JP7180593B2 - Method for producing fluorine-containing ether compound and fluorine-containing ether compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a fluorine-containing ether compound and a fluorine-containing ether compound.

A fluorine-containing ether compound having a poly(oxyperfluoroalkylene) chain can form a surface layer exhibiting high lubricity, water and oil repellency, etc. on the surface of a base material, and is therefore suitably used as a surface treatment agent. A surface treatment agent containing a fluorine-containing ether compound has the property that the water and oil repellency does not deteriorate even when the surface layer is rubbed repeatedly with fingers (friction resistance), and the property that fingerprints adhered to the surface layer can be easily removed by wiping. It is used as a surface treatment agent for a member that constitutes the surface touched by a finger of a touch panel, for example, in applications where (fingerprint stain removability) is required to be maintained for a long period of time.

As a fluorine-containing ether compound capable of forming a surface layer with excellent water and oil repellency, abrasion resistance, fingerprint stain removal, lubricity, chemical resistance and light resistance on the surface of a base material, one end of the fluorine-containing ether compound , proposed a fluorine-containing ether compound in which two hydrolyzable silyl groups are introduced via a branched structure with a nitrogen atom (Patent Document 1).
The fluorine-containing ether compound (compound represented by the following formula (1A)) described in Patent Document 1 is produced as follows.

A compound represented by the following formula (15) is obtained by subjecting the compound represented by the following formula (14) to hydrogen reduction using a reducing agent.
A ¹ -O-(CF ₂ CF ₂ O)(CF ₂ CF ₂ O)(R ^f11 O) _x -CF ₂ -COOR (14)
A ¹ —O—(CF ₂ CF ₂ O)(CF ₂ CF ₂ O)(R ^f11 O) _x —CF ₂ —CH ₂ OH (15)
However, A ¹ is a perfluoroalkyl group having 1 to 20 carbon atoms, R ^f11 is a perfluoroalkylene group, x is an integer of 1 to 198, and R is an alkyl group.

The compound represented by the formula (15) is reacted with CF ₃ SO ₂ Cl in a fluorine-containing solvent in the presence of a basic compound to obtain a compound represented by the following formula (16).
A ¹ —O—(CF ₂ CF ₂ O)(CF ₂ CF ₂ O)(R ^f11 O) _x —CF ₂ —CH ₂ OSO ₂ CF ₃ (16)

HN(CH ₂ CH=CH ₂ ) ₂ is reacted with the compound represented by the above formula (16) in the presence of a basic compound to obtain a compound represented by the following formula (17).
A ¹ —O—(CF ₂ CF ₂ O)(CF ₂ CF ₂ O)(R ^f11 O) _x —CF ₂ —CH ₂ —N(CH ₂ CH═CH ₂ ) ₂ (17)

The compound represented by the formula (17) and HSiR ¹³ _n1 X ¹ _3-n1 are hydrosilylated to obtain the compound represented by the following formula (1A).
A ¹ —O—(CF ₂ CF ₂ O)(CF ₂ CF ₂ O)(R ^f11 O) _x —CF ₂ —CH ₂ —N[CH ₂ CH ₂ CH ₂ —SiR ¹³ _n1 X ¹ _3-n1 ] ₂ (1A)
However, R ¹³ is a hydrogen atom or a monovalent hydrocarbon group, X ¹ is a hydrolyzable group, and n1 is an integer of 0-2.

WO2017/038832

However, the method described in Patent Document 1 has the following problems.
- CF ₃ SO ₂ Cl to be reacted with the compound represented by the formula (15) is expensive, which increases the production cost of the fluorine-containing ether compound.
- When the compound represented by formula (16) is reacted with HN(CH ₂ CH=CH ₂ ) ₂ to obtain the compound represented by formula (17), trifluoromethylsulfonic acid, which is difficult to handle, is produced as a by-product. do. Since the treatment of trifluoromethylsulfonic acid is troublesome, the productivity of the fluorine-containing ether compound is deteriorated.

The present invention provides a method for producing a fluorine-containing ether composition that can produce a fluorine-containing ether compound suitably used as a surface treatment agent or a fluorine-containing ether compound useful as an intermediate for the fluorine-containing ether compound at low cost and with high productivity. The 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 preferably used as a surface treatment agent.

The present invention provides a method for producing a fluorine-containing ether compound having the constitutions [1] and [2] below, a method for producing a fluorine-containing ether compound having the constitution [3] below, and constitutions [4] and [5] below. a method for producing a fluorine-containing ether compound having the structure [6] below, a method for producing a fluorine-containing ether compound having the structures [7] to [10] below, [11] below and [12], and a fluorine-containing ether compound having the following structures [13] and [14].

[1] A method for producing a fluorine-containing ether compound, which comprises reacting a compound represented by the following formula (1) with _NH3 to obtain a compound represented by the following formula (2).
A—O—Q—(R ^f1 O) _m —R ^f2 —R ¹ —CO—Z (1)
A—O—Q—(R ^f1 O) _m —R ^f2 —R ¹ —CO—NH ₂ (2)
however,
A is a perfluoroalkyl group having 1 to 20 carbon atoms,
Q is a single bond, a fluoroalkylene group containing one or more hydrogen atoms, or an ether at the end of a fluoroalkylene group containing one or more hydrogen atoms (limited to the side that bonds to (R ^f1 O) _m ) a group having an etheric oxygen atom, a group having an etheric oxygen atom between the carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms containing one or more hydrogen atoms, or a group having two carbon atoms containing one or more hydrogen atoms A group having an etheric oxygen atom between the terminal of the above fluoroalkylene group (limited to the side that bonds to (R ^f1 O) _m ) and carbon-carbon atoms,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is an integer from 2 to 200,
(R ^f1 O) _m may consist of two or more R ^f1 O,
R ¹ is a single bond, an alkylene group, a group having an etheric oxygen atom or —NH— at the terminal of the alkylene group (limited to the terminal on the side that bonds to R ^f2 ), or an alkylene group having 2 or more carbon atoms. A group having an etheric oxygen atom or -NH- between carbon-carbon atoms, or a terminal of an alkylene group having 2 or more carbon atoms (limited to the terminal on the side that bonds to R ^f2 ) and between carbon-carbon atoms A group having an etheric oxygen atom or -NH-,
Z is -OH, -OR ⁴ , -R ⁵ , a halogen atom or a hydrogen atom, and R ⁴ and R ⁵ are each monovalent hydrocarbon groups.
[2] The production method of [1], wherein Z is —OR ⁴ and the compound represented by formula (1) is reacted with NH ₃ in an alcoholic solvent or a fluorine-containing solvent.

[3] A method for producing a fluorine-containing ether compound, which comprises reacting a compound represented by the following formula (2) with a reducing agent to obtain a compound represented by the following formula (3).
A—O—Q—(R ^f1 O) _m —R ^f2 —R ¹ —CO—NH ₂ (2)
A—O—Q—(R ^f1 O) _m —R ^f2 —R ¹ —CH ₂ —NH ₂ (3)
however,
A is a perfluoroalkyl group having 1 to 20 carbon atoms,
Q is a single bond, a fluoroalkylene group containing one or more hydrogen atoms, or an ether at the end of a fluoroalkylene group containing one or more hydrogen atoms (limited to the side that bonds to (R ^f1 O) _m ) a group having an etheric oxygen atom, a group having an etheric oxygen atom between the carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms containing one or more hydrogen atoms, or a group having two carbon atoms containing one or more hydrogen atoms A group having an etheric oxygen atom between the terminal of the above fluoroalkylene group (limited to the side that bonds to (R ^f1 O) _m ) and carbon-carbon atoms,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is an integer from 2 to 200,
(R ^f1 O) _m may consist of two or more R ^f1 O,
R ¹ is a single bond, an alkylene group, a group having an etheric oxygen atom or -NH- at the terminal of the alkylene group (limited to the terminal on the side bonding to R ^f2 ), or an alkylene group having 2 or more carbon atoms. A group having an etheric oxygen atom or —NH— between carbon-carbon atoms, or the terminal of an alkylene group having 2 or more carbon atoms (limited to the terminal on the side that bonds to R ^f2 ) and between carbon-carbon atoms It is a group having an etheric oxygen atom or -NH-.

[4] A method for producing a fluorine-containing ether compound, which comprises reacting a compound represented by the following formula (3) with YR ²¹ to obtain a compound represented by the following formula (4).
A—O—Q—(R ^f1 O) _m —R ^f2 —R ¹ —CH ₂ —NH ₂ (3)
A—O—Q—(R ^f1 O) _m —R ^f2 —R ¹ —CH ₂ —NR ²¹ ₂ (4)
however,
A is a perfluoroalkyl group having 1 to 20 carbon atoms,
Q is a single bond, a fluoroalkylene group containing one or more hydrogen atoms, or an ether at the end of a fluoroalkylene group containing one or more hydrogen atoms (limited to the side that bonds to (R ^f1 O) _m ) a group having an etheric oxygen atom, a group having an etheric oxygen atom between the carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms containing one or more hydrogen atoms, or a group having two carbon atoms containing one or more hydrogen atoms A group having an etheric oxygen atom between the terminal of the above fluoroalkylene group (limited to the side that bonds to (R ^f1 O) _m ) and carbon-carbon atoms,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is an integer from 2 to 200,
(R ^f1 O) _m may consist of two or more R ^f1 O,
R ¹ is a single bond, an alkylene group, a group having an etheric oxygen atom or —NH— at the terminal of the alkylene group (limited to the terminal on the side that bonds to R ^f2 ), or an alkylene group having 2 or more carbon atoms. A group having an etheric oxygen atom or -NH- between carbon-carbon atoms, or a terminal of an alkylene group having 2 or more carbon atoms (limited to the terminal on the side that bonds to R ^f2 ) and between carbon-carbon atoms A group having an etheric oxygen atom or -NH-,
Y is HO—, R ⁶ O— or a halogen atom, R ⁶ is a monovalent hydrocarbon group,
R ²¹ is a monovalent organic group having a terminal vinyl group or a monovalent hydrocarbon group (excluding those having a terminal vinyl group).
[5] The production method of [4], wherein Y is a halogen atom and R ²¹ is an allyl group or an allyloxyalkyl group.

