JP7743352B2 - Fluorine-containing ether compound, fluorine-containing ether composition, coating liquid, article, and method for producing the same - Google Patents

Description

The present invention relates to a fluorinated ether compound, a fluorinated ether composition, a coating liquid, an article, and a method for producing the same.

Fluorinated ether compounds having poly(oxyperfluoroalkylene) chains are suitable for use in surface treatment agents because they can form a surface layer on the surface of a substrate that exhibits high lubricity, water and oil repellency, etc. Surface treatment agents containing fluorinated ether compounds are used in applications where the surface layer must maintain its water and oil repellency (abrasion resistance) even when repeatedly rubbed with fingers, and the surface layer must be easily wiped clean (fingerprint removability) for a long period of time, such as surface treatment agents for components that make up the surfaces of touch panels that are touched by fingers, eyeglass lenses, and displays of wearable devices.

The following compounds have been proposed as fluorine-containing ether compounds capable of forming a surface layer on the surface of a substrate that is excellent in abrasion resistance and fingerprint removability.
Compounds represented by the following formula I (Patent Document 1).
CF ₃ O-(CF ₂ O) _p1 -(C ₂ F ₄ O) _q1 -CF ₂ -C(OH) [-CH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ ] ₂ Formula I
However, p1:p2=47:53, and p1+q1≈43.

Compounds represented by the following formula II, etc. (Patent Document 2).
CF ₃ O-(CF ₂ O) _p1 -(C ₂ F ₄ O) _q1 -CF ₂ -C[-O-CH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ ][-CH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ ] ₂ Formula II
Here, p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, and p1+q1 is an integer of 10 to 105.

Compounds represented by the following formula III (Patent Document 3).
CF ₃ O-(CF ₂ O) _p1 -(C ₂ F ₄ O) _q1 -CF ₂ -C[-O-Si(OCH ₃ ) ₃ ][-CH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ ] ₂ Formula III
Here, p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, and p1+q1 is an integer of 10 to 105.

Compounds represented by the following formula IV (Patent Document 4).
CF ₃ O-(CF ₂ O) _p1 -(C ₂ F ₄ O) _q1 -CF ₂ -C[-OC(O)-CH ₃ ][-CH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ ] ₂ Formula IV
Here, p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, and p1+q1 is an integer of 10 to 105.

Japanese Patent Application Laid-Open No. 2015-199906 Japanese Patent Application Laid-Open No. 2016-204656 JP 2016-210854 A JP 2016-222859 A

The compound described in Patent Document 1 has a highly reactive hydroxyl group, which generates by-products through side reactions and results in poor storage stability (see paragraph [0008] of Patent Document 3 and paragraph [0008] of Patent Document 4). Furthermore, the remaining hydroxyl groups reduce the water and oil repellency, chemical resistance, and other properties of the surface layer made of the compound described in Patent Document 1.
The compounds described in Patent Documents 2 to 4 are derivatives in which the hydroxyl group of the compound described in Patent Document 1 is protected with another group. However, the compounds described in Patent Documents 2 to 4 have an ether bond, a C—O—Si bond, or an ester bond derived from the hydroxyl group of the compound described in Patent Document 1. Since the ether bond, the C—O—Si bond, and the ester bond are easily cleaved by light, chemicals, etc., the surface layers made of the compounds described in Patent Documents 2 to 4 have poor light resistance and chemical resistance.

The present invention aims to provide a fluorine-containing ether compound capable of forming a surface layer excellent in initial water and oil repellency, fingerprint stain removability, abrasion resistance, light fastness and chemical resistance; a fluorine-containing ether composition and coating liquid containing the fluorine-containing ether compound; an article having a surface layer excellent in initial water and oil repellency, fingerprint stain removability, abrasion resistance, light fastness and chemical resistance, and a method for producing the same.
Another object of the present invention is to provide a fluorine-containing ether compound that is useful as an intermediate for a fluorine-containing ether compound that is suitably used in a surface treatment agent.

The present invention provides a fluorinated ether compound, a fluorinated ether composition, a coating liquid, an article, a method for producing an article, and other aspects of the fluorinated ether compound, each having the following structures [1] to [8].

[1] A fluorine-containing ether compound represented by the following formula 1:
A ¹ -O-(R ^f1 O) _m -A ² Formula 1
Here, A ¹ is a perfluoroalkyl group having 1 to 20 carbon atoms or a group represented by the following formula g1, A ² is a group represented by the following formula g1, R ^f1 is a fluoroalkylene group, m is an integer of 2 to 500, and (R ^f1 O) _m may be composed of two or more types of R ^f1 O having different numbers of carbon atoms.
-R ^f2 -Q ¹ -C(X) [-Q ² -SiR _n L _3-n ] ₂ formula g1
wherein R ^f2 is a fluoroalkylene group (at least one fluorine atom is bonded to the terminal carbon atom on the Q ¹ side), Q ¹ is a single bond or an alkylene group, X is a fluorine atom, a hydrogen atom, an alkyl group or a fluoroalkyl group, Q ² is an alkylene group, R is a monovalent hydrocarbon group, L is a hydrolyzable group, n is an integer of 0 to 2, and the two [-Q ² -SiR _n L _3-n ] may be the same or different.
[2] A fluorinated ether composition comprising at least one fluorinated ether compound according to [1] above and another fluorinated ether compound.
[3] A coating liquid comprising the fluorinated ether compound of [1] or the fluorinated ether composition of [2], and a liquid medium.
[4] An article having a surface layer formed from the fluorinated ether compound of [1] or the fluorinated ether composition of [2] on the surface of a substrate.
[5] The article according to [4], having the surface layer on the surface of a member that constitutes the surface of a touch panel that is touched by a finger.
[6] A method for producing an article, comprising treating the surface of a substrate by a dry coating method using the fluorinated ether compound of [1] above or the fluorinated ether composition of [2] above, and forming a surface layer formed from the fluorinated ether compound or the fluorinated ether composition on the surface of the substrate.
[7] A method for producing an article, comprising applying the coating liquid of [3] to a surface of a substrate by a wet coating method, followed by drying to form a surface layer formed from the fluorinated ether compound or the fluorinated ether composition on the surface of the substrate.
[8] A fluorine-containing ether compound represented by the following formula 2:
A ^1a -O-(R ^f1 O) _m -A ^2a Formula 2
Here, A ^1a is a perfluoroalkyl group having 1 to 20 carbon atoms or a group represented by the following formula g2, A ^2a is a group represented by the following formula g2, R ^f1 is a fluoroalkylene group, m is an integer of 2 to 500, and (R ^f1 O) _m may be composed of two or more types of R ^f1 O having different numbers of carbon atoms.
-R ^f2 -Q ¹ -C(X) [-Q ^2a -CH=CH ₂ ] ₂ formula g2
Here, R ^f2 is a fluoroalkylene group (provided that at least one fluorine atom is bonded to the terminal carbon atom on the Q ¹ side), Q ¹ is a single bond or an alkylene group, X is a fluorine atom, a hydrogen atom, an alkyl group or a fluoroalkyl group, Q ^2a is a single bond or an alkylene group, and the two [-Q ^2a -CH═CH ₂ ]s may be the same or different.

