TWI875427B - Fluorinated ether compositions, coating liquids and articles - Google Patents

Abstract

The present invention provides a fluorine-containing ether composition and a coating liquid capable of forming a surface layer having excellent lubricity and durability, and an article having a surface layer having excellent lubricity and durability. A fluorine-containing ether composition comprises a fluorine-containing ether compound (A) and a fluorine-containing ether compound (B); the fluorine-containing ether compound (A) is a compound having a poly(oxyperfluoroalkylene) chain containing a ( _CF2O ) unit and a group represented by the following formula (I), and the fluorine-containing ether compound (B) is a compound having a poly(oxyperfluoroalkylene) chain not containing a ( _CF2O ) unit and a group represented by the above formula (I). _{-SiRnL3 -n} …(I); however, L is a hydroxyl group or a hydrolyzable group, and R is a hydrogen atom or a monovalent hydrocarbon group.

Description

Fluorinated ether compositions, coating liquids and articles

The present invention relates to a fluorine-containing ether composition, a coating liquid and an article.

Background of the invention Fluorine-containing compounds can exhibit high lubricity, water-repellency, and oil-repellency, so they can be used in surface treatment agents, etc. For example, if a surface treatment agent is used to form a surface layer on the surface of a substrate, lubricity, water-repellency, and oil-repellency can be imparted, making it easy to wipe off dirt on the surface of the substrate, thereby improving dirt removal performance. Among fluorine-containing compounds, fluorine-containing ether compounds have excellent dirt removal performance for grease and other dirt. The fluorine-containing ether compounds have a poly(oxyperfluoroalkylene) chain with an ether bond (-O-) in the perfluoroalkyl chain.

Some literatures suggest using hydrolyzable silicon groups as fluorine-containing ether compounds. Such fluorine-containing ether compounds can be used in applications that require long-term maintenance of abrasion resistance and fingerprint stain removal properties, such as surface treatment agents for components that constitute the finger touch surface of touch panels. Abrasion resistance refers to the performance of not being easily reduced in water and oil repellency even when repeatedly rubbed with fingers, and fingerprint stain removal properties refer to the performance of being able to easily remove fingerprints attached to the surface by wiping.

In order to improve the lubricity, a document proposes a fluorine-containing ether composition in which a fluorine-containing ether compound having a hydrolyzable silicon group is mixed with a fluorine-containing oil, that is, a non-reactive fluorine-containing ether compound having no hydrolyzable silicon group (for example, Patent Document 1).

Prior art documents Patent documents Patent document 1: Japanese Patent Publication No. 2014-65884

Summary of the invention Problems to be solved by the invention However, according to the research of the inventors, the surface layer formed by the above-mentioned fluorinated ether composition is easily degraded in lubricity, water-repellency and oil-repellency (low durability) after repeated rubbing with fingers, etc. Therefore, it is difficult to maintain high levels of both lubricity and durability at the same time.

The purpose of the present invention is to provide a fluorine-containing ether composition and coating liquid that can form a surface layer with excellent lubricity and durability, and an article having a surface layer with excellent lubricity and durability. Means for solving the problem

The present invention provides a fluorinated ether composition, a coating liquid and an article having the following compositions [1] to [15]. [1] A fluorinated ether composition, characterized in that it contains a fluorinated ether compound (A) and a fluorinated ether compound (B); the fluorinated ether compound (A) is a compound having a poly(oxyperfluoroalkylene) chain containing a ( _CF2O ) unit and a group represented by the following formula (I); the fluorinated ether compound (B) is a compound having a poly(oxyperfluoroalkylene) chain not containing a ( _CF2O ) unit and a group represented by the above formula (I). -SiR _n L _3-n …(I) except that L is a hydroxyl group or a hydrolyzable group; R is a hydrogen atom or a monovalent hydrocarbon group; n is an integer from 0 to 2; when n is 0 or 1, the (3-n) Ls may be the same or different; when n is 2, the n Rs may be the same or different; wherein the groups represented by the formula (I) possessed by the fluorinated ether compound (A) and the fluorinated ether compound (B) may be the same or different.

[2] The fluorinated ether composition of [1], wherein the fluorinated ether compound (A) and the fluorinated ether compound (B) are both fluorinated ether compounds represented by the following formula (A/B); ^Rf in the fluorinated ether compound (A) is a poly(oxyperfluoroalkylene) chain containing a ( _CF2O ) unit, and ^Rf in the fluorinated ether compound (B) is a poly(oxyperfluoroalkylene) chain not containing a ( _CF2O ) unit. [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, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 such oxyfluoroalkylene groups, and the oxyfluoroalkylene groups constituting the polyoxyfluoroalkylene group may be all the same or different; R ^f is a poly(oxyperfluoroalkylene) chain; Z is a (r+s)-valent linking group; -SiR _n L _3-n is a group represented by 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 represented by formula (I) are the same group; r and s are each an integer greater than 1 and r+s is 3 to 8.

[3] The fluorinated ether composition of [1] or [2], wherein the poly(oxyperfluoroalkylene) chain containing (CF ₂ O) units is a poly(oxyperfluoroalkylene) chain containing (CF ₂ O) units and (CF ₂ CF ₂ O) units. [4] The fluorinated ether composition of any one of [1] to [3], wherein the poly(oxyperfluoroalkylene) chain not containing (CF ₂ O) units is a poly(oxyperfluoroalkylene) chain containing at least one unit selected from the group consisting of (CF ₂ CF ₂ O) units, (CF ₂ CF ₂ CF ₂ O) units, and (CF ₂ CF ₂ CF ₂ CF ₂ O) units. [5] The fluorinated ether composition of any one of [1] to [4], wherein the poly(oxyperfluoroalkylene) chain not containing (CF ₂ O) units is a poly(oxyperfluoroalkylene) chain containing (CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) units. [6] The fluorinated ether composition of any one of [1] to [5], wherein at least one of the fluorinated ether compound (A) and the fluorinated ether compound (B) has three or more groups represented by the formula (I). [7] The fluorinated ether composition of any one of [1] to [5], wherein both the fluorinated ether compound (A) and the fluorinated ether compound (B) have two or more groups represented by the formula (I). [8] The fluorinated ether composition of any one of [1] to [5], wherein both the fluorinated ether compound (A) and the fluorinated ether compound (B) have three or more groups represented by the formula (I). [9] The fluorinated ether composition of any one of [1] to [8], wherein the number average molecular weight of the fluorinated ether compound (A) is 2,000 to 20,000. [10] The fluorinated ether composition of any one of [1] to [9], wherein the number average molecular weight of the fluorinated ether compound (B) is 2,000 to 20,000. [11] The fluorinated ether composition of any one of [1] to [10], comprising 10 to 80% by mass of the fluorinated ether compound (A) relative to the total amount of the fluorinated ether compound (A) and the fluorinated ether compound (B).

[12] A fluorine-containing ether composition comprising a fluorine-containing ether compound (A1) represented by the following formula (A1) and a fluorine-containing ether compound (B1) represented by the following formula (B1). [R ^f1a -OQ ^a -R ^fa -] _ra Z ^a [-SiR ^a _na L ^a _3-na ] _sa …(A1) [R ^f1b -OQ ^b -R ^fb -] _rb Z ^b [-SiR ^b _nb L ^b _3-nb ] _sb …(B1) However, R ^f1a and R ^f1b are perfluoroalkyl groups; Q ^a and Q ^b are single bonds, oxyfluoroalkylene groups containing one or more hydrogen atoms, or polyoxyfluoroalkylene groups formed by bonding 2 to 5 oxyfluoroalkylene groups, and the oxyfluoroalkylene groups constituting the polyoxyfluoroalkylene groups may be all the same or different; R ^fa is a poly(oxyperfluoroalkylene) chain containing a (CF ₂ O) unit; R ^fb is a poly(oxyperfluoroalkylene) chain not containing a (CF ₂ O) unit; Z ^a is a (ra+sa)-valent linking group; Z ^b is a (rb+sb)-valent linking group; ^La and ^Lb are hydroxyl groups or hydrolyzable groups; ^Ra and ^Rb are hydrogen atoms or monovalent hydrocarbon groups; na and nb are integers of 0 to 2; when na is 0 or 1, the (3-na) ^La and when nb is 0 or 1, the (3-nb) ^Lb may be the same or different; when na is 2, the na ^Ra and when nb is 2, the nb ^Rb may be the same or different; ra and rb are integers greater than 1, when ra is greater than 2, the ra [ ^Rf1a - ^OQa - ^Rfa- ] may be the same or different, when rb is greater than 2, the rb [ ^Rf1b - ^OQb - ^Rfb- ] may be the same or different; sa and sb are integers greater than 1, when sa is greater than 2, the sa [-SiR ^a _na L ^a _3-na ] may be the same or different, and when sb is 2 or more, the sb numbers [-SiR ^b _nb L ^b _3-nb ] may be the same or different. [13] The fluorinated ether composition as described in [12], which contains 10 to 80 mass % of the aforementioned fluorinated ether compound (A1) relative to the total amount of the aforementioned fluorinated ether compound (A1) and the aforementioned fluorinated ether compound (B1). [14] A coating liquid, characterized in that it contains the fluorinated ether composition as described in any one of the aforementioned [1] to [13] and a liquid medium. [15] An article, characterized in that it has a surface layer formed by the fluorinated ether composition as described in any one of the aforementioned [1] to [13].

Effect of the invention The fluorine-containing ether composition and coating liquid of the present invention can form a surface layer with excellent lubricity and durability. The article of the present invention has a surface layer with excellent lubricity and durability.

Forms for implementing the invention In this specification, the compound represented by formula (1) is referred to as compound (1). Compounds represented by other formulas are also referred to in the same manner. The following terms in this specification have the following meanings. "Hydrolyzable silyl group" refers to a group that can form a silanol group (Si-OH) by a hydrolysis reaction. For example, L in formula (I) is a hydrolyzable group. The chemical formula of an oxyperfluoroalkylene group is represented by recording its oxygen atom on the right side of the perfluoroalkylene group. "Surface layer" refers to a layer formed on the surface of a substrate. "Drying" after applying a coating liquid means that after applying the coating liquid to a substrate to form a coating film of the coating liquid on the substrate, the liquid medium is evaporated and removed from the coating film.

[Fluoroether composition] The fluorine-containing ether composition of the present invention (hereinafter also referred to as the present composition) 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)). The present composition does not contain a liquid medium as described below. The present composition may be composed of compound (A) and compound (B), and may contain other fluorine-containing ether compounds other than compound (A) and compound (B) or impurities other than compound (A), compound (B) and other fluorine-containing ether compounds as described below. Compound (A) has a poly(oxyperfluoroalkylene) chain (hereinafter also referred to as A chain) containing a (CF ₂ O) unit and a group (I). Compound (B) has a poly(oxyperfluoroalkylene) chain (hereinafter also referred to as B chain) not containing a (CF ₂ O) unit and a group (I). Compound (B) does not have an A chain. -SiR _n L _3-n …(I) except that L is a hydroxyl group or a hydrolyzable group; R is a hydrogen atom or a monovalent hydrocarbon group; n is an integer from 0 to 2; when n is 0 or 1, the (3-n) Ls may be the same or different; when n is 2, the n Rs may be the same or different; the groups (I) possessed by 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. ^Rf1 -OQ-…(II) However, Rf1 is a perfluoroalkyl group; Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 oxyfluoroalkylene groups. The oxyfluoroalkylene groups constituting the polyoxyfluoroalkylene group may all be the same or different.