[6] A fluorine-containing ether compound characterized by hydrosilylating a compound represented by the following formula (4a) with HSiR ³ _n X _3-n to obtain a compound represented by the following formula (5): manufacturing method.
A—O—Q—(R ^f1 O) _m —R ^f2 —R ¹ —CH ₂ —NR ²² ₂ (4a)
A—O—Q—(R ^f1 O) _m —R ^f2 —R ¹ —CH ₂ —N[—R ² —SiR ³ _n X _3-n ] ₂ (5)
however,
A is a perfluoroalkyl group having 1 to 20 carbon atoms,
Q is a single bond, a fluoroalkylene group containing one or more hydrogen atoms, or an ether at the end of a fluoroalkylene group containing one or more hydrogen atoms (limited to the side that bonds to (R ^f1 O) _m ) a group having an etheric oxygen atom, a group having an etheric oxygen atom between the carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms containing one or more hydrogen atoms, or a group having two carbon atoms containing one or more hydrogen atoms A group having an etheric oxygen atom between the terminal of the above fluoroalkylene group (limited to the side that bonds to (R ^f1 O) _m ) and carbon-carbon atoms,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is an integer from 2 to 200,
(R ^f1 O) _m may consist of two or more R ^f1 O,
R ¹ is a single bond, an alkylene group, a group having an etheric oxygen atom or —NH— at the terminal of the alkylene group (limited to the terminal on the side that bonds to R ^f2 ), or an alkylene group having 2 or more carbon atoms. A group having an etheric oxygen atom or -NH- between carbon-carbon atoms, or a terminal of an alkylene group having 2 or more carbon atoms (limited to the terminal on the side that bonds to R ^f2 ) and between carbon-carbon atoms A group having an etheric oxygen atom or -NH-,
R ²² is a monovalent organic group having a terminal vinyl group, and two R ²² may be the same or different,
R ² is a divalent organic group derived from R ²² ,
R ³ is a hydrogen atom or a monovalent hydrocarbon group,
X is a hydrolyzable group,
n is an integer of 0-2.

[7] A method for producing a fluorine-containing ether compound, which comprises obtaining a compound represented by the following formula (5) from a compound represented by the following formula (1) through the following steps 1 to 4.
Step 1: A step of reacting a compound represented by the following formula (1) with _NH3 to obtain a compound represented by the following formula (2).
Step 2: A step of reacting a compound represented by the following formula (2) with a reducing agent to obtain a compound represented by the following formula (3).
Step 3: A step of reacting a compound represented by the following formula (3) with YR ²² to obtain a compound represented by the following formula (4a).
Step 4: A step of hydrosilylating the compound represented by the following formula (4a) and HSiR ³ _n X _3-n to obtain the compound represented by the following formula (5).
A—O—Q—(R ^f1 O) _m —R ^f2 —R ¹ —CO—Z (1)
A—O—Q—(R ^f1 O) _m —R ^f2 —R ¹ —CO—NH ₂ (2)
A—O—Q—(R ^f1 O) _m —R ^f2 —R ¹ —CH ₂ —NH ₂ (3)
A—O—Q—(R ^f1 O) _m —R ^f2 —R ¹ —CH ₂ —NR ²² ₂ (4a)
A—O—Q—(R ^f1 O) _m —R ^f2 —R ¹ —CH ₂ —N[—R ² —SiR ³ _n X _3-n ] ₂ (5)
however,
A is a perfluoroalkyl group having 1 to 20 carbon atoms,
Q is a single bond, a fluoroalkylene group containing one or more hydrogen atoms, or an ether at the end of a fluoroalkylene group containing one or more hydrogen atoms (limited to the side that bonds to (R ^f1 O) _m ) a group having an etheric oxygen atom, a group having an etheric oxygen atom between the carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms containing one or more hydrogen atoms, or a group having two carbon atoms containing one or more hydrogen atoms A group having an etheric oxygen atom between the terminal of the above fluoroalkylene group (limited to the side that bonds to (R ^f1 O) _m ) and carbon-carbon atoms,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is an integer from 2 to 200,
(R ^f1 O) _m may consist of two or more R ^f1 O,
R ¹ is a single bond, an alkylene group, a group having an etheric oxygen atom or —NH— at the terminal of the alkylene group (limited to the terminal on the side that bonds to R ^f2 ), or an alkylene group having 2 or more carbon atoms. A group having an etheric oxygen atom or -NH- between carbon-carbon atoms, or a terminal of an alkylene group having 2 or more carbon atoms (limited to the terminal on the side that bonds to R ^f2 ) and between carbon-carbon atoms A group having an etheric oxygen atom or -NH-,
Z is —OH, —OR ⁴ , —R ⁵ , a halogen atom or a hydrogen atom, R ⁴ and R ⁵ are each a monovalent hydrocarbon group,
Y is HO—, R ⁶ O— or a halogen atom, R ⁶ is a monovalent hydrocarbon group,
R ²² is a monovalent organic group having a terminal vinyl group,
R ² is a divalent organic group derived from R ²² ,
R ³ is a hydrogen atom or a monovalent hydrocarbon group,
X is a hydrolyzable group,
n is an integer of 0-2.
[8] The production method of [7], wherein Z is —OR ⁴ and the compound represented by formula (1) is reacted with NH ₃ in an alcoholic solvent or a fluorine-containing solvent.
[9] The production method of [7] or [8], wherein Y is a halogen atom and R ²² is an allyl group or an allyloxyalkyl group.
[10] The production method according to any one of [7] to [9], wherein both Q and ^R1 are single bonds.

[11] A fluorine-containing ether compound represented by the following formula (2).
A—O—Q—(R ^f1 O) _m —R ^f2 —R ¹ —CO—NH ₂ (2)
however,
A is a perfluoroalkyl group having 1 to 20 carbon atoms,
Q is a single bond, a fluoroalkylene group containing one or more hydrogen atoms, or an ether at the end of a fluoroalkylene group containing one or more hydrogen atoms (limited to the side that bonds to (R ^f1 O) _m ) a group having an etheric oxygen atom, a group having an etheric oxygen atom between the carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms containing one or more hydrogen atoms, or a group having two carbon atoms containing one or more hydrogen atoms A group having an etheric oxygen atom between the terminal of the above fluoroalkylene group (limited to the side that bonds to (R ^f1 O) _m ) and carbon-carbon atoms,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is an integer from 2 to 200,
(R ^f1 O) _m may consist of two or more R ^f1 O,
R ¹ is a single bond, an alkylene group, a group having an etheric oxygen atom or -NH- at the terminal of the alkylene group (limited to the terminal on the side bonding to R ^f2 ), or an alkylene group having 2 or more carbon atoms. A group having an etheric oxygen atom or —NH— between carbon-carbon atoms, or the terminal of an alkylene group having 2 or more carbon atoms (limited to the terminal on the side that bonds to R ^f2 ) and between carbon-carbon atoms It is a group having an etheric oxygen atom or -NH-.
[12] The compound of [11], wherein both Q and ^R1 are single bonds.

[13] A fluorine-containing ether compound represented by the following formula (3).
A—O—Q—(R ^f1 O) _m —R ^f2 —R ¹ —CH ₂ —NH ₂ (3)
however,
A is a perfluoroalkyl group having 1 to 20 carbon atoms,
Q is a single bond, a fluoroalkylene group containing one or more hydrogen atoms, or an ether at the end of a fluoroalkylene group containing one or more hydrogen atoms (limited to the side that bonds to (R ^f1 O) _m ) a group having an etheric oxygen atom, a group having an etheric oxygen atom between the carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms containing one or more hydrogen atoms, or a group having two carbon atoms containing one or more hydrogen atoms A group having an etheric oxygen atom between the terminal of the above fluoroalkylene group (limited to the side that bonds to (R ^f1 O) _m ) and carbon-carbon atoms,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is an integer from 2 to 200,
(R ^f1 O) _m may consist of two or more R ^f1 O,
R ¹ is a single bond, an alkylene group, a group having an etheric oxygen atom or -NH- at the terminal of the alkylene group (limited to the terminal on the side bonding to R ^f2 ), or an alkylene group having 2 or more carbon atoms. A group having an etheric oxygen atom or —NH— between carbon-carbon atoms, or the terminal of an alkylene group having 2 or more carbon atoms (limited to the terminal on the side that bonds to R ^f2 ) and between carbon-carbon atoms It is a group having an etheric oxygen atom or -NH-.
[14] The compound of [13], wherein both Q and ^R1 are single bonds.

According to the method for producing a fluorine-containing ether compound of the present invention, a fluorine-containing ether compound suitable for use as a surface treatment agent or a fluorine-containing ether compound useful as an intermediate for the fluorine-containing ether compound can be produced at low cost and with good productivity. can.
INDUSTRIAL APPLICABILITY The fluorine-containing ether compound of the present invention is useful as an intermediate for a fluorine-containing ether compound that is suitably used as a surface treatment agent.