The fluorine-containing ether compound of the present invention can form a surface layer that is excellent in initial water and oil repellency, fingerprint stain removability, abrasion resistance, light resistance and chemical resistance.
The fluorine-containing ether composition of the present invention can form a surface layer that is excellent in initial water and oil repellency, fingerprint stain removability, abrasion resistance, light resistance and chemical resistance.
The coating liquid of the present invention can form a surface layer that is excellent in initial water and oil repellency, fingerprint stain removability, abrasion resistance, light resistance, and chemical resistance.
The article of the present invention has a surface layer that is excellent in initial water and oil repellency, fingerprint stain removability, abrasion resistance, light resistance and chemical resistance.
According to the method for producing an article of the present invention, an article can be produced having a surface layer that is excellent in initial water and oil repellency, fingerprint stain removability, abrasion resistance, light resistance, and chemical resistance.
Another embodiment of the fluorine-containing ether compound of the present invention is useful as an intermediate for fluorine-containing ether compounds that are suitably used in surface treatment agents.

In this specification, the compound represented by formula 1 will be referred to as compound 1. Compounds represented by other formulas will also be referred to in the same manner.
In addition, a group represented by formula g1 will be referred to as group g1. Groups represented by other formulas will be similarly referred to.
The chemical formula of an oxyfluoroalkylene unit shall be represented by writing the oxygen atom to the right of the fluoroalkylene group.
As used herein, the following terms have the following meanings:
The term "hydrolyzable silyl group" refers to a group that can form a silanol group (Si-OH) by hydrolysis, and is represented by SiR _n L _3-n in formula g1.
The term "surface layer" refers to a layer formed on the surface of a substrate.
The "number average molecular weight" of a fluorinated ether compound is calculated by determining the number (average value) of oxyperfluoroalkylene groups based on the number of terminal groups by ^1H -NMR and ^19F -NMR. The terminal groups are, for example, ^A1 in Formula 1 or _{SiRnL3 -n} in Formula g1.
The use of "to" to indicate a range of values means that the values before and after it are included as the lower and upper limits.

[Fluorine-containing ether compound]
The fluorine-containing ether compound of the present invention is Compound 1.
A ¹ -O-(R ^f1 O) _m -A ² Formula 1
Here, A ¹ is a perfluoroalkyl group having 1 to 20 carbon atoms or group g1, A ² is group g1, R ^f1 is a fluoroalkylene group, m is an integer of 2 to 500, and (R ^f1 O) _m may be composed of two or more types of R ^f1 O having different numbers of carbon atoms.
-R ^f2 -Q ¹ -C(X) [-Q ² -SiR _n L _3-n ] ₂ formula g1
wherein R ^f2 is a fluoroalkylene group (at least one fluorine atom is bonded to the terminal carbon atom on the Q ¹ side), Q ¹ is a single bond or an alkylene group, X is a fluorine atom, a hydrogen atom, an alkyl group or a fluoroalkyl group, Q ² is an alkylene group, R is a monovalent hydrocarbon group, L is a hydrolyzable group, n is an integer of 0 to 2, and the two [-Q ² -SiR _n L _3-n ] may be the same or different.

A ¹ is preferably a perfluoroalkyl group having 1 to 20 carbon atoms, since the lubricity and abrasion resistance of the surface layer are even more excellent. In compound 1 where A ¹ is a perfluoroalkyl group, A ¹ has a CF ₃ - at its terminal, so one terminal of compound 1 is CF ₃ - and the other terminal is a hydrolyzable silyl group. Compound 1 where one terminal is CF ₃ - and the other terminal is a hydrolyzable silyl group can form a surface layer with low surface energy, so the lubricity and abrasion resistance of the surface layer are even more excellent. On the other hand, compound 1 where A ¹ is group g1 has hydrolyzable silyl groups at both terminals, so the lubricity and abrasion resistance of the surface layer are somewhat insufficient.
The number of carbon atoms in the perfluoroalkyl group of ^A1 is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 3, in order to further improve the lubricity and abrasion resistance of the surface layer formed by compound 1.

The number of carbon atoms in R ^f1 is preferably 1 to 6, since this provides the surface layer with even better abrasion resistance and fingerprint removability.
R ^f1 is preferably a linear fluoroalkylene group, as this provides the surface layer with even better abrasion resistance and lubricity.
^Rf1 is preferably a perfluoroalkylene group, as this provides the surface layer with even better abrasion resistance and lubricity.
The proportion of perfluoroalkylene groups in all R ^f1 is preferably 60 mol % or more, more preferably 80 mol % or more, and particularly preferably 100 mol %, in order to provide a surface layer with even better abrasion resistance and lubricity.

m is preferably an integer between 2 and 200, more preferably an integer between 5 and 150, and particularly preferably an integer between 10 and 100. When m is equal to or greater than the lower limit of the above range, the water and oil repellency of the surface layer is even better. When m is equal to or less than the upper limit of the above range, the abrasion resistance of the surface layer is even better. In other words, if the number average molecular weight of compound 1 is too large, the number of hydrolyzable silyl groups present per unit molecular weight decreases, and the abrasion resistance of the surface layer decreases.

When two or more types of R f1 O are present in (R ^f1 O) _{m , the bonding order of each R f1 O is not limited. For example, when CF 2 O and CF 2 CF 2} ^O _{are present} ^, CF ₂ O and CF ₂ CF ₂ O may be arranged randomly, alternately, or in blocks.
The presence of two or more types of R ^f1 O means that there are two or more types of R ^f1 O with different numbers of carbon atoms, that there are two or more types of R ^f1 O with different numbers of hydrogen atoms, that there are two or more types of R ^f1 O with different positions of hydrogen atoms, and that there are two or more types of R ^f1 O with the same number of carbon atoms but different in the presence or absence of side chains or the type of side chain (the number of side chains, the number of carbon atoms in the side chain, etc.).
Regarding the arrangement of two or more types of R ^f1 O, for example, a structure represented by {(CF ₂ O) _m1 (CF ₂ CF ₂ O) _m2 } means that m1 (CF ₂ O)s and m2 (CF ₂ CF ₂ O)s are randomly arranged, and a structure represented by (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _m5 means that m5 (CF ₂ CF ₂ O)s and m5 (CF ₂ CF ₂ CF ₂ CF ₂ O)s are alternately arranged.

