TWI831741B - Fluorine-containing ether compositions, coating fluids and articles - Google Patents

Abstract

The present invention provides a fluorine-containing ether composition and coating liquid that can form a surface layer excellent in lubricity and durability, and an article having a surface layer excellent in lubricity and durability. A fluorine-containing ether composition, containing a fluorine-containing ether compound (A) and a fluorine-containing ether compound (B); the aforementioned fluorine-containing ether compound (A) is a poly(oxyperfluoroalkylene) group containing (CF ₂ O) units ) chain and a group represented by the following formula (I), the aforementioned fluoroether compound (B) is a poly(oxyperfluoroalkylene) chain that does not contain (CF ₂ O) units and the aforementioned formula (I) Compounds of the groups shown. -SiR _n L _3-n ...(I); however, L is a hydroxyl group or a hydrolyzable group, and R is a hydrogen atom or a monovalent hydrocarbon group.

Description

Fluorine-containing ether compositions, coating fluids and articles

The invention relates to a fluorine-containing ether composition, coating liquid and articles.

Background of the Invention Fluorine-containing compounds can exhibit high lubricity, water and oil repellency, etc., and therefore can be used as surface treatment agents and the like. For example, if a surface treatment agent is used to form a surface layer on the surface of a substrate, it can impart lubricity, water and oil repellency, etc., making it easier to wipe off dirt on the surface of the substrate and improve dirt removal performance. Among fluorine-containing compounds, fluorine-containing ether compounds are excellent in removing grease and other dirt. These fluorine-containing ether compounds have a poly(oxyperfluoroalkyl) group with an ether bond (-O-) in the perfluoroalkyl chain. chain.

Some literature proposes using those with hydrolyzable silicon groups as fluorine-containing ether compounds. This fluorine-containing ether compound can be used in applications that require long-term maintenance of friction resistance and fingerprint dirt removal properties. For example, it can be used as a surface treatment agent for the components that constitute the finger touch surface of touch panels. The friction resistance refers to the friction resistance even if the finger is repeatedly used. The water- and oil-repellent properties are not easily reduced by friction. The fingerprint dirt repellency refers to the ability to easily remove fingerprints attached to the surface by wiping.

In order to improve the lubricity, some documents propose a fluorine-containing ether composition in which a fluorine-containing ether compound with a hydrolyzable silicon group is blended with a fluorine-containing oil, that is, a non-reactive fluorine-containing ether compound without a hydrolyzable silicon group (for example, Patent Document 1 ).

Prior Art Document Patent Document Patent Document 1: Japanese Patent Application Publication No. 2014-65884

Summary of the Invention Problems to be Solved by the Invention However, studies by the present inventors revealed that the surface layer formed of the above-mentioned fluorine-containing ether composition easily deteriorates in properties such as lubricity and water- and oil-repellency (durability) after repeated rubbing with fingers or the like. low sex). Therefore, it is difficult to maintain high levels of both lubricity and durability properties at the same time.

An object of the present invention is to provide a fluoroether composition and coating liquid that can form a surface layer excellent in lubricity and durability, and an article having a surface layer excellent in lubricity and durability. means to solve problems

The present invention provides a fluorine-containing ether composition, coating liquid and article having the following compositions [1] to [15]. [1] A fluorine-containing ether composition, characterized in that it contains a fluorine-containing ether compound (A) and a fluorine-containing ether compound (B); the aforementioned fluorine-containing ether compound (A) is a poly((CF ₂ O)-containing unit). A compound containing an oxyperfluoroalkylene) chain and a group represented by the following formula (I); The aforementioned fluoroether compound (B) is a poly(oxyperfluoroalkylene) chain that does not contain (CF ₂ O) units And the compound of the group represented by the aforementioned formula (I). -SiR _n L _3-n …(I) However, L is a hydroxyl group or a hydrolyzable group; R is a hydrogen atom or a monovalent hydrocarbon group; n is an integer from 0 to 2; when n is 0 or 1, (3-n) L may be the same or different from each other; when n is 2, n R may be the same or different from each other; wherein, the aforementioned fluorine-containing ether compound (A) and the aforementioned fluorine-containing ether compound (B) each have the aforementioned formula ( The groups shown in I) may be the same or different from each other.

[2] The fluorine-containing ether composition of [1], wherein the aforementioned fluorine-containing ether compound (A) and the aforementioned fluorine-containing ether compound (B) are both fluorine-containing ether compounds represented by the following formula (A/B); R ^f in the fluoroether compound (A) is a poly(oxyperfluoroalkylene) chain containing (CF ₂ O) units, while R ^f in the aforementioned fluoroether compound (B) is a poly(oxyperfluoroalkylene) chain containing (CF ₂ O) units. ) unit of a poly(oxyperfluoroalkylene) chain. [R ^f1 -OQR ^f -] _r Z[-SiR _n L _3-n ] _s …(A/B) However, R ^f1 is a perfluoroalkyl group; Q is a single bond, oxygen fluorine containing more than 1 hydrogen atom An alkylene group or a polyoxyfluoroalkylene group formed by bonding 2 to 5 of the oxyfluoroalkylene groups, and the oxyfluoroalkylene groups constituting the polyoxyfluoroalkylene group may all be the same or different from each other; R ^f is a poly(oxyperfluoroalkylene) chain; Z is a (r+s) valent linking group; -SiR _n L _3-n is a group represented by the aforementioned formula (I); when r is 2 or more, r [R ^f1 -OQR ^f -] are the same group; when s is 2 or more, s groups shown in formula (I) are the same group; r and s are respectively an integer of 1 or more and r+s is 3 ~8.

[3] The fluorine-containing ether composition of [1] or [2], wherein the poly(oxyperfluoroalkylene) chain system containing (CF ₂ O) units contains (CF ₂ O) units and (CF ₂ Poly(oxyperfluoroalkylene) chains of CF ₂ O) units. [4] The fluorine-containing ether composition according to any one of [1] to [3], wherein the aforementioned poly(oxyperfluoroalkylene) chain system containing no (CF ₂ O) unit contains a chain selected from (CF ₂ A poly(oxyperfluoroalkylene) chain of at least one unit among a CF ₂ O) unit, a (CF ₂ CF ₂ CF ₂ O) unit and a (CF ₂ CF ₂ CF ₂ CF ₂ O) unit. [5] The fluorine-containing ether composition according to any one of [1] to [4], wherein the aforementioned poly(oxyperfluoroalkylene) chain system without (CF ₂ O) units contains (CF ₂ CF ₂ Poly(oxyperfluoroalkylene) chain of OCF ₂ CF ₂ CF ₂ CF ₂ O) units. [6] The fluorine-containing ether composition according to any one of [1] to [5], wherein at least one of the aforementioned fluorine-containing ether compound (A) and the aforementioned fluorine-containing ether compound (B) has three or more of the aforementioned formulas ( I) group shown. [7] The fluorine-containing ether composition according to any one of [1] to [5], wherein both the above-mentioned fluorine-containing ether compound (A) and the above-mentioned fluorine-containing ether compound (B) have two or more of the above-mentioned formulas (I) ) group shown. [8] The fluorine-containing ether composition according to any one of [1] to [5], wherein both the aforementioned fluorine-containing ether compound (A) and the aforementioned fluorine-containing ether compound (B) have three or more of the aforementioned formula (I) ) group shown. [9] The fluorine-containing ether composition according to any one of [1] to [8], wherein the number average molecular weight of the aforementioned fluorine-containing ether compound (A) is 2,000 to 20,000. [10] The fluorine-containing ether composition according to any one of [1] to [9], wherein the number average molecular weight of the aforementioned fluorine-containing ether compound (B) is 2,000 to 20,000. [11] The fluorine-containing ether composition according to any one of [1] to [10], which contains 10 to 80% of the total amount of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B). Mass % of the aforementioned fluoroether compound (A).

[12] A fluorine-containing ether composition characterized by containing 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) However, R ^f1a and R ^f1b are perfluoroalkyl groups; Q ^a and Q ^b are single bonds, oxyfluoroalkyl alkylene groups containing more than 1 hydrogen atom or 2 to 5 The oxyfluoroalkylene group is a polyoxyfluoroalkylene group formed by bonding the oxyfluoroalkylene group, and the oxyfluoroalkylene groups constituting the polyoxyfluoroalkylene group can all be the same or different from each other; R ^fa is containing (CF ₂ O) unit of poly(oxyperfluoroalkylene) chain; R ^fb is a poly(oxyperfluoroalkylene) chain that does not contain (CF ₂ O) units; Z ^a is a (ra+sa) valence 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 hydrogen atoms or monovalent hydrocarbon groups; na and nb are integers from 0 to 2; na is 0 or 1 The (3-na) L ^a when nb is 0 or 1, the (3-nb) L ^b can be the same or different respectively; the na R ^a when na is 2, and the nb when nb is 2 R ^b can be the same or different from each other; ra and rb are integers above 1. When ra is 2 or above, ra [R ^f1a -OQ ^a -R ^fa -] can be the same or different. When rb is 2 or above The rb numbers [R ^f1b -OQ ^b -R ^fb -] can be the same or different; sa and sb are integers above 1, and when sa is 2 or more, the sa numbers [-SiR ^a _na L ^a _3-na ] can be the same or different. Can be different from each other. When sb is 2 or more, the sb [-SiR ^b _nb L ^b _3-nb ] can be the same or different from each other. [13] The fluorine-containing ether composition of [12], which contains the above-mentioned fluorine-containing ether compound in an amount of 10 to 80% by mass relative to the total amount of the above-mentioned fluorine-containing ether compound (A1) and the above-mentioned fluorine-containing ether compound (B1) (A1). [14] A coating liquid characterized by containing the fluorine-containing ether composition according to any one of the above [1] to [13] and a liquid medium. [15] An article characterized by having a surface layer formed of the fluorine-containing ether composition according to any one of the above [1] to [13].

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

Modes for Carrying Out the Invention In this specification, the compound represented by formula (1) is represented as compound (1). Compounds represented by other formulas are also represented in the same manner. The following terms in this manual have the following meanings. "Hydrolyzable silicon group" refers to a group that can form a silanol group (Si-OH) through a hydrolysis reaction. For example, L in formula (I) is a hydrolyzable group. The chemical formula of the oxygen perfluoroalkylene group is represented by describing the oxygen atom on the right side of the perfluoroalkylene group. "Surface layer" refers to the layer formed on the surface of the substrate. "Drying" after applying the coating liquid means that the coating liquid is applied to the base material to form a coating film of the coating liquid on the base material, and then the liquid medium is evaporated and removed from the coating film.

[Fluorine-containing ether composition] The fluorine-containing ether composition (hereinafter also referred to as this composition) of the present invention contains a fluorine-containing ether compound (A) (hereinafter also referred to as compound (A)) and a fluorine-containing ether compound (B) (Hereinafter also referred to as compound (B)). This composition does not contain a liquid medium as mentioned later. The composition may be composed of Compound (A) and Compound (B), and may also contain other fluorine-containing ether compounds other than Compound (A) and Compound (B), or Compound (A), Compound (B) and other fluorine-containing ether compounds as described later. Impurities other than ether compounds. Compound (A) has a poly(oxyperfluoroalkylene) chain containing (CF ₂ O) units (hereinafter also referred to as A chain) and a group (I). Compound (B) has a poly(oxyperfluoroalkylene) chain (hereinafter also referred to as B chain) containing no (CF ₂ O) unit and a group (I). Compound (B) does not have an A chain. -SiR _n L _3-n …(I) However, L is a hydroxyl group or a 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) The L's may be the same or different; when n is 2, the n R's may be the same or different; the group (I) of the compound (A) and the compound (B) may be the same or different.

Compound (A) and compound (B) may each have a group (II). When both compound (A) and compound (B) have a group (II), the groups (II) they have may be the same or different from each other. R ^f1 -OQ-…(II) However, R ^f1 is a perfluoroalkyl group; Q is a single bond, an oxyfluoroalkylene group containing more than 1 hydrogen atom, or bonded by 2 to 5 of the oxyfluoroalkylene group. Made of polyoxyfluoroalkylene. The oxyfluoroalkylene groups constituting the polyoxyfluoroalkylene group may all be the same or different from each other.

(A chain) Examples of the A chain include poly(oxyperfluoroalkylene) chains containing (CF ₂ O) units and (R ^{f 2} O) units as shown in the following formula (a1). {(CF ₂ O) _m1 (R ^f2 O) _m2 }…(a1) However, R ^f2 is a perfluoroalkylene group with a carbon number of 2 or more; m1 is an integer of 1 or more, m2 is an integer of 0 or more, and ( m1+m2) is an integer from 2 to 200; when m2 is more than 1, the bonding order of m1 CF ₂ O and m2 R ^f2 O is not limited; when m2 is more than 2 (R ^f2 O) _m2 can also be composed of carbon numbers It is composed of two or more different types of R ^f2 O.

