JP7126891B2 - Method for producing fluorine-containing ether compound - Google Patents

Description

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

A fluorine-containing ether compound having a perfluoropolyether (hereinafter referred to as "PFPE") chain and having a hydrolyzable silyl group at the end is a surface layer that exhibits high lubricity, water and oil repellency, etc. can be formed on the surface of the surface, it is suitable for use as a surface treatment agent.

As a method for producing a fluorine-containing ether compound used as a surface treatment agent, CF ₂ ═CFOCF ₂ CF ₂ CF ₂ CH ₂ OH is used as a starting material and has (CF ₂ CHFO—CF ₂ CF ₂ CF ₂ CH ₂ O) units. producing an intermediate fluorine-containing ether compound having a polyfluoropolyether chain, further producing an intermediate having a PFPE chain having (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) units, A method for producing a fluorine-containing ether compound having a PFPE chain and a hydrolyzable silyl group at the end, which is the ultimate target substance, has been disclosed (Patent Document 1).

As a method for purifying the intermediate fluorine-containing ether compound, a method by chromatography using silica gel has been proposed (Patent Document 2).

WO2013/121986 Japanese Patent Publication No. 2015-535017

According to the findings of the present inventors, in the production method described in Patent Document 1, CF ₂ ═CFOCF when obtaining an intermediate fluorine-containing ether compound by increasing CF ₂ ═CFOCF ₂ CF ₂ CF ₂ CH ₂ OH. By _- products such as a cyclic fluorine _- containing ether compound (hereinafter also referred to as "cyclization") which is a dimer of _{2CF2CF2CH2OH are} produced. In addition to the fluorine-containing ether compound of the desired molecular weight, a low-molecular-weight fluorine-containing ether compound (hereinafter referred to as "low-molecular weight") and a high-molecular-weight fluorine-containing ether compound (hereinafter referred to as "high molecular weight") ) is generated.

Cyclized forms, low-molecular-weight forms, high-molecular-weight forms, etc. have the following problems, so it is necessary to separate the target fluorine-containing ether compound from the cyclized forms, low-molecular-weight forms, high-molecular-weight forms, etc. by purification.
・The cyclized form may inhibit subsequent reactions (esterification reaction, amidation reaction, halogenation reaction, hydrosilylation reaction, etc.).
- When the cyclized product remains in the surface treatment agent, the cyclized product does not adhere to the base material, so that the surface of the base material has a part where the surface layer is not formed.
- If the low-molecular-weight substance remains in the surface-treating agent, the low-molecular-weight substance does not have sufficient abrasion resistance, so the abrasion resistance of the surface layer is lowered.
- If the high molecular weight remains in the surface treatment agent, it is difficult to form a uniform surface layer because the high molecular weight is difficult to fly during, for example, vacuum deposition.

Further, according to the findings of the present inventors, the method by chromatography using silica gel described in Patent Document 2 has the following problems.
・Since the target fluorine-containing ether compound and the cyclized product have a short relative migration distance, it is difficult to separate the cyclized product.
- It takes a long time to separate the target fluorine-containing ether compound from the cyclized product, low molecular weight product, high molecular weight product, etc., resulting in poor productivity.
・Production costs are high due to the large consumption of liquid media.
・Because silica gel is used, the production cost is high.
・Since the desired fluorine-containing ether compound is adsorbed on silica gel, the yield of the desired fluorine-containing ether compound is poor.

INDUSTRIAL APPLICABILITY According to the present invention, a target fluorine-containing ether compound can be easily separated from a fluorine-containing ether compound other than the target fluorine-containing ether compound, and the target fluorine-containing ether compound can be produced in high yield and at low cost with good productivity. An object of the present invention is to provide a method for producing a fluorine-containing ether compound.