As (R ^f1 O) _m , those having the following structure in at least a part of (R ^f1 O) _m are preferred.
{(CF ₂ O) _m1 (CF ₂ CF ₂ O) _m2 },
(CF ₂ CF ₂ O) _m3 ,
(CF ₂ CF ₂ CF ₂ O) _m4 ,
(CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _m5 ,
(CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) _m6 (CF ₂ O) _m7 ,
(CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) _m6 (CF ₂ CF ₂ O) _m7 ,
(CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) _m6 (CF ₂ O) _m7 ,
_{( CF2CF2CF2CF2CF2CF2O ) m6 ( CF2CF2O ) m7 , ​}
(CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O-CF ₂ O) _m8 ,
(CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O-CF ₂ CF ₂ O) _m8 ,
(CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O-CF ₂ O) _m8 ,
(CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O-CF ₂ CF ₂ O) _m8 ,
(CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) _m8 ,
(CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) _m8 ,
(CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) _m8 ,
(CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) _m8 .
Here, m1 is an integer of 1 or more, m2 is an integer of 1 or more, m1+m2 is an integer of 2 to 500, m3 and m4 are each an integer of 2 to 500, m5 is an integer of 1 to 250, m6 and m7 are each an integer of 1 or more, m6+m7 is an integer of 2 to 500, and m8 is an integer of 1 to 250.

As (R ^f1 O) _m , the following are preferred in terms of ease of production of Compound 1.
{(CF ₂ O) _m1 (CF ₂ CF ₂ O) _m2 },
(CF ₂ CF ₂ CF ₂ O) _m4 ,
(CF ₂ CF ₂ O) ₂ {(CF ₂ O) _m1 (CF ₂ CF ₂ O) _m2-2 },
(CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _m5-1 CF ₂ CF ₂ O,
(CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O-CF ₂ O) _m8 ,
(CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O-CF ₂ O) _m8 ,
(CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) _m8-1 CF ₂ CF ₂ O,
_{( CF2CF2O - CF2CF2CF2CF2CF2CF2CF2O ) m8-1 CF2CF2O . ​ ​ ​}
However, the numbers m2, m5 and m8 are selected so that m2-2, m5-1 and m8-1 are integers of 1 or greater.

The number of carbon atoms in R ^f2 is preferably 1 to 8, more preferably 1 to 6, and particularly preferably 1 to 5, in order to provide a surface layer with even better abrasion resistance and fingerprint removability.
^Rf2 is preferably a linear fluoroalkylene group, as this provides the surface layer with even better abrasion resistance and lubricity.
^Rf2 is preferably a perfluoroalkylene group, as this provides the surface layer with even better abrasion resistance and lubricity.
The structure of R ^f2 depends on the raw material and synthesis method used to produce compound 1.

The alkylene group of ^Q1 preferably has 1 to 6 carbon atoms.
^Q1 is preferably a single bond, since compound 1 can be easily produced and the surface layer has better abrasion resistance, light resistance, and chemical resistance.

X is, for example, a group in which a hydroxyl group of Compound 4 described below is substituted with a fluorine atom, a hydrogen atom, an alkyl group, or a fluoroalkyl group. When X is a fluoroalkyl group, X is preferably a perfluoroalkyl group, since the surface layer will have even better abrasion resistance, light resistance, and chemical resistance.
The alkyl group or fluoroalkyl group of X preferably has 1 to 6 carbon atoms.
X is preferably a fluorine atom, since compound 1 can be easily produced and the surface layer has better abrasion resistance, light resistance and chemical resistance.

The number of carbon atoms in ^Q2 is preferably 1 to 10, more preferably 2 to 6, and particularly preferably 2 to 4, from the viewpoints of ease of production of compound 1 and further superior abrasion resistance, light resistance, and chemical resistance of the surface layer.

SiR _n L _3-n is a hydrolyzable silyl group.
Compound 1 has two hydrolyzable silyl groups at at least one end. Compound 1 having two or more hydrolyzable silyl groups at its ends forms a strong chemical bond with the substrate, resulting in a surface layer with excellent abrasion resistance.
It is also preferable that Compound 1 has a hydrolyzable silyl group at only one end. Compound 1 having a hydrolyzable silyl group at only one end is less likely to aggregate, and therefore the surface layer has an excellent appearance.

L is a hydrolyzable group. A hydrolyzable group is a group that becomes a hydroxyl group through a hydrolysis reaction. That is, Si-L at the end of compound 1 becomes a silanol group (Si-OH) through a hydrolysis reaction. The silanol group further reacts with other molecules to form an Si-O-Si bond. The silanol group also undergoes a dehydration condensation reaction with hydroxyl groups (substrate-OH) on the surface of the substrate to form a chemical bond (substrate-O-Si).

Examples of L include an alkoxy group, a halogen atom, an acyl group, and an isocyanate group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms. The halogen atom is particularly preferably a chlorine atom.
L is preferably an alkoxy group or a halogen atom from the viewpoint of ease of production of Compound 1. L is preferably an alkoxy group having 1 to 4 carbon atoms from the viewpoint of less outgassing during coating and excellent storage stability of Compound 1, an ethoxy group is particularly preferred when long-term storage stability of Compound 1 is required, and a methoxy group is particularly preferred when the reaction time after coating is to be short.

R is a monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, and an allyl group.
R is particularly preferably a monovalent saturated hydrocarbon group. The number of carbon atoms in the monovalent saturated hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2. When the number of carbon atoms in R is within this range, compound 1 can be easily produced.

n is preferably 0 or 1, and particularly preferably 0. The presence of multiple Ls in one hydrolyzable silyl group strengthens adhesion to the substrate.

Preferred examples of SiR _n L _3-n include 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 ease of handling in industrial production, Si(OCH ₃ ) ₃ is particularly preferred.
The two SiR _n L _3-n in the compound 1 may be the same or different, but are preferably the same group in terms of ease of production of the compound 1.

Examples of Compound 1 include Compounds 1-1 to 1-7. The compounds of the formula below are preferred because they are easy to produce industrially, easy to handle, and provide a surface layer with even better water and oil repellency, abrasion resistance, fingerprint stain removability, lubricity, chemical resistance, light resistance, and chemical resistance.

However, G is a polyfluoropolyether chain, i.e., A-O-(R ^f1 O) _m -R ^f2 - (where A is a perfluoroalkyl group having 1 to 20 carbon atoms) when compound 1 has a hydrolyzable silyl group at one end, and -R ^f2 -O-(R ^f1 O) _m -R ^f2 - when compound 1 has hydrolyzable silyl groups at both ends. A preferred form of G is a combination of the above-mentioned preferred A ¹ , (R ^f1 O) _m and R ^f2 .

(Method for producing compound 1)
Compound 1 can be produced by a method of subjecting compound 2 to a hydrosilylation reaction with HSiR _n L _3-n .
A ^1a -O-(R ^f1 O) _m -A ^2a Formula 2
Here, A ^1a is a perfluoroalkyl group having 1 to 20 carbon atoms or group g2, and A ^2a is group g2.
-R ^f2 -Q ¹ -C(X) [-Q ^2a -CH=CH ₂ ] ₂ formula g2
Here, Q ^2a is a single bond or an alkylene group, and the two [-Q ^2a -CH═CH ₂ ] groups may be the same or different.
(R ^f1 O) _m , R ^f2 , Q ¹ and X are the same as (R ^f1 O) _m , R ^f2 , Q ¹ and X described in Compound 1, and preferred forms are also the same.

