end on the side that bonds to A ³¹ —O) , a group having an etheric oxygen atom between the carbon-carbon atoms of a fluoroalkylene group having 2 to 6 carbon atoms that does not have a branched structure containing one or more hydrogen atoms, or containing one or more hydrogen atoms A group having an unbranched structure-free C 2-6 fluoroalkylene group end (excluding the end on the side that bonds to A ³¹ —O) and an etheric oxygen atom between carbon atoms ( provided that the number of oxygen atoms is 10 or less.); Q ⁵² is a fluoroalkylene group having 1 to 20 carbon atoms that does not have a branched structure containing one or more hydrogen atoms, or a branched structure containing one or more hydrogen atoms is a group having an etheric oxygen atom between carbon-carbon atoms of a fluoroalkylene group having 2 to 6 carbon atoms (provided that the number of oxygen atoms is 10 or less); R ^F3 does not have a branched structure a perfluoroalkylene group having 1 to 6 carbon atoms; m30 is an integer of 2 to 200; (R ^F3 O) _m30 may consist of two or more kinds of R ^F3 O having different carbon numbers. p3 is 0 when ^Q51 is a single bond and 1 when ^Q51 is other than a single bond;

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

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

(Composition of this composition)
In the present composition, the content of compound (A) with respect to the total of compound (A) and compound (B) (mass ratio of compound (A)/[compound (A) + compound (B)]) is 10 to 80. % by weight is preferred, and 20 to 50% by weight is particularly preferred. The higher the content of the compound (A) within the above range, the more excellent the lubricity of the surface layer. The lower the content of compound (A) within the above range (that is, the higher the content of compound (B) with respect to the total of compound (A) and compound (B)), the more excellent the durability of the surface layer.

In the composition, the total amount of compound (A) and compound (B) is preferably 50% by mass or more, particularly preferably 80% by mass or more, relative to the total mass of the composition. The upper limit is not particularly limited, and may be 100% by mass.

[Coating liquid]
The coating liquid of the present invention (hereinafter also referred to as the present coating liquid) contains the present composition and a liquid medium. The present coating liquid may be in a liquid state, and may be a solution or a dispersion liquid.
The present coating liquid only needs to contain the present composition, and may contain impurities such as by-products generated 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% by mass, still more preferably 0.05 to 10% by mass, and 0.1 to 1% by mass in the coating liquid. % is particularly preferred.

Organic solvents are preferred as the liquid medium. The organic solvent may be a fluorinated organic solvent, may be a non-fluorinated organic solvent, or may contain both solvents.

Fluorinated organic solvents include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols and the like.
As the fluorinated alkane, compounds having 4 to 8 carbon atoms are preferred. Commercially available products include, for example, C ₆ F ₁₃ H (manufactured by Asahi Glass Co., Ltd., Asahiklin (registered trademark) AC-2000) and C ₆ F ₁₃ C ₂ H ₅ (manufactured by Asahi Glass Co., Ltd., Asahiklin (registered trademark) AC-6000). , C ₂ F ₅ CHFCHFCF ₃ (Bertrell (registered trademark) XF, manufactured by Chemours) and the like.
Examples of fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, bis(trifluoromethyl)benzene and the like.
As the fluoroalkyl ether, compounds having 4 to 12 carbon atoms are preferred. Commercially available products include CF ₃ CH ₂ OCF ₂ CF ₂ H (manufactured by Asahi Glass Co., Ltd., Asahiklin (registered trademark) AE-3000), C ₄ F ₉ OCH ₃ (manufactured by 3M, Novec (registered trademark) 7100), C ₄ F ₉ OC ₂ H ₅ (manufactured by 3M, Novec (registered trademark) 7200), C ₂ F ₅ CF(OCH ₃ )C ₃ F ₇ (manufactured by 3M, Novec (registered trademark) 7300), etc. .
Examples of fluorinated alkylamines include perfluorotripropylamine and perfluorotributylamine.
Examples of fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol and the like.
The non-fluorine organic solvent is preferably a compound consisting only of hydrogen atoms and carbon atoms, and a compound consisting only of hydrogen atoms, carbon atoms and oxygen atoms. Hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, Examples include ether-based organic solvents and ester-based organic solvents.
The present coating liquid preferably contains 50 to 99.999% by mass of the liquid medium, more preferably 70 to 99.5% by mass, even more preferably 90 to 99.5% by mass, and 99 to 99.9% by mass. It is particularly preferable to contain 9% by mass.

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

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

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

(Surface layer)
In the present composition, when L in group (I) in compound (A) and compound (B) is a hydrolyzable group, group (I) undergoes a hydrolysis reaction to form a silanol group (Si- OH) is formed, and the silanol groups react intermolecularly to form Si—O—Si bonds, or the silanol groups undergo dehydration condensation reactions with hydroxyl groups on the surface of the substrate (substrate —OH) to chemically A bond (substrate-O-Si) is formed. Therefore, the surface layer contains the compound (A) and the compound (B) in a state in which part or all of the group (I) of each of the compound (A) and the compound (B) is hydrolyzed. When L in group (I) is a hydroxyl group, the above reaction proceeds without hydrolysis.

The thickness of the surface layer is preferably 1 to 100 nm, particularly preferably 1 to 50 nm. When the thickness of the surface layer is at least the lower limit of the above range, the effect of the surface treatment can be sufficiently obtained. When the thickness of the surface layer is equal to or less than the upper limit of the range, the utilization efficiency is high. The thickness of the surface layer is obtained by obtaining an interference pattern of reflected X-rays by the X-ray reflectance method using an X-ray diffractometer for thin film analysis (manufactured by RIGAKU, ATX-G), and from the oscillation period of the interference pattern. can be calculated.