The present invention provides a method for producing a fluorine-containing ether compound having the following constitutions [1] to [12].
[1] An object to be treated containing a liquid fluorine-containing ether compound (however, the object to be treated does not contain a liquid medium) is dissolved in a part of the liquid fluorine-containing ether compound. A process for producing a fluorine-containing ether compound, which comprises using the resulting liquid medium for dissolution to separate a material dissolved in the liquid medium for dissolution from a material not dissolved therein.
[2] The object to be treated and the liquid medium for dissolution are mixed, and a solution in which the part of the fluorine-containing ether compound is dissolved in the liquid medium for dissolution and the treatment in which the liquid medium for dissolution does not dissolve The production method of [1], wherein the part of the fluorine-containing ether compound is separated from the object to be treated by separating it from the rest of the object.
[3] The liquid fluorine-containing ether compound contains a cyclic fluorine-containing ether compound as one of the liquid fluorine-containing ether compounds, and the dissolution liquid medium capable of dissolving the cyclic fluorine-containing ether compound is used to dissolve the The production method of [1] or [2], wherein the cyclic fluorine-containing ether compound is separated from the object to be treated.
[4] Using a dissolving liquid medium capable of dissolving a fluorine-containing ether compound having a partial molecular weight range among the liquid fluorine-containing ether compounds, the fluorine-containing ether compound having a partial molecular weight range is removed from the object to be treated. The manufacturing method of [1] or [2], wherein the
[5] The liquid fluorine-containing ether compound includes a cyclic fluorine-containing ether compound as one of the liquid fluorine-containing ether compounds, and the cyclic fluorine-containing ether compound and a fluorine-containing ether compound other than the cyclic fluorine-containing ether compound. Separating the cyclic fluorine-containing ether compound and the fluorine-containing ether compound having a partial molecular weight range from the object to be treated by using a dissolving liquid medium capable of dissolving the fluorine-containing ether compound having a partial molecular weight range among The manufacturing method of [1] or [2].
[6] The production method of [4] or [5], wherein the fluorine-containing ether compound having a partial molecular weight range is a fluorine-containing ether compound having a low molecular weight range.
[7] The method according to any one of [1] to [6], wherein the liquid medium for dissolution has a Hansen solubility parameter dispersion term dD of 12 to 20 and a hydrogen bonding term dH of 0 to 28.
[8] The liquid fluorine-containing ether compound has —OR ² , —C(O)OR ² , —C(O)N(R ² ) ₂ or —C(O)X (where R ² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X is a halogen atom.).
[9] The production method of [8], wherein the polar group-containing fluorine-containing ether compound is a compound represented by the following formula 1.
A ¹ -O-[(R ^f1 O) _m1 (R ¹ O) _m2 ]-B ¹ Formula 1
provided that A ¹ is an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms or B ¹ ; R ^f1 is a fluoroalkylene group having ¹ to 6 carbon atoms; an alkylene group having 1 to 6 carbon atoms; _m1 is an integer of 2 or more; m2 is an integer of 0 or more; ^m1 +m2 is an integer of 2 to 200; (R ¹ O) ^m2 may consist of two or more R ¹ O when _m2 is an integer of 2 or more; B ¹ is -R ^f2 CH ₂ -OR ² , -R ^f2 -C(O)OR ² , -R ^f2 -C(O)N(R ² ) ₂ or -R ^f2 -C(O)X; R ^f2 is an alkylene group having 1 to 6 carbon atoms or a fluoroalkylene group having 1 to 6 carbon atoms; R ² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; X is a halogen atom .
[10] The production method of [8] or [9], wherein the liquid fluorine-containing ether compound further contains a cyclic fluorine-containing ether compound.
[11] from the fluorine-containing ether compound having —OR ² , —C(O)OR ² , —C(O)N(R ² ) ₂ or —C(O)X at the terminal, a linking group at the terminal; The production method according to any one of [8] to [10], wherein the hydrolyzable silyl group-containing fluorine-containing ether compound having a hydrolyzable silyl group is obtained through the process.
[12] The production method of [11], wherein the hydrolyzable silyl group-containing fluorine-containing ether compound is a compound represented by the following formula 2.
A ² —O—(R ^F1 O) _m —B ² Formula 2
with the proviso that A ² is a perfluoroalkyl group having 1 to 20 carbon atoms or B ² ; R ^F1 is a perfluoroalkylene group having 1 to 6 carbon atoms; m is an integer of 2 to 200; ^F1 O) _m may consist of two or more kinds of R ^F1 O; B ² is a group represented by any one of the following formulas g1 to g7.
—R ^F2 —(X ¹ ) _p —Q ¹ —SiR _n L _3-n Formula g1
—R ^F2 —(X ² ) _r —Q ²¹ —N[—Q ²² —SiR _n L _3-n ] ₂ formula g2
—R ^F2 —[C(O)N(R ³¹ )] _s —Q ³¹ —(O) _t —C[—(O) _u —Q ³² —SiR _n L _3-n ] ₃ formula g3
—R ^F2 —Q ⁴¹ —Si[—Q ⁴² —SiR _n L _3-n ] ₃ formula g4
-R ^F2 -[C(O)N(R ⁵ )] _v -Q ⁵¹ -Z[-Q ⁵² -SiR _n L _3-n ] _w formula g5
-R ^F2 -Q ⁶¹ -G(R ⁶ )[-Q ⁶² -SiR _n L _3-n ] ₂ formula g6
—R ^F2 —Q ⁷¹ —[CH ₂ C(R ⁷¹ )(-Q ⁷² —SiR _n L _3-n )] _y —R ⁷² formula g7
provided that R ^F2 is a perfluoroalkylene group having 1 to 6 carbon atoms; R is a hydrogen atom or a monovalent hydrocarbon group; L is a hydrolyzable group; is an integer.
In formula g1, X ¹ is an etheric oxygen atom or -C(O)N(R ¹ )- (where N is bonded to Q ¹ ), and R ¹ is a hydrogen atom or an alkyl group. , p is 0 or 1, Q ¹ is an alkylene group, a group having an etheric oxygen atom or a silphenylene skeleton between the carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or an alkylene group having 2 or more carbon atoms It is a group having a divalent organopolysiloxane residue or a dialkylsilylene group between the carbon atoms of the group or at the end of the side that bonds to (X ¹ ) _p .
In formula g2, X ² is an etheric oxygen atom, —NH— or —C(O)N(R ² )— (where N is bonded to Q ²¹ ), and R ² is a hydrogen atom or an alkyl group, r is 0 or ^{1 (} however, it is 0 when Q21 is a single bond), Q21 is a single bond, an alkylene group, or a carbon atom of an alkylene group having 2 or more carbon atoms - is a group having an etheric oxygen atom, -NH-, -C(O)-, -C(O)O- or -OC(O)- between carbon atoms, and Q ²² is an alkylene group or a carbon A group having an etheric oxygen atom, —NH— or a divalent organopolysiloxane residue between the carbon-carbon atoms of an alkylene group having a number of 2 or more, and having two [—Q ²² —SiR _n L _3-n ] may be the same or different.
In formula g3, R ³¹ is a hydrogen atom or an alkyl group, s is 0 or 1, and Q ³¹ is a single bond, an alkylene group, or between carbon atoms of an alkylene group having 2 or more carbon atoms. a group having an etheric oxygen atom, t is 0 or 1 (however, it is 0 when ^Q31 is a single bond), u is 0 or 1, and ^Q32 is an alkylene group , a group having an etheric oxygen atom or a silphenylene skeleton between the carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or between the carbon-carbon atoms of an alkylene group having 2 or more carbon atoms or the side that binds to (O) _u is a group having -C(O)N(R ³² )-, a divalent organopolysiloxane residue or a dialkylsilylene group at the terminal of R ³² is a hydrogen atom or an alkyl group, and three [- (O) _u —Q ³² —SiR _n L _3-n ] may be the same or different.
In formula g4, Q ⁴¹ is an alkylene group or a group having an etheric oxygen atom between the carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, and Q ⁴² is an alkylene group or an alkylene group having 2 or more carbon atoms. A group having an etheric oxygen atom or a divalent organopolysiloxane residue between the carbon-carbon atoms of the group, and three [-Q ⁴² -SiR _n L _3-n ] may be the same or different. may be
In formula g5, R ⁵ is a hydrogen atom or an alkyl group, v is 0 or 1, Q ⁵¹ is an alkylene group, or an etheric oxygen between the carbon-carbon atoms of an alkylene group having 2 or more carbon atoms is a group having atoms, Z is a (w+1)-valent organopolysiloxane residue, Q ⁵² is an alkylene group, or an etheric oxygen atom or a group having a divalent organopolysiloxane residue, w is an integer of 2 to 7, and w [-Q ⁵² -SiR _n L _3-n ] may be the same or different; good too.
In formula g6, Q ⁶¹ is a single bond, an alkylene group, or a group having an etheric oxygen atom between the carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, G is a carbon atom or a silicon atom, R ⁶ is a hydroxyl group or an alkyl group, and Q ⁶² is an alkylene group or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between the carbon-carbon atoms of an alkylene group having 2 or more carbon atoms. and two [-Q ⁶² -SiR _n L _3-n ] may be the same or different.
In formula g7, Q ⁷¹ is a single bond, an alkylene group, or a group having an etheric oxygen atom between the carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, and R ⁷¹ is a hydrogen atom or an alkyl group. , Q ⁷² is a single bond or an alkylene group, R ⁷² is a hydrogen atom or a halogen atom, y is an integer of 1 to 10, and 2 to 10 [-Q ⁷² -SiR _n L _{3 -n} ] may be the same or different.