A ^1a is preferably a perfluoroalkyl group having 1 to 20 carbon atoms, as this provides a surface layer with even better lubricity and abrasion resistance.
The number of carbon atoms in the perfluoroalkyl group for A ^1a is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 3, in terms of further improving the lubricity and abrasion resistance of the surface layer.

Q ^2a is preferably a single bond or an alkylene group having 1 to 4 carbon atoms, particularly preferably a single bond or an alkylene group having 1 to 2 carbon atoms, from the viewpoints of ease of production of compound 2 and of further improving the abrasion resistance, light resistance, and chemical resistance of the surface layer.
Q ^2a -CH═CH ₂ becomes Q ² in group g1 after hydrosilylation.

(Method for producing compound 2)
When X in formula g1 of compound 1 is a fluorine atom, compound 2 can be produced, for example, as follows.
Compound 4 is obtained by reacting compound 3 (wherein A is a perfluoroalkyl group having 1 to 20 carbon atoms) with a Grignard reagent (CH _{2 ═CH} —Q ^2a -MgBr or CH ₂ ═CH—Q ^2a -MgCl).
A-O-(R ^f1 O) _m -R ^f2 -Q ¹ -C(O)Z Formula 3
A-O-(R ^f1 O) _m -R ^f2 -Q ¹ -C(OH) [-Q ^2a -CH=CH ₂ ] ₂ Formula 4

Compound 4 is reacted with a nucleophilic fluorinating agent to give compound 2a.
A-O-(R ^f1 O) _m -R ^f2 -Q ¹ -CF[-Q ^2a -CH=CH ₂ ] ₂ Formula 2a
Here, Z is a fluorine atom, a chlorine atom, an acyloxy group, an alkoxy group, a hydroxyl group, or a dialkylamino group.
(R ^f1 O) _m , R ^f2 , Q ¹ and Q ^2a are the same as (R ^f1 O) _m , R ^f2 , Q ¹ and Q ^2a described in Compounds 1 and 2, and preferred forms are also the same.

Compound 3 can be produced by methods described in International Publication Nos. WO 2009/008380, WO 2013/121984, WO 2013/121986, WO 2015/087902, WO 2017/038830, WO 2017/038832, etc.

Nucleophilic fluorinating agents include 4-tert-butyl-2,6-dimethylphenylsulfur trifluoride, pyridinium poly(hydrogen fluoride), diethylaminosulfur trifluoride, bis(2-methoxyethyl)aminosulfur trifluoride, 1,1,2,2-tetrafluoroethyl-N,N-dimethylamine, (diethylamino)difluorosulfonium tetrafluoroborate, difluoro(morpholino)sulfonium tetrafluoroborate, and 1,3-bis(2,6-diisopropylphenyl)-2,2-difluoro-4-imidazoline.

When X in formula g1 of compound 1 is a hydrogen atom, compound 2 can be produced, for example, as follows.
Compound 4 is reacted with a halogenating agent or a sulfonate esterifying agent to obtain compound 5.
A-O-(R ^f1 O) _m -R ^f2 -Q ¹ -CT[-Q ^2a -CH=CH ₂ ] ₂ Formula 5
where T is chlorine, bromine, iodine, methanesulfonic acid, p-toluenesulfonic acid, or trifluoromethanesulfonic acid.

Examples of the halogenating agent include hydrogen chloride, thionyl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphoric trichloride, oxalyl chloride, carbon tetrachloride-triphenylphosphine, hydrogen bromide, phosphorus tribromide, phosphorus pentabromide, carbon tetrabromide-triphenylphosphine, hydrogen iodide, and iodine-triphenylphosphine.
Examples of the sulfonating agent include methanesulfonyl chloride, p-toluenesulfonyl chloride, and trifluoromethanesulfonic anhydride.

Compound 5 is then reacted with a hydride reducing agent to give compound 2b.
A-O-(R ^f1 O) _m -R ^f2 -Q ¹ -CH [-Q ^2a -CH=CH ₂ ] ₂ Formula 2b
Examples of the hydride reducing agent include sodium borohydride, sodium cyanoborohydride, lithium triethylborohydride, lithium aluminum hydride, and sodium bis(2-methoxyethoxy)aluminum hydride.

When X in formula g1 of compound 1 is an alkyl group or a fluoroalkyl group, compound 2 can be produced, for example, as follows.
Compound 5 is reacted with an alkylating agent or a fluoroalkylating agent to give compound 2c.
A-O-(R ^f1 O) _m -R ^f2 -Q ¹ -CR ¹ [-Q ^2a -CH=CH ₂ ] ₂ Formula 2c
Here, R ¹ is an alkyl group or a fluoroalkyl group.

Examples of the alkylating agent include organolithium reagents such as alkyllithium (e.g., methyllithium, ethyllithium), Grignard reagents such as alkylmagnesium bromides (e.g., methylmagnesium bromide, ethylmagnesium bromide), and organozinc reagents such as dialkylzinc (e.g., dimethylzinc, diethylzinc).
Examples of the fluoroalkylating agent include organolithium reagents such as fluoroalkyllithium (for example, 3,3,3-trifluoropropyllithium, 3,3,4,4,4-pentafluorobutyllithium, 3,3,4,4,5,5,6,6,6-nonafluorohexyllithium), Grignard reagents such as fluoroalkylmagnesium bromide (for example, 3,3,3-trifluoropropylmagnesium bromide, 3,3,4,4,4-pentafluorobutylmagnesium bromide, 3,3,4,4,5,5,6,6,6-nonafluorohexylmagnesium bromide), and trifluoromethylating reagents such as Ruppert-Prakash reagent ((trifluoromethyl)trimethylsilane).

Compound 1 described above can form a surface layer that is excellent in initial water and oil repellency, fingerprint stain removability, abrasion resistance, light resistance, and chemical resistance for the following reasons.
Compound 1 has (R ^f1 O) _m and therefore contains a large amount of fluorine atoms, and therefore can form a surface layer that is excellent in initial water and oil repellency, abrasion resistance, and fingerprint removability.
Compound 1 does not have a hydroxyl group, and therefore can form a surface layer that is excellent in water and oil repellency and chemical resistance. Furthermore, Compound 1 does not have an ether bond, a C—O—Si bond, or an ester bond between the polyfluoropolyether chain and the hydrolyzable silyl group, and therefore the bond between the polyfluoropolyether chain and the hydrolyzable silyl group is not easily cleaved by light, chemicals, etc. Therefore, Compound 1 can form a surface layer that is excellent in light resistance and chemical resistance.

[Fluorine-containing ether composition]
The fluorinated ether composition of the present invention (hereinafter also referred to as "the composition") contains one or more compounds 1 and other fluorinated ether compounds.