(Base material)
The substrate in the present invention is not particularly limited as long as it is required to impart lubricity and water/oil repellency. Materials for the substrate 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 substrate.
As the substrate, touch panel substrates, display substrates, and spectacle lenses are preferable, and touch panel substrates are particularly preferable. The touch panel substrate has translucency. The term "having translucency" means that the vertical incidence type visible light transmittance according to JIS R3106:1998 (ISO 9050:1990) is 25% or more. Glass and transparent resin are preferable as the material for the touch panel substrate.

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

<Dry coating method>
The composition can be used as such in a dry coating method. The composition is suitable for forming a surface layer with excellent adhesion by a dry coating method.
Examples of the dry coating method include a vacuum deposition method, a CVD method, a sputtering method, and the like. A vacuum 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 material such as iron or steel with the present composition or the present coating liquid may be used.

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

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

<Post-processing>
In order to improve the abrasion resistance of the surface layer, an operation for promoting the reaction between the compound (A) and compound (B) and the base material may be carried out, if necessary. The operation includes heating, humidification, light irradiation, and the like.
For example, by heating a substrate on which a surface layer is formed in an atmosphere containing moisture, hydrolysis reaction of hydrolyzable silyl groups to silanol groups, reaction of hydroxyl groups on the surface of the substrate with silanol groups, silanol Reaction such as generation of siloxane bond by condensation reaction of groups can be promoted.
After the surface treatment, compounds in the surface layer that are not chemically bonded to other compounds or the substrate may be removed if necessary. Specific methods include, for example, a method of pouring a solvent over the surface layer, a method of wiping off with a cloth impregnated with the solvent, and the like.

[Effect]
Since the present composition and the present coating liquid contain compound (A) and compound (B), a surface layer having excellent lubricity and durability can be formed. That is, by forming a surface layer on the surface of a substrate using the present composition or the present coating liquid, properties such as excellent initial lubricity and water and oil repellency are imparted, and the surface is repeatedly Excellent durability can be obtained in which these properties do not easily deteriorate even when rubbed. In addition, even if the surface is rubbed repeatedly, the water- and oil-repellency is not likely to deteriorate, so that the performance (fingerprint stain removability) of easily removing fingerprint stains on the surface of the base material can be obtained.
Since compound (A) contains (CF ₂ O) units in the A chain, it has excellent lubricity. On the other hand, the durability is inferior to the case where the (CF ₂ O) unit is not included. Since the compound (B) does not contain a (CF ₂ O) unit in the B chain, it has excellent durability. On the other hand, the lubricating properties are inferior to those containing (CF ₂ O) units. When these are combined, the excellent properties of each are sufficiently maintained, and both excellent lubricity and durability can be achieved. The reason for this is considered to be that the component with high lubricity (compound (A)) disperses the force applied to wear and the durability of the component with high durability (compound (B)) is further enhanced.

[Use]
Therefore, the substrate having a surface layer obtained in this manner is suitable as a member constituting a touch panel.
However, the uses of the present composition, the present coating liquid and the article are not limited to touch panels. For example, display input devices other than touch panels; surface protective coatings of transparent glass or transparent plastic (acrylic, polycarbonate, etc.) members, antifouling coatings for kitchens; water and moisture repellent coatings for electronic devices, heat exchangers, batteries, etc. and anti-fouling coating, anti-fouling coating for toiletry; coating for parts that require liquid repellency while conducting; water repellent, waterproof, and sliding coating for heat exchangers; be able to.
More specific examples of use include front protective plates for displays, anti-reflection plates, polarizing plates, anti-glare plates, or those with anti-reflection coatings on their surfaces, and touch panels for devices such as mobile phones and personal digital assistants. Various devices with display input devices that operate on the screen with fingers or palms such as seats and touch panel displays, decorative building materials around water such as toilets, baths, washrooms, kitchens, waterproof coating for circuit boards Repellent of heat exchangers Water/waterproof coatings, water-repellent coatings for solar cells, waterproof/water-repellent coatings for printed wiring boards, waterproof/water-repellent coatings for electronic device housings and electronic components, insulation-enhancing coatings for transmission lines, waterproofing/water-repellent coatings for various filters Water-repellent coating, waterproof coating for radio-wave absorbing and sound-absorbing materials, antifouling coating for bathrooms, kitchen equipment, toiletries, water-repellent, waterproof, and sliding coating for heat exchangers, surface low-friction coating for vibrating screens and inside cylinders, etc. Machine parts, vacuum equipment parts, bearing parts, automobile parts, surface protective coats for tools, and the like.

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

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

(water contact angle)
The contact angle (water contact angle) of approximately 2 μL of distilled water placed on the surface of the surface layer was measured at 20° C. using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., DM-701). Measurements were performed at five different points on the surface of the surface layer, and the average value was calculated. The 2θ method was used to calculate the contact angle. The larger the water contact angle, the more excellent the water repellency.

(Lubricity)
The dynamic friction coefficient of the surface layer against artificial skin (manufactured by Idemitsu Techno Fine Co., Ltd., PBZ13001) was measured using a variable load type friction and wear test system (manufactured by Shinto Kagaku Co., Ltd., HHS2000), contact area: 3 cm × 3 cm, load: 0.98 N was measured under the conditions of The smaller the coefficient of dynamic friction, the better the lubricity.

(Durability 1 (number of times the contact angle is maintained at 100° or more))
For the surface layer, a reciprocating traverse tester (manufactured by KNT) was used in accordance with JIS L0849: 2013 (ISO 105-X12: 2001), and a steel wool bontester (#0000) was used. Pressure: 98.07 kPa, speed: It was reciprocated at 320 cm/min. The water contact angle was measured every 1000 reciprocations, and the upper limit number of times a water contact angle of 100° or more was maintained (the number of times a contact angle of 100° or more was maintained) was determined. The greater the number of times, the less the surface layer is damaged by friction, and the more durable it is.