R ^f2 may be branched or linear. From the viewpoint of better lubricity of the surface layer, linear chain is preferred. From the perspective of better durability and lubricity of the surface layer, the carbon number of R ^f2 should be 2 to 6 and preferably 2 to 4; from the perspective of better lubricity of the surface layer, then 2 Excellent.

(m1+m2) is an integer between 2 and 200. Therefore, when m1 is 1, the minimum value of m2 is 1, that is, there is at least 1 (R ^f2 O). When m1 is 2 or more, the minimum value of m2 is 0, and (R ^f2 O) may or may not exist. (m1+m2) is preferably an integer between 10 and 150, and an integer between 20 and 100 is particularly preferred. As long as (m1+m2) is above the lower limit of the aforementioned range, the lubricity of the surface layer is good. As long as (m1+m2) is below the upper limit of the aforementioned range, the durability of the surface layer will be good. That is, if the number average molecular weight of compound (A) is too large, the number of groups (I) present per unit molecular weight will decrease, thereby reducing durability.

The ratio of m1 to m2 (m1/m2) should be 100/0~30/70, and 90/10~40/60 is especially good. The higher the ratio of m1 within the aforementioned range, the better 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 oxygen perfluoroalkylene groups with different carbon numbers, each oxygen perfluoroalkylene group (m1 CF ₂ The bonding order of O and m2 R ^f2 O) is not limited. For example, each oxygen perfluoroalkylene group can be arranged in any of random, staggered, and block configurations. In particular, the (CF ₂ O) unit and the (R ^{f 2} O) unit are preferably randomly arranged. When m2 is 2 or more, (R ^f2 O) _m2 may be composed of two or more types of R ^f2 O with different carbon numbers. In addition, the bonding order of m2 R ^f2 O is not limited.

Specific forms 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) Only , m01 is an integer from 2 to 200, m11 is an integer above 1, m12 is an integer above 1, (m11+m12) is an integer from 2 to 200. The ideal ranges of m01 and (m11+m12) are the same as (m1+m2). The ratio of m11 to m12 (m11/m12) should be 99/1~30/70, and 90/10~40/60 is especially good. Among the above, (a3) to (a5) are suitable, and (a3) is particularly preferred. Chain A is preferably the above-mentioned (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 randomly arranged in the above-mentioned (a3) ) is especially good.

(B chain) Examples of the B chain include an (oxyperfluoroalkylene) chain containing at least one (R ^f3 O) unit as represented by the following formula (b1). (R ^f3 O) _m3 ...(b1) However, R ^f3 is a perfluoroalkylene group with a carbon number of 2 or more; m3 is an integer from 2 to 200; (R ^f3 O) _m3 can be composed of two or more R ^f2 with different carbon numbers. O; (R ^f3 O) When _m3 is composed of two or more R ^f2 O with different carbon numbers, the bonding order of each R ^f2 O is not limited.

R ^f3 may be branched or linear. From the viewpoint of better lubricity of the surface layer, linear chain is preferred. From the perspective of better durability and lubricity of the surface layer, the carbon number of R ^f3 is preferably 2 to 6.

m3 is an integer from 2 to 200, preferably an integer from 10 to 150, and especially an integer from 15 to 100. As long as m3 is above the lower limit of the aforementioned range, the lubricity of the surface layer will be good. As long as m3 is below the upper limit of the aforementioned range, the durability of the surface layer will be good. That is, if the number average molecular weight of compound (B) is too large, the number of groups (I) present per unit molecular weight will decrease, thereby reducing durability.

When (R ^f3 O) _m3 is composed of two or more R ^f2 O with different carbon numbers, the bonding order of each R ^f3 O is not limited. For example, each R ^f3 O can be in any of random, staggered, and block configurations.

(R ^f3 O) When _m3 is composed of two or more types of R ^f2 O with different carbon numbers, the B chain is preferably represented by the following formula (b2). {(CF ₂ CF ₂ O) _m4 (R ^f4 O) _m5 }…(b2) However, R ^f4 is a perfluoroalkylene group with a carbon number of 3 to 6, m4 is an integer of 1 or more, and m5 is an integer of 1 or more. , (m4+m5) is an integer from 2 to 200, and the bonding order of m4 CF ₂ CF ₂ O and m5 R ^f4 O is not limited.

R ^f4 is preferably CF ₂ CF ₂ CF ₂ CF ₂ . The ideal range of (m4+m5) is the same as m3. The ratio of m4 to m5 (m4/m5) should be 90/10~10/90, and 70/30~30/70 is especially good. The higher the ratio of m4 within the aforementioned range, the better the lubricity tends to be. The higher the ratio of m5 within the aforementioned range, the better the durability tends to be.

One of the ideal forms 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 from 1 to 3, m51 is an integer from 1 to 3, m6 is an integer above 1, and (m41+m51)×m6 is an integer from 2 to 200. The poly(oxyperfluoroalkylene) chain is composed of one or more units composed of 1 to 3 (CF ₂ CF ₂ O) and units composed of 1 to 3 (R ^f3 O) connected in series composed of units. The ideal range of (m41+m51)×m6 is the same as (m4+m5). m41 and m51 should each be 1. In addition, {(CF ₂ CF ₂ O) _m41 -(R ^f4 O) _m51 } _m6 can also be regarded as a poly(oxyperfluoroethylene) with {(CF ₂ CF ₂ O) _m41 -(R ^f4 O) _m51 } as the unit. alkyl) chain, or can be regarded as a poly(oxyperfluoroalkyl) chain composed of (CF ₂ CF ₂ O) _m41 units and (R ^f4 O) _m51 units staggered.

The B chain is preferably a poly(oxyfluoride) unit containing at least one unit selected from the group consisting of (CF ₂ CF ₂ O) unit, (CF ₂ CF ₂ CF ₂ O) unit and (CF ₂ CF ₂ CF ₂ CF ₂ O) unit. Fluoroalkylene) chain. Particularly preferred are poly(oxyperfluoroalkylene) chains containing (CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) units. Ideal specific forms 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) Only, m13 and m14 are integers from 2 to 200 respectively, and m15 is an integer from 1 to 100. (b5) is a poly(oxyperfluoroalkylene) chain containing (CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) units, and the poly(oxyperfluoroalkylene) chain can also be regarded as (CF A poly(oxyperfluoroalkylene) chain formed by staggered bonding of ₂ CF ₂ O) units and (CF ₂ CF ₂ CF ₂ CF ₂ O) units.

(Group (I)) In the group (I), L is a hydroxyl group or a hydrolyzable group. The hydrolyzable group is a group that becomes a hydroxyl group through a hydrolysis reaction. That is, when L is a hydrolyzable group, Si-L of the group (I) becomes a silanol group (Si-OH) through a hydrolysis reaction. Examples of the hydrolyzable group include an alkoxy group, a halogen atom, a acyl group, an isocyanate group (-NCO), and the like. The carbon number of the alkoxy group is preferably 1 to 4. The carbon number of the hydroxyl group is preferably 2 to 5.

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

R is a hydrogen atom or a monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include saturated hydrocarbon groups such as alkyl groups and cycloalkyl groups, alkenyl groups, allyl groups, etc., and saturated hydrocarbon groups are preferred. From the viewpoint of easy preparation of compound (A), the carbon number of the monovalent hydrocarbon group is preferably 1 to 6, and 1 to 3 is more preferred, and 1 to 2 is particularly preferred.

n should be 0 or 1, and 0 is particularly preferred. By having multiple L's in one base (I), the adhesion to the base material can be strengthened and the durability of the surface layer can be improved. When n is 0 or 1, (3-n) L can be the same or different from each other. For example, part of L may be a hydrolyzable group and the remaining L may be a hydroxyl group.

The group (I) is preferably Si(OCH ₃ ) ₃ , SiCH ₃ (OCH ₃ ) ₂ , Si(OCH ₂ CH ₃ ) ₃ , SiCl ₃ , Si(OCOCH ₃ ) ₃ and Si(NCO) ₃ . From the viewpoint of easy disposal in industrial manufacturing, Si(OCH ₃ ) ₃ is particularly preferred.

(Group (II)) In the group (II), R ^f1 is a perfluoroalkyl group. From the viewpoint of superior lubricity and durability of the surface layer, the carbon number of the perfluoroalkyl group in R ^f1 is preferably 1 to 20, with 1 to 10 being preferred, 1 to 6 being more preferred, and 1 to 3 being preferred. Excellent. The perfluoroalkyl group may be branched or linear, and linear is preferred. Examples of linear perfluoroalkyl groups include CF ₃ -, CF ₃ CF ₂ -, CF ₃ CF ₂ CF ₂ -, and the like.

Q is a single bond, an oxyfluoroalkylene group containing more than 1 hydrogen atom, or a polyoxyfluoroalkylene group bonded by 2 to 5 (preferably 2 to 4) oxyfluoroalkylene groups. In polyoxyfluoroalkylene groups, multiple oxyfluoroalkylene groups are usually linked in series. If Q is an oxyfluoroalkylene group containing hydrogen atoms or a polyoxyfluoroalkylene group bonded by 2 to 5 of the oxyfluoroalkylene groups, the liquid resistance of compound (A) and compound (B) can be improved. Solubility of the medium. Therefore, compound (A) and compound (B) are not easy to aggregate in the coating liquid, and after coating on the surface of the substrate, compound (A) and compound (B) are not easy to aggregate during the drying period, so the surface layer The appearance is more excellent. The carbon number of the oxyfluoroalkylene group is preferably 1 to 6, preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 or 3. From the viewpoint of excellent appearance of the surface layer, 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 better water- and oil-repellent properties of the surface layer, the number of hydrogen atoms in the oxyfluoroalkylene group is preferably (number of carbon atoms in Q) × 2 or less, and particularly preferably (number of carbon atoms in Q) or less. . The oxyfluoroalkylene group may be branched or linear. From the viewpoint of better lubricity of the surface layer, the linear group is preferred. In the polyoxyfluoroalkylene group, 2 to 5 oxyfluoroalkylene groups may all be the same or different from each other. From the viewpoint of ease of preparation of compound (A) and compound (B), Q is preferably a single bond or selected from the group consisting of -CHFCF ₂ OCH ₂ CF ₂ O-, -CF ₂ CHFCF ₂ OCH ₂ CF ₂ O-, -CF ₂ CF ₂ CHFCF ₂ OCH ₂ CF ₂ O-, -CF ₂ CF ₂ OCHFCF ₂ OCH ₂ CF ₂ O-, -CF ₂ CF ₂ OCF ₂ CF ₂ OCHFCF ₂ OCH ₂ CF ₂ O-, -CF ₂ CH ₂ OCH ₂ CF ₂ O- and -CF ₂ CF ₂ OCF ₂ CH ₂ OCH ₂ CF ₂ O- groups in the group (but the left side is bonded to R ^f1 -O).

The A chain of compound (A) and the B chain of compound (B) may each be one or two or more. From the viewpoint of ease of preparation and ease of disposal, 1 to 3 are appropriate. 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 from each other.

The number of groups (I) each of compound (A) and compound (B) has may be one or two or more. From the viewpoint of better durability of the surface layer by increasing the bonding with the base material, the number is preferably 2 or more, and more preferably 3 or more. From the viewpoint of better durability of the surface layer by increasing the density of molecules bonded to the base material, the number is preferably 10 or less, more preferably 5 or less, and particularly preferably 4 or less. Therefore, the number of groups (I) each of compound (A) and compound (B) has is preferably 1 to 10, preferably 2 to 5, and particularly preferably 3 to 4. When compound (A) or compound (B) has two or more groups (I), each group (I) may be the same or different from each other. From the viewpoint of easy production of compound (A) and compound (B), it is preferable that they all have the same group.

It is preferable that one of the terminal ends of the A chain and the B chain is bonded with the group (II). That is, the compound (A) preferably further has a group (II) bonded to one terminal of the A chain. Compound (B) preferably further has a group (II) bonded to one end of the B chain. Thereby, the lubricity of the surface layer can be made more excellent.

The number average molecular weight (Mn) of compound (A) and compound (B) is preferably 2,000 to 20,000, preferably 3,000 to 15,000, and particularly preferably 4,000 to 12,000. As long as the number average molecular weight of the compound (A) and the compound (B) is more than the lower limit of the aforementioned range, the lubricity of the surface layer will be more excellent. As long as the number average molecular weight of the compound (A) and the compound (B) is more than the lower limit of the aforementioned range, the durability of the surface layer will be more excellent. The number average molecular weight (Mn) can be measured by the measurement method described in the Examples mentioned later.