Examples of other fluorine-containing ether compounds include fluorine-containing ether compounds produced as a by-product in the production process of Compound 1 (hereinafter also referred to as "by-product fluorine-containing ether compounds"), known fluorine-containing ether compounds used for the same purposes as Compound 1, and the like.
As the other fluorine-containing ether compound, a compound which is unlikely to deteriorate the properties of Compound 1 is preferred.

Examples of by-product fluorine-containing ether compounds include unreacted Compound 2, Compound 3, Compound 4, and the like; and fluorine-containing ether compounds in which part of the allyl group is isomerized to an inner olefin during hydrosilylation in the production of Compound 1.
Examples of known fluorine-containing ether compounds include commercially available fluorine-containing ether compounds, etc. When the present composition contains a known fluorine-containing ether compound, new effects such as compensating for the properties of Compound 1 may be exhibited.

The content of Compound 1 in the composition is preferably 60% by mass or more and less than 100% by mass, more preferably 70% by mass or more and less than 100% by mass, and particularly preferably 80% by mass or more and less than 100% by mass.
The content of the other fluorinated ether compounds in the present composition is preferably more than 0 mass % and not more than 40 mass %, more preferably more than 0 mass % and not more than 30 mass %, particularly preferably more than 0 mass % and not more than 20 mass %.
The total content of Compound 1 and the other fluorine-containing ether compounds is preferably from 80 to 100% by mass, particularly preferably from 85 to 100% by mass, of the present composition.
When the content of Compound 1 and the content of the other fluorinated ether compound are within the above ranges, the initial water and oil repellency, abrasion resistance, fingerprint stain removability, light resistance and chemical resistance of the surface layer are even more excellent.

The present composition may contain components other than Compound 1 and other fluorinated ether compounds, as long as the effects of the present invention are not impaired.
Examples of other components include compounds unavoidable in the production process, such as Compound 1 and by-products (excluding by-product fluorine-containing ether compounds) produced in the production process of known fluorine-containing ether compounds, and unreacted raw materials.
In addition, additives such as acid catalysts and basic catalysts that promote the hydrolysis and condensation reaction of hydrolyzable silyl groups can be used. Examples of acid catalysts include hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, and p-toluenesulfonic acid. Examples of basic catalysts include sodium hydroxide, potassium hydroxide, and ammonia.
The content of the other components in the composition is preferably 0 to 9.999 mass %, particularly preferably 0 to 0.99 mass %.

[Coating liquid]
The coating liquid of the present invention (hereinafter also referred to as "the present coating liquid") contains Compound 1 or the present composition and a liquid medium. The present coating liquid may be a solution or a dispersion.

The liquid medium is preferably an organic solvent. The organic solvent may be a fluorine-containing organic solvent or a non-fluorine-containing organic solvent, or may contain both solvents.
Examples of the fluorine-containing organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.
The fluorinated alkane is preferably a compound 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).
Examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene.
The fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms. 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-containing organic solvent is preferably a compound consisting of only hydrogen atoms and carbon atoms, or a compound consisting of only hydrogen atoms, carbon atoms, and oxygen atoms, and examples thereof include hydrocarbons, alcohols, ketones, ethers, and esters.
The liquid medium may be a mixed medium of two or more kinds.

The content of Compound 1 or the present composition in the present coating liquid is preferably 0.001 to 10 mass %, particularly preferably 0.01 to 1 mass %.
The content of the liquid medium in the coating liquid is preferably 90 to 99.999 mass %, and particularly preferably 99 to 99.99 mass %.

[Goods]
The article of the present invention (hereinafter also referred to as "the article") has a surface layer formed from Compound 1 or the composition on the surface of a substrate.
The surface layer contains Compound 1 in a state where some or all of the hydrolyzable silyl groups of Compound 1 have undergone hydrolysis and dehydration condensation.

The thickness of the surface layer is preferably 1 to 100 nm, and particularly preferably 1 to 50 nm. If the thickness of the surface layer is equal to or greater than the lower limit of the above range, the effects of the surface treatment are likely to be fully achieved. If the thickness of the surface layer is equal to or less than the upper limit of the above range, utilization efficiency is high. The thickness of the surface layer can be calculated from the oscillation period of the interference pattern obtained by X-ray reflectivity analysis using a thin film analysis X-ray diffractometer (RIGAKU Corporation, ATX-G).

The substrate may be a substrate that is required to be water- and oil-repellent. The substrate material may be metal, resin, glass, sapphire, ceramic, stone, or a composite material thereof. The glass may be chemically strengthened. A base film such as a _SiO2 film may be formed on the surface of the substrate.
The substrate is preferably a substrate for a touch panel, a substrate for a display, or a lens for glasses, and is particularly preferably a substrate for a touch panel.The material of the substrate for a touch panel is preferably glass or a transparent resin.

[Production method for articles]
The present article can be produced, for example, by the following method.
A method in which the surface of a substrate is treated by a dry coating method using Compound 1 or the present composition to form a surface layer made of Compound 1 or the present composition on the surface of the substrate.
A method in which the coating liquid is applied to the surface of a substrate by a wet coating method, and then dried to form a surface layer made of Compound 1 or the composition on the surface of the substrate.

Dry coating methods include vacuum deposition, CVD, sputtering, and other techniques. Vacuum deposition is preferred from the standpoint of suppressing decomposition of Compound 1 and simplifying the equipment. For vacuum deposition, a pellet-like material may be used in which a porous metal such as iron or steel is impregnated with Compound 1 or the present composition. The coating liquid may be impregnated into a porous metal such as iron or steel, the liquid medium may be dried, and the pellet-like material impregnated with Compound 1 or the present composition may be used.

Wet coating methods include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, Langmuir-Blodgett coating, and gravure coating.

The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. In the following, "%" means "% by mass" unless otherwise specified. Examples 1, 2, 4, and 5 are working examples, and Examples 3 and 6 are comparative examples.

[Example 1]
(Example 1-1)
Compound 3-1 was obtained according to the method described in Example 2-3 of the Examples of WO 2013/121984.
CF ₃ -O-(CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _x CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ -C(O)OCH ₃ Formula 3-1
Average value of number of units x: 13, number average molecular weight of compound 3-1: 4,730.

(Example 1-2)
A 50 mL three-necked recovery flask was charged with 5.0 g of tetrahydrofuran, 10 g of 1,3-bistrifluoromethylbenzene, and 4.0 mL of 1 M allyl magnesium bromide. 10 g of compound 3-1 obtained in Example 1-1 was added dropwise, and the mixture was heated at 60°C for 4 hours. The mixture was cooled to 25°C, and the solution was added dropwise to a 1.2 M aqueous hydrochloric acid solution. The organic layer was recovered by a separation operation and washed once with water. The recovered organic layer was concentrated using an evaporator to obtain 7.1 g of compound 4-1.

NMR spectrum of compound 4-1;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: tetramethylsilane (TMS)) δ (ppm): 2.4-2.6 (4H), 5.2-5.3 (4H), 5.9-6.0 (2H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -55 (3F), -82 (54F), -88 (54F), -90 (2F), -116 (2F), -121 (2F), -125 (52F).
Average value of number of units x: 13, number average molecular weight of compound 4-1: 4,780.