In this specification, the compound represented by formula (1) is referred to as compound (1). Compounds represented by other formulas are similarly described.
The meanings of the following terms and the description format of the chemical formulas used in this specification are as follows.
A chemical formula for an oxyperfluoroalkylene group shall be represented with the oxygen atom to the right of the perfluoroalkylene group.
"Etheric oxygen atom" means an oxygen atom that forms an ether bond (-O-) between carbon atoms.
“Hydrolyzable silyl group” means a group capable of forming a silanol group (Si—OH) by hydrolysis reaction. For example, SiR ³ _n X _3-n in formula (5).
A "surface layer" means a layer formed on the surface of a substrate.
The "number average molecular weight" of the fluorine-containing ether compound is calculated by the following method using NMR analysis.
It is calculated by determining the number (average value) of oxyperfluoroalkylene groups based on the terminal groups by ¹ H-NMR and ¹⁹ F-NMR. A terminal group is, for example, A or SiR ³ _n X _3-n in formula (5).

[Compound (5)]
Compound (5), which is preferably used as a surface treatment agent, is the target substance finally obtained in the method for producing a fluorine-containing ether compound of the present invention.
A—O—Q—(R ^f1 O) _m —R ^f2 —R ¹ —CH ₂ —N[—R ² —SiR ³ _n X _3-n ] ₂ (5)
However, A is a perfluoroalkyl group having 1 to 20 carbon atoms, Q is a single bond, a fluoroalkylene group containing one or more hydrogen atoms, a terminal of a fluoroalkylene group containing one or more hydrogen atoms (with the proviso that , (R ^f1 O) _m only on the side that bonds to), an etheric oxygen between the carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms containing one or more hydrogen atoms or a terminal of a fluoroalkylene group having 2 or more carbon atoms containing one or more hydrogen atoms (limited to the side that bonds to (R ^f1 O) _m ) and ether between carbon-carbon atoms a group having an oxygen atom, R ^f1 and R ^f2 are each independently a perfluoroalkylene group, m is an integer of 2 to 200, (R ^f1 O) _m is two or more R ^f1 O R ¹ is a single bond, an alkylene group, a group having an etheric oxygen atom or -NH- at the end of the alkylene group (limited to the end on the side that bonds to R ^f2 ) , a group having an etheric oxygen atom or —NH— between the carbon atoms of an alkylene group having 2 or more carbon atoms, or the terminal of an alkylene group having 2 or more carbon atoms (limited to the terminal on the side that bonds to R ^f2 ) and a group having an etheric oxygen atom or —NH— between carbon-carbon atoms, R ² is a divalent organic group derived from R ²² of compound (4) described later, and R ³ is , a hydrogen atom or a monovalent hydrocarbon group, X is a hydrolyzable group, and n is an integer of 0-2.

(A group)
A is preferably a perfluoroalkyl group having 1 to 10 carbon atoms, more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, because the surface layer formed by the compound (5) has better lubricity and abrasion resistance. Preferred are perfluoroalkyl groups having 1 to 3 carbon atoms.

Since A has CF ₃ — at the terminal, one terminal of compound (5) is CF ₃ — and the other terminal is a hydrolyzable silyl group. Since the compound (5) having this structure can form a surface layer with low surface energy, the surface layer is excellent in lubricity and abrasion resistance. On the other hand, with conventional fluorine-containing ether compounds having hydrolyzable silyl groups at both ends, the lubricity and abrasion resistance of the surface layer are insufficient.

(Q group)
Q is a single bond, a fluoroalkylene group having 1 to 10 carbon atoms containing one or more hydrogen atoms, a terminal of a fluoroalkylene group having 1 to 10 carbon atoms containing one or more hydrogen atoms (with the proviso that (R ^f1 O) a group having an etheric oxygen atom in (limited to the side that bonds to _m ), and having an etheric oxygen atom between carbon atoms of a fluoroalkylene group having 2 to 10 carbon atoms containing one or more hydrogen atoms group, and the end of a fluoroalkylene group having 2 to 10 carbon atoms containing one or more hydrogen atoms (limited to the side that bonds to (R ^f1 O) _m ) and an etheric oxygen between carbon atoms Groups with atoms are preferred.
When Q is not a single bond, the number of hydrogen atoms in Q is 1 or more, preferably 2 or more, and particularly preferably 3 or more, from the viewpoint of excellent appearance of the surface layer. The number of hydrogen atoms in Q is preferably (number of carbon atoms in Q)×2 or less, particularly preferably (number of carbon atoms in Q), from the viewpoint of further improving the water and oil repellency of the surface layer.
Having a hydrogen atom in Q increases the solubility of compound (5) in a liquid medium. Therefore, the compound (5) is less likely to aggregate in the coating liquid, and the compound (5) is less likely to aggregate during drying after coating on the surface of the substrate, so that the appearance of the surface layer is further excellent.

Q is particularly preferably a single bond, —R ^f5 O— and —R ^f5 OR ^f6 O—. However, R ^f5 and R ^f6 each independently represent a C 2-6 fluoroalkylene group having a hydrogen atom. The number of hydrogen atoms in R ^f5 and R ^f6 is preferably 1 or 2.
R ^f5 O is preferably an oxyfluoroalkylene group having a hydrogen atom at the carbon atom to which A—O— is bonded, and particularly preferably CHFCF ₂ O. R ^f6 O is preferably an oxyfluoroalkylene group having a hydrogen atom at the carbon atom to which R ^f5 O is bonded, such as CH ₂ CF ₂ O, CH ₂ CF ₂ CF ₂ O, CH ₂ CF ₂ CF ₂ CF ₂ O, and the like. is mentioned. —R ^f5 OR ^f6 O— includes —CHFCF ₂ O—CH ₂ CF ₂ O— and the like.
Q is particularly preferably a single bond.

((R ^f1 O) _m )
R ^f1 is preferably a perfluoroalkylene group having 1 to 6 carbon atoms, more preferably a perfluoroalkylene group having 1 to 4 carbon atoms, from the viewpoint of further improving the abrasion resistance and fingerprint stain removability of the surface layer. A perfluoroalkylene group having 1 to 2 carbon atoms is particularly preferred from the viewpoint of even better lubricity.

Since compound (5) has (R ^f1 O) _m , the content of fluorine atoms is large. Therefore, compound (5) can form a surface layer that is excellent in water and oil repellency, abrasion resistance, and fingerprint stain removability.
Further, when R ^f1 is a perfluoroalkylene group having no branched structure, (R ^f1 O) _m has a linear structure. According to the compound (5) having this structure, the surface layer is excellent in friction resistance and lubricity. On the other hand, when the poly(oxyperfluoroalkylene) chain has a branched structure, the surface layer is slightly inferior in abrasion resistance and lubricity.

m is preferably an integer of 5-150, particularly preferably an integer of 10-100. When m is at least the lower limit of the above range, the surface layer has excellent water and oil repellency. When m is equal to or less than the upper limit of the above range, the surface layer has excellent abrasion resistance. That is, when the number average molecular weight of compound (5) is too large, the number of hydrolyzable silyl groups present per unit molecular weight decreases, and the abrasion resistance of the surface layer decreases.

In (R ^f1 O) _m , when two or more types of R ^f1 O are present, the order of bonding of each R ^f1 O is not limited. For example, if CF ₂ O and CF ₂ CF ₂ O are present, the CF ₂ O and CF ₂ CF ₂ O may be arranged randomly, alternately, in blocks.
The presence of two or more types of R ^f1 O means that two or more types of R ^f1 O with different carbon numbers are present, and even if the number of carbons is the same, the presence or absence of a side chain and the type of side chain (side chain , the number of carbon ^atoms in the side chain, etc.).
Regarding the arrangement of two or more types of R ^f1 O, for example, in the case of the fluorine-containing ether compounds of Examples, the structure represented by {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } has x1 ( CF ₂ O) and x2 (CF ₂ CF ₂ O) are randomly arranged. Also, the structure represented by (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _{x 3} is composed of x 3 (CF ₂ CF ₂ O) and x 3 (CF ₂ CF ₂ CF ₂ CF ₂ O) are alternately arranged.

(R ^f1 O) _m is {(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 and 1 to 4 other ( Groups with R ^f1 O) are preferred. In particular, when Q is a single bond, a group having 1 to 4 other (R ^f1 O) on the AO- side is preferred. Groups having 1 to 4 other (R ^f1 O) at one end or both ends thereof include, for example, (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), and the like. (R ^f1 O) _m is particularly preferably a group having {(CF ₂ O) _m1 (CF ₂ CF ₂ O) _m2 }.
provided that m1 is an integer of 1 or more, m2 is an integer of 1 or more, m1+m2 is an integer of 2 to 200, and the order of bonding of m1 CF ₂ O and m2 CF ₂ CF ₂ O is limited. not. m3 and m4 are each an integer of 2-200, and m5 is an integer of 1-100.

(R ^f2 group)
R ^f2 is preferably a perfluoroalkylene group having 1 to 6 carbon atoms, more preferably a perfluoroalkylene group having 1 to 4 carbon atoms, from the viewpoint of further improving the abrasion resistance and fingerprint stain removability of the surface layer. A perfluoroalkylene group having 1 to 2 carbon atoms is particularly preferred because of its superior lubricity.
R ^f2 is, for example, a perfluoroalkylene group having 1 carbon atoms when (R ^f1 O) _m is {(CF ₂ O) _m1 (CF ₂ CF ₂ O) _m2 } and (CF ₂ CF ₂ O) _m3 and (CF ₂ CF ₂ CF ₂ O) _m4 is a perfluoroalkylene group having 2 carbon atoms, and (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _m5 is a carbon It is a linear perfluoroalkylene group of number 3. When R ^f1 is a branched perfluoroalkylene group, R ^f2 may be a branched perfluoroalkylene group. For example, when R ^f1 is (CF(CF ₃ )CF ₂ O), R ^f2 becomes CF (CF ₃ ).
If R ^f2 is a perfluoroalkylene group that does not have a branched structure, the surface layer will be excellent in abrasion resistance and lubricity.