Compound (A) and compound (B) are not particularly limited as long as they have an A chain or a B chain and a group (I) respectively. For example, it can be appropriately selected from known fluorine-containing ether compounds described in the following documents. Japanese Patent Publication No. 2013-91047, Japanese Patent Publication No. 2014-80473, International Publication No. 2013/042732, International Publication No. 2013/042733, International Publication No. 2013/121984, International Publication No. 2013/121985, International Publication No. 2013/121986, International Publication No. 2014/163004, International Publication No. 2014/175124, International Publication No. 2015/087902, Japanese Patent Application Publication No. 2013-227279, Japanese Patent Application Publication No. 2013-241569, Japanese Patent Application Publication No. 2013-256643, Japanese Patent Application Publication No. 2014-15609, Japanese Patent Application Publication No. 2014-37548, Japanese Patent Application Publication No. 2014-65884, Japanese Patent Application Publication No. 2014-210258, Japanese Patent Application Publication No. 2014- Publication No. 218639, Japanese Patent Application Publication No. 2015-200884, Japanese Patent Application Publication No. 2015-221888, International Publication No. 2013/146112, International Publication No. 2013/187432, International Publication No. 2014/069592, International Publication No. 2015 /099085, International Publication No. 2015/166760, Japanese Patent Publication No. 2013-144726, Japanese Patent Publication No. 2014-77836, Japanese Patent Publication No. 2013-117012, Japanese Patent Publication No. 2014-214194, Japanese Patent Publication No. Japanese Patent Application Publication No. 2014-198822, Japanese Patent Application Publication No. 2015-129230, Japanese Patent Application Publication No. 2015-196723, Japanese Patent Application Publication No. 2015-13983, Japanese Patent Application Publication No. 2015-199915, Japanese Patent Application Publication No. 2015-199906 Gazette etc.

In the present composition, compound (A) may be a single compound consisting of one compound (A), or a mixture consisting of two or more compounds (A). In this specification, fluorine-containing ether compounds that are the same compound group are regarded as a single compound except that the numerical value of the repeating number of oxygen perfluoroalkylene groups in the poly(oxyperfluoroalkylene) chain has a distribution. For example, when the poly(oxyperfluoroalkylene) chain is compound (A) with (CF ₂ O) _m1 (R ^f2 O) _m2 , the group of compounds that are the same except that m1 and m2 have distributions is regarded as a single compound. Fluorine-containing ether compounds.

(Ideal combination of compound (A) and compound (B)) One of the ideal aspects of the present composition is that at least one of compound (A) and compound (B) has 3 or more groups (I), and preferably has 3 groups (I). ~5. If at least one of them has three or more groups (I), the durability of the surface layer will be excellent. When only one of them has three or more groups (I), the number of groups (I) that the other one has is 1 or 2, and preferably 2 from the viewpoint of durability.

Another ideal form of the present composition is that both compound (A) and compound (B) have two or more groups (I), preferably three or more, and more preferably three to five. If both have two or more groups (I), the durability of the surface layer will be excellent.

When the surface layer is formed by a dry coating method, the difference between the number average molecular weight (Mn) of the compound (A) and the number average molecular weight (Mn) of the compound (B) is preferably small. In the case of the dry coating method, those with small molecular weights tend to evaporate first and be deposited on the substrate. The smaller the difference in number average molecular weight (Mn), the less likely it is to form a surface layer that causes uneven distribution of compound (A) and compound (B). 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, and particularly preferably 2,000 or less. When forming a surface layer by a wet coating method, even if there is a difference between the number average molecular weight (Mn) of compound (A) and the number average molecular weight (Mn) of compound (B), it is difficult to form a surface layer that produces compounds The distribution of (A) and compound (B) is uneven, so the difference is not particularly limited.

Examples of ideal combinations of compound (A) and compound (B) in the present composition include the following combinations. Combination Example 1: Combination of compound (A) having one A chain and three groups (I) and compound (B) having one B chain and three groups (I). Combination Example 2: Combination of compound (A) having 2 A chains and 4 groups (I) and compound (B) having 2 B chains and 4 groups (I). Combination Example 3: Combination of compound (A) having one A chain and five groups (I) and compound (B) having one B chain and five groups (I). In each of these combinations, compound (A) preferably has a group (II) bonded to one end of the A chain. Furthermore, compound (B) preferably has a group (II) bonded to one terminal of the chain B.

It is preferable that both compound (A) and compound (B) are 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 not containing (CF ₂ O). ) unit of a poly(oxyperfluoroalkylene) chain. [R ^f1 -OQR ^f -] _r Z[-SiR _n L _3-n ] _s ...(A/B) In the above formula (A/B), R ^f1 is the aforementioned R ^f1 , Q is the aforementioned Q, and - SiR _n L _3-n is a group represented by the aforementioned formula (I). Z is the (r+s) valence linking base. r is an integer of 1 or more and is a number corresponding to the number of poly(oxyperfluoroalkylene) chains in the aforementioned 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 aforementioned compound (A) and compound (B). According to the aforementioned poly(oxyperfluoroalkylene) chain number and group (I) number, r+s is preferably 2 to 13, and 3 to 8 is preferred, and 4 to 7 is particularly preferred. Examples of Z of the (r+s) valence linking group include groups represented by Z ^a and Z ^b described later. In addition, when r is 2 or more, the r [R ^f1 -OQR ^f -] are preferably the same group; when s is 2 or more, the s groups represented by formula (I) are preferably the same group.

(Ideal Aspect) One of the ideal aspects of this composition is that the compound (A) is a fluoroether compound (A1) represented by the following formula (A1) (hereinafter also referred to as the compound (A1)) and the compound (B) It is an aspect of the fluorine-containing ether compound (B1) represented by formula (B1) (hereinafter also referred to as compound (B1)). That is, the composition of this aspect 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) However, R ^f1a and R ^f1b are perfluoroalkyl groups; Q ^a and Q ^b are single bonds, oxyfluoroalkyl alkylene groups containing more than 1 hydrogen atom or 2 to 5 The oxyfluoroalkylene group is a polyoxyfluoroalkylene group formed by bonding the oxyfluoroalkylene group, and the oxyfluoroalkylene groups constituting the polyoxyfluoroalkylene group can all be the same or different from each other; R ^fa is the A chain; R ^fb is B chain; Z ^a is a (ra+sa) valence linking group; Z ^b is a (rb+sb) valence linking group; L ^a and L ^b are hydroxyl groups or hydrolyzable groups; R ^a and R ^b are hydrogen atoms or monovalent Hydrocarbon group; na and nb are integers from 0 to 2; when na is 0 or 1, the (3-na) L ^a and when nb is 0 or 1, the (3-nb) L ^b can be the same or different respectively. ; when na is 2, na R ^a and when nb is 2, nb R ^b can be the same or different; ra and rb are integers above 1, and when ra is 2 or above, ra [R ^f1a -OQ ^a -R ^fa -] can be the same or different. When rb is 2 or more, rb numbers [R ^f1b -OQ ^b -R ^fb -] can be the same or different; sa and sb are integers of 1 or more, and sa is 2 or more. When sa [-SiR ^a _na L ^a _3-na ] can be the same or different, when sb is 2 or more, sb [-SiR ^b _nb L ^b _3-nb ] can be the same or different.

R ^f1a and R ^f1b are respectively the same as R ^f1 in the aforementioned base (II), and the ideal form is also the same. When ra is 2 or more, ra and R ^f1a should preferably have the same carbon number. From the viewpoint of ease of production, they should be the same group, that is, a group with the same carbon number and the same chemical structure. Groups with the same carbon number and the same chemical structure mean that, for example, when ra is 2, it is 2 R ^f1a is CF ₃ CF ₂ CF ₂ - (not 2 R ^fa with the same carbon number but different CF ₃ CF ₂ CF ₂ -, CF ₃ CF (combination of CF ₃ )-). When rb is 2 or more, it is preferable that rb R ^f1b have the same carbon number. From the viewpoint of ease of production, they are preferably the same group, that is, a group with the same carbon number and the same chemical structure.

Q ^a and Q ^b are the same as Q in the aforementioned base (II), and the ideal state is also the same. The A chain of R ^fa and the B chain of R ^fb are the same as above, and the ideal state is also the same. L ^a and L ^b are the same as L in the aforementioned base (I), and the ideal form is also the same. R ^a and R ^b are the same as R in the aforementioned group (I), and the ideal form is also the same. na and nb are the same as n in the aforementioned base (I), and the ideal state is also the same. The ideal values of ra and rb are the same as the respective ideal numbers of the A chain of compound (A) and the B chain of compound (B). That is, ra and rb are preferably integers between 1 and 3 respectively. The ideal values of s1 and s2 are the same as the ideal numbers of the group (I) possessed by each of compound (A) and compound (B). That is, s1 and s2 are each preferably an integer from 1 to 10, and an integer from 2 to 5 is more preferred, and an integer from 3 to 4 is particularly preferred.

Z ^a can include a substituted or unsubstituted hydrocarbon group with a (ra+sa) valence, a substituted or unsubstituted hydrocarbon group with a group other than a hydrocarbon group between the carbon atoms or/and the end of the substituted or unsubstituted hydrocarbon group, or a (ra+sa) valence atom. base, (ra+sa)-valent organic polysiloxy base, etc. Z ^b can be exemplified by things that are the same as Z ^a except that the valence is (rb+sb).

Examples of unsubstituted hydrocarbon groups include linear or branched saturated hydrocarbon groups and aromatic hydrocarbon cyclic groups (for example, removing (ra+sa) or (rb+sb) from aromatic hydrocarbon rings such as benzene rings and naphthalene rings. a hydrogen atom), a group composed of a combination of a linear or branched saturated hydrocarbon group and an aromatic hydrocarbon cyclic group (for example, a group in which an alkyl group is bonded to the aforementioned aromatic hydrocarbon cyclic group as a substituent, A group having an aryl group such as a phenylene group between carbon atoms of the aforementioned saturated hydrocarbon group or/and at the terminal end, etc.), a group composed of a combination of two or more aromatic hydrocarbon cyclic groups, etc. Among these, linear or branched saturated hydrocarbon groups are preferred. The carbon number of the unsubstituted hydrocarbon group is preferably 20 or less. A substituted hydrocarbon group is a group in which part or all of the hydrogen atoms of the hydrocarbon group are substituted by substituents. Examples of the substituent include halogen atoms such as a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, an amino group, a nitro group, a cyano group, an aminocarbonyl group, and the like.

Examples of groups or atoms other than the hydrocarbon group between the carbon-carbon atoms of the hydrocarbon group or/and at the terminal include etheric oxygen atom (-O-), thioetheric sulfur atom (-S-), and 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 )-, organic polysiloxy, -C(O)-, -C(O)-O-, -C(O)-S-, etc. 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 to 6. The organic polysiloxy group can be linear, branched, or cyclic.

<Ideal form of compound (A1)> From the viewpoint of more excellent friction resistance and fingerprint stain removal properties of the surface layer, compound (A1) is preferably selected from the group consisting of the following compound (A11), compound (A12) and compound (A13) At least one compound in the group.

"Compound (A11)" Compound (A11) is represented by the following formula (A11). R ^f1a -OQ ^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) Only, R ^f1a , Q ^a , R ^fa , R ^a , L ^a and na are respectively synonymous with the above. Q ^32a is a fluoroalkylene group with 1 to 20 carbon atoms or the carbon-carbon of a fluoroalkylene group with 2 to 20 carbon atoms. A group with etheric oxygen atoms between atoms (except when the fluoroalkylene group bonded to an etheric oxygen atom at one end and the other end bonded to R ^fa is a perfluoroalkylene group), R ^33a is a hydrogen atom or Alkyl group with 1 to 6 carbon atoms, pa is 0 or 1, R ^34a is a single bond, an alkylene group with 1 to 6 carbon atoms, at the end of the alkylene group (but, with C[-R ^34a -SiR _na L _3-na ] ₃ bonding side end) a group having an etheric oxygen atom, a group having an etheric oxygen atom between the carbon-carbon atoms of the alkylene group having 2 to 6 carbon atoms, or a group having an etheric oxygen atom between the carbon atoms of the alkylene group having 2 to 6 carbon atoms The alkylene end (only the end of the bonding side with C[-R ^34a -SiR _na L _3-na ] ₃ ) and the group with an etheric oxygen atom between carbon and carbon atoms, R ^35a is a carbon number of 1~ The alkylene group of 6 has an etheric oxygen atom at the end of the alkylene group (excluding the end bonded to Si), or between the carbon-carbon atoms of the alkylene group with 2 to 6 carbon atoms. As a base of etheric oxygen atoms, the three [-R ^34a -SiR _na L _3-na ] may be the same or different from each other.

Compound (A11) is in the above formula (A1), ra is 1, sa is 3, and Z ^a is -Q ^32a -[C(O)N(R ^33a )] _pa -R ^34a -C[-R ^35a -] ₃ compounds. 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. From the viewpoint of friction resistance and lubricity of the surface layer, the fluoroalkylene group is preferably linear. Examples of the group having an etheric oxygen atom between the carbon atoms of the fluoroalkylene group having 2 to 20 carbon atoms include the group (ii) described below. Q ^32a is preferably a perfluoroalkylene group with 1 to 20 carbon atoms, a fluoroalkylene group with 1 to 20 carbon atoms containing more than 1 hydrogen atom, and a fluorine alkylene group with 2 to 20 carbon atoms containing more than 1 hydrogen atom. An alkyl group has an etheric oxygen atom between its carbon atoms.