(Chain A) Chain A may be a poly(oxyperfluoroalkylene) chain containing (CF ₂ O) units and (R ^f2 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 having 2 or more carbon atoms; m1 is an integer greater than 1, m2 is an integer greater than 0, and (m1+m2) is an integer from 2 to 200; When m2 is greater than 1, the bonding sequence of m1 CF ₂ O and m2 R ^f2 O is not limited; When m2 is greater than 2, (R ^f2 O) _m2 may also be composed of two or more R ^f2 O groups having different carbon atoms.

R ^f2 may be branched or linear. From the perspective of better lubricity of the surface layer, it is preferably linear. From the perspective of better durability and lubricity of the surface layer, the carbon number of R ^f2 is preferably 2 to 6, preferably 2 to 4. From the perspective of better lubricity of the surface layer, 2 is particularly preferred.

(m1+m2) is an integer of 2 to 200. Therefore, when m1 is 1, the minimum value of m2 is 1, that is, at least one (R ^f2 O) exists. 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 of 10 to 150, and an integer of 20 to 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 is good. That is, if the number average molecular weight of compound (A) is too large, the number of bases (I) present per unit molecular weight will decrease, thereby reducing durability.

The ratio of m1 to m2 (m1/m2) is preferably 100/0~30/70, and 90/10~40/60 is particularly preferred. 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 oxyperfluoroalkylene groups with different carbon numbers, the bonding order of each oxyperfluoroalkylene group (m1 CF ₂ O and m2 R ^f2 O) is not limited. For example, each oxyperfluoroalkylene group may be arranged in any of random, staggered, and block configurations. In particular, the (CF ₂ O) unit and the (R ^f2 O) unit are preferably arranged in a random configuration. When m2 is 2 or more, (R ^f2 O) _m2 may also be composed of two or more R ^f2 O groups with different carbon numbers. In addition, the bonding order of m2 R ^f2 O groups is not limited.

Specific forms of chain A can be listed below (a2) to (a6). (CF ₂ O) _m01 …(a2) {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 }…(a3) {(CF ₂ O) _m11 (CF ₂ CF ₂ CF ₂ O) _m12 }…(a4) {(CF ₂ O) _m11 (CF ₂ CF ₂ CF ₂ CF ₂ O) _m12 }…(a5) {(CF ₂ O) _m11 (CF(CF ₃ )CF ₂ O) _m12 }…(a6) However, m01 is an integer between 2 and 200, m11 is an integer greater than 1, m12 is an integer greater than 1, and (m11+m12) is an integer between 2 and 200. The preferred ranges of m01 and (m11+m12) are the same as those of (m1+m2). The ratio of m11 to m12 (m11/m12) is preferably 99/1 to 30/70, and more preferably 90/10 to 40/60. Among the above, (a3) to (a5) are preferred, and (a3) is particularly preferred. Chain A is preferably (a3) containing (CF ₂ O) units and (CF ₂ CF ₂ O) units, and (a3) containing (CF ₂ O) units and (CF ₂ CF ₂ O) units in a random arrangement is particularly preferred.

(Chain B) Chain B may be an (oxyperfluoroalkylene) chain containing at least one (R ^f3 O) unit as shown in the following formula (b1). (R ^f3 O) _m3 …(b1) However, R ^f3 is a perfluoroalkylene group having 2 or more carbon atoms; m3 is an integer from 2 to 200; (R ^f3 O) _m3 may be composed of two or more R ^f2 O groups having different carbon atoms; When (R ^f3 O) _m3 is composed of two or more R ^f2 O groups having different carbon atoms, the bonding order of each R ^f2 O group is not limited.

^Rf3 may be branched or linear. From the perspective of better lubricity of the surface layer, it is preferably linear. From the perspective of better durability and lubricity of the surface layer, the carbon number of ^Rf3 is preferably 2 to 6.

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

When (R ^f3 O) _m3 is composed of two or more R ^f2 O groups having different carbon numbers, the bonding order of each R ^f3 O group is not limited. For example, each R ^f3 O group may be arranged in any of a random, staggered, or block arrangement.

When (R ^f3 O) _m3 is composed of two or more R ^f2 O groups having 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 having 3 to 6 carbon numbers, m4 is an integer greater than 1, m5 is an integer greater than 1, (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 that of m3. The ratio of m4 to m5 (m4/m5) is preferably 90/10~10/90, and 70/30~30/70 is particularly preferred. 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 of 1 to 3, m51 is an integer of 1 to 3, m6 is an integer greater than 1, and (m41+m51)×m6 is an integer of 2 to 200. The poly(oxyperfluoroalkylene) chain is composed of one or more units consisting of 1 to 3 (CF ₂ CF ₂ O) and 1 to 3 (R ^f3 O) connected in series. The ideal range of (m41+m51)×m6 is the same as that of (m4+m5). m41 and m51 are preferably 1 each. In addition, {(CF ₂ CF ₂ O) _m41 -(R ^f4 O) _m51 } _m6 can also be regarded as a poly(oxyperfluoroalkylene) chain having {(CF ₂ CF ₂ O) _m41 -(R ^f4 O) _m51 } as a unit, or can be regarded as a poly(oxyperfluoroalkylene) chain formed by alternating (CF ₂ CF ₂ O) _m41 units and (R ^f4 O) _m51 units.

The B chain is preferably a poly(oxyperfluoroalkylene ₎ chain containing at least one unit selected from the group consisting of (CF ₂ CF ₂ O) units, (CF ₂ CF ₂ CF ₂ O) units, and (CF ₂ CF ₂ CF ₂ CF 2 O) units. In particular, it is preferably a poly(oxyperfluoroalkylene) chain containing (CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) units. Preferred specific aspects of the B chain include the following (b3) to (b5) and the like. (CF ₂ CF ₂ O) _m13 …(b3) (CF ₂ CF ₂ CF ₂ O) _m14 …(b4) (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _m15 …(b5) However, m13 and m14 are integers of 2 to 200, respectively, and m15 is an integer of 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 a poly( _{oxyperfluoroalkylene} ) chain formed by alternating bonding of (CF ₂ CF ₂ CF ₂ CF ₂ O) units.

(Group (I)) In group (I), L is a hydroxyl group or a hydrolyzable group. A hydrolyzable group is a group that is converted into a hydroxyl group by a hydrolysis reaction. That is, when L is a hydrolyzable group, Si-L of group (I) is converted into a silanol group (Si-OH) by a hydrolysis reaction. Examples of hydrolyzable groups include alkoxy groups, halogen atoms, acyl groups, and isocyanate groups (-NCO). The number of carbon atoms in an alkoxy group is preferably 1 to 4. The number of carbon atoms in an acyl group is preferably 2 to 5.

From the viewpoint of easy preparation of compound (A), L is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom. A chlorine atom is particularly preferred as the halogen 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; and when compound (A) is required to have long-term storage stability, an ethoxy group is particularly preferred, and when the reaction time after coating is to be shortened, a methoxy group is particularly preferred.

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

n is preferably 0 or 1, and 0 is particularly preferred. The presence of multiple L in one group (I) can make the adhesion with the substrate stronger and the durability of the surface layer better. When n is 0 or 1, the (3-n) Ls can be the same or different. For example, some Ls can be hydrolyzable groups and the remaining Ls can be hydroxyl groups.

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 handling in industrial production, Si(OCH ₃ ) ₃ is particularly preferred.

(Group (II)) In group (II), ^Rf1 is a perfluoroalkyl group. From the viewpoint of better lubricity and durability of the surface layer, the carbon number of the perfluoroalkyl group in ^Rf1 is preferably 1 to 20, preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to _3. The perfluoroalkyl group may be branched or linear, and the linear one is preferred. Examples of the linear perfluoroalkyl group include _CF3- , _CF3CF2- , _CF3CF2CF2- , and _{the like} .

Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 (preferably 2 to 4) such oxyfluoroalkylene groups. In the polyoxyfluoroalkylene group, multiple oxyfluoroalkylene groups are usually bonded in series. If Q is an oxyfluoroalkylene group containing a hydrogen atom, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 such oxyfluoroalkylene groups, the solubility of compound (A) and compound (B) in the liquid medium can be improved. Therefore, compound (A) and compound (B) are not easy to condense in the coating liquid, and after being coated on the surface of the substrate, compound (A) and compound (B) are not easy to condense during the drying period, so the appearance of the surface layer 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 more preferably 3 or more. From the viewpoint of better water-repellency and oil-repellency of the surface layer, the number of hydrogen atoms in the oxyfluoroalkylene group is preferably (the number of carbon atoms of Q) × 2 or less, and more preferably (the number of carbon atoms of Q) or less. The oxyfluoroalkylene group may be branched or linear, and from the viewpoint of better lubricity of the surface layer, it is preferably linear. In the polyoxyfluoroalkylene group, 2 to 5 oxyfluoroalkylene groups may be all the same or different. _From the viewpoint of easy preparation of compound (A) and compound (B) _, Q is _preferably a single _{bond or a group} selected from _{the group consisting} of _{-CHFCF2OCH2CF2O- , -CF2CHFCF2OCH2CF2O- , -CF2CF2CHFCF2OCH2CF2O- ,} -CF2CF2OCHFCF2OCH2CF2O-, _{-CF2CF2OCF2CF2OCHFCF2OCH2CF2O-} , _{-CF2CH2OCH2CF2O- , -CF2CH2OCH2CF2O- , and -CF2CF2OCF2CH2OCH2CF2O- ( however , the} left _{side is} bonded ^to _{Rf1 - O ) .}

The A chain of compound (A) and the B chain of compound (B) may be 1 or 2 or more. From the perspective of ease of preparation and disposal, 1 to 3 chains are preferred. When compound (A) has 2 or more A chains, each A chain may be the same or different. When compound (B) has 2 or more B chains, each B chain may be the same or different.

The number of groups (I) possessed by each of compound (A) and compound (B) may be 1 or 2 or more. From the perspective of having better surface layer durability by increasing the bonding with the substrate, it is preferably 2 or more, and 3 or more is particularly preferred. From the perspective of having better surface layer durability by increasing the molecular density of bonding with the substrate, it is preferably 10 or less, and 5 or less is preferably, and 4 or less is particularly preferred. Therefore, the number of groups (I) possessed by each of compound (A) and compound (B) is preferably 1 to 10, and 2 to 5 is preferably, and 3 to 4 is particularly preferred. When compound (A) and compound (B) have 2 or more groups (I), each group (I) may be the same or different. From the perspective of the ease of preparation of compound (A) and compound (B), it is preferred that all of them are the same group.