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

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

(B-1): Compound (B-1) obtained in Production Example B-1 described later.
(B-2): Composition (B-2) obtained in Production Example B-2 described later.
(B-3): Compound (B-3) obtained in Production Example B-3 described later.
(B-4): Compound (B-4) obtained in Production Example B-4 described later.
(B-5): Compound (B-5) obtained in Production Example B-5 described later.
(B-6): The solvent of "2634 Coating" manufactured by Dow Corning Toray Co., Ltd. was distilled off and used. _{CF3CF2CF2O ( CF2CF2CF2O ) 21CF2CF2CH2OCH2CH2CH2Si ( OCH3 ) 3 . _ _ _ _ _}

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

(A-1) to (A-5), (B-1) to (B-5), repeating unit of poly (oxyperfluoroalkylene) chain possessed by (C-1), poly (oxyperfluoroalkylene) chain (hereinafter also referred to as PEPE number), the number of groups (I) and the number average molecular weight (Mn) are shown in Table 1.
The repeating unit "(CF ₂ O) (CF ₂ CF ₂ O)" in (A-1) to (A-5) and (C-1) is a (CF ₂ O) unit and a (CF ₂ CF ₂ O) units are randomly arranged poly(oxyperfluoroalkylene) chains.

[Production Example A-1]
24.4 g of 24% KOH aqueous solution, 33 g of tert-butyl alcohol, and 220 g of compound (1) (manufactured by Solvay Solexis, FLUOROLINK (registered trademark) D4000) were placed in a 300 mL three-necked flask and CF ₃ CF was added. 19.4 g of _{2CF 2} -O-CF=CF ₂ (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added. The mixture was stirred at 60° C. for 8 hours under nitrogen atmosphere. After washing once with a dilute aqueous hydrochloric acid solution, the organic phase was collected and concentrated by an evaporator to obtain 233 g of a crude product. The crude product was separated by developing with silica gel column chromatography. As a developing solvent, C ₆ F ₁₃ CH ₂ CH ₃ (manufactured by Asahi Glass Co., Ltd., AC-6000), AC-6000/CF ₃ CH ₂ OCF ₂ CF ₂ H (manufactured by Asahi Glass Co., Ltd., AE-3000) = 1/2 ( AE-3000/ethyl acetate=9/1 (mass ratio) were used in this order. For each fraction, the average values of the structure of the terminal group and the number of units (x1, x2) of the constituent units were obtained from the integrated values of ¹ H-NMR and ¹⁹ F-NMR. It was found that the crude product contained 42 mol %, 49 mol % and 9 mol % of compound (2), compound (3) and compound (1), respectively. 98.6 g (yield: 44.8%) of compound (2) and 51.9 g (yield: 23.6%) of compound (3) were obtained.
HO—CH ₂ —(CF ₂ O){(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 }—CF ₂ —CH ₂ —OH (1)
_{CF3CF2CF2 -} O- _CHFCF2OCH2- ( _{CF2O )} {( _CF2O ) _x1 ( _CF2CF2O ) _x2 } _{-CF2 - CH2- OH} (2)
_{CF3CF2CF2 -} O- _CHFCF2OCH2- ( _{CF2O ) {} ( _CF2O ) _x1 ( _{CF2CF2O ) x2} }-CF2 _{- CH2OCF2CHF -} O- _{CF2CF 2} CF ₃ (3)
Compound (2): Average value of unit number x1: 21, average value of unit number x2: 20, number average molecular weight: 4,150.
Compound (3): Average value of unit number x1: 21, average value of unit number x2: 20, number average molecular weight: 4,420.

30.0 g of compound (2), 0.9 g of sodium fluoride powder, and 30 g of dichloropentafluoropropane (AK-225, manufactured by Asahi Glass Co., Ltd.) were placed in a 100 mL eggplant flask, and CF ₃ CF ₂ CF ₂ OCF ( 3.5 g of CF ₃ )COF was added. The mixture was stirred at 50° C. for 24 hours under nitrogen atmosphere. After removing sodium fluoride powder with a pressure filter, excess CF ₃ CF ₂ CF ₂ OCF(CF ₃ )COF and AK-225 were distilled off under reduced pressure. The resulting crude product was diluted with C ₆ F ₁₃ H (manufactured by Asahi Glass Co., Ltd., AC-2000), passed through a silica gel column, and the collected solution was concentrated by an evaporator to yield 31.8 g of compound (4) (yield: 98.8%) was obtained.
_{CF3CF2CF2 -} O- _CHFCF2OCH2- ( _CF2O ) _{ ( _CF2O ) _x1 ( _{CF2CF2O ) x2} }-CF2 _- CH2 _- OCOCF _{( CF3} ) _{OCF2CF 2} CF ₃ (4)
Compound (4): Average number of units x1: 21, average number of units x2: 20, number average molecular weight: 4,460.

At the gas outlet of a 1 L nickel autoclave, a cooler kept at 20°C, a NaF pellet packed bed and a cooler kept at 0°C were installed in series. A liquid return line was installed to return the condensed liquid from the cooler held at 0°C back to the autoclave.
750 g of ClCF ₂ CFClCF ₂ OCF ₂ CF ₂ Cl (hereinafter also referred to as CFE-419) was placed in an autoclave and stirred while maintaining the temperature at 25°C. After nitrogen gas was blown into the autoclave at 25° C. for 1 hour, 20% fluorine gas was blown at 25° C. at a flow rate of 2.0 L/hour for 1 hour. While blowing 20% fluorine gas at the same flow rate, a solution of 31.0 g of compound (4) dissolved in 124 g of CFE-419 was injected into the autoclave over 4.3 hours. While blowing 20% fluorine gas at the same flow rate, the internal pressure of the autoclave was increased to 0.15 MPa (gauge pressure). 4 mL of a benzene solution containing 0.05 g/mL benzene in CFE-419 was injected into the autoclave while heating from 25° C. to 40° C., and the benzene solution inlet of the autoclave was closed. After stirring for 15 minutes, 4 mL of the benzene solution was again injected while maintaining the temperature at 40° C., and the injection port was closed. A similar operation was repeated three more times. The total amount of benzene injected was 0.17 g. Stirring was continued for 1 hour while blowing 20% fluorine gas at the same flow rate. The pressure inside the autoclave was adjusted to atmospheric pressure, and nitrogen gas was blown thereinto for 1 hour. The contents of the autoclave were concentrated by an evaporator to obtain 31.1 g of compound (5) (yield 98.5%).
_{CF3CF2CF2 - O-} ( _{CF2CF2O )(CF2CF2O){(CF2O)x1 ( CF2CF2O ) x2 } ( CF2CF2O )} -COCF ₍ CF ₃ ) _{OCF2CF2CF3 ( 5} )
Compound (5): Average number of units x1: 21, average number of units x2: 20, number average molecular weight: 4,550.