(R ¹ group)
R ^{1 is} a single bond, an alkylene group having 1 to 10 carbon atoms, or an etheric oxygen atom or —NH a group having -, a group having an etheric oxygen atom or -NH- between carbon atoms of an alkylene group having 2 to 10 carbon atoms, and a terminal of an alkylene group having 2 to 10 carbon atoms (provided that R ^f2 and (Limited to the end of the binding side.) and a group having an etheric oxygen atom or -NH- between carbon atoms is preferable, and an alkylene group having 1 to 7 carbon atoms and an alkylene group having 2 to 7 carbon atoms Groups having an etheric oxygen atom or -NH- between carbon-carbon atoms are particularly preferred. A group selected from the group consisting of a single bond, —CH ₂ —, —CH ₂ CH ₂ —, —CH ₂ OCH ₂ — and —CH ₂ NHCH ₂ — from the viewpoint of ease of production of compound (5) (where the left side binds to R ^f2 ) is preferred.
R ¹ is particularly preferably a single bond.
Since ^R1 has a high polarity and does not have an ester bond that causes insufficient chemical resistance and light resistance, the surface layer is excellent in initial water repellency, chemical resistance and light resistance.

(R ² groups)
R ² is preferably an alkylene group having 2 to 10 carbon atoms, and a group having an etheric oxygen atom or —NH— between the carbon-carbon atoms of the alkylene group having 3 to 10 carbon atoms, and having 2 to 7 carbon atoms. and groups having an etheric oxygen atom or —NH— between the carbon atoms of the alkylene group having 3 to 7 carbon atoms are particularly preferred. -CH ₂ CH ₂ CH ₂ - and -CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ - (where the right side is bonded to Si) are preferred from the viewpoint of ease of production of compound (5).
Since ^R2 has a high polarity and does not have an ester bond that is insufficient in chemical resistance and light resistance, the initial water repellency, chemical resistance and light resistance of the surface layer are excellent.
As ^R2 , those having no etheric oxygen atom are particularly preferable from the viewpoint of excellent light resistance of the surface layer.
Two R ² in compound (5) may be the same or different. From the viewpoint of ease of production of compound (5), two R ² are preferably the same group.

(SiR ³ _n X _3-n group)
SiR ³ _n X _3-n is a hydrolyzable silyl group.
Compound (5) has two hydrolyzable silyl groups at its terminals. Since the compound (5) having this structure strongly chemically bonds with the base material, the surface layer has excellent abrasion resistance.
Moreover, compound (5) has a hydrolyzable silyl group only at one end. Since the compound (5) having this structure does not aggregate easily, the surface layer has an excellent appearance.

X is a hydrolyzable group. A hydrolyzable group is a group that becomes a hydroxyl group through a hydrolysis reaction. That is, Si--X at the terminal of compound (5) becomes a silanol group (Si--OH) by a hydrolysis reaction. The silanol groups further react intermolecularly to form Si--O--Si bonds. In addition, the silanol group undergoes a dehydration condensation reaction with the hydroxyl group (substrate-OH) on the surface of the substrate to form a chemical bond (substrate-O-Si).

Examples of X include an alkoxy group, a halogen atom, an acyl group, and an isocyanate group (--NCO). As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable. A chlorine atom is particularly preferred as the halogen atom.
As X, an alkoxy group and a halogen atom are preferable from the viewpoint of ease of production of compound (5). X 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 (5), and when long-term storage stability of compound (5) is required. is particularly preferably an ethoxy group, and is particularly preferably a methoxy group when the reaction time after coating is to be shortened.

^R3 is a hydrogen atom or a monovalent hydrocarbon group. Examples of monovalent hydrocarbon groups include alkyl groups, aryl groups, cycloalkyl groups, alkenyl groups, groups in which two or more of these groups are combined, and the like.
R ³ is preferably a monovalent hydrocarbon group, particularly preferably a monovalent saturated hydrocarbon group. The monovalent saturated hydrocarbon group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms. When the number of carbon atoms in R ³ is within this range, compound (5) can be easily produced.

n is preferably 0 or 1, particularly preferably 0. The presence of a plurality of Xs in one hydrolyzable silyl group enhances the adhesion to the substrate.

SiR ³ _n X _3-n includes 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 is preferred. Si(OCH ₃ ) ₃ is particularly preferred from the viewpoint of ease of handling in industrial production.
Two SiR ³ _n X _3-n in compound (5) may be the same or different. From the viewpoint of ease of production of compound (5), the same groups are preferred.

(Preferred form of compound (5))
Compound (5) includes, for example, compounds of the following formula. The compound is preferable because it is easy to industrially produce, easy to handle, and further excellent in water and oil repellency, abrasion resistance, fingerprint stain removability, lubricity, chemical resistance and light resistance.

where G is a polyfluoropolyether chain, ie AOQ-(R ^f1 O) _m -R ^f2 -. Preferred forms of G are combinations of the preferred A, Q, (R ^f1 O) _m and R ^f2 described above.

[Compound (1)]
Compound (1) is a starting material in the method for producing a fluorine-containing ether compound of the present invention.
A—O—Q—(R ^f1 O) _m —R ^f2 —R ¹ —CO—Z (1)
However, A, Q, (R ^f1 O) _m , R ^f2 and R ¹ are the same as A, Q, (R ^f1 O) _m , R ^f2 and R ¹ described in compound (5), and preferred forms is also the same. Z is -OH, -OR ⁴ , -R ⁵ , a halogen atom or a hydrogen atom, and R ⁴ and R ⁵ are each monovalent hydrocarbon groups.

As Z, —OH, —OR ⁴ , —R ⁵ and a halogen atom are preferred from the viewpoint of excellent reactivity, and —OR ⁴ and —R ⁵ are particularly preferred from the viewpoint of fewer reaction steps.

Examples of monovalent hydrocarbon groups for R ⁴ and R ⁵ include alkyl groups, aryl groups, cycloalkyl groups, alkenyl groups, groups in which two or more of these groups are combined, and the like. Among them, an alkyl group is preferable because the number of reaction steps is small. The number of carbon atoms in the monovalent hydrocarbon group is preferably from 1 to 20, more preferably from 1 to 10, more preferably from 1 to 6, more preferably from 1 to 1, in terms of ease of separation during synthesis and less influence on the reaction system. Especially preferred.

Compound (1) can be produced by known methods such as the method described in Patent Document 1, the method described in International Publication No. 2013/121984, and the method described in International Publication No. 2015/087902.

[Method for producing compound (2)]
Compound (2) is useful as an intermediate for fluorine-containing ether compounds, such as compound (5), which are suitably used as surface treatment agents.
A first aspect of the method for producing a fluorine-containing ether compound of the present invention is a method of reacting compound (1) with _NH3 to obtain compound (2). Further, when the present invention is a method for producing compound (5) from compound (1), step 1 is a step of reacting compound (1) with _NH3 to obtain compound (2).
A—O—Q—(R ^f1 O) _m —R ^f2 —R ¹ —CO—NH ₂ (2)
However, A, Q, (R ^f1 O) _m , R ^f2 and R ¹ are the same as A, Q, (R ^f1 O) _m , R ^f2 and R ¹ described in compound (5), and preferred forms The same is true for

In the method for producing a fluorine-containing ether compound of the present invention, since inexpensive NH ₃ is used instead of conventional expensive acid chlorides such as CF ₃ SO ₂ Cl, compound (2) and compound (2 ) can be used as raw materials to produce compounds (3) to (5) at low cost. In addition, since trifluoromethylsulfonic acid and the like, which are difficult to handle, are not by-produced, compound (2) and compounds (3) to (5) using compound (2) as a raw material can be produced with high productivity. In addition, since the reaction between compound (1) and NH ₃ proceeds under mild conditions of relatively low temperature and normal pressure, compound (2) can be easily produced without requiring special equipment.

(solvent)
The reaction of compound (1) with _NH3 is preferably carried out in a solvent. As the solvent, when Z is —OR ⁴ , the alcohol corresponding to Z (HOR ⁴ ) is preferable. As the solvent, it is also preferable to use a fluorine-containing solvent.

Alcohols corresponding to Z include alkyl alcohols (methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butyl alcohol, tert-butyl alcohol, etc.).
Fluorine-containing solvents include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols, and the like.

As the fluorinated alkane, compounds having 4 to 8 carbon atoms are preferred. Commercially available products include, for example, C ₆ F ₁₃ H (manufactured by Asahi Glass Co., Ltd., Asahiklin (registered trademark) AC-2000) and C ₆ F ₁₃ C ₂ H ₅ (manufactured by Asahi Glass Co., Ltd., Asahiklin (registered trademark) AC-6000). , C ₂ F ₅ CHFCHFCF ₃ (Bertrell (registered trademark) XF, manufactured by Chemours) and the like.
Examples of fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, bis(trifluoromethyl)benzene and the like.
As the fluoroalkyl ether, compounds having 4 to 12 carbon atoms are preferred. Commercially available products include CF ₃ CH ₂ OCF ₂ CF ₂ H (manufactured by Asahi Glass Co., Ltd., Asahiklin (registered trademark) AE-3000), C ₄ F ₉ OCH ₃ (manufactured by 3M, Novec (registered trademark) 7100), C ₄ F ₉ OC ₂ H ₅ (manufactured by 3M, Novec (registered trademark) 7200), C ₂ F ₅ CF(OCH ₃ )C ₃ F ₇ (manufactured by 3M, Novec (registered trademark) 7300), etc. .
Examples of fluorinated alkylamines include perfluorotripropylamine and perfluorotributylamine.
Examples of fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol and the like.