When pa is 0 and R ^fa is {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 }, Q ^32a is typically a perfluoroalkylene group having 1 carbon atoms. When pa is 1, examples of Q ^32a include the following groups. (i) Perfluoroalkylene group. (ii) It has R ^F CH ₂ O on the bonding side with R ^fa (but, R ^F is a perfluoroalkylene group with a carbon number of 1 to 6) and has R F CH 2 O on the bonding side with C(O)N (R ^33a ) A fluoroalkylene group containing more than one hydrogen atom (which may also have an etheric oxygen atom between carbon and carbon atoms).

Q ^32a in (ii) is preferably the following group from the viewpoint of the durability and lubricity of the surface layer and the ease of preparation of the compound (A11). -R ^F CH ₂ O-CF ₂ CHFOCF ₂ CF ₂ CF ₂ -, -R ^F CH ₂ O-CF ₂ CHFCF ₂ OCF ₂ CF ₂ -, -R ^F CH ₂ O-CF ₂ CHFCF ₂ OCF ₂ CF ₂ CF ₂ -, -R ^F CH ₂ O-CF ₂ CHFOCF ₂ CF ₂ CF ₂ OCF ₂ CF ₂ -.

[C(O)N(R ^33a )] When pa in _{the pa} group is 0 or 1, the characteristics of the fluorine-containing ether compound are almost unchanged. When pa is 1, it has a amide bond. Since the carbon atom at the end of Q ^32a 's bonding side with [C(O)N(R ^33a )] is bonded with at least one fluorine atom, the polarity of the amide bond changes. Small, the water and oil repellency of the surface layer is not easily reduced. Whether pa is 0 or 1 can be selected from the perspective of ease of manufacturing. From the viewpoint of ease of preparation of compound (A11), R ^33a in the [C(O)N(R ^33a )] _pa group is preferably a hydrogen atom. 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, from the viewpoint of ease of preparation of compound (A11), R ^34a is preferably a single bond or selected from the group consisting of -CH ₂ O-, -CH ₂ OCH ₂ -, -CH ₂ OCH ₂ CH ₂ O - and -CH ₂ OCH ₂ CH ₂ OCH ₂ - groups in the group (but the left side is bonded to Q ³² ). When pa is 1, from the viewpoint of ease of preparation of compound (A11), R ^34a is preferably a single bond or a group selected from the group consisting of -CH ₂ - and -CH ₂ CH ₂ -.

From the viewpoint of ease of preparation of compound (A11), R ^35a is preferably selected from -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ OCH ₂ CH ₂ CH ₂ -, -OCH ₂ CH ₂ CH ₂ -groups in the group (but the right side is bonded to Si). From the viewpoint of excellent light resistance of the surface layer, it is particularly preferable that R ^35a does not have an etheric oxygen atom. For touch panels used outdoors (digital signs such as vending machines and guide boards) and automotive touch panels, the water- and oil-repellent layer must be light-resistant. The three R ^35a in compound (A11) may be the same or different from each other.

Examples of the compound (A11) include compounds of the following formula. This compound is ideal from the viewpoint of being easy to manufacture and easy to handle industrially, and the surface layer has excellent water and oil repellency, friction resistance, fingerprint dirt removal ability, lubricity, and appearance.

[Chemical formula 1]

However, W in this equation is R ^f1a -OQ ^a -R ^fa -. The ideal form of W is a combination of the above ideal R ^f1a , Q ^a and R ^fa . The ideal range of Q ^32a is 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) Only, R ^f1a , Q ^a , R ^fa , R ^a , L ^a and na are synonymous with the above respectively, R ^42a is a perfluoroalkylene group with 1 to 6 carbon atoms, R ^43a is a single bond, an alkylene group with 1 to 6 carbon atoms, and is at the end of the alkylene group (but, with N (Excluding the end of the bonding side) has an etheric oxygen atom or -NH- group, has an etheric oxygen atom or -NH- group between the carbon-carbon atoms of the alkylene group with 2 to 6 carbon atoms, or has an etheric oxygen atom or -NH- group between carbon atoms. Alkylene terminals with numbers 2 to 6 (excluding the end bonded to N) and groups with etheric oxygen atoms or -NH- between carbon-carbon atoms. R ^44a is an alkylene group with 1 to 6 carbon atoms. group, or a group with an etheric oxygen atom or -NH- between the carbon atoms of an alkylene group with 2 to 6 carbon atoms. The two [-R ^44a -SiR _na L _3-na ] can be the same or each other. Different.

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

R ^42a is preferably a linear perfluoroalkylene group. If R ⁴² is a linear perfluoroalkylene group, the friction resistance and lubricity of the surface layer will be even better. When R ^fa is {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 }, R ^42a is typically a perfluoroalkylene group having 1 carbon atoms.

From the viewpoint of ease of preparation of compound (A12), R ^43a is preferably selected from -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ OCH ₂ CH ₂ -. and -CH ₂ NHCH ₂ CH ₂ - groups in the group (but the left side is bonded to R ^42a ). R ^43a does not have an ester bond that is highly polar and lacks chemical resistance and light resistance, so the surface layer has good initial water repellency, chemical resistance and light resistance.

From the viewpoint of ease of preparation of compound (A12), R ^44a is preferably -CH ₂ CH ₂ CH ₂ - and -CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ - (however, the right side is bonded to Si). R ^44a does not have an ester bond that is highly polar and lacks chemical resistance and light resistance, so the surface layer has good initial water repellency, chemical resistance and light resistance. From the viewpoint of excellent light resistance of the surface layer, R ^44a is particularly preferably one that does not have etheric oxygen atoms. The two R ^44a's in compound (A12) may be the same or different from each other.

Examples of the compound (A12) include compounds of the following formula. This compound is suitable from the viewpoint of being industrially easy to produce, easy to handle, and has excellent water and oil repellency, friction resistance, fingerprint stain removal ability, lubricity, chemical resistance, and light resistance.

[Chemical formula 2]

However, W in this equation is R ^f1a -OQ ^a -R ^fa -. The ideal form of W is a combination of the above ideal R ^f1a , Q ^a and R ^fa . The ideal range of R ^42a is as described above.

"Compound (A13)" Compound (A13) is represented by the following formula (A13). [R ^f1a -OQ ^a -R ^fa -R ^51a -R ^52a -O-] _ea Z ^3a [-OR ^53a -SiR ^a _na L _3-na ] _fa … (A13) Only, R ^f1a , Q ^a , R ^fa , R ^a , L ^a and na are respectively synonymous with the above, R ^51a is a perfluoroalkylene group with 1 to 6 carbon atoms, R ^52a is an alkylene group with 1 to 6 carbon atoms, and Z ^3a is (ea+fa) valence Hydrocarbon group, or a (ea+fa) valent group with more than one etheric oxygen atom and more than 2 carbon atoms between the carbon atoms of the hydrocarbon group, R ^53a is an alkylene group with 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, and ea is 2 or more, ea [R ^f1a -OQ ^a -R ^fa -R ^51a -R ^52a -O-] They 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) is a compound in which ra is ea, sa is fa, and Z ^a is -R ^51a -R ^52a -O-] _ea Z ^3a [-OR ^53a -] _fa in the above formula (A1).

ea should be an integer between 1 and 3. fa should be an integer from 1 to 10, and an integer from 2 to 5 is preferred, and an integer from 3 to 4 is particularly preferred.

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

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

R ^f1a -OQ ^a -R ^fa - from the viewpoint of the water and oil repellency of the surface layer, durability, fingerprint dirt repellency, lubricity, and superior appearance, as well as the ease of preparation of the compound (A13). R ^51a -group is preferably group (R ^f -1) and group (R ^f -2). R ^f11 O{(CF ₂ O) _m21 (CF ₂ CF ₂ O) _m22 }CF ₂ -…(R ^f -1) R ^f11 OCHFCF ₂ OCH ₂ CF ₂ O{(CF ₂ O) _m21 (CF ₂ CF ₂ O) _m22 }CF ₂ -…(R ^f -2) However, R ^f11 is a linear perfluoroalkyl group with 1 to 20 carbon atoms; m21 and m22 are integers above 1 respectively, and m21+m22 is 2 to 200 is an integer, and the bonding order of m21 CF ₂ O and m22 CF ₂ CF ₂ O is not limited.

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

[Chemical formula 3]

From the viewpoint of ease of preparation of compound (A13), R ^53a is preferably an alkylene group having 3 to 14 carbon atoms. In addition, from the viewpoint that by-products in which part or all of the allyl group (-CH ₂ CH=CH ₂ ) is isomerized into the internal olefin (-CH=CHCH ₃ ) are less likely to be produced during hydrosilylation in the production of the compound (A13) described later. In view of this, an alkylene group having 4 to 10 carbon atoms is particularly preferred.

Examples of the compound (A13) include compounds (A13-1) to (A13-6) of the following formulas. This compound is ideal from the viewpoint of being easy to manufacture and easy to handle industrially, and the surface layer has excellent water and oil repellency, friction resistance, fingerprint dirt removal ability, lubricity, and appearance.

[Chemical formula 4]

However, W in this equation is R ^f1a -OQ ^a -R ^fa -. The ideal form of W is a combination of the above ideal R ^f1a , Q ^a and R ^fa . The ideal form of R ^51a is as described above.

<Ideal form of compound (B1)> From the viewpoint of more excellent friction resistance and fingerprint stain removal properties of the surface layer, compound (B1) is preferably the following compound (B11), compound (B12) and compound (B13) .

"Compound (B11)" Compound (B11) is represented by the following formula (B11). R ^f1b -OQ ^b -R ^fb -Q ^32b -[C(O)N(R ^33b )] _pb -R ^34b -C[-R ^35b -SiR _nb L _3-nb ] ₃ …(B11) Only, R ^f1b , Q ^b , R ^fb , R ^b , L ^b and nb are synonymous with the above respectively. Q ^32b is a fluoroalkylene group with 1 to 20 carbon atoms or between the carbon-carbon atoms of a fluoroalkylene group with 2 to 20 carbon atoms. A group having an etheric oxygen atom (except when the fluoroalkylene group bonded to an etheric oxygen atom at one end and the other end bonded to R ^fb is a perfluoroalkylene group), R ^33b is a hydrogen atom or a carbon number Alkyl group of 1 to 6, pb is 0 or 1, R ^34b is a single bond, an alkylene group with 1 to 6 carbon atoms, at the end of the alkylene group (but, with C[-R ^34b -SiR _nb L _{3- nb} ] ₃ The end of the bonding side) has a group with an etheric oxygen atom, a group with an etheric oxygen atom between the carbon-carbon atoms of the alkylene group with 2 to 6 carbon atoms, or a group with an etheric oxygen atom in the alkylene group with 2 to 6 carbon atoms. The end of the alkyl group (only the end of the bonding side with C[-R ^34b -SiR _nb L _3-nb ] ₃ ) and the group with etheric oxygen atoms between carbon and carbon atoms, R ^35b is a carbon number of 1 to 6 Alkylene group, a group having an etheric oxygen atom at the end of the alkylene group (excluding the end bonded to Si), or a group having etheric properties between the carbon-carbon atoms of the alkylene group having 2 to 6 carbon atoms The three bases of oxygen atoms [-R ^34b -SiR _nb L _3-nb ] may be the same or different from each other.

Compound (B11) is a compound in the above formula (B1) in which rb is 1, sb is 3, and Z ^b is -Q ^32b -[C(O)N(R ^33b )] _pb -R ^34b -C[-R ^35b -] ₃ of compounds.

The fluoroalkylene group in Q ^32b and the group having an etheric oxygen atom between the carbon atoms of the fluoroalkylene group are respectively the same as the fluoroalkylene group and the fluoroalkylene group of Q ^32a in the aforementioned formula (A11). A carbon-carbon base with etheric oxygen atoms between carbon atoms. The number of (CF ₂ O) in Q ^32b is preferably 0 to 3. When p1 is 0 and R ^fb is (CF ₂ CF ₂ O) _m13 , Q ^32b is typically a perfluoroalkylene group with 1 carbon atoms. When p1 is 0 and R ^fb is (CF ₂ CF ₂ CF ₂ O) _m14 , Q ^32b 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 , Q ^32b is typically a linear perfluoroalkylene group with 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 the aforementioned formula (A11), and the ideal form is also the same.