(Example 1-3)
A 50 mL three-neck flask was charged with 1.0 g of 4-tert-butyl-2,6-dimethylphenylsulfur trifluoride (FLUOLEAD (registered trademark) manufactured by Ube Industries, Ltd.) and 14 g of AC-2000, and cooled in an ice bath. 0.26 mL of pyridinium poly(hydrogen fluoride) was added, and 7.0 g of compound 4-1 obtained in Example 1-2 was added dropwise. The mixture was stirred at 25°C for 10 hours and cooled again in an ice bath. 2 mL of ethanol was added, and the mixture was stirred at 25°C for 1 hour. The mixture was neutralized with an aqueous potassium carbonate solution and washed once with water to recover the organic layer. The recovered organic layer was concentrated using an evaporator to obtain 7.1 g of a crude product. The crude product was applied to silica gel column chromatography, and 6.3 g of compound 2-1 (yield 90%) was isolated. The average number of units x of Compound 2-1 is 13, and the number average molecular weight of Compound 2-1 is 4,780.

(Example 1-4)
Into a 10 mL recovery flask made of tetrafluoroethylene-perfluoro(alkoxy vinyl ether) copolymer (PFA), 5.0 g of compound 2-1 obtained in Example 1-3, 0.03 g of a xylene solution of platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2% by mass), 0.36 g of trimethoxysilane, 0.01 g of aniline, and 2.0 g of 1,3-bis(trifluoromethyl)benzene were placed, and the mixture was stirred at 25°C for 8 hours. The solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.5 µm, yielding 5.2 g of compound 1-1a (purity of 99% or more, yield 99%). The average number of units x of compound 1-1a was 13, and the number average molecular weight of compound 1-1a was 5,020.

[Example 2]
(Example 2-1)
Compound 3-2 was obtained according to the method described in Examples 4-1 to 4-3 of WO 2014/163004.
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)OCH ₃ Formula 3-2
Average value of number of units x1: 21, average value of number of units x2: 20, number average molecular weight of compound 3-2: 4,230.

(Example 2-2)
10 g of compound 3-2 obtained in Example 2-1 and 15 g of AC-2000 were placed in a 50 mL three-necked recovery flask and cooled to 0°C. 2 g of a 5 M methanol solution of sodium methoxide was added and stirred, and then 1 g of 5-hexen-2-one was added and further stirred. After raising the temperature to room temperature, the solution was added dropwise to a 1 M aqueous hydrochloric acid solution. The organic layer was recovered by a separation operation and washed once with water. The recovered organic layer was concentrated using an evaporator to obtain 9 g of compound 3-3.

NMR spectrum of compound 3-3;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 5.8 (1H), 5.0 (2H), 2.5 (2H), 2.0 (4H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -52.4 to -55.8 (42F), -82.2 (3F), -89.4 to -91.1 (92F), -130.5 (2F).
Average value of number of units x1: 21, average value of number of units x2: 20, number average molecular weight of compound 3-3: 4,250.

(Example 2-3)
30 g of 1,3-bistrifluoromethylbenzene and 8.0 mL of 1 M allyl magnesium chloride were placed in a 100 mL three-necked recovery flask. 9 g of compound 3-3 obtained in Example 2-2 was added dropwise, and the mixture was stirred at room temperature. The solution was added dropwise to a 1 M aqueous hydrochloric acid solution. The organic layer was recovered by a separation operation and washed once with water. The recovered organic layer was concentrated using an evaporator to obtain 3 g of compound 4-2.

NMR spectrum of compound 4-2;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 5.8 (2H), 5.0 (4H), 2.5 (4H), 2.0 (4H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -52.4 to -55.8 (42F), -82.2 (3F), -89.4 to -91.1 (92F), -130.5 (2F).
Average value of number of units x1: 21, average value of number of units x2: 20, number average molecular weight of compound 4-2: 4,300.

(Example 2-4)
A 50 mL three-neck flask was charged with 1.0 g of 4-tert-butyl-2,6-dimethylphenylsulfur trifluoride (FLUOLEAD (registered trademark), manufactured by Ube Industries, Ltd.) and 15 g of AC-2000, and cooled in an ice bath. 0.3 mL of pyridinium poly(hydrogen fluoride) was added, and 3 g of compound 4-2 obtained in Example 2-3 was added dropwise. The mixture was stirred at 25°C and cooled again in an ice bath. 2 mL of ethanol was added, and the mixture was stirred at 25°C. After neutralization with an aqueous potassium carbonate solution, the mixture was washed once with water and the organic layer was recovered. The recovered organic layer was concentrated using an evaporator to obtain 3 g of a crude product. The crude product was developed using silica gel column chromatography, and 2 g of compound 2-2 was separated.

NMR spectrum of compound 2-2;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 5.8 (2H), 5.0 (4H), 2.5 (4H), 1.9 (4H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -52.4 to -55.8 (42F), -82.2 (3F), -89.4 to -91.1 (92F), -120 (2F), -130.5 (2F), -160 (1F).
Average value of number of units x1: 21, average value of number of units x2: 20, number average molecular weight of compound 2-2: 4,300.

(Example 2-5)
A 10 mL PFA recovery flask was charged with 2.0 g of compound 2-2 obtained in Example 2-4, 0.03 g of a xylene solution of platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2% by mass), 0.36 g of trimethoxysilane, 0.01 g of aniline, and 2.0 g of 1,3-bis(trifluoromethyl)benzene, and the mixture was stirred at 25° C. The solvent and other components were distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.5 μm, yielding 2 g of compound 1-7a.

NMR spectrum of compound 1-7a;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 3.4-3.8 (18H), 1.2-1.9 (12H), 0.7 (4H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -52.4 to -55.8 (42F), -82.2 (3F), -89.4 to -91.1 (92F), -120 (2F), -130.5 (2F), -160 (1F).
Average value of number of units x1: 21, average value of number of units x2: 20, number average molecular weight of compound 1-7a: 4,400.

[Example 3]
A 10 mL PFA recovery flask was charged with 5.0 g of compound 4-1 obtained in Example 1-2, 0.03 g of a xylene solution of platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2% by mass), 0.36 g of trimethoxysilane, 0.01 g of aniline, and 2.0 g of 1,3-bis(trifluoromethyl)benzene, and the mixture was stirred for 8 hours at 25° C. The solvent and other components were distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.5 μm, yielding 5.2 g of compound 10-1 (purity of 99% or more, yield 99%).

NMR spectrum of compound 10-1;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.6-0.8 (4H), 1.6-1.8 (4H), 1.9-2.0 (4H), 3.6 (27H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -55 (3F), -82 (54F), -88 (54F), -90 (2F), -116 (2F), -121 (2F), -125 (52F).
Average value of number of units x: 13, number average molecular weight of compound 10-1: 5,020.