It is preferable that a group (II) is bonded to one end of the A chain or the B chain. That is, the compound (A) preferably further has a group (II) bonded to one end of the A chain. The compound (B) preferably further has a group (II) bonded to one end of the B chain. This can make the lubricity of the surface layer even better.

The number average molecular weight (Mn) of compound (A) and compound (B) is preferably 2,000-20,000, preferably 3,000-15,000, and particularly preferably 4,000-12,000. As long as the number average molecular weight of compound (A) and compound (B) is above 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 compound (A) and compound (B) is above 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 following examples.

Compound (A) and compound (B) are not particularly limited as long as they have chain A or chain B and group (I). For example, they can be appropriately selected from the 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 Publication No. 2013-227279, Japanese Patent Publication No. 2013-241569, Japanese Patent Publication No. 2013-256643, Japanese Patent Publication No. 2014-15609, Japanese Patent Publication No. 2014-37548, Japanese Patent Publication No. 2014-65884, Japanese Patent Publication No. 2014-210258, Japanese Patent Publication No. 2014-2186 39, Japanese Patent Publication No. 2015-200884, Japanese Patent 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. 2014-198822, Japanese Patent Publication No. 2015-129230, Japanese Patent Publication No. 2015-196723, Japanese Patent Publication No. 2015-13983, Japanese Patent Publication No. 2015-199915, Japanese Patent Publication No. 2015-199906, 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 the present specification, a group of fluorinated ether compounds that are identical except for the distribution of the number of repetitions of oxyperfluoroalkylene groups in the poly(oxyperfluoroalkylene) chain are considered to be a single compound. For example, when the poly(oxyperfluoroalkylene) chain is compound (A) with ( _CF2O ) _m1 ( ^Rf2O ) _m2 , a group of compounds that are identical except for the distribution of m1 and m2 are considered to be a single compound fluorinated ether compound.

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

Another preferred embodiment 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 3 to 5. If both have two or more groups (I), the durability of the surface layer is excellent.

When forming a surface layer by dry coating, the difference between the number average molecular weight (Mn) of compound (A) and the number average molecular weight (Mn) of compound (B) is preferably small. In the case of dry coating, there is a tendency for the compound with a smaller molecular weight to evaporate first and be deposited onto the substrate. The smaller the difference in the number average molecular weight (Mn), the less likely it is that the distribution of compound (A) and compound (B) will be uneven in the formed surface layer. The difference between the number average molecular weight (Mn) of compound (A) and the number average molecular weight (Mn) of compound (B) is preferably 3,000 or less, and preferably 2,000 or less. When the surface layer is formed 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 not easy to produce uneven distribution of compound (A) and compound (B) in the formed surface layer, so the difference is not particularly limited.

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

Compound (A) and compound (B) are preferably both fluorine-containing ether compounds represented by the following formula (A/B). In the following formula (A/B), ^Rf of compound (A) is a poly(oxyperfluoroalkylene) chain containing a ( _CF2O ) unit, and ^Rf of compound (B) is a poly( _{oxyperfluoroalkylene} ) chain not containing a (CF2O) unit. [ ^Rf1 - ^OQRf- ] _rZ [ _{-SiRnL3 -n} ] _s ...(A/B) In the above formula (A/B), ^Rf1 is the aforementioned ^Rf1 , Q is the aforementioned Q, and _{-SiRnL3 -n} is a group represented by the above formula (I). Z is a (r+s)-valent linking group. r is an integer greater than 1 and is a number equal to the number of poly(oxyperfluoroalkylene) chains in the above compound (A) and compound (B). s is an integer greater than or equal to the number of radicals (I) in the aforementioned compound (A) and compound (B). According to the number of poly(oxyperfluoroalkylene) chains and the number of radicals (I), r+s is preferably 2 to 13, preferably 3 to 8, and particularly preferably 4 to 7. The (r+s)-valent linking group Z may be a group represented by ^Za and ^Zb described below. In addition, when r is greater than or equal to 2, the r [ ^Rf1 - ^OQRf- ] groups are preferably the same group; when s is greater than or equal to 2, the s groups represented by formula (I) are preferably the same group.

(Ideal Aspect) One ideal aspect of the present composition is that compound (A) is a fluorine-containing ether compound (A1) represented by the following formula (A1) (hereinafter also referred to as compound (A1)) and compound (B) is a fluorine-containing ether compound (B1) represented by the following formula (B1) (hereinafter also referred to as compound (B1)). That is, the composition of this 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, oxyfluoroalkylene groups containing one or more hydrogen atoms, or polyoxyfluoroalkylene groups formed by bonding 2 to 5 oxyfluoroalkylene groups, and the oxyfluoroalkylene groups constituting the polyoxyfluoroalkylene groups may be all the same or different; R ^fa is chain A; R ^fb is chain B; Z ^a is a (ra+sa)-valent linking group; Z ^b is a (rb+sb)-valent linking group; L ^a and L ^b are hydroxyl groups or hydrolyzable groups; R ^a and R ^b is a hydrogen atom or a monovalent hydrocarbon group; na and nb are integers from 0 to 2; when na is 0 or 1, the (3-na) ^La and when nb is 0 or 1, the (3-nb) L ^b may be the same or different; when na is 2, the na ^Ra and when nb is 2, the nb R ^b may be the same or different; ra and rb are integers greater than 1, when ra is greater than 2, the ra [R ^f1a -OQ ^a -R ^fa -] may be the same or different, when rb is greater than 2, the rb [R ^f1b -OQ ^b -R ^fb -] may be the same or different; sa and sb are integers greater than 1, when sa is greater than 2, the sa [-SiR ^a _na L ^a _3-na ] may be the same or different, when sb is greater than 2, the 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 above group (II), and the ideal state is the same. When ra is 2 or more, the ra R ^f1a preferably have the same carbon number, and from the viewpoint of ease of manufacture, they are preferably the same group, that is, groups with the same carbon number and the same chemical structure. Groups with the same carbon number and the same chemical structure mean, for example, when ra is 2, the two R ^f1a are CF ₃ CF ₂ CF ₂ - (not a combination of CF ₃ CF ₂ CF ₂ - or CF ₃ CF(CF ₃ )-, which are two R ^fa groups with the same carbon number but different chemical structures). When rb is 2 or more, the rb R ^f1b preferably have the same carbon number, and from the viewpoint of ease of manufacture, they are preferably the same group, that is, groups with the same carbon number and the same chemical structure.

^Qa and ^Qb are the same as Q in the aforementioned group (II), and the ideal aspect is also the same. The A chain of ^Rfa and the B chain of ^Rfb are the same as those described above, and the ideal aspect is also the same. ^La and ^Lb are the same as L in the aforementioned group (I), and the ideal aspect is also the same. ^Ra and ^Rb are the same as R in the aforementioned group (I), and the ideal aspect is also the same. Na and nb are the same as n in the aforementioned group (I), and the ideal aspect is also the same. The ideal values of ra and rb are the same as the ideal numbers of the A chain of compound (A) and the B chain of compound (B), respectively. That is, ra and rb are preferably integers of 1 to 3, respectively. The ideal values of s1 and s2 are the same as the ideal number of the group (I) of compound (A) and compound (B), respectively. That is, s1 and s2 are preferably integers of 1 to 10, preferably integers of 2 to 5, and particularly preferably integers of 3 to 4, respectively.

^Za may be, for example, a (ra+sa)-valent substituted or unsubstituted alkyl group, a (ra+sa)-valent group having a group or atom other than a alkyl group between carbon atoms or/and at the end of a substituted or unsubstituted alkyl group, a (ra+sa)-valent organic polysiloxy group, etc. ^Zb may be, for example, a group that is the same as ^Za except that the valence is (rb+sb).

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

Examples of groups or atoms other than alkyl groups between carbon atoms or/and at the ends of alkyl groups include etheric oxygen atoms (-O-), thioetheric sulfur atoms (-S-), nitrogen atoms (-N＜), silicon atoms (＞Si＜), carbon atoms (＞C＜), -N(R ¹⁵ )-, -C(O)N(R ¹⁵ )-, -OC(O)N(R 15 )-, -Si(R ¹⁶ )(R ¹⁷ )-, organic polysiloxy groups, -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 independently alkyl groups or phenyl ^groups . The number of carbon atoms in the alkyl group is preferably 1 to 6. The organic polysiloxy group may be a straight chain, a branched chain, or a ring.

<Ideal form of compound (A1)> From the perspective of improving the friction resistance and fingerprint stain removal performance of the surface layer, compound (A1) is preferably selected from at least one compound in the group consisting of the following compounds (A11), (A12) and (A13).

"Compound (A11)" Compound (A11) is represented by the following formula (A11). ^Rf1a - ^OQa - ^Rfa - ^Q32a- [C(O)N( ^R33a )] _pa - ^R34a -C[ ^-R35a - ^SiRa _{naLa3 -na} ^] ₃ ... (A11) However, ^Rf1a , ^Qa , ^Rfa , ^Ra , ^La and na have the same meanings as above, ^Q32a is a fluoroalkylene group having 1 to 20 carbon atoms or a group having an etheric oxygen atom between carbon atoms of a fluoroalkylene group having 2 to 20 carbon atoms (except the case where the fluoroalkylene group having one end bonded to the etheric oxygen atom and the other end bonded to ^Rfa is a perfluoroalkylene group), ^R33a is a hydrogen atom or an alkylene group having 1 to 6 carbon atoms, pa is 0 or 1, R ^{R 34a} is a single bond, an alkylene group having 1 to 6 carbon atoms, a group having an etheric oxygen atom at the terminal of the alkylene group (but at the terminal on the side bonded to C[-R ^34a -SiR _na L _3- na ] ₃ ), a group having an etheric oxygen atom between carbon atoms of an alkylene group having 2 to 6 carbon atoms, or a group having an etheric oxygen atom at the terminal of the alkylene group having 2 to 6 carbon atoms (but at the terminal on the side bonded to C[-R ^34a -SiR _na L _3-na ] ₃ ) and between carbon atoms, R ^35a is an alkylene group having 1 to 6 carbon atoms, a group having an etheric oxygen atom at the terminal of the alkylene group (but excluding the terminal on the side bonded to Si), or a group having an etheric oxygen atom between carbon atoms of an alkylene group having 2 to 6 carbon atoms, 3 [-R ^34a -SiR _na L _3-na ] can be the same or different.