"Compound (B12)" Compound (B12) is represented by the following formula (B12). R ^f1b -OQ ^b -R ^fb -R ^42b -R ^43b -N[-R ^44b -SiR _nb L _3-nb ] ₂ ...(B12) Only, R ^f1b , Q ^b , R ^fb , R ^b , L ^b and nb are synonymous with the above respectively, R ^42a is a perfluoroalkylene group with 1 to 6 carbon atoms, R ^43a is a single bond, an alkylene group with 1 to 6 carbon atoms, and is bonded to N at the end of the alkylene group (but, (Excluding the end of the side) has an etheric oxygen atom or -NH- group, has an etheric oxygen atom or -NH- group between the carbon atoms of the alkylene group with 2 to 6 carbon atoms, or has an etheric oxygen atom or -NH- group between the carbon atoms of the alkylene group with 2 carbon atoms. The alkylene group end of ~6 (excluding the end bonded to N) and the group with etheric oxygen atom or -NH- between carbon-carbon atoms, R ^44a is an alkylene group with carbon number of 1 to 6, Or there is an etheric oxygen atom or -NH- group between the carbon atoms of the alkylene group having 2 to 6 carbon atoms, and the two [-R ⁴⁴ -SiR _n L _3-n ] may be the same or different from each other.

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 the aforementioned formula (A12). However, when R ^fb is (CF ₂ CF ₂ O) _m13 , R ^42b is typically a perfluoroalkylene group having 1 carbon atoms. When R ^fb is (CF ₂ CF ₂ CF ₂ O) _m14 , R ^42b 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 , R ^42b is typically a linear perfluoroalkylene group with 3 carbon atoms.

"Compound (B13)" Compound (B13) is represented by the following formula (B13). [R ^f1b -OQ ^b -R ^fb -R ^51b -R ^52b -O-] _eb Z ^3b [-OR ^53b -SiR ^b _nb L ^b _3-nb ] _f ...(B13) Only, R ^f1b , Q ^b , R ^fb , R ^b , L ^b and nb are synonymous with the above respectively, R ^51b is a perfluoroalkylene group with 1 to 6 carbon atoms, R ^52b is an alkylene group with 1 to 6 carbon atoms, and Z ^3b is (eb+fb) A valent hydrocarbon group, or a (eb+fb) valence group with more than one etheric oxygen atom and more than 2 carbon atoms between the carbon atoms of the hydrocarbon group, R ^53b is an alkylene group with 1 to 20 carbon atoms, eb is an integer greater than 1, fb is an integer greater than 1, (eb+fb) is greater than 3, and eb is greater than 2, eb [R ^f1b -OQR ^fb -R ^51b -R ^52b -O-] may be the same or the same mutually 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) is a compound in the above formula (B1) in which rb is eb, sb is fb, and Z ^b is [-R ^51b -R ^52b -O-] _eb Z ^3b [-OR ^53b -] _fb .

R ^51b , R ^52b , Z ^3b , R ^53b , eb and fb are respectively the same as R ^51a , R ^52a , Z ^3a , R ^53a , ea and fa in the aforementioned formula (A13). R ^f1b -OQ ^b -R ^fb -R ^51b from the viewpoint of superior water and oil repellency of the surface layer, durability, fingerprint dirt removal ability, lubricity and appearance, and the ease of preparation of the compound (B13) The group -R ^52b - is preferably the group (R ^f -3). R ^f11 O(CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) _m25 CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ -…(R ^f -3) However, R ^f11 is a straight chain with 1 to 20 carbon atoms. Like perfluoroalkyl; m25 is an integer from 1 to 100.

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

Examples of compound (C) include compound (C1). A ³¹ -OQ ⁵¹ -(R ^F3 O) _m30 -[Q ⁵² -O] _p3 -A ³² …(C1) However, A ³¹ and A ³² are independently perfluoroalkyl groups with 1 to 20 carbon atoms; Q ⁵¹ It is a single bond, a fluoroalkylene group with 1 to 6 carbon atoms containing one or more hydrogen atoms and having no branched structure, and a fluoroalkylene group with 1 to 6 carbon atoms containing more than 1 hydrogen atom and having no branched structure. A group with an etheric oxygen atom at the end (excluding the end on the bonding side with A ³¹ -O), a carbon-carbon group of a fluoroalkylene group with 2 to 6 carbon atoms containing one or more hydrogen atoms and not having a branched structure. A group with etheric oxygen atoms between carbon atoms, or a fluoroalkylene group with 2 to 6 carbon atoms at the end containing one or more hydrogen atoms and not having a branched structure (excluding the end on the bonding side with A ³¹ -O ) and a group with an etheric oxygen atom between carbon-carbon atoms (but the oxygen number is less than 10); Q ⁵² is a fluoroalkyl group with 1 to 20 carbon atoms containing more than 1 hydrogen atom and without a branched structure, Or a group with an etheric oxygen atom between the carbon atoms of a fluoroalkylene group with 2 to 6 carbon atoms containing more than 1 hydrogen atom and without a branched structure (but the oxygen number is less than 10); R ^F3 is Perfluoroalkylene group with 1 to 6 carbon atoms without branched structure; m30 is an integer from 2 to 200; ( ^RF3 O) _m30 can also be composed of two or more ^RF3 O with different carbon numbers; Q ⁵¹ is a single bond When p3 is 0, p3 is 1 when Q ⁵¹ is other than a single bond.

Compound (C1) may be one produced by a known production method, or a commercially available compound may be used. For example, commercially available products of the compound (C1) in which Q ⁵¹ is a single bond and p3 is 0 include FOMBLIN (registered trademark) M, FOMBLIN (registered trademark) Y, FOMBLIN (registered trademark) Z (the above manufactured by Solvay Solexis), Krytox (registered trademark) (manufactured by DuPont), DEMNUM (registered trademark) (manufactured by Daikin Industries, Ltd.), etc.

The present composition may also 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 this composition, the content of compound (A) relative to the total amount of compound (A) and compound (B) (compound (A)/[compound (A) + compound (B)] The mass ratio) is preferably 10 to 80 mass %, and 20 to 50 mass % is particularly preferred. The higher the content of compound (A) is within the aforementioned range, the better the lubricity of the surface layer is. The lower the content of compound (A) is within the aforementioned range (that is, the higher the content of compound (B) relative to the total amount of compound (A) and compound (B)), the better the durability of the surface layer.

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

[Coating Liquid] The coating liquid of the present invention (hereinafter also referred to as the present coating liquid) contains the present composition and a liquid medium. This coating liquid only needs to be in a liquid state, and may be a solution or a dispersion liquid. The coating liquid only needs to contain the present composition, and may also contain impurities such as by-products such as Compound (A) and Compound (B) generated during the production process. The concentration of this composition in this coating liquid is preferably 0.001~50% by mass, preferably 0.05~30% by mass, more preferably 0.05~10% by mass, and especially preferably 0.1~1% by mass.

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

Examples of fluorine-based organic solvents include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols. Fluorinated alkanes are preferably compounds with 4 to 8 carbon atoms. Examples of commercially available products include C ₆ F ₁₃ H (manufactured by Asahi Glass Co., Ltd., ASAHIKLIN (registered trademark) AC-2000), 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 (manufactured by Chemours, Vertrel (registered trademark) XF), etc. Examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, bis(trifluoromethyl)benzene, and the like. The fluoroalkyl ether is preferably a compound with 4 to 12 carbon atoms. Examples of 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 Company, Novec (registered trademark) 7100), C ₄ F ₉ OC ₂ H ₅ (manufactured by 3M Company, Novec (registered trademark) 7200), C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ (manufactured by 3M Company, Novec (registered trademark) 7300), etc. Examples of the fluorinated alkylamine include perfluorotripropylamine, perfluorotributylamine, and the like. Examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol. Non-fluorine-based organic solvents are preferably compounds composed only of hydrogen atoms and carbon atoms and compounds composed only of hydrogen atoms, carbon atoms and oxygen atoms. Examples of the non-fluorine-based organic solvents include hydrocarbon-based organic solvents, alcohol-based organic solvents, ketone-based organic solvents, Ether-based organic solvents and ester-based organic solvents. The coating liquid should contain 50 to 99.999 mass% of the liquid medium, preferably 70 to 99.5 mass%, more preferably 90 to 99.5 mass%, and even more preferably 99 to 99.9 mass%.

In addition to the present composition and medium, the coating liquid may also contain other components within the scope that does not impair the effects of the present invention. Other ingredients include known additives such as acid catalysts or alkaline catalysts that can promote the hydrolysis and condensation reaction of the hydrolyzable silicon group. In this coating liquid, the content of other components is preferably 10% by mass or less, particularly preferably 1% by mass or less.

The solid content concentration of the coating liquid is preferably 0.001 to 50 mass%, preferably 0.05 to 30 mass%, more preferably 0.05 to 10 mass%, and especially 0.01 to 1 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 with a convection dryer at 120° C. for 4 hours. The concentration of this composition can be calculated from the solid content concentration and the feed amounts of this composition, solvent, etc.

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

(Surface layer) In this composition, when L in the group (I) in the compound (A) and the compound (B) is a hydrolyzable group, the group (I) undergoes a hydrolysis reaction to form a silanol group (Si- OH), and then the silanol group reacts intermolecularly to form a Si-O-Si bond, or the silanol group undergoes a dehydration condensation reaction with the hydroxyl group on the surface of the substrate (substrate-OH) to form a chemical bond (substrate-O- Si). Therefore, the surface layer contains compound (A) and compound (B) in a state in which part or all of the group (I) of compound (A) and compound (B) has undergone a hydrolysis reaction. When L in group (I) is a hydroxyl group, the above reaction proceeds without hydrolysis reaction.

The thickness of the surface layer should be 1~100nm, especially 1~50nm. As long as the thickness of the surface layer is above the lower limit of the aforementioned range, the effect of surface treatment can be easily obtained. As long as the thickness of the surface layer is below the upper limit of the aforementioned range, the utilization efficiency will be high. The thickness of the surface layer can be calculated from the vibration period of the interference pattern after obtaining an interference pattern of reflected X-rays using the X-ray reflectivity method using an X-ray diffractometer for thin film analysis (ATX-G manufactured by RIGAKU Corporation).

(Substrate) The base material of the present invention is not particularly limited as long as it is required to provide lubricity and water- and oil-repellency. Substrate materials include metal, resin, glass, sapphire, ceramics, stone and composite materials thereof. Glass can be chemically strengthened. A base film such as an SiO ₂ film may also be formed on the surface of the base material. As the base material, a touch panel base material, a display base material and an ophthalmic lens are suitable, and a touch panel base material is particularly preferred. The base material for touch panels is light-transmissive. "Light-transmitting" means that the normal incidence visible light transmittance specified in JIS R3106:1998 (ISO 9050:1990) is 25% or more. The material of the base material for the touch panel is preferably glass and transparent resin.

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

<Dry coating method> This composition can be used directly in the dry coating method. This composition is very suitable for forming a surface layer with excellent adhesion by dry coating method. Examples of the dry coating method include vacuum evaporation method, CVD method, sputtering method, and the like. From the viewpoint of suppressing the decomposition of the compound (A) and the compound (B) and the simplicity of the apparatus, the vacuum evaporation method is particularly preferred. During vacuum evaporation, a granular substance in which the present composition or the present coating liquid is impregnated into a metal porous body such as iron or steel can also be used.

The temperature during vacuum evaporation should be 20~300℃, and 30~200℃ is especially suitable. The pressure during vacuum evaporation is preferably 1×10 ^-1 Pa or less, and particularly preferably 1×10 ^-2 Pa or less.

<Wet coating method> Examples of wet coating methods include spin coating, wipe coating, spray coating, blade coating, dip coating, die coating, inkjet, flow coating, and roller coating. , casting method, Langmuir-Blodgett method and gravure coating method, etc.

<Post-treatment> In order to improve the friction resistance of the surface layer, operations to promote the reaction between compound (A) and compound (B) and the base material can be performed as needed. This operation includes heating, humidification, light irradiation, etc. For example, heating a substrate with a surface layer formed in an atmosphere containing moisture can promote the hydrolysis reaction of hydrolyzable silicon groups into silanol groups, and the reaction of hydroxyl groups on the surface of the substrate with silanol groups. The condensation reaction of radicals produces siloxane bonds and other reactions. After surface treatment, compounds that are compounds in the surface layer and are not chemically bonded with other compounds or the substrate can be removed if necessary. Specific methods include rinsing the surface layer with solvent, wiping with a cloth soaked in solvent, etc.