30.0 g of compound (5) and 60 g of AK-225 were placed in a round bottom flask made of tetrafluoroethylene-perfluoro(alkoxyvinyl ether) copolymer (hereinafter also referred to as PFA). The mixture was stirred while being cooled in an ice bath, and 2.0 g of methanol was slowly added dropwise from the dropping funnel under a nitrogen atmosphere. Stirred for 12 hours with nitrogen bubbling. The reaction mixture was concentrated by an evaporator to obtain 27.6 g of compound (6) (yield 98.8%).
CF ₃ CF ₂ CF ₂ —O—(CF ₂ CF ₂ O) (CF ₂ CF ₂ O) {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } —CF ₂ —COOCH ₃ (6 )
Compound (6): Average number of units x1: 21, average number of units x2: 20, number average molecular weight: 4,230.

In a 100 mL three-neck eggplant flask, 0.18 g of lithium chloride was dissolved in 18.3 g of ethanol. 25.0 g of compound (6) was added thereto, and while cooling with an ice bath, a solution of 0.75 g of sodium borohydride dissolved in 22.5 g of ethanol was slowly added dropwise. The ice bath was removed, and stirring was continued while the temperature was slowly raised to room temperature. After stirring at room temperature for 12 hours, an aqueous hydrochloric acid solution was added dropwise until the liquid became acidic. 20 mL of AC-2000 was added, washed once with water and once with saturated brine, and the organic phase was recovered. The collected organic phase was concentrated by an evaporator to obtain 24.6 g of compound (7) (yield 99.0%).
CF ₃ CF ₂ CF ₂ —O—(CF ₂ CF ₂ O) (CF ₂ CF ₂ O) {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 }—CF ₂ —CH ₂ OH ( 7)
Compound (7): Average value of unit number x1: 21, average value of unit number x2: 20, number average molecular weight: 4,200.

20.0 g of compound (7), 0.21 g of tetrabutylammonium hydrogensulfate, 1.76 g of BrCH ₂ CH═CH ₂ and 2.6 g of 30% aqueous sodium hydroxide solution were placed in a 100 mL two-neck eggplant flask. and stirred at 60° C. for 8 hours. After completion of the reaction, 20 g of AC-2000 was added, washed once with a dilute hydrochloric acid aqueous solution, and the organic phase was recovered. The recovered organic phase was passed through a silica gel column, and the recovered solution was concentrated by an evaporator to obtain 19.8 g of compound (8) (yield 98.2%).
_{CF3CF2CF2 - O- ( CF2CF2O} )(CF2CF2O) _{ ( _CF2O ) _x1 ( _CF2CF2O ) _{x2 } -CF2 - CH2OCH2CH =} CH ₂ (8)
Compound (8): Average number of units x1: 21, average number of units x2: 20, number average molecular weight: 4,250.

In a 100 mL PFA eggplant flask, 5.0 g of compound (8), a xylene solution of platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%). 0.005 g, 0.25 g of HSi(OCH ₃ ) ₃ , 0.005 g of dimethylsulfoxide and 0.20 g of 1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were added and heated at 40°C. Stirred for 4 hours. After completion of the reaction, the solvent and the like were distilled off under reduced pressure, filtered through a membrane filter with a pore size of 0.2 μm, and one compound (9) in which one allyl group of compound (8) was hydrosilylated and one compound (8) were obtained. 4.9 g (yield 95%) of composition (A-1) consisting of a by-product of isomerization of the allyl group of to inner olefin (--CH=CHCH ₃ ) was obtained. The hydrosilylation conversion rate was 100% and no compound (8) remained. The hydrosilylation selectivity was 95%.
_{CF3CF2CF2 - O- ( CF2CF2O ) (} CF2CF2O ₎ { _{( CF2O} ) _x1 ( _{CF2CF2O ) x2} } _{-CF2 -CH2OCH2CH2CH 2-} Si( _OCH3 ) ₃ (9)

NMR spectrum of compound (9);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.7 (6H), 1.7 (6H), 3.6 (11H), 3.8 (2H) .
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: C ₆ F ₆ ) δ (ppm): -52.4 to -55.8 (42F), -78.2 (1F), -80. 2 (1F), -82.2 (3F), -89.4 to -91.1 (90F), -130.5 (2F).
Average value of unit number x1: 21, average value of unit number x2: 20, number average molecular weight of compound (9): 4,370.

[Production Example A-2]
In a 100 mL two-neck eggplant flask, 20.0 g of compound (7) obtained in Production Example A-1, 20.0 g of 1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Chemical Industry Co., Ltd.), CF 1.01 g of ₃ SO ₂ Cl (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.00 g of triethylamine were added and stirred at room temperature for 4 hours under nitrogen atmosphere. After completion of the reaction, 15 g of AK-225 was added, washed once each with water and saturated brine, and the organic phase was recovered. The collected organic phase was concentrated by an evaporator to obtain 20.3 g of compound (10) (yield 99%).
_{CF3CF2CF2 - O- ( CF2CF2O ) (} CF2CF2O){ _{( CF2O} ) _x1 ( _{CF2CF2O ) x2} } _{-CF2 - CH2OSO2CF3} . (10)
Compound (10): Average number of units x1: 21, average number of units x2: 20, number average molecular weight: 4,340.