Compound (A11) is a compound of the above formula (A1) wherein ra is 1, sa is 3 and ^Za is -Q ^32a -[C(O)N(R ^33a )] _pa -R ^34a -C[-R ^35a -] _3. Preferably, 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 having one or more hydrogen atoms. From the viewpoint of the friction resistance and lubricity of the surface layer, the fluoroalkylene group is preferably a linear chain. The group having an etheric oxygen atom between carbon atoms of the fluoroalkylene group having 2 to 20 carbon atoms may be exemplified by the group described later in (ii). Q ^32a is preferably a perfluoroalkylene group having 1 to 20 carbon atoms, a fluoroalkylene group having 1 to 20 carbon atoms containing one or more hydrogen atoms, and a group having an etheric oxygen atom between carbon atoms of the fluoroalkylene group having 2 to 20 carbon atoms containing one or more hydrogen 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 number. When pa is 1, Q ^32a can be exemplified by the following groups. (i) a perfluoroalkylene group. (ii) a group having ^RFCH ₂ O (however, ^RF is a perfluoroalkylene group having 1 to 6 carbon numbers) on the side bonded to R ^fa and a fluoroalkylene group having one or more hydrogen atoms (which may have an ethereal oxygen atom between carbon atoms) on the side bonded to C(O)N(R ^33a ).

From the viewpoint of durability and lubricity of the surface layer and ease of preparation of compound (A11), ^Q32a in ( ⁱⁱ _{) is preferably the following :} ^-RFCH2O _- ^{CF2CHFOCF2CF2CF2CF2-} _{, -RFCH2O - CF2CHFCF2OCF2CF2- , -RFCH2O - CF2CHFCF2OCF2CF2CF2- , -RFCH2O - CF2CHFCF2OCF2CF2CF2- , -RFCH2O - CF2CHFOCF2CF2CF2OCF2CF2-} ^.

When pa in the [C(O)N(R ^33a )] _pa group is 0 or 1, the properties of the fluorine-containing ether compound are almost unchanged. When pa is 1, there is an amide bond. Since at least one fluorine atom is bonded to the terminal carbon atom of the side where Q ^32a is bonded to [C(O)N(R ^33a )], the polarity of the amide bond becomes smaller, and the water-repellency and oil-repellency of the surface layer are not easily reduced. Whether pa is 0 or 1 can be determined from the viewpoint of ease of manufacture. From the viewpoint of ease of manufacture 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 easy preparation of compound (A11), R ^34a is preferably a single bond or a group 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 - (however, the left side is bonded to Q ³² ). When pa is 1, from the viewpoint of easy 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 easy preparation of compound (A11), R ^35a is preferably a group selected from the group consisting of -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ OCH ₂ CH ₂ CH ₂ -, and -OCH ₂ CH ₂ CH ₂ - (however, the right side is bonded to Si). From the viewpoint of excellent light resistance of the surface layer, R ^35a is particularly preferably one without an ethereal oxygen atom. For touch panels used outdoors (digital signs such as vending machines and navigation boards) and car touch panels, light resistance is important for the water-repellent and oil-repellent layer. The three R ^35a in compound (A11) may be the same or different.

The compound (A11) may be a compound of the following formula: This compound is very desirable from the viewpoints of being easy to manufacture industrially, easy to handle, and having excellent water and oil repellency, abrasion resistance, fingerprint stain removal, lubricity, and appearance of the surface layer.

[Chemical formula 1]

However, W in the equation is R ^f1a -OQ ^a -R ^fa -. The ideal form of W is a combination of the above-mentioned ideal R ^f1a , Q ^a and R ^fa . The ideal range of Q ^32a is the same as above.

"Compound (A12)" Compound (A12) is represented by the following formula (A12). ^Rf1a - ^OQa - ^Rfa - ^R42a - ^R43a -N[ ^{-R44a -SiRa} _{naLa3 -na} ^] ₂ …(A12) except that ^Rf1a , ^Qa , ^Rfa , ^Ra , ^La and na have the same meanings as above, respectively, ^R42a is a perfluoroalkylene group having 1 to 6 carbon atoms, ^R43a is a single bond, an alkylene group having 1 to 6 carbon atoms, a group having an etheric oxygen atom or -NH- at the terminal of the alkylene group (except the terminal on the N-bonding side), a group having an etheric oxygen atom or -NH- between carbon atoms of an alkylene group having 2 to 6 carbon atoms, or a group having an etheric oxygen atom or -NH- at the terminal of an alkylene group having 2 to 6 carbon atoms (except the terminal on the N-bonding side) and between carbon atoms, R ^44a is an alkylene group having 1 to 6 carbon atoms, or an alkylene group having 2 to 6 carbon atoms having an ethereal oxygen atom or -NH- between carbon atoms. The two [-R ^44a -SiR _na L _3-na ] may be the same or different.

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

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 number.

From the viewpoint of the ease of preparation of compound (A12), R ^43a is preferably a group selected from the group consisting of -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 - (however, the left side is bonded to R ^42a ). R ^43a does not have an ester bond with high polarity and insufficient drug resistance and light resistance, so the initial hydrophobicity, drug resistance, and light resistance of the surface layer are good.

From the viewpoint of easy 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 which is highly polar and has poor drug resistance and light resistance, so the initial hydrophobicity, drug resistance and light resistance of the surface layer are good. From the viewpoint of excellent light resistance of the surface layer, R ^44a is particularly preferably one which does not have an ethereal oxygen atom. The two R ^44a in compound (A12) may be the same or different.

The compound (A12) may be a compound of the following formula: This compound is preferred from the viewpoint of being easy to manufacture industrially, easy to handle, having excellent water and oil repellency, abrasion resistance, fingerprint stain removal, lubricity, chemical resistance and light resistance.

[Chemical formula 2]

However, W in the equation is R ^f1a -OQ ^a -R ^fa -. The ideal form of W is a combination of the above-mentioned ideal R ^f1a , Q ^a and R ^fa . The ideal range of R ^42a is the same as 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) However, R ^f1a , Q ^a , R ^fa , ^Ra , ^La and na have the same meanings as above, R ^51a is a perfluoroalkylene group having 1 to 6 carbon atoms, R ^52a is an alkylene group having 1 to 6 carbon atoms, Z ^3a is a (ea+fa)-valent alkyl group, or a (ea+fa)-valent group having 2 or more carbon atoms and having one or more ethereal oxygen atoms between carbon atoms of the alkyl group, R ^53a is an alkylene group having 1 to 20 carbon atoms, ea is an integer of 1 or more, fa is an integer of 1 or more, (ea+fa) is 3 or more, and when ea is 2 or more, ea [R ^f1a -OQ ^a -R ^[ -OR ^53a -SiR a ^{na L a 3} -na ] may be the same or different from each other. When fa is 2 or more, fa [-OR ^53a -SiR ^a _na L ^a _3-na ] may be the same or different from each other.

Compound (A13) is a compound of the above formula (A1) wherein ra is ea, sa is fa and ^Za is ^-R51a - ^R52a -O-] _eaZ3a ^{[ -OR53a-} ] _fa .

ea should be an integer between 1 and 3. fa should be an integer between 1 and 10, preferably between 2 and 5, and especially between 3 and 4.

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 a linear chain. The compound (A13) in which R ^51a is a linear chain can form a surface layer having excellent friction resistance and lubricity.

From the viewpoint of the 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.

From the viewpoint of improving the water- and oil-repellency, durability, fingerprint stain removal, lubricity and appearance of the surface layer and the ease of preparation of compound (A13), the group ^Rf1a - ^OQa - ^Rfa - ^R51a- is preferably the group ( ^Rf -1) and the group ( ^Rf -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 having 1 to 20 carbon atoms; m21 and m22 are each an integer greater than 1, m21+m22 is an integer of 2 to 200, and the bonding order of m21 CF ₂ O and m22 CF ₂ CF ₂ O is not limited.

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

[Chemical formula 3]

From the viewpoint of easy preparation of compound (A13), R ^53a is preferably an alkylene group having 3 to 14 carbon atoms. Furthermore, from the viewpoint that part or all of the allyl group (-CH ₂ CH=CH ₂ ) is unlikely to be isomerized to an internal olefin (-CH=CHCH ₃ ) as a byproduct during the hydrosilylation of compound (A13) described later, an alkylene group having 4 to 10 carbon atoms is particularly preferred.

Compound (A13) includes compounds (A13-1) to (A13-6) as shown below. The compound is ideal from the viewpoints of being easy to manufacture and dispose of in industry, and having excellent water and oil repellency, abrasion resistance, fingerprint stain removal, lubricity, and appearance of the surface layer.

[Chemical formula 4]

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

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

"Compound (B11)" Compound (B11) is represented by the following formula (B11). Rf1b- ^OQb - ^{Rfb - Q32b-} [C(O)N( ^R33b )] _pb - ^R34b -C[ ^-R35b -SiRnbL3 _{-nb ] 3} ... (B11) However, ^Rf1b , ^Qb , ^Rfb , ^Rb , ^Lb and nb have the same meanings as above, ^Q32b is a fluoroalkylene group having 1 to 20 carbon atoms or a group having an etheric oxygen atom between carbon atoms of a fluoroalkylene group having 2 to 20 carbon atoms (except the case where the fluoroalkylene group having one end bonded to the etheric oxygen atom and the other end bonded to ^Rfb is a perfluoroalkylene group), ^R33b is a hydrogen atom or an alkylene group having 1 to 6 carbon atoms, pb is 0 or 1, R ^{R 34b} is a single bond, an alkylene group having 1 to 6 carbon atoms, a group having an etheric oxygen atom at the terminal of the alkylene group (but at the terminal on the ₃ -bonding side to C[-R ^34b -SiR _nb L 3 _- nb ]), a group having an etheric oxygen atom between carbon atoms of an alkylene group having 2 to 6 carbon atoms, or a group having an etheric oxygen atom at the terminal of the alkylene group having 2 to 6 carbon atoms (but at the terminal on the ₃ -bonding side to C[-R ^34b -SiR _nb L _3-nb ]) and between carbon atoms, R ^35b is an alkylene group having 1 to 6 carbon atoms, a group having an etheric oxygen atom at the terminal of the alkylene group (but excluding the terminal on the 3-bonding side to Si), or a group having an etheric oxygen atom between carbon atoms of an alkylene group having 2 to 6 carbon atoms, 3 [-R ^34b -SiR _nb L _3-nb ] can be the same or different.

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

The fluoroalkylene group and the group having an etheric oxygen atom between carbon atoms of the fluoroalkylene group in Q ^32b are respectively the same as the fluoroalkylene group and the group having an etheric oxygen atom between carbon atoms of the fluoroalkylene group in Q ^32a in the aforementioned formula (A11). 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 having 1 carbon number. 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 numbers. When p1 is 0 and R ^fb is (CF ₂ CF ₂ O-CF ₂ CF ₂ CF _{2 O} ) _m15 , Q ^32b is typically a linear perfluoroalkylene group having 3 carbon numbers. R ^33b , pb, R ^34b , and R ^35b are respectively the same as R ^33a , pb, R ^34a , and R ^35a in the aforementioned formula (A11), and the ideal aspects are also the same.