[Function and effect] This composition and this coating liquid contain compound (A) and compound (B), and therefore can form a surface layer excellent in lubricity and durability. That is, by using the present composition or the present coating liquid to form a surface layer on the surface of a substrate, it is possible to impart excellent initial lubricity, water and oil repellency and other properties, and at the same time, it is possible to obtain such properties that are not easy to maintain even if the surface is repeatedly rubbed. Reduced excellent durability. In addition, even if the surface is repeatedly rubbed, the water- and oil-repellent properties are not easily reduced, so the performance of easily removing fingerprint stains on the surface of the base material (fingerprint stain removal performance) can be obtained. Compound (A) contains a (CF ₂ O) unit in the A chain, so it has good lubricity. On the other hand, the durability is worse than the case without (CF ₂ O) unit. Compound (B) does not contain (CF ₂ O) units in the B chain, so it has good durability. On the other hand, compared with the case containing (CF ₂ O) unit, the lubricity is poorer. Therefore, when these are combined, the excellent characteristics of each can be fully maintained, and both good lubricity and durability can be achieved. The reason for this is believed to be that the component with high lubricity (compound (A)) disperses the force of wear, thereby improving the durability of the component with high durability (compound (B)).

[Application] Therefore, the base material having a surface layer prepared as described above is suitable as a member constituting a touch panel. However, the uses of this composition, this coating liquid and articles are not limited to touch panels. For example, it can be used for display input devices other than touch panels; surface protective coatings for transparent glass or transparent plastic (acrylic, polycarbonate, etc.) components, kitchen antifouling coatings; electronic equipment, heat exchangers, batteries, etc. Water-repellent and moisture-repellent coatings or anti-fouling coatings, anti-fouling coatings for bathrooms and toilets; coatings used on components that need to be conductive and liquid-repellent at the same time; water-repellent, waterproof, and hydrophobic coatings for heat exchangers; surfaces of vibrating screens or inside cylinders, etc. Low friction coatings, etc. More specific examples of use include display front protection panels, anti-reflective panels, polarizing panels, anti-glare panels, or items with anti-reflective coatings on these surfaces, as well as touch controls on mobile phones, portable information terminals, etc. Waterproof coating thermal insulation for various machines such as panel panels or touch panel monitors that have display input devices that can be operated on the screen with human fingers or palms, decorative building materials for toilets, bathrooms, sinks, kitchens and other sinks, and wiring boards Water-repellent and waterproof coatings for switches, water-repellent coatings for solar cells, waterproof and water-repellent coatings for printed wiring boards, waterproof and water-repellent coatings for electronic machine casings or electronic parts, insulation-improving coatings for transmission lines, waterproof and water-repellent coatings for various filters Water coatings, waterproof coatings for radio wave absorbing materials or sound-absorbing materials, antifouling coatings for bathrooms, kitchen machines, bathrooms and toilets, water-repellent, waterproof, hydrophobic coatings for heat exchangers, low-friction coatings for surfaces such as vibrating screens or cylinder interiors, Surface protective coatings for mechanical parts, vacuum machine parts, bearing parts, automobile parts, tools, etc. Example

Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited thereto. Hereinafter, the symbol "%" means "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 is calculated by using ¹ H-NMR and ¹⁹ F-NMR to determine the number (average) of oxygen perfluoroalkyl groups based on the terminal group. . Terminal groups are, for example, radical (I) or radical (II).

(Water Contact Angle) The contact angle (water contact angle) of approximately 2 μL of distilled water remaining on the surface of the surface layer was measured at 20° C. using a contact angle measuring device (DM-701 manufactured by Kyowa Interface Science Co., Ltd.). Measurements were made at 5 different locations on the surface of the surface layer and the average value was calculated. The contact angle is calculated using the 2θ method. The larger the water contact angle, the better the water repellency.

(Lubricity) Using a load-fluctuating friction and wear test system (HHS2000 manufactured by Shinto Scientific Co., Ltd.), the surface layer's resistance to artificial skin (manufactured by Idemitsu Precision Technology Co., Ltd.) was measured under the conditions of contact area: 3cm×3cm and load: 0.98N. PBZ13001) dynamic friction coefficient. The smaller the dynamic friction coefficient, the better the lubricity.

(Durability 1 (number of times the contact angle is maintained at 100° or more)) For the surface layer, a reciprocating friction testing machine (manufactured by KNT Corporation) was used in accordance with JIS L0849:2013 (ISO 105-X12:2001) at a pressure of 98.07kPa and a speed of Reciprocate Bonstar steel wool (#0000) at 320cm/min. The water contact angle is measured every thousand times of reciprocation, and the upper limit of the number of times the water contact angle can be maintained at 100° or above is determined (the number of times the contact angle is maintained at 100° or above). The greater the number of times, the less likely the surface layer is to be damaged by friction and the better the durability.

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

[Raw materials] (A-1): Composition (A-1) obtained in Production Example A-1 described below. (A-2): Composition (A-2) obtained in Production Example A-2 described below. (A-3): Compound (A-3) obtained in Production Example A-3 described below. (A-4): Compound (A-4) obtained in Production Example A-4 described below. (A-5): Compound (A-5) obtained in Production Example A-5 described below.

(B-1): Compound (B-1) obtained in Production Example B-1 described below. (B-2): Composition (B-2) obtained in Production Example B-2 described below. (B-3): Compound (B-3) obtained in Production Example B-3 described below. (B-4): Compound (B-4) obtained in Production Example B-4 described below. (B-5): Compound (B-5) obtained in Production Example B-5 described below. (B-6): Distill off the solvent of "2634 Coating" manufactured by Dow Corning Toray Co. Ltd. before use. CF ₃ CF ₂ CF ₂ O(CF ₂ CF ₂ CF ₂ O) ₂₁ CF ₂ CF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ .

(C-1): Fluorine-containing ether compound 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 Co., Ltd. "FOMBLIN M03 ”).

The aforementioned (A-1)~(A-5), (B-1)~(B-5), and (C-1) have a repeating unit of a poly(oxyperfluoroalkylene) chain, a poly(oxyperfluoroalkylene) chain, The number of fluoroalkylene) chains (hereinafter also expressed as the number of PEPE), the number of groups (I) and the number average molecular weight (Mn) are listed in Table 1. In addition, the repeating unit "(CF ₂ O)(CF ₂ CF ₂ O)" in (A-1) ~ (A-5) and (C-1) means the (CF ₂ O) unit and (CF ₂ CF ₂ A poly(oxyperfluoroalkylene) chain composed of randomly arranged O) units.

[Table 1]

[Production Example A-1] In a 300 mL 3-neck flask, 24.4 g of 24% KOH aqueous solution, 33 g of tertiary butanol, and 220 g of compound (1) (FLUOROLINK (registered trademark) D4000, manufactured by Solvay Solexis) were placed, and CF was added ₃ CF ₂ CF ₂ -O-CF=CF ₂ (manufactured by Tokyo Chemical Industry Co., Ltd.) 19.4 g. Stir at 60°C for 8 hours under nitrogen atmosphere. After washing once with dilute hydrochloric acid aqueous solution, the organic phase was recovered, and then concentrated with an evaporator to obtain 233 g of crude product. The crude product was developed on a silica column chromatograph and fractionated. The developing solvent system used C ₆ F ₁₃ CH ₂ CH ₃ (AC-6000, manufactured by Asahi Glass Co., Ltd.), AC-6000/CF ₃ CH ₂ OCF ₂ CF ₂ H (AE-3000, manufactured by Asahi Glass Co., Ltd.) = 1/ 2 (mass ratio), AE-3000/ethyl acetate = 9/1 (mass ratio). For each liquid separation, the average value of the structure of the terminal group and the number of units (x1, x2) of the structural units was determined from the integrated values of ¹ H-NMR and ¹⁹ F-NMR. It can be seen that the crude product contains 42 mol% of compound (2), 49 mol% of compound (3) and 9 mol% of compound (1) respectively. And 98.6 g of compound (2) (yield: 44.8%) and 51.9 g of compound (3) (yield: 23.6%) were obtained. HO-CH ₂ -(CF ₂ O){(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 }-CF ₂ -CH ₂ -OH…(1) CF ₃ CF ₂ CF ₂ -O-CHFCF ₂ OCH ₂ -(CF ₂ O){(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 }-CF ₂ -CH ₂ -OH…(2) CF ₃ CF ₂ CF ₂ -O-CHFCF ₂ OCH ₂ -( CF ₂ O){(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 }-CF ₂ -CH ₂ OCF ₂ CHF-O-CF ₂ CF ₂ CF ₃ …(3) Compound (2): Number of units x1 The average value is 21, the average number of units x2 is 20, and the number average molecular weight is 4,150. Compound (3): The average number of units x1 is 21, the average number of units x2 is 20, and the number average molecular weight is 4,420.

In a 100 mL eggplant-shaped flask, 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, and CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) was added. COF 3.5g. Stir at 50°C for 24 hours under nitrogen atmosphere. After removing the sodium fluoride powder with a pressure filter, the excess CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COF and AK-225 were distilled off under reduced pressure. The obtained crude product was diluted with C ₆ F ₁₃ H (AC-2000 manufactured by Asahi Glass Co., Ltd.) and passed through a silica column. The recovered solution was concentrated with a distiller to obtain 31.8 g of compound (4) (yield 98.8%). CF ₃ CF ₂ CF ₂ -O-CHFCF ₂ OCH ₂ -(CF ₂ O){(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 }-CF ₂ -CH ₂ -OCOCF(CF ₃ )OCF ₂ CF ₂ CF ₃ ...(4) Compound (4): The average number of units x1 is 21, the average number of units x2 is 20, and the number average molecular weight is 4,460.

A cooler maintained at 20°C, a NaF particle filling layer, and a cooler maintained at 0°C were installed inline at the gas outlet of the 1L nickel autoclave. And a liquid return pipeline is provided, which can return the condensed liquid from the cooler maintained at 0°C to the autoclave. 750 g of ClCF ₂ CFClCF ₂ OCF ₂ CF ₂ Cl (hereinafter also referred to as CFE-419) was put into the autoclave and stirred while maintaining the temperature at 25°C. After nitrogen gas was sprayed into the autoclave at 25°C for 1 hour, 20% fluorine gas was sprayed into the autoclave at 25°C and a flow rate of 2.0 L/hour for 1 hour. 20% fluorine gas was sprayed at the same flow rate, and a solution containing 31.0 g of compound (4) dissolved in 124 g of CFE-419 was injected into the autoclave over 4.3 hours. Inject 20% fluorine gas at the same flow rate, and at the same time pressurize the internal pressure of the autoclave to 0.15MPa (gauge pressure). While heating from 25°C to 40°C in the autoclave, 4 mL of a benzene solution containing 0.05g/mL benzene in CFE-419 was injected, and then the benzene solution injection port of the autoclave was closed. After stirring for 15 minutes, another 4 mL of benzene solution was injected while maintaining 40°C, and then the injection port was closed. The same operation is further repeated 3 times. The total amount of benzene injected was 0.17g. Spray 20% fluorine gas at the same flow rate and continue stirring for 1 hour. The pressure in the autoclave was brought to atmospheric pressure, and nitrogen was blown for 1 hour. The contents of the autoclave were concentrated using a distiller to obtain 31.1 g of compound (5) (yield 98.5%). CF ₃ CF ₂ CF ₂ -O-(CF ₂ CF ₂ O)(CF ₂ CF ₂ O){(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 }(CF ₂ CF ₂ O)-COCF(CF ₃ )OCF ₂ CF ₂ CF ₃ …(5) Compound (5): The average value of the number of units x1 is 21, the average value of the number of units x2 is 20, and the number average molecular weight is 4,550.

30.0 g of compound (5) and 60 g of AK-225 were placed in a round-bottomed flask made of tetrafluoroethylene-perfluoro(alkoxyvinyl ether) copolymer (hereinafter also referred to as PFA). Cool in an ice bath while stirring, and slowly drop 2.0 g of methanol from a dropping funnel under a nitrogen atmosphere. The mixture was stirred for 12 hours while bubbling with nitrogen. The reaction mixture was concentrated with an evaporator to obtain 27.6 g 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) Compounds (6): The average number of units x1 is 21, the average number of units x2 is 20, and the number average molecular weight is 4,230.

In a 100 mL 3-neck eggplant-shaped 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 a solution of 0.75 g of sodium borohydride dissolved in 22.5 g of ethanol was slowly dropped while cooling in an ice bath. Remove the ice bath and slowly bring the temperature to room temperature while continuing to stir. After stirring at room temperature for 12 hours, the hydrochloric acid aqueous solution was dropped 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 recovered organic phase was concentrated with a distiller 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): The average number of units x1 is 21, the average number of units x2 is 20, and the number average molecular weight is 4,200.

Add 20.0 g of compound (7), 0.21 g of tetrabutylammonium hydrogen sulfate, 1.76 g of BrCH ₂ CH=CH ₂ and 2.6 g of 30% sodium hydroxide aqueous solution into a 100 mL 2-neck eggplant-shaped flask, and stir at 60°C for 8 hours. After the reaction, 20 g of AC-2000 was added, washed once with dilute hydrochloric acid aqueous solution, and then the organic phase was recovered. The recovered organic phase was passed through a silica gel column and the recovered solution was concentrated with a distiller to obtain 19.8 g of compound (8) (yield 98.2%). CF ₃ CF ₂ CF ₂ -O-(CF ₂ CF ₂ O)(CF ₂ CF ₂ O){(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 }-CF ₂ -CH ₂ OCH ₂ CH=CH ₂ ...(8) Compound (8): The average number of units x1 is 21, the average number of units x2 is 20, and the number average molecular weight is 4,250.