[Examples 4 to 6: Production and evaluation of articles]
Substrates were surface-treated using each of the compounds obtained in Examples 1 to 3, to obtain articles in Examples 4 to 6. The surface treatment method used in each example was the dry coating method described below. Chemically strengthened glass was used as the substrate. The obtained articles were evaluated by the following methods. The results are shown in Table 1.

(Dry coating method)
Dry coating was performed using a vacuum deposition apparatus (ULVAC, VTR350M) (vacuum deposition method). 0.5 g of each compound obtained in Examples 1 and 2 was loaded into a molybdenum boat in the vacuum deposition apparatus, and the vacuum deposition apparatus was evacuated to 1 × 10 ^-3 Pa or less. The boat containing the compound was heated at a temperature increase rate of 10 °C/min or less, and when the deposition rate measured by a quartz crystal oscillator film thickness meter exceeded 1 nm/sec, the shutter was opened to initiate film formation on the surface of the substrate. When the film thickness reached approximately 50 nm, the shutter was closed to terminate film formation on the surface of the substrate. The substrate on which the compound had been deposited was heat-treated at 200 °C for 30 minutes and washed with dichloropentafluoropropane (Asahi Glass Co., Ltd., AK-225) to obtain an article having a surface layer on the surface of the substrate.

(Evaluation method)
<Method for measuring contact angle>
The contact angle of approximately 2 μL of distilled water or n-hexadecane placed on the surface of the surface layer was measured using a contact angle measuring device (DM-500, manufactured by Kyowa Interface Science Co., Ltd.). Measurements were taken at five different points on the surface of the surface layer, and the average value was calculated. The 2θ method was used to calculate the contact angle.

<Initial contact angle>
The surface layer was measured for the initial water contact angle and the initial n-hexadecane contact angle by the above-mentioned measuring method. The evaluation criteria were as follows:
Initial water contact angle:
◎ (Excellent): Over 115 degrees.
○ (Good): 110 degrees or more and less than 115 degrees.
△ (Acceptable): 100 degrees or more but less than 110 degrees.
× (unacceptable): Less than 100 degrees.
Initial n-hexadecane contact angle:
◎ (Excellent): Over 66 degrees.
○ (Good): 65 degrees or more but less than 66 degrees.
△ (Acceptable): Between 63 and 65 degrees.
× (unacceptable): Less than 63 degrees.

<Abrasion resistance (steel wool)>
For the surface layer, a reciprocating traverse tester (manufactured by KNT Corporation) was used in accordance with JIS L0849:2013 (ISO 105-X12:2001) to measure the water contact angle after 10,000 reciprocating strokes of steel wool Bonstar (#0000) at a pressure of 98.07 kPa and a speed of 320 cm/min. The smaller the decrease in water repellency (water contact angle) after friction, the smaller the decrease in performance due to friction, and the more excellent the friction resistance. The evaluation criteria are as follows.
◎ (Excellent): The change in water contact angle after 10,000 reciprocating strokes is 2 degrees or less.
○ (Good): The change in the water contact angle after 10,000 reciprocating strokes is more than 2 degrees and not more than 5 degrees.
△ (Acceptable): The change in water contact angle after 10,000 reciprocating strokes is more than 5 degrees and 10 degrees or less.
× (unacceptable): The change in water contact angle after 10,000 reciprocating cycles exceeds 10 degrees.

<Abrasion resistance (eraser)>
For the surface layer, a reciprocating traverse tester (manufactured by KNT Corporation) was used in accordance with JIS L0849:2013 (ISO 105-X12:2001), and a Rubber Eraser (manufactured by Minoan Co., Ltd.) was reciprocated 30,000 times at a load of 4.9 N and a speed of 60 rpm, after which the water contact angle was measured. The smaller the decrease in water repellency (water contact angle) after friction, the smaller the decrease in performance due to friction, and the more excellent the friction resistance. The evaluation criteria are as follows.
◎ (Excellent): The change in water contact angle after 10,000 reciprocating strokes is 2 degrees or less.
○ (Good): The change in the water contact angle after 10,000 reciprocating strokes is more than 2 degrees and not more than 5 degrees.
△ (Acceptable): The change in water contact angle after 10,000 reciprocating strokes is more than 5 degrees and 10 degrees or less.
× (unacceptable): The change in water contact angle after 10,000 reciprocating cycles exceeds 10 degrees.

<Fingerprint removal>
An artificial fingerprint liquid (a liquid consisting of oleic acid and squalene) was applied to the flat surface of a silicone rubber stopper, and then excess oil was wiped off with a nonwoven fabric (Bencotto (registered trademark) M-3, manufactured by Asahi Kasei Corporation) to prepare a fingerprint stamp. The fingerprint stamp was placed on the surface layer and pressed with a load of 9.8 N for 10 seconds. The haze of the area where the fingerprint was attached was measured with a haze meter and recorded as the initial value. The area where the fingerprint was attached was wiped with a load of 4.9 N using a reciprocating traverse tester (manufactured by KNT Corporation) equipped with tissue paper. The haze value was measured for each wiping stroke, and the number of wiping strokes until the haze was 10% or less of the initial value was counted. The fewer the wiping strokes, the easier it was to remove fingerprint stains, and the better the fingerprint stain wiping ability. The evaluation criteria are as follows.
◎ (Excellent): Wiping required 3 times or less.
○ (Good): Wiping was performed 4 to 5 times.
△ (Acceptable): Wiping was performed 6 to 8 times.
× (unacceptable): Wiping is performed 9 or more times.

<Light resistance>
The surface layer was irradiated with light (650 W/m ² , 300-700 nm) for 1,000 hours at a black panel temperature of 63°C using a desktop xenon arc lamp accelerated light resistance tester (SUNTEST XLS+, manufactured by Toyo Seiki Seisakusho), and then the water contact angle was measured. The smaller the decrease in water contact angle after the accelerated light resistance test, the smaller the deterioration in performance due to light and the more excellent the light resistance. The evaluation criteria are as follows:
◎ (Excellent): The change in water contact angle after the accelerated light resistance test is 2 degrees or less.
○ (Good): The change in water contact angle after the accelerated light resistance test was more than 2 degrees and not more than 5 degrees.
△ (Acceptable): The change in water contact angle after the accelerated light resistance test was more than 5 degrees and 10 degrees or less.
× (unacceptable): The change in water contact angle after the accelerated light resistance test is more than 10 degrees.

<Lightfastness + Rub resistance (steel wool)>
After the light resistance test, the abrasion resistance (steel wool) test was carried out and evaluated according to the evaluation criteria for abrasion resistance (steel wool).

<Chemical resistance (alkali resistance)>
The article was immersed in a 1N sodium hydroxide aqueous solution (pH = 14) for 5 hours, then rinsed with water, air-dried, and the water contact angle was measured. The smaller the decrease in water contact angle after the test, the smaller the deterioration in performance due to alkali and the more excellent the alkali resistance. The evaluation criteria are as follows.
◎ (Excellent): The change in water contact angle after the alkali resistance test is 2 degrees or less.
◯ (Good): The change in water contact angle after the alkali resistance test was more than 2 degrees and not more than 5 degrees.
△ (Acceptable): The change in water contact angle after the alkali resistance test was more than 5 degrees and 10 degrees or less.
× (unacceptable): The change in the water contact angle after the alkali resistance test was more than 10 degrees.