"Compound (B12)" Compound (B12) is represented by the following formula (B12). Rf1b- ^OQb - ^Rfb - ^R42b - ^R43b -N[ ^-R44b -SiRnbL3 _{-nb ] 2} ... ⁽ B12) However, ^Rf1b , ^Qb , ^Rfb , ^Rb , ^Lb and nb have the same meanings as above, ^R42a is a perfluoroalkylene group having 1 to 6 carbon atoms, ^R43a is a single bond, an alkylene group having 1 to 6 carbon atoms, a group having an etheric oxygen atom or -NH- at the terminal of the alkylene group (except the terminal on the N-bonding side), a group having an etheric oxygen atom or -NH- between carbon atoms of an alkylene group having 2 to 6 carbon atoms, or a group having an etheric oxygen atom or -NH- at the terminal of an alkylene group having 2 to 6 carbon atoms (except the terminal on the N-bonding side) and between carbon atoms, R ^44a is an alkylene group having 1 to 6 carbon atoms, or an alkylene group having 2 to 6 carbon atoms having an ethereal oxygen atom or -NH- between carbon atoms. The two [-R ⁴⁴ -SiR _n L _3-n ] groups may be the same or different.

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

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 number. When R ^fb is (CF ₂ CF ₂ CF ₂ O) _m14 , R ^42b is typically a perfluoroalkylene group having 2 carbon numbers. _When R ^fb is (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ O) _m15 , R ^42b is typically a linear perfluoroalkylene group having 3 carbon numbers.

"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) However, R f1b , Q b , R fb , R b , L b and nb have the same meanings as above, R} ^{51b is a} _{perfluoroalkylene} ^group _{having 1} ^{to 6 carbon atoms ,} R ^52b is an alkylene group having 1 to 6 carbon atoms, Z 3b is a (eb+fb)-valent alkyl group, or a (eb+fb)-valent group having 1 or more etheric oxygen atoms between carbon atoms of the alkyl group and having 2 or more carbon atoms, R ^53b is an alkylene group having 1 to 20 carbon atoms, eb is an integer of 1 or more, fb is an integer of 1 or more, (eb+fb) is 3 or more, and when eb is 2 or more, the number of eb [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) wherein R f1b , Q b , R fb , R b , L b and nb are the same as above, R ^51b is a perfluoroalkylene group having 1 to 6 carbon atoms, R ^52b is an alkylene group having 1 to 6 carbon atoms, Z 3b is a (eb+fb)-valent alkyl group, or a (eb+fb)-valent group having 2 or more carbon atoms and having 1 or more etheric oxygen atoms between carbon atoms of the alkyl group, R 53b is an alkylene group having 1 to 20 carbon atoms, ^fb -R ^51b -R ^52b -O-] may be the same or different from each other. When fb is 2 or more, fb pieces of [-OR ^53b -SiR ^b _nb L ^b _3-nb ] may be the same or different from each other.

Compound (B13) is a compound of the above formula (B1) wherein 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). From the viewpoint of the water-repellency and oil-repellency, durability, fingerprint stain removal, lubricity, and appearance of the surface layer, and the ease of preparation of the compound (B13), the group R ^f1b -OQ ^b -R ^fb -R ^51b -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 linear perfluoroalkyl group having 1 to 20 carbon atoms; and m25 is an integer of 1 to 100.

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

Compound (C) can be exemplified by compound (C1). A ³¹ -OQ ⁵¹ -(R ^F3 O) _m30 -[Q ⁵² -O] _p3 -A ³² …(C1) except that A ³¹ and A ³² are each independently a perfluoroalkyl group having 1 to 20 carbon atoms; Q ⁵¹ is a single bond, a fluoroalkylene group having 1 to 6 carbon atoms which contains one or more hydrogen atoms and does not have a branched structure, a group having an etheric oxygen atom at the end of a fluoroalkylene group having 1 to 6 carbon atoms which contains one or more hydrogen atoms and does not have a branched structure (except the end on the side bonded to A ³¹ -O), a group having an etheric oxygen atom between carbon atoms of a fluoroalkylene group having 2 to 6 carbon atoms which contains one or more hydrogen atoms and does not have a branched structure, or a group having an etheric oxygen atom at the end of a fluoroalkylene group having 2 to 6 carbon atoms which contains one or more hydrogen atoms and does not have a branched structure (except the end bonded to A ³¹ -O); -O bonding side) and a group having an etheric oxygen atom between carbon atoms (however, the number of oxygen atoms is 10 or less); Q ⁵² is a fluoroalkylene group having 1 to 20 carbon atoms and having one or more hydrogen atoms and having no branching structure, or a group having an etheric oxygen atom between carbon atoms of a fluoroalkylene group having 2 to 6 carbon atoms and having no branching structure (however, the number of oxygen atoms is 10 or less); ^RF3 is a perfluoroalkylene group having 1 to 6 carbon atoms and having no branching structure; m30 is an integer of 2 to 200; ( ^RF3O ) _m30 may also be composed of two or more ^RF3O groups having different carbon numbers; when Q ⁵¹ is a single bond, p3 is 0, and when Q ⁵¹ is not a single bond, p3 is 1.

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

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

(Composition of the present composition) In the present composition, the content of compound (A) relative to the total amount of compound (A) and compound (B) (mass ratio of compound (A)/[compound (A)+compound (B)]) is preferably 10-80% by mass, and 20-50% by mass is particularly preferred. The higher the content of compound (A) within the aforementioned range, the better the lubricity of the surface layer. The lower the content of compound (A) within the aforementioned range (i.e., 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% by mass or more, and more preferably 80% by mass or more relative to the total mass of the present composition. The upper limit is not particularly limited and may be 100% by mass.

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

Fluorine-based organic solvents include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkyl amines, fluoroalcohols, and the like. Fluorinated alkanes are preferably compounds having 4 to 8 carbon atoms. 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), and C ₂ F ₅ CHFCHFCF ₃ (manufactured by Chemours, Vertrel (registered trademark) XF). Fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene. Fluoroalkyl ethers are preferably compounds having 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, Novec (registered trademark) 7100), C ₄ F ₉ OC ₂ H ₅ (manufactured by 3M, Novec (registered trademark) 7200), and C ₂ F ₅ CF(OCH ₃ )C ₃ F ₇ (manufactured by 3M, Novec (registered trademark) 7300). Examples of fluorinated alkylamines include perfluorotripropylamine and perfluorotributylamine. Examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol. The non-fluorine organic solvent is preferably a compound consisting of only hydrogen atoms and carbon atoms and a compound consisting of only hydrogen atoms, carbon atoms and oxygen atoms, and can be exemplified by hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents, and ester organic solvents. The coating liquid preferably contains 50-99.999 mass% of the liquid medium, preferably 70-99.5 mass%, more preferably 90-99.5 mass%, and particularly preferably 99-99.9 mass%.

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

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

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

(Surface layer) In the present composition, when L of 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 between molecules to form a Si-O-Si bond, or the silanol group undergoes a dehydration condensation reaction with a hydroxyl group (substrate-OH) on the surface of the substrate to form a chemical bond (substrate-O-Si). Therefore, the surface layer contains the compound (A) and the compound (B) in a state where a part or all of the group (I) of each of the compound (A) and the compound (B) has undergone a hydrolysis reaction. When L in the group (I) is a hydroxyl group, the above reaction is performed without undergoing a hydrolysis reaction.

The thickness of the surface layer is preferably 1 to 100 nm, and 1 to 50 nm is particularly preferred. As long as the thickness of the surface layer is above the lower limit of the aforementioned range, the effect of the surface treatment can be easily and fully obtained. As long as the thickness of the surface layer is below the upper limit of the aforementioned range, the utilization efficiency is high. The thickness of the surface layer can be calculated from the vibration period of the interference pattern obtained by using an X-ray diffraction meter for thin film analysis (manufactured by RIGAKU, ATX-G) using the X-ray reflectivity method to obtain the interference pattern of the reflected X-ray.

(Substrate) The substrate of the present invention is not particularly limited as long as it is a substrate that is desired to be lubricated and water-repellent and oil-repellent. Examples of substrate materials include metals, resins, glass, sapphire, ceramics, stones, and composite materials thereof. Glass may have been chemically strengthened. A base film such as a _SiO2 film may also be formed on the surface of the substrate. The substrate is preferably a substrate for a touch panel, a substrate for a display, and an ophthalmic lens, and is particularly preferably a substrate for a touch panel. The substrate for a touch panel is light-transmissive. "Light-transmissive" means that the vertical incidence visible light transmittance specified in JIS R3106:1998 (ISO 9050:1990) is 25% or more. The material of the substrate for a touch panel is preferably glass and a transparent resin.

(Production method of 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 by a dry coating method using the present composition. ・A method of obtaining the article of the present invention by applying the present coating liquid to the surface of a substrate by a wet coating method and then drying the substrate.

<Dry coating method> This composition can be used directly in dry coating. This composition is very suitable for forming a surface layer with excellent adhesion by dry coating. Examples of dry coating methods include vacuum evaporation, CVD, and sputtering. From the perspective of inhibiting the decomposition of compound (A) and compound (B) and the simplicity of the device, vacuum evaporation is particularly preferred. When vacuum evaporation is performed, a granular material in which this composition or this coating liquid is impregnated in a porous metal body such as iron or steel can also be used.

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

<Wet coating method> Wet coating methods include spin coating, rubbing coating, spray coating, scraping coating, dipping coating, die coating, inkjet coating, flow coating, roller coating, casting, Langmuir-Blodgett coating and gravure coating.

<Post-treatment> In order to improve the friction resistance of the surface layer, an operation to promote the reaction between compound (A) and compound (B) and the substrate can be performed as required. Such operations include heating, humidification, light irradiation, etc. For example, heating the substrate with the surface layer formed in an atmosphere containing moisture can promote the hydrolysis reaction of hydrolyzable silyl groups to hydrolyze silanol groups, the reaction of hydroxyl groups on the surface of the substrate with silanol groups, and the formation of siloxane bonds through the condensation reaction of silanol groups. After the surface treatment, compounds that are compounds in the surface layer and are not chemically bonded to other compounds or the substrate can be removed as required. Specific methods include a method of rinsing the surface layer with a solvent, a method of wiping with a cloth soaked in a solvent, etc.