In a 100 mL eggplant-shaped flask made of PFA, 5.0 g of compound (8) and a xylene solution of platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex ( Platinum content: 2%) 0.005g, HSi(OCH ₃ ) ₃ 0.25g, dimethyl sulfoxide 0.005g and 1,3-bis(trifluoromethyl)benzene (Tokyo Chemical Industry Co., Ltd.) 0.20g, at 40°C Stir for 4 hours. After 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 to obtain 4.9 g of composition (A-1) (yield 95%). This composition (A-1) is composed of compound (8) It consists of compound (9) in which one allyl group is hydrosilylated, and a by-product of compound (8) in which one allyl group is isomerized into an internal olefin (-CH=CHCH ₃ ). The conversion rate of hydrosilation is 100%, and no compound (8) remains. The selectivity of hydrogenation is 95%. CF ₃ CF ₂ CF ₂ -O-(CF ₂ CF ₂ O)(CF ₂ CF ₂ O){(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 }-CF ₂ -CH ₂ OCH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ …(9)

NMR spectrum of compound (9); ¹ H-NMR (300.4MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.7 (6H), 1.7 (6H), 3.6 (11H), 3.8 (2H). ¹⁹ F-NMR (282.7MHz, solvent: CDCl ₃ , standard: C ₆ F ₆ ) δ (ppm): -52.4~-55.8(42F), -78.2(1F), -80.2(1F), -82.2(3F ), -89.4~-91.1(90F), -130.5(2F). The average value of the number of units x1: 21, the average value of the number of units x2: 20, and the number average molecular weight of compound (9): 4,370.

[Production Example A-2] In a 100 mL 2-neck eggplant-shaped flask, 20.0 g of the compound (7) obtained in Production Example A-1 and 1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed 20.0g, 1.01g of CF ₃ SO ₂ Cl (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.00g of triethylamine were stirred at room temperature under a nitrogen atmosphere for 4 hours. After the reaction, 15 g of AK-225 was added, and the mixture was washed once with water and saturated brine, and then the organic phase was recovered. The recovered organic phase was concentrated using a distiller to obtain 20.3 g of compound (10) (yield 99%). CF ₃ CF ₂ CF ₂ -O-(CF ₂ CF ₂ O)(CF ₂ CF ₂ O){(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 }-CF ₂ -CH ₂ OSO ₂ CF ₃ … (10) Compound (10): The average number of units x1 is 21, the average number of units x2 is 20, and the number average molecular weight is 4,340.

15.0 g of compound (10), 15.0 g of 1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Chemical Industry Co., Ltd.), and HN (CH ₂ CH=CH ₂ ) ₂ (Tokyo Chemical Industry Co., Ltd.) were placed in a 50 mL eggplant-shaped flask. Industrial Co., Ltd.) 2.27g and triethylamine 0.68g, stirred at 90°C for 24 hours in a nitrogen atmosphere. After the reaction, add 15g of AK-225, wash once with water and saturated brine once and recover the organic phase, mix with 1.5g of silica gel, filter with a filter and recover the organic phase. The recovered organic phase was concentrated using a distiller to obtain 14.4 g of compound (11) (yield 98%). CF ₃ CF ₂ CF ₂ -O-(CF ₂ CF ₂ O)(CF ₂ CF ₂ O){(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 }-CF ₂ -CH ₂ -N(CH ₂ CH=CH ₂ ) ₂ ...(11) Compound (11): The average number of units x1 is 21, the average number of units x2 is 20, and the number average molecular weight is 4,280.

In a 100 mL eggplant-shaped flask made of PFA, 12.0 g of compound (11) and a xylene solution of platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex ( Platinum content: 2%) 0.03g, HSi(OCH ₃ ) ₃ 1.3g, dimethyl sulfoxide 0.01g and 1,3-bis(trifluoromethyl)benzene (Tokyo Chemical Industry Co., Ltd.) 0.5g, at 40°C Stir for 10 hours. After 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 to obtain 11.9 g of composition (A-2) (yield 92%). This composition (A-2) is composed of compound (11) It consists of compound (12) in which two allyl groups are hydrosilylated, and a by-product produced by intramolecular cyclization of two allyl groups in compound (11). The conversion rate of hydrosilation is 100%, and no compound (11) remains. The selectivity of hydrosilation is 81%. CF ₃ CF ₂ CF ₂ -O-(CF ₂ CF ₂ O)(CF ₂ CF ₂ O){(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 }-CF ₂ -CH ₂ -N［CH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ ] ₂ …(12)

NMR spectrum of compound (12); ¹ H-NMR (300.4MHz, 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 (282.7MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -52.4~-55.7(42F), -74.4(1F), -76.6(1F), -82.2(3F), -89.4~-91.1(90F), -130.5(2F). The average value of the number of units x1: 21, the average value of the number of units x2: 20, and the 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-shaped flask and stirred for 12 hours. It was confirmed from NMR that all of compound (6) was converted into compound (13). Furthermore, methanol is produced as a by-product. The resulting solution was diluted with 9.0 g of AE-3000 and purified with a silica gel column chromatograph (developing solvent: AE-3000) to obtain 4.4 g of compound (13) (yield 85%). CF ₃ CF ₂ CF ₂ -O-(CF ₂ CF ₂ O)(CF ₂ CF ₂ O){(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 }-CF ₂ -C(O)NH-CH ₂ -C(CH ₂ CH=CH ₂ ) ₃ ...(13) Compound (13): The average value of the number of units x1 is 21, the average value of the number of units x2 is 20, and the number average molecular weight is 4,360.

Put 4 g of compound (13) and a xylene solution of platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum) into a 10 mL PFA sample tube. Content: 2%) 0.4 mg, HSi(OCH ₃ ) ₃ 0.33 g, dimethyl sulfoxide 0.01 g, 1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.2 g and at 40°C Stir for 10 hours. After the reaction, the solvent and the like were distilled off under reduced pressure and filtered through a membrane filter with a pore size of 1.0 μm to obtain 4.3 g of compound (A-3) (yield 100%). CF ₃ CF ₂ CF ₂ -O-(CF ₂ CF ₂ O)(CF ₂ CF ₂ O){(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 }-CF ₂ -C(O)NH-CH ₂ -C[CH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ ] ₃ …(A-3)

NMR spectrum of compound (A-3): ¹ H-NMR (300.4MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.75 (6H), 1.3~1.6 (12H), 3.4 (2H), 3.7 (27H). ¹⁹ F-NMR (282.7MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -52.4~-55.8(42F), -82.2(3F), -89.4~-91.1(92F), -130.8( 2F). The average value of the number of units x1: 21, the average value of the number of units x2: 20, and the number average molecular weight of the compound (A-3): 4,720.

[Production Example A-4] In a 300 mL 3-necked flask, 15.0 g of dipenterythritol (manufactured by ACROS), 29.5 g of a 48% NaOH aqueous solution, and 150 g of dimethylsulfoxide were placed. It was heated to 40°C, and 39.5 g of 5-bromo-1-pentene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, followed by stirring for 4 hours. After washing once with dilute hydrochloric acid aqueous solution, 200 g of cyclopentyl methyl ether was added, and the organic phase was recovered. The recovered solution was concentrated with a distiller to obtain 29.4 g of crude product. The crude product was developed on a silica column chromatograph, and 5.3 g of compound (14) and 6.0 g of compound (15) were fractionated.

[Chemical formula 5]

Put 1.0g of compound (14), 0.4g of 2,6-lutidine, and 5g of AE-3000 into a 50 mL 2-neck eggplant-shaped flask. Cool in an ice bath while stirring, and slowly drop 0.5 g of trifluoromethanesulfonic anhydride in a nitrogen atmosphere. After further stirring for 1 hour, the mixture was washed once with a dilute hydrochloric acid aqueous solution, and the organic phase was recovered. The recovered solution was concentrated using a distiller to obtain a crude product. The crude product was developed in a silica column chromatograph, and 1.2 g of compound (16) in which HO- of compound (14) was converted into CF ₃ SO ₃ - was fractionated.

In a 50 mL eggplant-shaped flask, 1.0 g of compound (16), 6.6 g of compound (17) obtained by the method described in Production Example 6 of International Publication No. 2015/087902, 2.7 g of cesium carbonate, and 1,3-bis( Trifluoromethyl)benzene 6.6g, and stirred under reflux conditions at 80°C for 4 hours. After adding 10g of AE-3000, wash once with dilute hydrochloric acid aqueous solution and recover the organic phase. The recovered solution was concentrated using a distiller to obtain a crude product. The crude product was developed in a silica column chromatograph, and CF ₃ SO ₃ of compound (16) was fractionated and converted into CF ₃ CF ₂ CF ₂ O{(CF ₂ O) _m21 (CF ₂ CF ₂ O) _m22 }CF 6.6 g of compound (18) of ₂ -CH ₂ -O-. CF ₃ CF ₂ CF ₂ O{(CF ₂ O) _m21 (CF ₂ CF ₂ O) _m22 }CF ₂ -CH ₂ -OH…(17)

In a 100 mL eggplant-shaped flask made of PFA, 6.0 g of compound (18) and a xylene solution of platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex ( Platinum content: 2%) 0.03g, trimethoxysilane (made by Tokyo Chemical Industry Co., Ltd.) 1.2g, dimethylsulfoxide 0.01g and 1,3-bis(trifluoromethyl)benzene 0.9g, stir at 40°C for 4 hours. The solvent and the like were evaporated under reduced pressure, and then 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 conversion rate of hydrosilation is 100%, and no compound (18) remains. The selectivity of hydrogenation is 100%. Here, compound (A-4) is a compound in which WR ^51a - of the aforementioned compound (A13-3) is a group represented by formula (R ^f -1).

[Production Example A-5] Compound (15) was obtained in the same manner as in Production Example A-4, except that the compound (15) obtained in Production Example A-4 was used instead of the compound (14). _{3SO 3} - compound (19). Next, except that compound (19) is used instead of compound (16), two CF ₃ SO ₃ of compound (19) are obtained in the same manner as in Production Example A-4 (3) - all of which are converted into CF ₃ CF ₂ CF ₂ O Compound (20) of {(CF ₂ O) _m21 (CF ₂ CF ₂ O) _m22 }CF ₂ -CH ₂ -O-. Next, except that compound (20) was used instead of compound (18), 6.4 g of compound (A-5) in which four allyl groups of compound (20) were hydrosilylated was obtained in the same manner as in Production Example A-4. Here, compound (A-5) is a compound in which WR ^51a - of the aforementioned 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 International Publication No. 2013/121984. CF ₃ -O-(CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _x3 (CF ₂ CF ₂ O)-CF ₂ CF ₂ CF ₂ -CONHCH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ ...(B-1) Compound (B-1): The average number of units x3 is 13, and the number average molecular weight is 4,870.

[Production Example B-2] Compound (21) was obtained according to the method described in Example 7 of International Publication No. 2013/121984. CF ₃ -O-(CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _x3 (CF ₂ CF ₂ O)-CF ₂ CF ₂ CF ₂ -CH ₂ OH…(21) Compound (21): The average number of units x3 is 13, and the number average molecular weight is 4,700.

Except that compound (7) was changed to compound (21), the amount of CF ₃ SO ₂ Cl (manufactured by Wako Pure Chemical Industries, Ltd.) was changed to 0.86 g, and the amount of triethylamine was changed to 1.02 g, it was the same as in Production Example A. -2 Obtained 30.6 g of compound (22) in the same manner (yield 99%). CF ₃ -O-(CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _x3 (CF ₂ CF ₂ O)-CF ₂ CF ₂ CF ₂ -CH ₂ OSO ₂ CF ₃ …(22) Compound ( 22): The average number of units x3 is 13, and the number average molecular weight is 4,830.

It is the same as Production Example A-2 except that compound (10) is changed to compound (22), the amount of HN(CH ₂ CH=CH ₂ ) ₂ is changed to 2.08 g, and the amount of triethylamine is changed to 0.63 g. 14.6 g of compound (23) was obtained in this way (yield 98%). CF ₃ -O-(CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _x3 (CF ₂ CF ₂ O)-CF ₂ CF ₂ CF ₂ -CH ₂ -N(CH ₂ CH=CH ₂ ) ₂ ...(23) Compound (23): The average number of units x3 is 13, and the number average molecular weight is 4,780.