(Reaction conditions)
The reaction temperature is preferably 0 to 400°C, more preferably 0 to 300°C, and particularly preferably 10 to 150°C.
The reaction pressure is preferably 0 to 30 MPa [gauge], more preferably 0 to 20 MPa [gauge], and particularly preferably 0 to 10 MPa [gauge].
The reaction time is preferably longer than 0 to 400 hours, more preferably 0.01 to 200 hours, and particularly preferably 1 to 150 hours.
High temperature and high pressure are preferable when high productivity is considered, but mild conditions are preferable when safety, operability, and high selectivity of the target are considered.

_NH3 to be reacted with compound (1) may be gas or liquid, and may be dissolved in a solvent.
The amount of NH ₃ is preferably 0.5 mol or more, particularly preferably 1 mol or more, per 1 mol of compound (1). There is no particular upper limit, but 1,000 mol is preferable.
The reaction between compound (1) and _NH3 may be a continuous reaction or a batch reaction (batch reaction).

[Method for producing compound (3)]
Compound (3) is useful as an intermediate for fluorine-containing ether compounds, such as compound (5), which are suitably used as surface treatment agents.
A second aspect of the method for producing a fluorine-containing ether compound of the present invention is a method of obtaining compound (3) by reacting compound (2) with a reducing agent. When the present invention is a method for producing compound (5) from compound (1), step 2 is a step of reacting compound (2) with a reducing agent to obtain compound (3).
A—O—Q—(R ^f1 O) _m —R ^f2 —R ¹ —CH ₂ —NH ₂ (3)
However, A, Q, (R ^f1 O) _m , R ^f2 and R ¹ are the same as A, Q, (R ^f1 O) _m , R ^f2 and R ¹ described in compound (5), and preferred forms is also the same.

(reducing agent)
Reducing agents include sodium borohydride, lithium aluminum hydride, borane (monoborane, diborane, etc.), metallic sodium, sodium bis(2-methoxyethoxy)aluminum hydride, diisobutylaluminum hydride, lithium borohydride, Lithium triethylborate, hydrogen gas in the presence of a metal catalyst (palladium catalyst, platinum catalyst, etc.), and the like.
Two of these may be used in combination, and a promoter may be used in addition to the reducing agent.
A Lewis acid etc. are mentioned as a co-catalyst. Examples of Lewis acids include metal halides and iodine. Examples of metal halides include aluminum fluoride, aluminum chloride, boron trifluoride, chromium chloride, nickel chloride hexahydrate, titanium chloride, lithium chloride, and the like.

(Reaction conditions)
The reaction temperature is preferably -20 to 180°C, more preferably -10 to 150°C, still more preferably 0 to 100°C, and particularly preferably 20 to 90°C.
The reaction time is preferably 0.1 to 48 hours, particularly preferably 3 to 24 hours.
The reaction between compound (2) and the reducing agent may be a continuous reaction or a batch reaction (batch reaction).

[Method for producing compound (4)]
Compound (4) is useful as an intermediate for fluorine-containing ether compounds, such as compound (5), which are suitably used as surface treatment agents.
A third aspect of the method for producing a fluorine-containing ether compound of the present invention is a method of reacting compound (3) with YR ²¹ to obtain compound (4). When the present invention is a method for producing compound (5) from compound (1), step 3 is a step of reacting compound (3) with YR ²² to obtain compound (4a). However, R ²² means only a monovalent organic group having a terminal vinyl group among R ²¹ .
A—O—Q—(R ^f1 O) _m —R ^f2 —R ¹ —CH ₂ —NR ²¹ ₂ (4)
A—O—Q—(R ^f1 O) _m —R ^f2 —R ¹ —CH ₂ —NR ²² ₂ (4a)
However, A, Q, (R ^f1 O) _m , R ^f2 and R ¹ are the same as A, Q, (R ^f1 O) _m , R ^f2 and R ¹ described in compound (5), and preferred forms The same is true for Y is HO—, R ⁶ O— or a halogen atom, R ⁶ is a monovalent hydrocarbon group, and R ²¹ is a monovalent organic group or monovalent hydrocarbon having a terminal vinyl group group (excluding those having a terminal vinyl group), and R ²² is a monovalent organic group having a terminal vinyl group.

( ^YR21 , ^YR22 )
From the viewpoint of excellent reactivity, Y is preferably HO— or a halogen atom, and particularly preferably a halogen atom. Halogen atoms include F, Cl, Br and I.
Examples of monovalent hydrocarbon groups for R ⁶ include alkyl groups, aryl groups, cycloalkyl groups, alkenyl groups, and groups in which two or more of these groups are combined. Among them, an alkyl group is preferable because the number of reaction steps is small. The number of carbon atoms in the monovalent hydrocarbon group is preferably from 1 to 20, more preferably from 1 to 10, more preferably from 1 to 6, more preferably from 1 to 1, in terms of ease of separation during synthesis and less influence on the reaction system. Especially preferred.

R ²¹ is preferably a monovalent organic group having a terminal vinyl group, and R ²² is a monovalent organic group having a terminal vinyl group, from the viewpoint of easy production of compound (5).
In R ²¹ and R ²² , the monovalent organic group having a terminal vinyl group includes an aliphatic hydrocarbon group having a terminal vinyl group and having 2 to 10 carbon atoms and a vinyl group having a terminal vinyl group and having 3 carbon atoms. A group having an etheric oxygen atom or -NH- between the carbon-carbon atoms of an aliphatic hydrocarbon group of ~10 (excluding the carbon-carbon atoms of a vinyl group) is preferable, and the number of carbon atoms having a vinyl group at the end Ether between carbon atoms of 2 to 7 aliphatic hydrocarbon groups and vinyl group-terminated aliphatic hydrocarbon groups of 3 to 7 carbon atoms (excluding between carbon atoms of vinyl groups) A group having a functional oxygen atom or -NH- is more preferred.
As R ²² and R ²¹ which is a monovalent organic group having a terminal vinyl group, an allyl group and an allyloxyalkyl group are preferable because YR ²¹ and YR ²² are easily available, and the allyl group and the carbon atom of the alkyl moiety More preferred are allyloxyalkyl groups with numbers from 2 to 6, with -CH ₂ CH=CH ₂ and -CH ₂ CH ₂ OCH ₂ CH=CH ₂ being particularly preferred.
Also, the two R ²¹ in compound (4) and the two R ²² in compound (4a) may be different. Two R ²¹ and two R ²² are preferably the same group from the viewpoint of ease of production of compound (4) and compound (4a).

In R ²¹ , monovalent hydrocarbon groups (excluding those having a terminal vinyl group) include alkyl groups, aryl groups, cycloalkyl groups, and alkenyl groups (providing that those having a terminal vinyl group are ), groups in which two or more of these are combined, and the like. The number of carbon atoms in the monovalent hydrocarbon group (excluding those having a terminal vinyl group) is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, and particularly preferably 1.

Preferred specific examples of YR ²¹ and YR ²² include FCH ₂ CH=CH ₂ , ClCH ₂ CH=CH ₂ , BrCH ₂ CH=CH ₂ , ICH ₂ CH=CH ₂ , FCH ₂ CH ₂ OCH ₂ CH=CH _{2 , ClCH2CH2OCH2CH = CH2} , _{BrCH2CH2OCH2CH = CH2 , ICH2CH2OCH2CH = CH2} , _{FCH2CH2OCH = CH2 , ClCH2CH2OCH =} CH ₂ , _BrCH2CH2OCH = _CH2 , _{and ICH2CH2OCH = CH2} .

(basic compound)
The reaction of compound (3) with YR ²¹ and YR ²² is preferably carried out in the presence of a basic compound in order to promote the reaction.
Basic compounds include basic organic compounds and basic inorganic compounds.

Examples of basic organic compounds include alkylamine compounds, arylamine compounds, alkenylamine compounds, heterocyclic amine compounds, and the like, and alkylamine compounds and heterocyclic amine compounds are preferable from the viewpoint of excellent versatility.
Alkylamine compounds include triethylamine.
Heterocyclic amine compounds include pyridine, lutidine, collidine, pyrrole, pyrimidine, N,N-dimethyl-4-aminopyridine, 2,6-dimethylpyridine, 2,6-di-tert-butylpyridine and the like.

Basic inorganic compounds include alkali metal hydrides (sodium hydride, etc.), carbonates (sodium carbonate, potassium carbonate, cesium carbonate, etc.), hydrogen carbonates (sodium hydrogen carbonate, potassium hydrogen carbonate, etc.), and alkali metal water. Examples include oxides (sodium hydroxide, potassium hydroxide, etc.), alkali metal alkoxides (potassium tert-butoxide, etc.), and the like.
A basic compound may be used individually by 1 type, or may be used in combination of 2 or more types.

(Phase transfer catalyst)
The reaction of compound (3) with YR ²¹ and YR ²² may be carried out in the presence of a phase transfer catalyst.
Phase transfer catalysts include quaternary ammonium salts such as tetrabutylammonium bromide and benzyltriethylammonium chloride.