15.0 g of compound (10), 15.0 g of 1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Chemical Industry Co., Ltd.), HN(CH ₂ CH=CH ₂ ) ₂ ( Tokyo Chemical Industry Co., Ltd.) and 0.68 g of triethylamine were added and stirred at 90° C. for 24 hours in a nitrogen atmosphere. After completion of the reaction, 15 g of AK-225 was added, washed once each with water and saturated brine, and the organic phase was recovered, mixed with 1.5 g of silica gel, and filtered through a filter to recover the organic phase. The collected organic phase was concentrated by an evaporator to obtain 14.4 g of compound (11) (yield 98%).
_{CF3CF2CF2 - O- ( CF2CF2O )(CF2CF2O){(CF2O)x1 ( CF2CF2O ) x2 } -CF2 -} CH2 _- N( _CH2 CH=CH ₂ ) ₂ (11)
Compound (11): Average value of unit number x1: 21, average value of unit number x2: 20, number average molecular weight: 4,280.

In a 100 mL PFA eggplant flask, 12.0 g of compound (11), a xylene solution of platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%). 0.03 g, 1.3 g of HSi(OCH ₃ ) ₃ , 0.01 g of dimethylsulfoxide and 0.5 g of 1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were added and heated at 40°C. Stirred 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 with a pore size of 0.2 μm. 11.9 g (yield 92%) of composition (A-2) consisting of a by-product produced by intramolecular cyclization of the allyl group of was obtained. The hydrosilylation conversion was 100% and no compound (11) remained. The hydrosilylation selectivity was 81%.
_{CF3CF2CF2 - O- ( CF2CF2O )(CF2CF2O){(CF2O)x1 ( CF2CF2O ) x2 } -CF2- CH2} - _N [ _CH2 CH ₂ CH ₂ —Si(OCH ₃ ) ₃ ] ₂ (12)

NMR spectrum of compound (12);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.7 (4H), 1.6 (4H), 2.6 (4H), 3.1 (2H) , 3.6 (18H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −52.4 to −55.7 (42F), −74.4 (1F), −76.6 ( 1F), -82.2 (3F), -89.4 to -91.1 (90F), -130.5 (2F). Average value of unit number x1: 21, average value of unit number x2: 20, number average molecular weight of compound (12): 4,530.

[Production Example A-3]
5.0 g of the compound (6) obtained in Production Example A-1 and 0.2 g of H ₂ N—CH ₂ —C(CH ₂ CH=CH ₂ ) ₃ were placed in a 50 mL eggplant flask and stirred for 12 hours. bottom. NMR confirmed that compound (6) was completely converted to compound (13). In addition, methanol, which is a by-product, was produced. The resulting solution was diluted with 9.0 g of AE-3000 and purified by silica gel column chromatography (developing solvent: AE-3000) to obtain 4.4 g of compound (13) (yield 85%).
_{CF3CF2CF2 -} O- _{( CF2CF2O )} ( _CF2CF2O ){( _CF2O ) _x1 ( _CF2CF2O ) _{x2 }} -CF2 _- C(O) _NH -CH ₂ -C(CH ₂ CH=CH ₂ ) ₃ (13)
Compound (13): Average value of unit number x1: 21, average value of unit number x2: 20, number average molecular weight: 4,360.

A 10 mL PFA sample tube was charged with 4 g of compound (13) and a xylene solution of platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%). 4 mg, 0.33 g of HSi(OCH ₃ ) ₃ , 0.01 g of dimethylsulfoxide, and 0.2 g of 1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were added, and the mixture was heated at 40° C. for 10 hours. Stirred. After completion of the reaction, the solvent and the like were distilled off under reduced pressure, and the residue was filtered through a membrane filter with a pore size of 1.0 μm to obtain 4.3 g of compound (A-3) (yield 100%).
_{CF3CF2CF2 -} O- _{( CF2CF2O )(CF2CF2O){(CF2O)x1(CF2CF2O ) x2 } -CF2 - C (} O) _NH -CH ₂ -C[CH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ ] ₃ (A-3)

NMR spectrum of compound (A-3);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.75 (6H), 1.3-1.6 (12H), 3.4 (2H); 7 (27H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -52.4 to -55.8 (42F), -82.2 (3F), -89.4 to -91.1 (92F), -130.8 (2F).
Average value of unit number x1: 21, average value of unit number x2: 20, number average molecular weight of compound (A-3): 4,720.

[Production Example A-4]
15.0 g of dipentaerythritol (manufactured by ACROS), 29.5 g of 48% NaOH aqueous solution, and 150 g of dimethyl sulfoxide were placed in a 300 mL three-necked flask. The mixture was heated to 40° C., 39.5 g of 5-bromo-1-pentene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred for 4 hours. After washing once with dilute aqueous hydrochloric acid, 200 g of cyclopentyl methyl ether was added and the organic phase was recovered. The collected solution was concentrated by an evaporator to obtain 29.4 g of a crude product. The crude product was developed by silica gel column chromatography to separate 5.3 g of compound (14) and 6.0 g of compound (15).

1.0 g of compound (14), 0.4 g of 2,6-lutidine, and 5 g of AE-3000 were placed in a 50 mL two-neck eggplant flask. The mixture was stirred while being cooled in an ice bath, and 0.5 g of trifluoromethanesulfonic anhydride was slowly added dropwise under a nitrogen atmosphere. The mixture was further stirred for 1 hour, washed once with a dilute aqueous hydrochloric acid solution, and the organic phase was recovered. The collected solution was concentrated by an evaporator to obtain a crude product. The crude product was developed by silica gel column chromatography to obtain 1.2 g of compound (16) in which HO- of compound (14) was converted to CF ₃ SO ₃ -.