[Effects] The present composition and the present coating liquid contain compound (A) and compound (B), and thus can form a surface layer with excellent 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, excellent initial lubricity, water-repellency and oil-repellency can be imparted, and at the same time, excellent durability can be obtained in which these properties are not easily reduced even if the surface is repeatedly rubbed. In addition, the water-repellency and oil-repellency are not easily reduced even if the surface is repeatedly rubbed, so that the performance of easily removing fingerprint stains on the surface of the substrate (fingerprint stain removal) can be obtained. Compound (A) contains a (CF ₂ O) unit in the A chain, so it has excellent lubricity. On the other hand, the durability is poorer than when the (CF ₂ O) unit is not included. Compound (B) does not contain a (CF ₂ O) unit in the B chain, so the durability is good. On the other hand, the lubricity is poorer than when the (CF ₂ O) unit is included. Therefore, when these are combined, the superior properties 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 substrate with a surface layer prepared as described above is suitable as a component constituting a touch panel. However, the application of this composition, this coating liquid and the article is not limited to the touch panel. For example, it can be used for display input devices other than touch panels; surface protection coatings for transparent glass or transparent plastic (acrylic, polycarbonate, etc.) components, anti-fouling coatings for kitchens; water-repellent and moisture-proof coatings or anti-fouling coatings for electronic equipment, heat exchangers, batteries, etc., and anti-fouling coatings for bathrooms; coatings used on components that need to conduct and repel liquids at the same time; water-repellent, waterproof, and water-slip coatings for heat exchangers; low-friction coatings on the surface of vibrating screens or the inside of cylinders, etc. More specific examples of use include display front protection plates, anti-reflection plates, polarizing plates, anti-glare plates or objects with anti-reflection film treatment on the surface, touch panel panels or touch panel displays of mobile phones, portable information terminals and other devices with display input devices that can be operated by human fingers or palms on the screen, decorative building materials for sinks in toilets, bathrooms, sinks, kitchens, etc., waterproof coatings for wiring boards, water-repellent coatings for heat exchangers, and water-repellent coatings for solar batteries. Water-repellent coatings, waterproof and water-repellent coatings for printed wiring boards, waterproof and water-repellent coatings for electronic machine housings or electronic parts, coatings to enhance the insulation of power lines, waterproof and water-repellent coatings for various filters, waterproof coatings for radio wave absorbers or sound-absorbing materials, anti-fouling coatings for bathrooms, kitchen machines, and toilets, water-repellent, waterproof, and water-slide coatings for heat exchangers, low-friction coatings on the surfaces of vibrating screens or cylinder interiors, surface protective coatings for mechanical parts, vacuum machine parts, bearing parts, automotive parts, tools, etc. Implementation examples

The present invention is described in detail below with examples, but the present invention is not limited thereto. In the following, the symbol "%" represents "mass %" unless otherwise specified. Examples 1 to 5, 7 to 11, 13 to 17, 19 to 23, 25 to 29, 42 to 49, 52 to 59, 61 to 65 are examples, and Examples 6, 12, 18, 24, 30 to 41, 50 to 51, 60, 66 to 67 are comparative examples.

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

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

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

(Durability 1 (Number of times a contact angle of 100° or more is maintained)) For the surface layer, a reciprocating friction tester (manufactured by KNT) was used at a pressure of 98.07 kPa and a speed of 320 cm/min to reciprocate Bonstar steel wool (#0000) according to JIS L0849:2013 (ISO 105-X12:2001). The water contact angle was measured every thousand reciprocations, and the upper limit of the number of times a water contact angle of 100° or more can be maintained (the number of times a contact angle of 100° or more is maintained) was calculated. 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 the Bonstar steel wool was reciprocated 3,000 times under the conditions of <Durability 1> above, the dynamic friction coefficient was measured under the same conditions as the <Lubricity> above. 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 material] (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 Preparation Example B-1 described later. (B-2): Composition (B-2) obtained in Preparation Example B-2 described later. (B-3): Compound (B-3) obtained in Preparation Example B-3 described later. (B-4): Compound (B-4) obtained in Preparation Example B-4 described later. (B-5): Compound (B-5) obtained in Preparation Example B-5 described later. (B-6): Used after diluting out the solvent of "2634 Coating" manufactured by Dow Corning Toray Co. Ltd. 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): A fluorinated ether compound represented by CF ₃ O{(CF ₂ O) _r1 (CF ₂ CF ₂ O) _r2 }CF ₃ (r1/r2=20/21) (“FOMBLIN M03” manufactured by Solvay Solexis).

The repeating units of the poly(oxyperfluoroalkylene) chains, the number of poly(oxyperfluoroalkylene) chains (hereinafter also referred to as the number of PEPE), the number of groups (I) and the number average molecular weight (Mn) of the aforementioned (A-1) to (A-5), (B-1) to (B-5) and (C-1) are listed in Table 1. In addition, the repeating unit "(CF ₂ O)(CF ₂ CF 2 O)" in (A-1) to (A-5) and (C-1) represents a poly(oxyperfluoroalkylene) chain composed of a random arrangement of (CF ₂ O) units and (CF ₂ CF ₂ O) _units .

[Table 1]

[Preparation Example A-1] In a 300 mL three-necked flask, 24.4 g of 24% KOH aqueous solution, 33 g of tertiary butanol, 220 g of compound (1) (manufactured by Solvay Solexis, FLUOROLINK (registered trademark) D4000) and 19.4 g of CF ₃ CF ₂ CF ₂ -O-CF=CF ₂ (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. The mixture was stirred at 60°C for 8 hours under a nitrogen atmosphere. The organic phase was recovered after washing once with a dilute hydrochloric acid aqueous solution and then concentrated with an evaporator to obtain 233 g of a crude product. The crude product was developed on a silica gel column chromatograph for fractionation. The developing solvents used were 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), and AE-3000/ethyl acetate = 9/1 (mass ratio). For each fraction, the structure of the terminal group and the average value of the number of units (x1, x2) of the constituent units were determined from the integrated values of ¹ H-NMR and ¹⁹ F-NMR. It was found that the crude product contained 42 mol% of compound (2), 49 mol% of compound (3), and 9 mol% of compound (1), respectively. 98.6 g (yield: 44.8%) of compound (2) and 51.9 g (yield: 23.6%) of compound (3) were obtained. HO-CH ₂ -(CF ₂ O){(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 }-CF ₂ -CH ₂ -OH…(1) 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): 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 4,150. Compound (3): average value of unit number x1 is 21, average value of unit number x2 is 20, 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, 30 g of dichloropentafluoropropane (AK-225, manufactured by Asahi Glass Co., Ltd.), and 3.5 g of CF ₃ CF ₂ CF ₂ OCF(CF ₃ )COF were added. The mixture was stirred at 50°C for 24 hours under a 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 gel column. The recovered solution was concentrated with a distillation device to obtain 31.8 g (yield 98.8%) of compound (4). 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): average value of the number of units x1 is 21, average value of the number of units x2 is 20, number average molecular weight is 4,460.

A cooler maintained at 20°C, a NaF pellet packing layer and a cooler maintained at 0°C were installed in series at the gas outlet of a 1L _nickel autoclave. A liquid return line was also installed to return the condensed liquid from the cooler maintained at 0°C to the autoclave. 750g _{of ClCF2CFClCF2OCF2CF2Cl} (hereinafter also referred to as _CFE -419) was added to the autoclave and maintained at 25°C with stirring. After nitrogen was sprayed into the autoclave at 25°C for 1 hour, 20% fluorine gas was sprayed at 25°C and a flow rate of 2.0L/hour for 1 hour. While blowing 20% fluorine gas at the same flow rate, a solution of 31.0 g of compound (4) dissolved in 124 g of CFE-419 was injected into the autoclave over a period of 4.3 hours. While blowing 20% fluorine gas at the same flow rate, the pressure inside the autoclave was increased to 0.15 MPa (gauge pressure). While heating the autoclave from 25°C to 40°C, 4 mL of a benzene solution containing 0.05 g/mL of benzene in CFE-419 was injected, and then the benzene solution injection port of the autoclave was closed. After stirring for 15 minutes, 4 mL of benzene solution was injected again while maintaining 40°C, and then the injection port was closed. The same operation was repeated 3 more times. The total amount of benzene injected was 0.17 g. 20% fluorine gas was purged at the same flow rate and stirring was continued for 1 hour. The pressure in the autoclave was brought to atmospheric pressure and nitrogen was purged for 1 hour. The contents of the autoclave were concentrated with a distillation vessel to obtain 31.1 g (yield 98.5%) of compound (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): average value of unit number x1 is 21, average value of unit number x2 is 20, number average molecular weight is 4,550.

In a round-bottom flask made of tetrafluoroethylene-perfluoro(alkoxyvinyl ether) copolymer (hereinafter also referred to as PFA), 30.0 g of compound (5) and 60 g of AK-225 were placed. The mixture was cooled in an ice bath and stirred at the same time, and 2.0 g of methanol was slowly dropped 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) Compound (6): the average value of the unit number x1 is 21, the average value of the unit number x2 is 20, and the number average molecular weight is 4,230.

In a 100 mL three-necked eggplant flask, 0.18 g of lithium chloride was dissolved in 18.3 g of ethanol. 25.0 g of compound (6) was added thereto, and the mixture was cooled in an ice bath while a solution of 0.75 g of sodium borohydride dissolved in 22.5 g of ethanol was slowly dropped. The ice bath was removed, and the temperature was slowly raised to room temperature while continuously stirring. After stirring at room temperature for 12 hours, an aqueous hydrochloric acid solution was dropped until the liquid became acidic. 20 mL of AC-2000 was added, and the organic phase was recovered after washing once with water and once with saturated saline. 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 value of the unit number x1 is 21, the average value of the unit number x2 is 20, and the number average molecular weight is 4,200.

In a 100 mL two-necked eggplant-shaped flask, 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 a 30% aqueous sodium hydroxide solution, and stir at 60°C for 8 hours. After the reaction is complete, add 20 g of AC-2000, wash once with a dilute aqueous hydrochloric acid solution, and then recover the organic phase. Pass the recovered organic phase through a silica gel column and concentrate the recovered solution with a distillation device 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 value of the unit number x1 is 21, the average value of the unit number x2 is 20, and the number average molecular weight is 4,250.

In a 100 mL PFA eggplant flask were placed 5.0 g of compound (8), 0.005 g of a xylene solution of platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), 0.25 g of HSi(OCH ₃ ) ₃ , 0.005 g of dimethyl sulfoxide and 0.20 g of 1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Chemical Industry Co., Ltd.), and the mixture was stirred at 40° C. for 4 hours. After the reaction was completed, the pressure was reduced and the solvent was distilled off. The mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 4.9 g (yield 95%) of composition (A-1). The composition (A-1) was composed of a compound (9) in which one allyl group of compound (8) was hydrosilylated, and a byproduct of an internal olefin (-CH=CHCH ₃ ) isomerized to one allyl group of compound (8). The conversion rate of hydrosilylation was 100%, and no compound (8) remained. The selectivity of hydrosilylation was 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 (300.4 MHz, solvent: CDCl ₃ , reference: TMS) δ (ppm): 0.7 (6H), 1.7 (6H), 3.6 (11H), 3.8 (2H). ¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: C ₆ F ₆ ) δ (ppm): -52.4 to -55.8 (42F), -78.2 (1F), -80.2 (1F), -82.2 (3F), -89.4 to -91.1 (90F), -130.5 (2F). Average value of unit number x1: 21, average value of unit number x2: 20, number average molecular weight of compound (9): 4,370.