(solvent)
The reaction of compound (3) with YR ²¹ and YR ²² is preferably carried out in a fluorine-containing solvent from the viewpoint of excellent solubility.
Examples of the fluorine-containing solvent include the same fluorine-containing solvents as the fluorine-containing solvent that can be used in the production of compound (2), and preferred embodiments are also the same.
A solvent may be used individually by 1 type, or may be used in combination of 2 or more types.

(Reaction conditions)
The reaction temperature is preferably 0 to 200°C, more preferably 20 to 150°C, and particularly preferably 50 to 100°C.
The reaction time is preferably 0.01 to 24 hours, more preferably 0.3 to 20 hours, particularly preferably 0.3 to 15 hours.
The amount of YR ²¹ and YR ²² is preferably 0.5 to 20 mol, more preferably 1 to 15 mol, particularly preferably 2 to 8 mol, per 1 mol of compound (3).
The reaction of compound (3) with YR ²¹ and YR ²² may be a continuous reaction or a batch reaction (batch reaction).

[Method for producing compound (5)]
A fourth aspect of the method for producing a fluorine-containing ether compound of the present invention is a method of obtaining compound (5) by subjecting compound (4a) and HSiR ³ _n X _3-n to a hydrosilylation reaction. Further, when the present invention is a method for producing compound (5) from compound (1), step 4 includes hydrosilylation reaction of compound (4a) and HSiR ³ _n X _3-n to obtain compound (5). is the process of obtaining

(HSiR ³ _n X _3-n )
R ^{3 ,} X and n in HSiR ³ _n X _3-n are the same as R ³ , X and n described in compound (5), and preferred forms are also the same.
HSiR ³ _n X _3-n includes HSi(OCH ₃ ) ₃ , HSiCH ₃ (OCH ₃ ) ₂ , HSi(OCH ₂ CH ₃ ) ₃ , HSiCl ₃ , Si(OCOCH ₃ ) ₃ and HSi(NCO) ₃ is preferred. HSi(OCH ₃ ) ₃ is particularly preferred from the viewpoint of ease of handling in industrial production.

(Hydrosilylation reaction)
The hydrosilylation reaction is preferably carried out using a transition metal catalyst such as platinum, palladium, silver, gold and rhodium, or a radical generator such as an organic peroxide.
The reaction temperature is preferably 0 to 150°C, more preferably 10 to 100°C, and particularly preferably 20 to 60°C.
The reaction time is preferably 0.01 to 24 hours, more preferably 1 to 15 hours, particularly preferably 3 to 10 hours.

EXAMPLES The present invention will be described in more detail below using examples, but the present invention is not limited to these examples.
Hereinafter, "%" means "% by mass" unless otherwise specified.
Examples 1-13 are examples.

[evaluation]
(Conversion and selectivity)
The reaction product was analyzed by gas chromatography, ¹ H-NMR and ¹⁹ F-NMR for composition analysis, and the conversion and selectivity were calculated.

(Number average molecular weight)
The number average molecular weight of the fluorine-containing ether compound was calculated by determining the number (average value) of oxyperfluoroalkylene groups based on the terminal groups by ¹ H-NMR and ¹⁹ F-NMR.

[Example 1]
Compound (1-1) was obtained with reference to Examples 1-1 to 1-4 of Examples in Patent Document 1.
CF ₃ CF ₂ CF ₂ —O—(CF ₂ CF ₂ O) ₂ {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 }—CF ₂ —CO—OCH ₃ (1-1)
Average value of unit number x1: 18, average value of unit number x2: 20, number average molecular weight of compound (1-1): 4,030.

Next, 10.1 g of compound (1-1) and 30 g of methanol (manufactured by Junsei Chemical Co., Ltd.) are placed in a 100 mL autoclave made of nickel, and 42 g of liquid NH ₃ is filled in the autoclave at a pressure of 1.0 MPa, The reaction was carried out at 50°C for 150 hours. After completion of the reaction, the reaction crude liquid was concentrated by an evaporator to obtain 7.6 g of compound (2-1). Conversion and selectivity are shown in Table 1.
CF ₃ CF ₂ CF ₂ —O—(CF ₂ CF ₂ O) ₂ {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } —CF ₂ —CO—NH ₂ (2-1)

NMR spectrum of compound (2-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: tetramethylsilane (TMS)) δ (ppm): 7.2 (2H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −52.5 to −55.9 (36F), −81.7 (1F), −82.5 ( 3F), -83.2 (1F), -89.3 to -91.1 (90F), -130.9 (2F).
Average value of unit number x1: 18, average value of unit number x2: 20, number average molecular weight of compound (2-1): 4,020.

[Examples 2-4]
Compound (2-1) was obtained in the same manner as in Example 1 except that the reaction conditions of compound (1-1) and liquid NH ₃ were changed to those shown in Table 1. Conversion and selectivity are shown in Table 1.

Comparing Examples 1, 2 and 4, in the reaction of compound (1-1) with _NH3 , the higher the reaction temperature, the shorter the reaction time until the same amount of compound (2-1) is obtained. However, the selectivity tends to decrease. Comparing Examples 2 and 3, the longer the reaction time, the higher the conversion rate.
If unreacted substances or by-products remain in compound (2-1), they affect compound (5-1), which is the final product (product). Therefore, a higher conversion rate is desired in order to reduce unreacted substances. Also, a higher selectivity is desired in order to reduce by-products. Therefore, the reaction between compound (1-1) and NH ₃ is desirably carried out at a low temperature for a long period of time.

[Example 5]
A 100 mL autoclave made of nickel was charged with 10.0 g of compound (1-1), 100 g of dichloropentafluoropropane (AK-225, manufactured by Asahi Glass Co., Ltd.), and 5.0 g of a 2.0 mol/L ammonia-methanol solution. at 25° C. for 8 hours. The solvent was distilled off to obtain 14.8 g of compound 2-1 (conversion rate 99.0, yield 98.9%).

[Example 6]
In a 100 mL three-necked flask, 20 g of the compound (2-1) obtained in Example 3 was dissolved in 20 g of tetrahydrofuran (hereinafter referred to as THF), and this was cooled in an ice bath while adding lithium aluminum hydride to 0. It was slowly added dropwise to a THF solution in which .34 g was dissolved. After dropping, the temperature was raised to 70° C. and the mixture was stirred for 15 hours. Then, it is cooled with ice, quenched with an aqueous potassium hydroxide solution and water, filtered through celite, the solvent is distilled off, and 19.9 g of compound (3-1) (yield 99%, conversion 99.0%) is obtained. , selectivity 100.0%).
CF ₃ CF ₂ CF ₂ —O—(CF ₂ CF ₂ O) ₂ {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } —CF ₂ —CH ₂ —NH ₂ (3-1)

NMR spectrum of compound (3-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 3.2 (2H), 5.2 (2H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −52.0 to −55.7 (36F), −74.3 (1F), −82.1 ( 3F), -89.5 to -91.1 (90F), -130.3 (2F).
Average value of unit number x1: 18, average value of unit number x2: 20, number average molecular weight of compound (3-1): 4,010.

[Example 7]
In a 50 mL three-necked flask, 0.1 g of potassium hydrogen carbonate (manufactured by Kanto Kagaku Co., Ltd.) was dissolved in a mixed solvent of 23.7 g of THF and 10.5 g of dimethylsulfoxide. To the solution in the flask were added 10.3 g of the compound (3-1) obtained in Example 6 and 1.2 g of BrCH ₂ CH═CH ₂ (manufactured by Tosoh Organic Chemical Co., Ltd.) and stirred at 70° C. for 20 hours. After completion of the reaction, the reaction crude liquid was filtered, the solvent was distilled off under reduced pressure, and fractionation was performed using a gas chromatograph to obtain 10.1 g of compound (4-1) (yield 94%).
_{CF3CF2CF2 -} O- _{( CF2CF2O ) 2} {( _CF2O ) _x1 ( _CF2CF2O ) _x2 }-CF2 _{- CH2 -} N( _-CH2CH = _CH2 ) ₂ (4-1)

NMR spectrum of compound (4-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 2.9 (2H), 3.1 (4H), 5.2 (4H), 5.7 (2H) .
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −52.1 to −55.7 (36F), −74.3 (1F), −82.2 ( 3F), -89.5 to -91.0 (90F), -130.4 (2F).
Average value of unit number x1: 18, average value of unit number x2: 20, number average molecular weight of compound (4-1): 4,090.

[Example 8]
10.1 g of compound (4-1) obtained in Example 7, xylene solution of platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%) 0.03 g, 1.2 g of HSi(OCH ₃ ) ₃ , 0.01 g of dimethyl sulfoxide and 0.4 g of 1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were added and heated at 40° C. for 10 minutes. Stirred for an hour. After completion of the reaction, the solvent and the like were distilled off under reduced pressure, filtered through a membrane filter with a pore size of 0.2 μm, and 9.5 g of compound (5-1) in which two allyl groups of compound (4-1) were hydrosilylated ( Yield 89%) was obtained.
_{CF3CF2CF2 - O-} ( _{CF2CF2O ) 2} {( _{CF2O ) x1} ( _CF2CF2O ) _x2 }-CF2 _{- CH2 -} N _{[ -CH2CH2CH2-} Si(OCH ₃ ) ₃ ] ₂ (5-1)

NMR spectrum of compound (5-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.5 (4H), 1.5 (4H), 2.5 (4H), 3.0 (2H) , 3.4 (18H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −52.2 to −55.5 (36F), −74.1 (1F), −76.9 ( 1F), -82.3 (3F), -89.3 to -91.2 (90F), -130.8 (2F).
Average value of unit number x1: 18, average value of unit number x2: 20, number average molecular weight of compound (5-1): 4,330.