In a 50 mL eggplant flask, 1.0 g of compound (16), 6.6 g of compound (17) obtained by the method described in Production Example 6 of WO 2015/087902, 2.7 g of cesium carbonate, 1 6.6 g of ,3-bis(trifluoromethyl)benzene was added, and the mixture was stirred at 80° C. under reflux conditions for 4 hours. 10 g of AE-3000 was added, washed once with a dilute hydrochloric acid aqueous solution, and the organic phase was recovered. The collected solution was concentrated by an evaporator to obtain a crude product. The crude product was developed by silica gel column chromatography, and CF ₃ SO ₃ — in compound (16) was converted to CF ₃ CF ₂ CF ₂ O {(CF ₂ O) _m21 (CF ₂ CF ₂ O) _m22 } CF ₂ —CH. 6.6 g of compound (18) converted to ₂ -O- was collected.
CF ₃ CF ₂ CF ₂ O {(CF ₂ O) _m21 (CF ₂ CF ₂ O) _m22 } CF ₂ —CH ₂ —OH (17)

In a 100 mL PFA eggplant flask, 6.0 g of compound (18), a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%) 0.03 g, 1.2 g of trimethoxysilane (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 0.01 g of dimethylsulfoxide and 0.9 g of 1,3-bis(trifluoromethyl)benzene are added and stirred at 40° C. for 4 hours. bottom. The solvent and the like were distilled off under reduced pressure, and the residue was filtered through a membrane filter with a pore size of 0.2 μm to obtain 6.4 g of compound (A-4) in which five allyl groups of compound (18) were hydrosilylated. The hydrosilylation conversion was 100% and no compound (18) remained. The hydrosilylation selectivity was 100%.
Here, compound (A-4) is a compound in which WR ^51a — of compound (A13-3) is a group represented by formula (R ^f -1).

[Production Example A-5]
In the same manner as in Production Example A-4, except that compound (15) obtained in Production Example A-4 was used instead of compound (14), two HO— in compound (15) were all CF ₃ SO ₃ -converted compound (19) was obtained. Next, in the same manner as in Production Example A-4(3) except that compound (19) was used instead of compound (16), two CF ₃ SO ₃ — in compound (19) were all CF ₃ CF _{2CF 2} O{(CF ₂ O) _m21 (CF ₂ CF ₂ O) _m22 }CF ₂ --CH ₂ --O-- to obtain compound (20). Next, compound (A-5) obtained by hydrosilylating the four allyl groups of compound (20) in the same manner as in Production Example A-4 except that compound (20) was used instead of compound (18). 6.4 g was obtained.
Here, compound (A-5) is a compound in which WR ^51a — of compound (A13-4) is a group represented by formula (R ^f -1).

[Production Example B-1]
Compound (B-1) was obtained according to the method described in Example 6 of WO 2013/121984.
_{CF3 - O- (} CF2CF2O _{- CF2CF2CF2CF2O)x3 ( CF2CF2O ) -CF2CF2CF2 - CONHCH2CH2CH2 - Si ( OCH3 ) 3} (B-1)
Compound (B-1): unit number x 3 average value 13, number average molecular weight 4,870.

[Production Example B-2]
Compound (21) was obtained according to the method described in Example 7 of WO2013/121984.
CF ₃ —O—(CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _×3 (CF ₂ CF ₂ O)—CF ₂ CF ₂ CF ₂ —CH ₂ OH (21)
Compound (21): unit number x 3 average value 13, number average molecular weight 4,700.

Example A-2 except that the compound (7) was replaced by the compound (21), the amount of CF ₃ SO ₂ Cl (manufactured by Wako Pure Chemical Industries, Ltd.) was changed to 0.86 g, and the amount of triethylamine was changed to 1.02 g. Similarly, 30.6 g (yield 99%) of compound (22) was obtained.
CF ₃ —O—(CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _×3 (CF ₂ CF ₂ O)—CF ₂ CF ₂ CF ₂ —CH ₂ OSO ₂ CF ₃ (22)
Compound (22): unit number x 3 average value 13, number average molecular weight 4,830.

In the same manner as in Production Example A-2, except that compound (10) was replaced with compound (22), the amount of HN(CH ₂ CH═CH ₂ ) ₂ was changed to 2.08 g, and the amount of triethylamine was changed to 0.63 g. , 14.6 g (yield 98%) of compound (23) was obtained.
CF3 _- O-( _{CF2CF2O - CF2CF2CF2CF2O ) x3 ( CF2CF2O} ) _{-CF2CF2CF2 - CH2 - N} ( _{CH2CH = CH2} ) ₂ (23)
Compound (23): unit number x 3 average value 13, number average molecular weight 4,780.

_{A compound} Composition (B-2) consisting of compound (24) in which two allyl groups of (23) are hydrosilylated and by-products produced by intramolecular cyclization of two allyl groups of compound (23) 11.8 g (94% yield) were obtained. The hydrosilylation conversion was 100% and no compound (23) remained. The hydrosilylation selectivity was 80%.
_{CF3 - O- ( CF2CF2O - CF2CF2CF2CF2O ) x3 (} CF2CF2O _{) -CF2CF2CF2 - CH2 - N} [ _CH2CH2CH2- Si( _OCH3 ) ₃ ] ₂ (24)

NMR spectrum of compound (24);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.7 (4H), 1.6 (4H), 2.6 (4H), 3.2 (2H) , 3.6 (18H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: C ₆ F ₆ ) δ (ppm): −56.3 (3F), −84.0 (54F), −89.2 (54F), -91.4 (2F) -120.9 (2F), -126.6 (54F).
Average value of number of units x3: 13, number average molecular weight of compound (24): 5,020.

[Production Example B-3]
Compound (25) was obtained according to the method described in Example 6 of WO2013/121984.
CF ₃ —O—(CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _x3 (CF ₂ CF ₂ O)—CF ₂ CF ₂ CF ₂ —C(O)OCH ₃ (25)
Compound (25): unit number x 3 average value 13, number average molecular weight 4,700.