<Chemical resistance (saltwater resistance)>
A salt spray test was conducted in accordance with JIS H8502. Specifically, the article was exposed to a saltwater atmosphere for 300 hours in a salt spray tester (manufactured by Suga Test Instruments Co., Ltd.), and then the water contact angle was measured. The smaller the decrease in water contact angle after the test, the smaller the deterioration in performance due to saltwater, and the more excellent the saltwater resistance. The evaluation criteria are as follows.
◎ (Excellent): The change in water contact angle after the salt spray test is 2 degrees or less.
○ (Good): The change in water contact angle after the salt spray test was more than 2 degrees and not more than 5 degrees.
△ (Acceptable): The change in water contact angle after the salt spray test was more than 5 degrees and 10 degrees or less.
× (unacceptable): The change in water contact angle after the salt spray test is more than 10 degrees.

<Lubricity>
The dynamic friction coefficient of the surface layer against artificial skin (PBZ13001, manufactured by Idemitsu Technofine Co., Ltd.) was measured using a variable load friction and wear testing system (HHS2000, manufactured by Shinto Scientific Co., Ltd.) under conditions of a contact area of 3 cm x 3 cm and a load of 0.98 N. The smaller the dynamic friction coefficient, the better the lubricity. The evaluation criteria are as follows:
◎ (Excellent): Coefficient of dynamic friction is 0.2 or less.
○ (Good): Coefficient of dynamic friction is greater than 0.2 and equal to or less than 0.3.
△ (Acceptable): Coefficient of dynamic friction is greater than 0.3 and equal to or less than 0.4.
× (unacceptable): Coefficient of dynamic friction exceeds 0.4.

It was confirmed that Examples 4 and 5, which used Compound 1, were excellent in initial water and oil repellency, abrasion resistance, fingerprint stain removability, light resistance and chemical resistance.
Example 6, in which a conventional fluorine-containing ether compound was used, was poor in light resistance and chemical resistance.

The fluorine-containing ether compounds of the present invention can be used in a variety of applications requiring lubricity or water and oil repellency. For example, they can be used in display and input devices such as touch panels; surface protective coatings for transparent glass or transparent plastic components; anti-fouling coatings for kitchens; water-repellent, moisture-proof, and anti-fouling coatings for electronic devices, heat exchangers, batteries, etc.; and anti-fouling coatings for toiletries; coatings for components that require electrical conductivity and liquid repellency; water-repellent, waterproof, and water-slip coatings for heat exchangers; and low-friction surface coatings for the inside of vibrating sieves and cylinders, etc. More specific examples of use include front protective plates for displays, anti-reflection plates, polarizing plates, anti-glare plates, or plates with anti-reflection coatings applied to their surfaces; various devices with display input devices that allow operations on the screen with fingers or palms, such as touch panel sheets and touch panel displays for devices such as mobile phones and personal digital assistants; decorative building materials for wet areas such as toilets, bathrooms, washrooms, and kitchens; waterproof coatings for wiring boards; water-repellent and waterproof coatings for heat exchangers; water-repellent coatings for solar cells; waterproof and water-repellent coatings for printed wiring boards; waterproof and water-repellent coatings for electronic device housings and electronic components; coatings to improve the insulation of power transmission lines; waterproof and water-repellent coatings for various filters; waterproof coatings for radio wave absorbers and sound-absorbing materials; anti-fouling coatings for baths, kitchen equipment, and toiletries; water-repellent, waterproof, and water-slip coatings for heat exchangers; low-friction surface coatings for vibrating sieves and the inside of cylinders; and surface protective coatings for machine parts, vacuum equipment parts, bearing parts, automotive parts, tools, etc.

Claims (8)

A fluorine-containing ether compound which is a compound represented by the following formula 1:
A ¹ -O-(R ^f1 O) _m -A ² Formula 1
however,
^A1 is a perfluoroalkyl group having 1 to 20 carbon atoms or a group represented by the following formula g1:
^A2 is a group represented by the following formula g1:
R ^f1 is a fluoroalkylene group;
m is an integer from 2 to 500,
(R ^f1 O) _m may consist of two or more types of R ^f1 O having different numbers of carbon atoms.
-R ^f2 -Q ¹ -C(X) [-Q ² -SiR _n L _3-n ] ₂ formula g1
however,
R ^f2 is a fluoroalkylene group (provided that at least one fluorine atom is bonded to the terminal carbon atom on the ^Q1 side),
^Q1 is a single bond or an alkylene group;
X is an alkyl group or a fluoroalkyl group;
^Q2 is an alkylene group;
R is a monovalent hydrocarbon group;
L is a hydrolyzable group;
n is an integer from 0 to 2,
The two [-Q ² -SiR _n L _3-n ] may be the same or different. A fluorinated ether composition comprising one or more fluorinated ether compounds according to claim 1 and other fluorinated ether compounds. The fluorinated ether compound according to claim 1 or the fluorinated ether composition according to claim 2;
A coating liquid comprising a liquid medium. An article having a surface layer formed on the surface of a substrate from the fluorinated ether compound of claim 1 or the fluorinated ether composition of claim 2. The article described in claim 4, wherein the surface layer is provided on the surface of a member that constitutes the surface of a touch panel that is touched by a finger. A method for producing an article, comprising treating the surface of a substrate by a dry coating method using the fluorinated ether compound of claim 1 or the fluorinated ether composition of claim 2, and forming a surface layer formed from the fluorinated ether compound or the fluorinated ether composition on the surface of the substrate. A method for producing an article, comprising applying the coating liquid described in claim 3 to the surface of a substrate by a wet coating method and drying the coating liquid to form a surface layer formed from the fluorinated ether compound or the fluorinated ether composition on the surface of the substrate. A fluorine-containing ether compound which is a compound represented by the following formula 2:
A ^1a -O-(R ^f1 O) _m -A ^2a Formula 2
however,
A ^1a is a perfluoroalkyl group having 1 to 20 carbon atoms or a group represented by the following formula g2:
A ^2a is a group represented by the following formula g2:
R ^f1 is a fluoroalkylene group;
m is an integer from 2 to 500,
(R ^f1 O) _m may consist of two or more types of R ^f1 O having different numbers of carbon atoms.
-R ^f2 -Q ¹ -C(X) [-Q ^2a -CH=CH ₂ ] ₂ formula g2
however,
R ^f2 is a fluoroalkylene group (provided that at least one fluorine atom is bonded to the terminal carbon atom on the ^Q1 side),
^Q1 is a single bond or an alkylene group;
X is an alkyl group or a fluoroalkyl group;
^Q2a is a single bond or an alkylene group;
The two [-Q ^2a -CH═CH ₂ ] groups may be the same or different.