[Example 9]
Compound (1-2) was obtained with reference to Examples 6-1 to 6-4 of Examples of WO 2013/121984.
CF ₃ —O—(CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _x3 —CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ —CO—OCH ₃ (1-2)
Average value of number of units x 3: 13, number average molecular weight of compound (1-2): 4,800.

Next, 10.0 g of compound (1-2) and 20 g of methanol (manufactured by Junsei Chemical Co., Ltd.) are placed in a 100 mL autoclave made of nickel, and 35 g of liquid NH ₃ is filled in the autoclave at a pressure of 1.0 MPa, The reaction was carried out at 25°C for 210 hours. After completion of the reaction, the reaction crude liquid was concentrated by an evaporator to obtain 9.6 g of compound (2-2) (yield 96%, conversion 94.1%, selectivity 98.6%).
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 —CO—NH ₂ (2-2)

NMR spectrum of compound (2-2);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 7.4 (2H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): 56.1 (3F), −83.1 to −83.5 (54F), −88.5 to − 89.2 (54F), -91.1 (2F), -119.5 (2F), -126.7 (52F), -126.8 (2F).
Average value of number of units x 3: 13, number average molecular weight of compound (2-2): 4,790.

[Example 10]
20 g of the compound (2-2) obtained in Example 9 was dissolved in 20 g of THF in a 100 mL three-necked flask, and this was cooled in an ice bath while 0.32 g of lithium aluminum hydride was dissolved in THF solution. slowly dripped into the After dropping, the temperature was raised to 70° C. and the mixture was stirred for 15 hours. Then, it is cooled with ice, quenched with an aqueous potassium hydroxide solution and water, filtered through celite, the solvent is distilled off, and 19.9 g of compound (3-2) (yield 99%, conversion 99.0%) is obtained. , selectivity 100.0%).
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 —NH ₂ (3-2)

NMR spectrum of compound (3-2);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 3.1 (2H), 5.4 (2H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): 55.9 (3F), −83.8 to −84.2 (54F), −89.5 to − 89.1 (54F), -91.1 (2F), -119.1 (2F), -126.3 (52F), -126.3 (2F).
Average value of number of units x 3: 13, number average molecular weight of compound (3-2): 4,770.

[Example 11]
In a 50 mL three-necked flask, 0.1 g of potassium hydrogen carbonate (manufactured by Kanto Kagaku Co., Ltd.) was dissolved in a mixed solvent of 23.7 g of THF and 10.5 g of dimethylsulfoxide. 10.0 g of the compound (3-2) obtained in Example 10 and 1.0 g of BrCH ₂ CH═CH ₂ (manufactured by Tosoh Organic Chemical Co., Ltd.) were added to the solution in the flask, and the mixture was stirred at 70° C. for 20 hours. After completion of the reaction, the reaction crude liquid was filtered, the solvent was distilled off under reduced pressure, and fractionation was performed using a gas chromatograph to obtain 9.6 g of compound (4-2) (yield 95%).
_{CF3 - O- ( CF2CF2O -} CF2CF2CF2CF2O) _{x3- CF2CF2O} - _{CF2CF2CF2 - CH2- N ( -CH2CH = CH2} ) ₂ (4-2)

NMR spectrum of compound (4-2);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 3.1 (2H), 3.2 (4H), 5.2 (4H), 5.8 (2H) .
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): 56.3 (3F), −84.0 (54F), −89.1 (54F), −91. 4 (2F), -120.8 (2F), -126.7 (54F).
Average value of number of units x 3: 13, number average molecular weight of compound (4-2): 4,800.

[Example 12]
9.0 g of compound (4-2) obtained in Example 11, xylene solution of platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%) 0.03 g, 1.0 g of HSi(OCH ₃ ) ₃ , 0.01 g of dimethyl sulfoxide and 0.4 g of 1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were added and heated at 40° C. for 10 minutes. Stirred for an hour. After completion of the reaction, the solvent and the like were distilled off under reduced pressure, filtered through a membrane filter with a pore size of 0.2 μm, and 8.5 g of compound (5-2) in which two allyl groups of compound (4-2) were hydrosilylated ( Yield 90%) was obtained.
CF3 _{- O- ( CF2CF2O - CF2CF2CF2CF2O ) x3- CF2CF2O - CF2CF2CF2 - CH2 - N [ -CH2CH2CH2-} Si(OCH ₃ ) ₃ ] ₂ (5-2)

NMR spectrum of compound (5-2);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.7 (4H), 1.6 (4H), 2.6 (4H), 3.2 (2H) , 3.6 (18H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): 56.2 (3F), −83.9 (54F), −89.3 (54F), −91. 4 (2F), -121.0 (2F), -126.8 (54F).
Average value of number of units x 3: 13, number average molecular weight of compound (5-2): 5,040.

[Example 13]
In a 50 mL three-necked flask, 0.1 g of potassium hydrogen carbonate (manufactured by Kanto Kagaku Co., Ltd.) was dissolved in a mixed solvent of 23.7 g of THF and 10.5 g of dimethylsulfoxide. 10.0 g of the compound (3-1) obtained in Example 6 and 1.7 g of BrCH ₂ CH ₂ OCH ₂ CH═CH ₂ were added to the solution in the flask and stirred at 70° C. for 20 hours. After completion of the reaction, the reaction crude liquid was filtered, the solvent was distilled off under reduced pressure, and fractionation was performed using a gas chromatograph to obtain 9.8 g of compound (4-3) (yield 95%).
_{CF3CF2CF2 -} O-( _{CF2CF2O ) 2} {( _{CF2O ) x1} ( _{CF2CF2O ) x2} } _{-CF2- CH2 - N} ( _{-CH2CH2OCH2CH} =CH ₂ ) ₂ (4-3)

NMR spectrum of compound (4-3);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 2.5 (4H), 2.7 (2H), 3.7 (4H), 4.1 (4H) , 5.3 (2H), 5.5 (2H), 6.1 (2H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −52.1 to −55.6 (36F), −74.4 (1F), −82.2 ( 3F), -89.5 to -91.1 (90F), -130.4 (2F).
Average value of unit number x1: 18, average value of unit number x2: 20, number average molecular weight of compound (4-3): 4,170.

[Example 14]
9.0 g of compound (4-3) obtained in Example 13, xylene solution of platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%) 0.03 g, 1.1 g of HSi(OCH ₃ ) ₃ , 0.01 g of dimethyl sulfoxide and 0.4 g of 1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were added and heated at 40° C. for 10 minutes. Stirred for an hour. After completion of the reaction, the solvent and the like were distilled off under reduced pressure, filtered through a membrane filter with a pore size of 0.2 μm, and 8.6 g of compound (5-3) in which two allyl groups of compound (4-3) were hydrosilylated ( Yield 90%) was obtained.
_{CF3CF2CF2 - O-} ( _{CF2CF2O ) 2} {(CF2O _{) x1 ( CF2CF2O} ) _{x2 }} -CF2 _{- CH2 -} N[ _{-CH2CH2OCH2CH 2} CH ₂ —Si(OCH ₃ ) ₃ ] ₂ (5-3)

NMR spectrum of compound (5-3);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.6 (4H), 1.5 (4H), 2.5 (4H), 2.7 (2H) , 3.4 (4H), 3.5 (18H), 3.6 (4H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −52.3 to −55.2 (36F), −74.4 (1F), −77.1 ( 1F), -82.4 (3F), -89.3 to -91.3 (90F), -130.9 (2F).
Average value of unit number x1: 18, average value of unit number x2: 20, number average molecular weight of compound (5-3): 4,410.

The fluorine-containing ether compound obtained by the production method of the present invention can be used in various applications where lubricity and water/oil repellency are required. For example, a display input device such as a touch panel; a surface protective coating of a transparent glass or transparent plastic member, an antifouling coating for kitchens; Antifouling coating; coating on members that require liquid repellency while conducting; water-repellent, waterproof, and water-sliding coating for heat exchangers;
In addition, the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2017-091740 filed on May 02, 2017 are cited here and incorporated as disclosure of the specification of the present invention. is.