[Preparation Example A-2] In a 100 mL two-necked eggplant-shaped flask, 20.0 g of the compound (7) obtained in Preparation Example A-1, 20.0 g of 1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.01 g of CF ₃ SO ₂ Cl (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.00 g of triethylamine were placed and stirred at room temperature for 4 hours under a nitrogen atmosphere. After the reaction was completed, 15 g of AK-225 was added, and the organic phase was recovered after washing with water and saturated saline once each. The recovered organic phase was concentrated with a distillation device 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 value of the unit number x1 is 21, the average value of the unit number x2 is 20, and the number average molecular weight is 4,340.

In a 50 mL eggplant-shaped flask, 15.0 g of compound (10), 15.0 g of 1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.27 g of HN(CH ₂ CH=CH ₂ ) ₂ (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.68 g of triethylamine were placed and stirred at 90°C for 24 hours under a nitrogen atmosphere. After the reaction was completed, 15 g of AK-225 was added, and the mixture was washed once with water and saturated salt water, and the organic phase was recovered. It was then mixed with 1.5 g of silica gel and filtered with a filter to recover the organic phase. The recovered organic phase was concentrated with a distillation device 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 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 4,280.

In a 100 mL PFA eggplant flask were placed 12.0 g of compound (11), 0.03 g of a xylene solution of a platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), 1.3 g of HSi(OCH ₃ ) ₃ , 0.01 g of dimethyl sulfoxide and 0.5 g of 1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Chemical Industry Co., Ltd.), and the mixture was stirred at 40° C. for 10 hours. After the reaction was completed, the pressure was reduced and the solvent was distilled off. The mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 11.9 g (yield 92%) of composition (A-2). The composition (A-2) was composed of compound (12) in which two allyl groups of compound (11) were silanized, and byproducts generated by intramolecular cyclization of two allyl groups of compound (11). The conversion rate of silanization was 100%, and no compound (11) remained. The selectivity of silanization was 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 (300.4 MHz, solvent: CDCl ₃ , reference: TMS) δ (ppm): 0.7 (4H), 1.6 (4H), 2.6 (4H), 3.1 (2H), 3.6 (18H). ¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -52.4 to -55.7 (42F), -74.4 (1F), -76.6 (1F), -82.2 (3F), -89.4 to -91.1 (90F), -130.5 (2F). Average value of unit number x1: 21, average value of unit number x2: 20, number average molecular weight of compound (12): 4,530.

[Preparation Example A-3] 5.0 g of the compound (6) obtained in Preparation 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 the compound (6) was completely converted into the compound (13). In addition, methanol was generated as a by-product. The obtained 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 the 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.

In a 10 mL PFA sample tube were placed 4 g of compound (13), 0.4 mg of a xylene solution of a platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), 0.33 g of HSi(OCH ₃ ) ₃ , 0.01 g of dimethyl sulfoxide, and 0.2 g of 1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 40°C for 10 hours. After the reaction was completed, the pressure was reduced to distill off the solvent and the mixture was filtered through a membrane filter with a pore size of 1.0 μm to obtain 4.3 g of compound (A-3) (yield 100%). 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 (300.4 MHz, solvent: CDCl ₃ , reference: TMS) δ (ppm): 0.75 (6H), 1.3~1.6 (12H), 3.4 (2H), 3.7 (27H). ¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -52.4~-55.8 (42F), -82.2 (3F), -89.4~-91.1 (92F), -130.8 (2F). Average value of unit number x1: 21, average value of unit number x2: 20, number average molecular weight of compound (A-3): 4,720.

[Production Example A-4] In a 300 mL three-necked flask, place 15.0 g of dipentyletritol (manufactured by ACROS), 29.5 g of 48% NaOH aqueous solution, and 150 g of dimethyl sulfoxide. Heat to 40°C and add 39.5 g of 5-bromo-1-pentene (manufactured by Tokyo Chemical Industry Co., Ltd.), then stir for 4 hours. After washing once with a dilute hydrochloric acid aqueous solution, add 200 g of cyclopentyl methyl ether and recover the organic phase. Concentrate the recovered solution with a distillation device to obtain 29.4 g of a crude product. Develop the crude product on a silica gel column chromatograph to separate 5.3 g of compound (14) and 6.0 g of compound (15).

[Chemical formula 5]

In a 50 mL two-necked eggplant flask, place 1.0 g of compound (14), 0.4 g of 2,6-dimethylpyridine, and 5 g of AE-3000. Cool with an ice bath and stir at the same time, slowly drop 0.5 g of trifluoromethanesulfonic anhydride in a nitrogen atmosphere. After further stirring for 1 hour, wash once with a dilute hydrochloric acid aqueous solution and recover the organic phase. Concentrate the recovered solution with a distillation device to obtain a crude product. Develop the crude product on a silica gel column chromatograph and fractionate 1.2 g of compound (16) in which the HO- of compound (14) is converted to CF ₃ SO ₃ -.

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 Preparation Example 6 of International Publication No. 2015/087902, 2.7 g of cesium carbonate, and 6.6 g of 1,3-bis(trifluoromethyl)benzene were placed and stirred at 80°C for 4 hours under reflux conditions. After adding 10 g of AE-3000, the mixture was washed once with a dilute hydrochloric acid aqueous solution and the organic phase was recovered. The recovered solution was concentrated with a distillation device to obtain a crude product. The crude product was developed on a silica gel column chromatograph to separate out 6.6 g of compound (18) in which CF ₃ SO ₃ - of compound (16) was converted into CF ₃ CF ₂ CF ₂ O{(CF ₂ O) _m21 (CF ₂ CF ₂ O) _m22 }CF 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 PFA flask, 6.0 g of compound (18), 0.03 g of a xylene solution of a platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), 1.2 g of trimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.01 g of dimethyl sulfoxide and 0.9 g of 1,3-bis(trifluoromethyl)benzene were placed and stirred at 40°C for 4 hours. The solvent was distilled off under reduced pressure and filtered through a membrane filter with a pore size of 0.2 μm to obtain 6.4 g of compound (A-4) in which the five allyl groups of compound (18) were hydrosilylated. The conversion rate of hydrosilylation was 100%, and no compound (18) remained. The selectivity of hydrosilylation was 100%. Here, compound (A-4) is a compound wherein WR ^51a - of the aforementioned compound (A13-3) is a group represented by formula (R ^f -1).

[Production Example A-5] Compound (19) in which two HO- in compound (15) were completely converted to CF 3 SO _{3 -} was obtained in the same manner as in Production Example A-4 except that compound (15) obtained in Production Example A-4 was used instead of compound (14). Next, compound (20) in which two CF ₃ SO ₃ - in compound (19) were completely converted to CF ₃ CF ₂ CF _{2 O} {(CF 2 O) _m21 (CF ₂ CF ₂ O) m22 }CF ₂ - CH _{2 -O-} was obtained in the same manner as in Production Example A-4 (3) except that compound (19) was used instead of compound (16). Next, compound (A-5 ₎ in which four allyl groups _in compound (20) were hydrosilylated was obtained in the same manner as in Production Example A-4 except that compound (20) was used instead of compound (18). 6.4 g of compound (A-5) was obtained. Here, the compound (A-5) is a compound in which WR ^51a - in the aforementioned compound (A13-4) is a group represented by the 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 . CF3 _- O-( _{CF2CF2O -} CF2CF2CF2CF2O ₎ x3 ₍ CF2CF2O _{) -CF2CF2CF2} -CONHCH2CH2CH2 _{- Si (} OCH3) ₃ …(B-1) Compound (B- ₁ ): average value of the number of units x3 _{was 13} , and the number average molecular weight _was 4,870.

[Preparation Example B-2] Compound (21) was obtained according to the method described in Example 7 of International Publication No. 2013/121984. CF3 _{- O- (} CF2CF2O _- CF2CF2CF2CF2O) _x3 ( _{CF2CF2O ) -CF2CF2CF2 -} CH2OH ( ₂₁ ) Compound (21): average value of _the number of units x3 is 13, _number average molecular weight _{is 4,700} .

30.6 g (yield 99%) of compound (22) was obtained in the same manner as in Production Example A-2 except that compound (7) was replaced by 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. 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): average value of the number of units x3 is 13, number average molecular weight is 4,830.

Compound (23) (14.6 g, yield 98%) was obtained in the same manner as in Preparation Example A- ₂ except that compound (10) was replaced by compound (22), the amount of HN(CH ₂ CH=CH ₂ ) 2 was changed to 2.08 g, and the amount of triethylamine was changed to 0.63 g. 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): average value of number of units x3: 13, number average molecular weight: 4,780.

11.8 g (yield 94%) of composition (B-2) was obtained in the same manner as in Preparation Example A-2 except that compound (11) was replaced by compound ( ₂₃ ), the amount of platinum complex solution was changed to 0.029 g, and the amount of HSi(OCH 3 ) ₃ was changed to 1.2 g. The composition (B-2) consisted of compound (24) in which two allyl groups of compound (23) were silylated, and byproducts generated by intramolecular cyclization of two allyl groups of compound (23). The conversion rate of silylation was 100%, and no compound (23) remained. The selectivity of silylation was 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 (300.4 MHz, solvent: CDCl ₃ , reference: TMS) δ (ppm): 0.7 (4H), 1.6 (4H), 2.6 (4H), 3.2 (2H), 3.6 (18H). ¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: C ₆ F ₆ ) δ (ppm): -56.3 (3F), -84.0 (54F), -89.2 (54F), -91.4 (2F) -120.9 (2F), -126.6 (54F). Average value of number of units x 3: 13, number average molecular weight of compound (24): 5,020.

[Preparation Example B-3] Compound (25) was obtained according to the method described in Example 6 of International Publication No. 2013/121984. CF3 _- O-( _{CF2CF2O- CF2CF2CF2CF2O ) x3} ( _{CF2CF2O )} -CF2CF2CF2 _{- C (} O _{) OCH3} ( ₂₅ ) Compound (25): average value of the number of units x3 is 13, _number average molecular weight is 4,700.

Compound (26) 7.6 g (yield 84%) was obtained in the same manner as in Production Example A-3 except that compound (6) was replaced by _compound (25) 9.0 g and the amount of H ₂ N-CH ₂ -C(CH 2 CH=CH ₂ ) ₃ was replaced by 0.45 g. 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): average value of the number of units x3 was 13, number average molecular weight was 4,800.

6.7 g (yield 100%) of compound (B- ₃ ) was obtained in the same manner as in Production Example A-3 except that compound (13) was replaced with 6.0 g of compound (26), the amount of platinum complex solution was changed to 0.07 g, the amount of HSi(OCH 3 ) ₃ was changed to 0.78 g, the amount of dimethyl sulfoxide was changed to 0.02 g, and the amount of 1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was changed to 0.49 g. 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 (300.4 MHz, solvent: CDCl ₃ , reference: TMS) δ (ppm): 0.75 (6H), 1.3~1.6 (12H), 3.4 (2H), 3.7 (27H). ¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -55.2 (3F), -82.1 (54F), -88.1 (54F), -90.2 (2F), -119.6 (2F), -125.4 (52F), -126.2 (2F). Average value of unit number x3: 13, number average molecular weight of compound (B-3): 5,400.