It was obtained in the same manner as in Production Example A-2 except that compound (11) was changed to compound (23), the amount of platinum complex solution was changed to 0.029g, and the amount of HSi(OCH ₃ ) ₃ was changed to 1.2g. 11.8 g of composition (B-2) (yield 94%), which is composed of compound (24) in which two allyl groups of compound (23) are hydrosilylated, and compound (23) It consists of by-products generated by the intramolecular cyclization of two allyl groups. The conversion rate of hydrosilylation was 100%, and no compound (23) remained. The selectivity of hydrogenation is 80%. CF ₃ -O-(CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _x3 (CF ₂ CF ₂ O)-CF ₂ CF ₂ CF ₂ -CH ₂ -N[CH ₂ CH ₂ CH ₂ - Si(OCH ₃ ) ₃ ] ₂ …(24)

NMR spectrum of compound (24); ¹ H-NMR (300.4MHz, 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 (282.7MHz, 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). The average number of units x3: 13, the 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 International Publication No. 2013/121984. CF ₃ -O-(CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _x3 (CF ₂ CF ₂ O)-CF ₂ CF ₂ CF ₂ -C(O)OCH ₃ …(25) Compound ( 25): The average number of units x3 is 13, and the number average molecular weight is 4,700.

The same procedure as in Production Example A-3 was performed except that the compound (6) was replaced by 9.0 g of the compound (25) and the amount of H ₂ N-CH ₂ -C (CH ₂ CH=CH ₂ ) ₃ was changed to 0.45 g. 7.6 g of compound (26) was obtained (yield 84%). CF ₃ -O-(CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _x3 (CF ₂ CF ₂ O)-CF ₂ CF ₂ CF ₂ -C(O)NH-CH ₂ -C(CH ₂ CH=CH ₂ ) ₃ ...(25) Compound (26): The average number of units x3 is 13, and the number average molecular weight is 4,800.

Change compound (13) to 6.0g of compound (26), change the amount of platinum complex solution to 0.07g, change the amount of HSi(OCH ₃ ) ₃ to 0.78g, change the amount of dimethyl sulfoxide to 0.02g, Except that the amount of 1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was changed to 0.49 g, 6.7 g of compound (B-3) was obtained in the same manner as in Production Example A-3 (yield 100%). CF ₃ -O-(CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _x3 (CF ₂ CF ₂ O)-CF ₂ CF ₂ CF ₂ -C(O)NH-CH ₂ -C[CH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ ] ₃ …(B-3)

NMR spectrum of compound (B-3): ¹ H-NMR (300.4MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.75 (6H), 1.3~1.6 (12H), 3.4 (2H), 3.7 (27H). ¹⁹ F-NMR (282.7MHz, 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). The average number of units x3: 13, the number average molecular weight of compound (B-3): 5,400.

[Production Example B-4] Instead of compound (17), compound (27) (average value of m25: 13, number average molecular weight: 4,700) prepared by the method described in Example 7 of International Publication No. 2013/121984 was used. Except for this, the CF ₃ SO ₃ of compound (16) was obtained in the same manner as in Production Example A-4 - 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 _{2CF 2} -CH ₂ -O- compound (28). Next, except that compound (28) was used instead of compound (18), 6.3 g of compound (B-4) in which five allyl groups of compound (28) were hydrosilylated was obtained in the same manner as in Production Example A-4. 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, compound (B-4) is the aforementioned compound WR ^51a - of (A13-3) is a compound having a group represented by formula (R ^f -3).

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

[Example 1] 50 parts by mass (A-1) and 50 parts by mass (B-1) were mixed to prepare a composition. Using this composition, the substrate surface was treated by the following dry coating method to prepare the article of Example 1. The base material is chemically strengthened glass. The obtained article was evaluated for durability 1 (the number of times the contact angle is maintained at 100° or more), lubricity, and durability 2 (difficulty in reducing the dynamic friction coefficient). The results are listed in Tables 3~5.

(Dry coating method) Dry coating is performed using a vacuum evaporation device (SGC-22WA manufactured by Showa Vacuum Co., Ltd.) (vacuum evaporation method). After filling 35 mg of the composition into a molybdenum boat in a vacuum evaporation device, the vacuum evaporation device was exhausted to 5×10 ^-3 Pa or less. The boat disposed with the composition is heated to deposit the composition on the surface of the substrate, thereby forming an evaporated film on the surface of the substrate. The substrate on which the evaporated film is formed is placed overnight under the conditions of temperature: 25°C and humidity: 40% to prepare an article with a surface layer on the surface of the substrate.

[Examples 2 to 40] In the same manner as in Example 1, except that the types and combinations of the compounds used were changed to those shown in Table 2, a composition was prepared, a surface layer was formed, and an article was produced, and the obtained article was evaluated. In the example of combining two compounds, the mass ratio of each compound is 50:50. The results are listed in Tables 3~5.

[Table 2]

Durability 1 (number of times the contact angle is maintained above 100°) [Table 3]

Lubricity (dynamic friction coefficient) [Table 4]

Durability 2 (Difficulty in reducing dynamic friction coefficient) [Table 5]

Compared with the compositions of Examples 36 to 40 in which compound (B) is combined with compound (C-1) without group (I), Examples 1 to 5, 7 to 11, and 13 in which compound (A) is combined with compound (B) The compositions of ~17, 19~23, and 25~29 have better durability and lubricity. In addition, compared with Examples 31 to 35 in which compound (B) was used alone, the lubricity was better. In addition, as the number of groups (I) each of compound (A) and compound (B) has increases, the durability tends to improve.

(Examples 41 to 50) Except that the mixing ratio (mass ratio) of (A-3) and (B-3) was changed to that shown in Table 6, the composition was prepared in the same manner as in Example 15 and used the aforementioned dry coating. An article is produced by forming a surface layer on a substrate, and the obtained article is evaluated. The results are listed in Table 6. Furthermore, using each composition, the surface of the base material was treated by the following wet coating method to prepare an article. The base material uses chemically strengthened glass. The resulting articles were evaluated for durability1 and lubricity. The results are listed in Table 7.

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

[Table 6]

[Table 7]

(Examples 51 to 60) Except that the mixing ratio (mass ratio) of (A-4) and (B-4) was changed to that shown in Table 8, the composition was prepared in the same manner as in Example 22 and the aforementioned dry coating method was used. An article was produced by forming a surface layer on the substrate, and the obtained article was evaluated. The results are listed in Table 8.

[Table 8]

By using compound (A) and compound (B) in combination, it is possible to achieve both lubricity and durability at a higher level than when each compound is used alone. When the mass ratio of compound (A)/compound (B) is in the range of 20/80~50/50, the durability and lubricity are particularly good. industrial availability

This composition and this coating liquid can be used in various applications requiring lubricity and water- and oil-repellency. For example, it can be used for display input devices such as touch panels; surface protective coatings for transparent glass or transparent plastic components, and antifouling coatings for kitchens; water-repellent and moisture-proof coatings or antifouling coatings for electronic equipment, heat exchangers, batteries, etc. Antifouling coatings for bathrooms and toilets; coatings for components that need to be conductive and liquid-repellent at the same time; water-repellent, waterproof, and hydrophobic coatings for heat exchangers; surface low-friction coatings for vibrating screens or inside cylinders, etc. In addition, the entire contents of the specification, patent scope and abstract of Japanese Patent Application No. 2017-050558 filed on March 15, 2017 are quoted and incorporated into the disclosure of the specification of the present invention.

Claims (12)

A fluorine-containing ether composition, characterized in that it contains a fluorine-containing ether compound (A) and a fluorine-containing ether compound (B); the aforementioned fluorine-containing ether compound (A) is a poly(oxyperfluorofluoroethylene) containing (CF ₂ O) unit Alkylene) chain and three or more groups represented by the following formula (I); the aforementioned fluorine-containing ether compound (B) is a poly(oxyperfluoroalkylene) containing no (CF ₂ O) unit A compound with a chain and more than 3 groups represented by the aforementioned formula (I); -SiR _n L _3-n ... (I) However, L is a hydroxyl group or a hydrolyzable group; R is a hydrogen atom or a monovalent hydrocarbon group; n is an integer from 0 to 2; when n is 0 or 1, the (3-n) L's can be the same or different; when n is 2, the n R's can be the same or different; among them, the aforementioned fluorine-containing ether The groups represented by the aforementioned formula (I) that the compound (A) and the aforementioned fluorine-containing ether compound (B) each have may be the same or different from each other. The fluorine-containing ether composition of claim 1, wherein the aforementioned fluorine-containing ether compound (A) and the aforementioned fluorine-containing ether compound (B) are both fluorine-containing ether compounds represented by the following formula (A/B); the aforementioned fluorine-containing ether compound R ^f in (A) is a poly(oxyperfluoroalkylene) chain containing (CF ₂ O) units, and R ^f in the aforementioned fluoroether compound (B) is a poly(oxyperfluoroalkylene) chain containing no (CF ₂ O) units. (oxyperfluoroalkyl) chain; [R ^f1 -OQR ^f -] _r Z[-SiR _n L _3-n ] _s ...(A/B) However, R ^f1 is perfluoroalkyl; Q is A single bond, an oxyfluoroalkylene group containing more than 1 hydrogen atom, or a polyoxyfluoroalkylene group composed of 2 to 5 oxyfluoroalkylene groups, and the oxygen constituting the polyoxyfluoroalkylene group The fluoroalkylene groups can 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 the aforementioned formula (I) The groups shown; when r is 2 or more, r [R ^f1 -OQR ^f -] are the same group; s groups shown in formula (I) are the same group; r is an integer more than 1, s is An integer above 3, and r+s is 4~8. The fluorine-containing ether composition of claim 1 or 2, wherein the poly(oxyperfluoroalkylene) chain system containing (CF ₂ O) units contains (CF ₂ O) units and (CF ₂ CF ₂ O) units. of poly(oxyperfluoroalkylene) chains. The fluorine-containing ether composition of claim 1 or 2, wherein the poly(oxyperfluoroalkylene) chain system without (CF ₂ O) units contains units selected from (CF ₂ CF ₂ O), (CF ₂ A poly(oxyperfluoroalkylene) chain of at least one unit among a CF ₂ CF ₂ O) unit and a (CF ₂ CF ₂ CF ₂ CF ₂ O) unit. The fluorine-containing ether composition of claim 1 or 2, wherein the poly(oxyperfluoroalkylene) chain system without (CF ₂ O) units contains (CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O ) unit of the poly(oxyperfluoroalkylene) chain. The fluorine-containing ether composition of claim 1 or 2, wherein the number average molecular weight of the aforementioned fluorine-containing ether compound (A) is 2,000~20,000. For example, the fluorine-containing ether composition of claim 1 or 2, wherein the number average molecular weight of the aforementioned fluorine-containing ether compound (B) is 2,000~20,000. The fluorine-containing ether composition of claim 1 or 2, which contains the aforementioned fluorine-containing ether compound (B) in an amount of 10 to 80% by mass relative to the total amount of the aforementioned fluorine-containing ether compound (A) and the aforementioned fluorine-containing ether compound (B). A). A fluorine-containing ether composition, characterized by containing 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) However, R ^f1a and R ^f1b are perfluoroalkyl groups; Q ^a and Q ^b are single bond oxyfluoroalkyl groups containing more than 1 hydrogen atom or composed of 2 to 5 oxyfluoroalkyl groups. A polyoxyfluoroalkylene group formed by bonding with bases, and the oxyfluoroalkylene groups constituting the polyoxyfluoroalkylene group can all be the same or different from each other; R ^fa is a poly(oxyfluoroalkylene) group containing (CF ₂ O) units. perfluoroalkylene) chain; R ^fb is a poly(oxyperfluoroalkylene) chain without (CF ₂ O) units; Z ^a is a (ra+sa) valence linking group; Z ^b is (rb+sb ) valent linking group; L ^a and L ^b are hydroxyl groups or hydrolyzable groups; R ^a and R ^b are hydrogen atoms or monovalent hydrocarbon groups; na and nb are integers from 0 to 2; when na is 0 or 1, (3- When na) L ^a and nb are 0 or 1, (3-nb) L ^b can be the same or different respectively; when na is 2, na R ^a can be, and when nb is 2, nb R ^b can be They can be the same or different; ra and rb are integers above 1. When ra is 2 or above, ra numbers [R ^f1a -OQ ^a -R ^fa -] can be the same or different; when rb is 2 or above, rb numbers [R ^f1b -OQ ^b -R ^fb -] can be the same or different; sa and sb are integers above 3, sa [-SiR ^a _na L ^a _3-na ] can be the same or different, sb [-SiR ^b _nb L ^b _3-nb ] can be the same or different. The fluorine-containing ether composition of claim 9, which contains the aforementioned fluorine-containing ether compound (A1) in an amount of 10 to 80% by mass relative to the total amount of the aforementioned fluorine-containing ether compound (A1) and the aforementioned fluorine-containing ether compound (B1). . A coating liquid, characterized by containing the fluorine-containing ether composition of claim 1 or 9 and a liquid medium. An article with a surface layer, characterized by having a surface layer formed of the fluorine-containing ether composition of claim 1 or 9.