Same as Production Example A-3 except that the amount of compound (6) was changed to 9.0 g of compound (25) and the amount of H ₂ N—CH ₂ —C(CH ₂ CH═CH ₂ ) ₃ was changed to 0.45 g. As a result, 7.6 g of compound (26) was obtained (yield 84%).
_{CF3 - O-} ( _{CF2CF2O - CF2CF2CF2CF2O} ) _{x3 (} CF2CF2O) _-CF2CF2CF2 -C(O ₎ NH _{- CH2 - C} (CH ₂ CH=CH ₂ ) ₃ (25)
Compound (26): unit number x 3 average value 13, number average molecular weight 4,800.

compound (13) to 6.0 g of compound (26), the amount of platinum complex solution to 0.07 g, the amount of HSi(OCH ₃ ) ₃ to 0.78 g, the amount of dimethylsulfoxide to 0.02 g, 6.7 g of compound (B-3) ( Yield 100%) was obtained.
_CF3 - _O- ( _{CF2CF2O - CF2CF2CF2CF2O ) x3 (} CF2CF2O) _-CF2CF2CF2 -C(O ₎ NH _{- CH2- C [} CH _{2CH 2} CH ₂ —Si(OCH ₃ ) ₃ ] ₃ (B-3)

NMR spectrum of compound (B-3);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.75 (6H), 1.3-1.6 (12H), 3.4 (2H), 3.4 (2H); 7 (27H). ¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −55.2 (3F), −82.1 (54F), −88.1 (54F), −90 .2 (2F), -119.6 (2F), -125.4 (52F), -126.2 (2F). Average value of number of units x3: 13, number average molecular weight of compound (B-3): 5,400.

[Production Example B-4]
Instead of compound (17), compound (27) obtained by the method described in Example 7 of WO 2013/121984 (average value of m25: 13, number average molecular weight: 4,700) was used. In the same manner as in Production Example A-4 except that CF ₃ SO ₃ — in compound (16) was converted to CF ₃ O(CF ₂ CF ₂ OCF ₂ CF 2 CF _{2 CF 2 O} ) _m25 CF ₂ CF ₂ OCF ₂ CF ₂ Compound (28) converted to CF ₂ —CH ₂ —O— was obtained. Next, in the same manner as in Production Example A-4 except that compound (28) was used instead of compound (18), five allyl groups of compound (28) were hydrosilylated to produce compound (B-4). 6.3 g was obtained.
CF ₃ O(CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) _m25 CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ —CH ₂ —OH (27)
Here, the compound (B-4) is a compound in which WR ^51a — of the compound (A13-3) is a group represented by the formula (R ^f -3).

[Production Example B-5]
In the same manner as in Production Example A-5 except that compound (27) was used instead of compound (17), two CF ₃ SO ₃ — in compound (19) were all replaced by CF ₃ CF ₂ CF ₂ O {( CF ₂ O) _m21 (CF ₂ CF ₂ O) _m22 } CF ₂ —CH ₂ —O— to give compound (29). Next, compound (B-5) obtained by hydrosilylating the four allyl groups of compound (29) in the same manner as in Production Example A-4 except that compound (29) was used instead of compound (18). 6.1 g was obtained.
Here, compound (B-5) is a compound in which W—R ^51a — of compound (A13-4) is a group represented by formula (R ^f -3).

[Example 1]
A composition was prepared by mixing 50 parts by mass of (A-1) and 50 parts by mass of (B-1). Using this composition, a substrate was surface-treated by the following dry coating method to obtain an article of Example 1. Chemically strengthened glass was used as the substrate. The resulting article was evaluated for durability 1 (number of times a contact angle of 100° or more was maintained), lubricity and durability 2 (difficulty in reducing dynamic friction coefficient). The results are shown in Tables 3-5.

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

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

Durability 1 (Number of times a contact angle of 100° or more is maintained)

Lubricity (dynamic friction coefficient)

Durability 2 (Difficulty in reducing dynamic friction coefficient)

The compositions of Examples 1 to 5, 7 to 11, 13 to 17, 19 to 23, 25 to 29 in which compound (A) and compound (B) are combined do not have compound (B) and group (I) Compared to the compositions of Examples 36 to 40 in which the compound (C-1) was combined, the durability and lubricity were excellent. Moreover, compared with Examples 31 to 35 in which the compound (B) was used alone, the lubricating properties were excellent. In addition, there was a tendency that durability improved as the number of groups (I) possessed by compound (A) and compound (B) increased.

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

(Wet coating method)
Each composition obtained in Examples 41 to 50 and C ₄ F ₉ OC ₂ H ₅ (manufactured by 3M, Novec (registered trademark) 7200) as a liquid medium were mixed to obtain a solid concentration of 0.05%. A coating solution was prepared. The substrate was dipped in the coating liquid, left for 30 minutes, and then pulled up (dip coating method). The coating film was dried at 120° C. for 30 minutes and washed with AK-225 to obtain an article having a surface treatment layer on the surface of the substrate.

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

By using the compound (A) and the compound (B) in combination, it was possible to achieve both lubricity and durability at a higher level than when each compound was used alone. Durability and lubricity were particularly excellent when the mass ratio of compound (A)/compound (B) was within the range of 20/80 to 50/50.

The present composition and the present coating liquid can be used in various applications requiring the provision of lubricity and water/oil repellency. For example, a display input device such as a touch panel; a surface protective coating made of transparent glass or transparent plastic members, an antifouling coating for kitchens; It can be used for antifouling coating; coating on members that require liquid repellency while conducting; water-repellent, water-proof, and water-sliding coating for heat exchangers;
In addition, the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2017-050558 filed on March 15, 2017 are cited here and incorporated as disclosure of the specification of the present invention. is.