[Production Example B-4] Compound (28) in which CF 3 SO 3 - of compound (16) was converted to CF 3 O (CF 2 CF 2 OCF 2 CF 2 CF 2 CF 2 O) m25 CF ₂ CF 2 OCF ₂ CF 2 CF ₂ -CH ₂ -O- was obtained in the same manner as in Production Example A-4, except that compound (27) (average value of m25: 13, number average molecular _{weight : 4,700} ) obtained by _the method described in Example _{7 of International Publication No.} 2013/121984 instead of compound (17) _was used. Next _, 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, except that compound (28) was used instead of compound (18). 6.3 g of the compound (B-4) was obtained. CF ₃ O(CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) _m25 CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ -CH ₂ -OH (27) Here, compound (B-4) is a compound wherein WR ^51a - of the aforementioned compound (A13-3) is a group represented by formula (R ^f -3).

[Production Example B-5] Compound (29) in which two CF ₃ SO ₃ - in compound (19) were completely converted to CF _{3 CF 2} CF 2 O{(CF ₂ O) m21 (CF ₂ CF ₂ O) _m22 }CF ₂ - CH _{2 -O-} was obtained in the same manner as _in Production Example A-5 except that compound (27) _was used instead of compound (17). Next, compound (B-5) 6.1 g in which four allyl groups in compound (29) were hydrosilylated was obtained in the same manner as in Production Example A-4 except that compound (29) was used instead of compound (18). Compound (B-5) is a compound in which WR ^51a - in compound (A13-4) is a group represented by formula (R ^f -3).

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

(Dry coating method) Dry coating is performed using a vacuum evaporation device (Showa Vacuum Co., Ltd., SGC-22WA) (vacuum evaporation method). After filling 35 mg of the composition into a molybdenum boat in the vacuum evaporation device, the vacuum evaporation device is vented to below 5×10 ^-3 Pa. The boat with the composition is heated to deposit the composition on the surface of the substrate to form an evaporation film on the surface of the substrate. The substrate with the evaporation film formed is placed overnight at a temperature of 25°C and a humidity of 40% to obtain an article having a surface layer on the surface of the substrate.

[Examples 2-40] Except that the types and combinations of the compounds used were changed to those shown in Table 2, the composition was prepared and the surface layer was formed in the same manner as in Example 1 to produce and evaluate the obtained articles. In the case of combining two compounds, the mass ratio of each compound was 50:50. The results are shown 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 of reducing the dynamic friction coefficient) [Table 5]

The compositions of Examples 1 to 5, 7 to 11, 13 to 17, 19 to 23, and 25 to 29 in which Compound (A) and Compound (B) are combined have better durability and lubricity than the compositions of Examples 36 to 40 in which Compound (B) and Compound (C-1) without Group (I) are combined. Moreover, the compositions of Examples 31 to 35 in which Compound (B) is used alone have better lubricity. In addition, as the number of Groups (I) possessed by Compound (A) and Compound (B) increases, the durability tends to be improved.

(Examples 41-50) 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 the surface layer of the substrate was formed by the aforementioned dry coating method to produce an article, and the obtained article was evaluated. The results are shown in Table 6. In addition, each composition was used to treat the surface of the substrate by the following wet coating method to produce an article. The substrate used was chemically strengthened glass. The durability 1 and lubricity of the obtained article were evaluated. The results are shown in Table 7.

(Wet coating method) The compositions obtained in Examples 41 to 50 were mixed with C ₄ F ₉ OC ₂ H ₅ (3M, Novec (registered trademark) 7200) as a liquid medium to prepare a coating solution with a solid content of 0.05%. The substrate was immersed in the coating solution and left for 30 minutes before being 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 substrate surface.

[Table 6]

[Table 7]

(Examples 51-60) 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 surface layer of the substrate was formed by the aforementioned dry coating method to produce an article, and the obtained article was evaluated. The results are shown in Table 8.

[Table 8]

Compared with the case where each compound is used alone, the combined use of compound (A) and compound (B) can achieve both lubricity and durability at a higher level. When the mass ratio of compound (A)/compound (B) is in the range of 20/80~50/50, durability and lubricity are particularly good. Industrial applicability

This composition and this coating liquid can be used in various applications that require lubricity and water and oil repellency. For example, it can be used for display input devices such as touch panels; surface protection coatings for transparent glass or transparent plastic components, anti-fouling coatings for kitchens; water-repellent and moisture-proof coatings or anti-fouling coatings for electronic equipment, heat exchangers, batteries, etc., anti-fouling coatings for bathrooms; coatings for components that need to conduct and repel liquids at the same time; water-repellent, waterproof, and water-slip coatings for heat exchangers; low-friction coatings on the surfaces of vibrating screens or the inside of cylinders, etc. In addition, the entire contents of the specification, patent application scope and abstract of Japanese patent application No. 2017-050558 filed on March 15, 2017 are cited and incorporated as a disclosure of this invention specification.

Claims (13)

A fluorine-containing ether composition, characterized in that it contains a fluorine-containing ether compound (A) and a fluorine-containing ether compound (B); the fluorine-containing ether compound (A) is a compound having a poly(oxyperfluoroalkylene) chain containing a ( _CF2O ) unit and two or more groups represented by the following formula (I); the fluorine-containing ether compound (B) is a compound having a poly(oxyperfluoroalkylene) chain not containing a ( _CF2O ) unit and two or more groups represented by the above formula (I); at least one of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) has two groups represented by the above formula (I); -SiRnL3 _{- n} ... (I) However, L is a hydroxyl group or a hydrolyzable group; R is a hydrogen atom or a monovalent hydrocarbon group; n is an integer of 0 to 2; when n is 0 or 1, the (3-n) Ls may be the same or different; When n is 2, the n Rs may be the same or different; wherein the groups represented by the formula (I) possessed by the fluorinated ether compound (A) and the fluorinated ether compound (B) may be the same or different. The fluorinated ether composition of claim 1, wherein the fluorinated ether compound (A) and the fluorinated ether compound (B) are both fluorinated ether compounds represented by the following formula (A/B); ^Rf in the fluorinated ether compound (A) is a poly(oxyperfluoroalkylene) chain containing a ( _CF2O ) unit, and ^Rf in the fluorinated ether compound (B) is a poly(oxyperfluoroalkylene) chain not containing a ( _CF2O ) unit; [ ^Rf1 - ^OQRf- ] _rZ [ _{-SiRnL3 -n} ] _s ...(A/B) except that ^Rf1 is a perfluoroalkyl group; Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 oxyfluoroalkylene groups, and the oxyfluoroalkylene groups constituting the polyoxyfluoroalkylene group may be all the same or different; ^Rf 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; s groups represented by formula (I) are the same group; r is an integer greater than 1, s is an integer greater than 2, and r+s is 3-8. The fluorinated ether composition of claim 1 or 2, wherein the poly(oxyperfluoroalkylene) chain containing a (CF ₂ O) unit is a poly(oxyperfluoroalkylene) chain containing a (CF ₂ O) unit and a (CF ₂ CF ₂ O) unit. The fluorinated ether composition of claim 1 or 2, wherein the poly(oxyperfluoroalkylene) chain not containing a (CF ₂ O) unit is a poly(oxyperfluoroalkylene) chain containing at least one unit selected from the group consisting of a (CF ₂ 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. The fluorinated ether composition of claim 1 or 2, wherein the poly(oxyperfluoroalkylene) chain not containing a (CF ₂ O) unit is a poly(oxyperfluoroalkylene) chain containing a (CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) unit. The fluorinated ether composition of claim 1 or 2, wherein one of the fluorinated ether compound (A) and the fluorinated ether compound (B) has three or more groups represented by the aforementioned formula (I). The fluorinated ether composition of claim 1 or 2, wherein the number average molecular weight of the fluorinated ether compound (A) is 2,000-20,000. The fluorinated ether composition of claim 1 or 2, wherein the number average molecular weight of the fluorinated ether compound (B) is 2,000-20,000. The fluorinated ether composition of claim 1 or 2 contains 10-80 mass % of the fluorinated ether compound (A) relative to the total amount of the fluorinated ether compound (A) and the fluorinated ether compound (B). A fluorine-containing ether composition, characterized by comprising a fluorine-containing ether compound (A1) represented by the following formula (A1) and a fluorine-containing ether compound (B1) represented by the following formula (B1); [R ^f1a -OQ ^a -R ^fa -] _ra Z ^a [-SiR ^a _na L ^a _3-na ] _sa …(A1) [R ^f1b -OQ b -R ^fb -] _{rb Z} ^b [-SiR ^b _nb L ^b _3-nb ^] _sb …(B1) However, R ^f1a and R ^f1b are perfluoroalkyl groups; Q ^a and Q ^b are single bonds, oxyfluoroalkylene groups containing one or more hydrogen atoms, or polyoxyfluoroalkylene groups formed by bonding 2 to 5 oxyfluoroalkylene groups, and the oxyfluoroalkylene groups constituting the polyoxyfluoroalkylene groups may be all the same or different; R ^fa is a poly(oxyperfluoroalkylene) chain containing a (CF ₂ O) unit; R ^fb is a poly(oxyperfluoroalkylene) chain not containing a ( _CF2O ) unit; ^Za is a (ra+sa)-valent linking group; ^Zb is a (rb+sb)-valent linking group; ^La and ^Lb are hydroxyl groups or hydrolyzable groups; ^Ra and ^Rb are hydrogen atoms or monovalent hydrocarbon groups; na and nb are integers of 0 to 2; when na is 0 or 1, the (3-na) ^La and when nb is 0 or 1, the (3-nb) ^Lb may be the same or different; when na is 2, the na ^Ra and when nb is 2, the nb ^Rb may be the same or different; ra and rb are integers greater than 1; when ra is greater than 2, the ra [ ^Rf1a - ^OQa - ^Rfa- ] may be the same or different; when rb is greater than 2, the rb [ ^Rf1b - ^OQb - ^Rfb -] may be the same or different; sa and sb are integers greater than 2 and at least one of them is 2, the sa [-SiR ^a _na L ^a _3-na ] may be the same or different, and the sb [-SiR ^b _nb L ^b _3-nb ] may be the same or different. The fluorinated ether composition of claim 10 contains 10-80 mass % of the fluorinated ether compound (A1) relative to the total amount of the fluorinated ether compound (A1) and the fluorinated ether compound (B1). A coating liquid characterized by comprising the fluorine-containing ether composition of claim 1 or 10 and a liquid medium. An article with a surface layer, characterized in that it has a surface layer formed of the fluorine-containing ether composition as claimed in claim 1 or 10.