Claims (13)

A method for producing a fluorine-containing ether compound, which comprises reacting a compound represented by the following formula (1) with _NH3 to obtain a compound represented by the following formula (2).
A—O—Q—(R ^f1 O) _m —R ^f2 —C O—Z (1)
A—O—Q—(R ^f1 O) _m —R ^f2 —C O—NH ₂ (2)
however,
A is a perfluoroalkyl group having 1 to 20 carbon atoms,
Q is a single bond, a fluoroalkylene group containing one or more hydrogen atoms, or an ether at the end of a fluoroalkylene group containing one or more hydrogen atoms (limited to the side that bonds to (R ^f1 O) _m ) a group having an etheric oxygen atom, a group having an etheric oxygen atom between the carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms containing one or more hydrogen atoms, or a group having two carbon atoms containing one or more hydrogen atoms A group having an etheric oxygen atom between the terminal of the above fluoroalkylene group (limited to the side that bonds to (R ^f1 O) _m ) and carbon-carbon atoms,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is an integer from 2 to 200,
(R ^f1 O) _m is represented by {(CF ₂ O) _m1 (CF ₂ CF ₂ O) _m2 }, (CF ₂ CF ₂ O) _m3 , (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O ) _m5 and any group having 1 to 4 other (R ^f1 O) at one or both ends thereof, where m1 is an integer of 1 or more and m2 is an integer of 1 or more , m1+m2 are integers from 2 to 200, the order of bonding of m1 CF ₂ O and m2 CF ₂ CF ₂ O is not limited, m3 is an integer from 2 to 200, m5 is an integer from 1 to 100 is an integer and
Z is -OH, -OR ⁴ , -R ⁵ , a halogen atom or a hydrogen atom, and R ⁴ and R ⁵ are each monovalent hydrocarbon groups. 2. The production method according to claim 1, wherein Z is -OR ⁴ and the compound represented by formula (1) is reacted with NH ₃ in an alcoholic solvent or a fluorine-containing solvent. A method for producing a fluorine-containing ether compound, which comprises reacting a compound represented by the following formula (2) with a reducing agent to obtain a compound represented by the following formula (3).
A—O—Q—(R ^f1 O) _m —R ^f2 —C O—NH ₂ (2)
A—O—Q—(R ^f1 O) _m —R ^f2 —C H ₂ —NH ₂ (3)
however,
A is a perfluoroalkyl group having 1 to 20 carbon atoms,
Q is a single bond, a fluoroalkylene group containing one or more hydrogen atoms, or an ether at the end of a fluoroalkylene group containing one or more hydrogen atoms (limited to the side that bonds to (R ^f1 O) _m ) a group having an etheric oxygen atom, a group having an etheric oxygen atom between the carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms containing one or more hydrogen atoms, or a group having two carbon atoms containing one or more hydrogen atoms A group having an etheric oxygen atom between the terminal of the above fluoroalkylene group (limited to the side that bonds to (R ^f1 O) _m ) and carbon-carbon atoms,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is an integer from 2 to 200,
(R ^f1 O) _m is represented by {(CF ₂ O) _m1 (CF ₂ CF ₂ O) _m2 }, (CF ₂ CF ₂ O) _m3 , (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O ) _m5 and any group having 1 to 4 other (R ^f1 O) at one or both ends thereof, where m1 is an integer of 1 or more and m2 is an integer of 1 or more , m1+m2 are integers from 2 to 200, the order of bonding of m1 CF ₂ O and m2 CF ₂ CF ₂ O is not limited, m3 is an integer from 2 to 200, m5 is an integer from 1 to 100 is an integer . A method for producing a fluorine-containing ether compound, which comprises reacting a compound represented by the following formula (3) with YR ²¹ to obtain a compound represented by the following formula (4).
A—O—Q—(R ^f1 O) _m —R ^f2 —C H ₂ —NH ₂ (3)
A—O—Q—(R ^f1 O) _m —R ^f2 —C H ₂ —NR ²¹ ₂ (4)
however,
A is a perfluoroalkyl group having 1 to 20 carbon atoms,
Q is a single bond, a fluoroalkylene group containing one or more hydrogen atoms, or an ether at the end of a fluoroalkylene group containing one or more hydrogen atoms (limited to the side that bonds to (R ^f1 O) _m ) a group having an etheric oxygen atom, a group having an etheric oxygen atom between the carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms containing one or more hydrogen atoms, or a group having two carbon atoms containing one or more hydrogen atoms A group having an etheric oxygen atom between the terminal of the above fluoroalkylene group (limited to the side that bonds to (R ^f1 O) _m ) and carbon-carbon atoms,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is an integer from 2 to 200,
(R ^f1 O) _m may consist of two or more R ^f1 O ,
Y is HO—, R ⁶ O— or a halogen atom, R ⁶ is a monovalent hydrocarbon group,
R ²¹ is a monovalent organic group or monovalent hydrocarbon group having a terminal vinyl group (excluding those having a terminal vinyl group). 5. The production method according to claim 4, wherein Y is a halogen atom and ^R21 is an allyl group or an allyloxyalkyl group. A method for producing a fluorine-containing ether compound, which comprises obtaining a compound represented by the following formula (5) from a compound represented by the following formula (1) through the following steps 1 to 4.
Step 1: A step of reacting a compound represented by the following formula (1) with _NH3 to obtain a compound represented by the following formula (2).
Step 2: A step of reacting a compound represented by the following formula (2) with a reducing agent to obtain a compound represented by the following formula (3).
Step 3: A step of reacting a compound represented by the following formula (3) with YR ²² to obtain a compound represented by the following formula (4a).
Step 4: A step of hydrosilylating the compound represented by the following formula (4a) and HSiR ³ _n X _3-n to obtain the compound represented by the following formula (5).
AOQ-(R ^f1 O) _m -R ^f2 -CO-Z (1)
A—O—Q—(R ^f1 O) _m —R ^f2 —CO—NH ₂ (2)
A—O—Q—(R ^f1 O) _m —R ^f2 —CH ₂ —NH ₂ (3)
A—O—Q—(R ^f1 O) _m —R ^f2 —CH ₂ —NR ²² ₂ (4a)
A—O—Q—(R ^f1 O) _m —R ^f2 —CH ₂ —N[—R ² —SiR ³ _n X _3-n ] ₂ (5)
however,
A is a perfluoroalkyl group having 1 to 20 carbon atoms,
Q is a single bond, a fluoroalkylene group containing one or more hydrogen atoms, or an ether at the end of a fluoroalkylene group containing one or more hydrogen atoms (limited to the side that bonds to (R ^f1 O) _m ) a group having an etheric oxygen atom, a group having an etheric oxygen atom between the carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms containing one or more hydrogen atoms, or a group having two carbon atoms containing one or more hydrogen atoms A group having an etheric oxygen atom between the terminal of the above fluoroalkylene group (limited to the side that bonds to (R ^f1 O) _m ) and carbon-carbon atoms,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is an integer from 2 to 200,
(R ^f1 O) _m may consist of two or more R ^f1 O,
Z is —OH, —OR ⁴ , —R ⁵ , a halogen atom or a hydrogen atom, R ⁴ and R ⁵ are each a monovalent hydrocarbon group,
Y is HO—, R ⁶ O— or a halogen atom, R ⁶ is a monovalent hydrocarbon group,
R ²² is a monovalent organic group having a terminal vinyl group,
R ² is a divalent organic group derived from R ²² ,
R ³ is a hydrogen atom or a monovalent hydrocarbon group,
X is a hydrolyzable group,
n is an integer of 0-2.

7. The production method according to claim 6 , wherein Z is -OR ⁴ and the compound represented by formula (1) is reacted with NH ₃ in an alcoholic solvent or a fluorine-containing solvent. 8. The production method according to claim 6 or 7 , wherein Y is a halogen atom and ^R22 is an allyl group or an allyloxyalkyl group. The production method according to any one of claims 6 to 8 , wherein said Q is a single bond. A fluorine-containing ether compound represented by the following formula (2).
A—O—Q—(R ^f1 O) _m —R ^f2 —C O—NH ₂ (2)
however,
A is a perfluoroalkyl group having 1 to 20 carbon atoms,
Q is a single bond, a fluoroalkylene group containing one or more hydrogen atoms, or an ether at the end of a fluoroalkylene group containing one or more hydrogen atoms (limited to the side that bonds to (R ^f1 O) _m ) a group having an etheric oxygen atom, a group having an etheric oxygen atom between the carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms containing one or more hydrogen atoms, or a group having two carbon atoms containing one or more hydrogen atoms A group having an etheric oxygen atom between the terminal of the above fluoroalkylene group (limited to the side that bonds to (R ^f1 O) _m ) and carbon-carbon atoms,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is an integer from 2 to 200,
(R ^f1 O) _m is represented by {(CF ₂ O) _m1 (CF ₂ CF ₂ O) _m2 }, (CF ₂ CF ₂ O) _m3 , (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O ) _m5 and any group having 1 to 4 other (R ^f1 O) at one or both ends thereof, where m1 is an integer of 1 or more and m2 is an integer of 1 or more , m1+m2 are integers from 2 to 200, the order of bonding of m1 CF ₂ O and m2 CF ₂ CF ₂ O is not limited, m3 is an integer from 2 to 200, m5 is an integer from 1 to 100 is an integer . 11. The compound of Claim 10 , wherein said Q is a single bond. A fluorine-containing ether compound represented by the following formula (3).
A—O—Q—(R ^f1 O) _m —R ^f2 —C H ₂ —NH ₂ (3)
however,
A is a perfluoroalkyl group having 1 to 20 carbon atoms,
Q is a single bond, a fluoroalkylene group containing one or more hydrogen atoms, or an ether at the end of a fluoroalkylene group containing one or more hydrogen atoms (limited to the side that bonds to (R ^f1 O) _m ) a group having an etheric oxygen atom, a group having an etheric oxygen atom between the carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms containing one or more hydrogen atoms, or a group having two carbon atoms containing one or more hydrogen atoms A group having an etheric oxygen atom between the terminal of the above fluoroalkylene group (limited to the side that bonds to (R ^f1 O) _m ) and carbon-carbon atoms,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is an integer from 2 to 200,
(R ^f1 O) _m is represented by {(CF ₂ O) _m1 (CF ₂ CF ₂ O) _m2 }, (CF ₂ CF ₂ O) _m3 , (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O ) _m5 and any group having 1 to 4 other (R ^f1 O) at one or both ends thereof, where m1 is an integer of 1 or more and m2 is an integer of 1 or more , m1+m2 are integers from 2 to 200, the order of bonding of m1 CF ₂ O and m2 CF ₂ CF ₂ O is not limited, m3 is an integer from 2 to 200, m5 is an integer from 1 to 100 is an integer . 13. The compound of claim 12 , wherein said Q is a single bond.