Claims (10)

including a fluorine-containing ether compound (A) and a fluorine-containing ether compound (B) (excluding compounds represented by the following formula (A)) ,
The fluorine-containing ether compound (A) is a compound having a poly(oxyperfluoroalkylene) chain containing (CF ₂ O) units and two or more groups represented by the following formula (I),
The fluorine-containing ether compound (B) is a compound having a poly(oxyperfluoroalkylene) chain containing no (CF ₂ O) units and two or more groups represented by the formula (I). Fluorine-containing ether composition.
—SiR _n L _3-n (I)
provided that L is a hydroxyl group or a hydrolyzable group,
R is a hydrogen atom or a monovalent hydrocarbon group,
n is an integer from 0 to 2,
When n is 0 or 1, (3-n) L may be the same or different,
When n is 2, n R may be the same or different,
The groups represented by the formula (I) in the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) may be the same or different.
R ^F1 O(CF ₂ CF ₂ O) _a CF ₂ —(Q) _b (—(CH ₂ ) _d —SiL _p R _3-p ) _c (A).
However, the symbols in the formula (A) have the following meanings.
R ^F1 : a perfluoro monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a perfluoro monovalent saturated hydrocarbon group having 2 to 20 carbon atoms in which an etheric oxygen atom is inserted between carbon atoms and carbon atoms; A group in which the —OCF ₂ O— structure does not exist.
a: an integer from 1 to 200;
b: 0 or 1;
Q: When b is 0, Q does not exist, and when b is 1, Q is a divalent or trivalent linking group.
c: c is 1 when Q does not exist or Q is a divalent linking group, and c is 2 when Q is a trivalent linking group.
d: an integer from 2 to 6;
L: hydrolyzable group.
R: hydrogen atom or monovalent hydrocarbon group.
p: an integer from 1 to 3; 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),
R ^f in the fluorine-containing ether compound (A) is a poly(oxyperfluoroalkylene) chain containing (CF ₂ O) units,
The fluorine-containing ether composition according to claim 1, wherein ^Rf in the fluorine-containing ether compound (B) is a poly(oxyperfluoroalkylene) chain containing no ( _CF2O ) unit.
[R ^f1 -OQR ^f -] _r Z [-SiR _n L _3-n ] _s (A/B)
provided that R ^f1 is a perfluoroalkyl group,
Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group in which 2 to 5 of the oxyfluoroalkylene groups are bonded, and the polyoxyfluoroalkylene group is The constituent oxyfluoroalkylene groups may all be the same or different,
R ^f is a poly(oxyperfluoroalkylene) chain,
Z is a (r+s)-valent linking group,
—SiR _n L _3-n is a group represented by formula (I) above,
when r is 2 or more, r pieces of [R ^f1 -OQR ^f -] are the same group;
s groups represented by formula (I) are the same group,
r is an integer of 1 or more, s is an integer of 2 or more, and r+s is 3-8. 3. The poly(oxyperfluoroalkylene) chain comprising ( _CF2O ) units is a poly( _{oxyperfluoroalkylene} ) chain comprising ( _CF2O ) units and ( _CF2CF2O ) units, or 2. The fluorine-containing ether composition according to 2. _The poly( _{oxyperfluoroalkylene} ) chain containing no ( _{CF2O )} units comprises ( _CF2CF2O ) units, _{( CF2CF2CF2O} ) units and ( _{CF2CF2CF2CF2O} ) _{units .} The fluorine-containing ether composition according to any one of claims 1 to 3, which is a poly(oxyperfluoroalkylene) chain containing at least one selected from units. 2. The poly( _{oxyperfluoroalkylene )} chain containing no ( _CF2O ) units is a poly _{( oxyperfluoroalkylene} ) chain containing ( _{CF2CF2CF2CF2O} ) _units . 5. The fluorine-containing ether composition according to any one of -4. 6. The group according to any one of claims 1 to 5, wherein at least one of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) has three or more groups represented by the formula (I). fluorine-containing ether composition. A fluorine-containing ether composition comprising a fluorine-containing ether compound (A1) represented by the following formula (A1) and a fluorine-containing ether compound (B1) represented by the following formula (B1).
[R ^f1a —OQ ^a —R ^fa —] _ra Z ^a [—SiR ^a _na L ^a _3-na ] _sa (A1)
[R ^f1b —OQ ^b —R ^fb —] _rb Z ^b [—SiR ^b _nb L ^b _3-nb ] _sb (B1)
provided that R ^f1a and R ^f1b are perfluoroalkyl groups,
Q ^a and Q ^b are a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group in which 2 to 5 of the oxyfluoroalkylene groups are bonded, and the polyoxy All of the oxyfluoroalkylene groups constituting the fluoroalkylene group may be the same or different,
R ^fa is a poly(oxyperfluoroalkylene) chain containing (CF ₂ O) units,
R ^fb is a poly(oxyperfluoroalkylene) chain containing no (CF ₂ O) units;
Z ^a is a (ra + sa) valent linking group,
Z ^b is a (rb+sb)-valent linking group,
L ^a and L ^b are hydroxyl groups or hydrolyzable groups,
R ^a and R ^b are a hydrogen atom or a monovalent hydrocarbon group,
na and nb are integers from 0 to 2;
(3-na) L ^a when na is 0 or 1 and (3-nb) L ^b when nb is 0 or 1 may be the same or different,
When na is 2, na R ^a 's, and when nb is 2, nb R ^b 's may be the same or different,
ra and rb are integers of 1 or more, and when ra is 2 or more, ra [R ^f1a -OQ ^a -R ^fa -] may be the same or different, and rb is 2 In the above case, rb [R ^f1b -OQ ^b -R ^fb -] may be the same or different,
sa and sb are integers of 2 or more, sa [-SiR ^a _na L ^a _3-na ] may be the same or different, and sb [-SiR ^b _nb L ^b _{3 -nb} ] may be the same or different. 8. The fluorine-containing ether composition according to claim 7 , comprising 10 to 80% by mass of said fluorine-containing ether compound (A1) with respect to the total of said fluorine-containing ether compound (A1) and said fluorine-containing ether compound (B1). A coating liquid comprising the fluorine-containing ether composition according to any one of claims 1 to 8 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 8 .