According to the method for producing a fluorine-containing ether compound of the present invention, the target fluorine-containing ether compound can be easily separated from the target fluorine-containing ether compound other than the target fluorine-containing ether compound, and the target fluorine-containing ether compound can be produced in high yield. It can be manufactured productively at low cost.

BRIEF DESCRIPTION OF THE DRAWINGS It is a flowchart which shows an example of the manufacturing method of the fluorine-containing ether compound of this invention.

In this specification, the compound represented by formula 1 is referred to as compound 1. Compounds represented by other formulas are similarly described.
Also, the group represented by formula g1 is referred to as group g1. Groups represented by other formulas are similarly described.
The following terms used herein have the following meanings.
A "fluorine-containing ether compound" means a compound having a fluorine atom and an etheric oxygen atom bonded to a carbon atom.
A chemical formula of an oxyfluoroalkylene group or oxyalkylene group is represented by writing the oxygen atom to the right of the fluoroalkylene group or oxyalkylene 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 hydrolysis to form a silanol group (Si—OH). For example, SiR _n L _3-n in Formula 1.
A "surface layer" means a layer formed on the surface of a substrate.
"Hansen Solubility Parameter" is the solubility parameter introduced by Hildebrand divided into three components, dispersion term dD, polar term dP, and hydrogen bonding term dH by Hansen, and shown in three-dimensional space. It is a thing. The dispersion term dD indicates the effect due to dispersion forces. The polar term dP indicates the effect due to the force between dipoles. The hydrogen bonding term dH indicates the effect of hydrogen bonding strength. The definition and calculation method of the Hansen Solubility Parameter are described in the following references.
Charles M. Hansen, "Hansen Solubility Parameters: A Users Handbook," CRC Press, 2007.
For liquid media for which literature values of Hansen solubility parameters are not known, computer software (Hansen Solubility Parameters in Practice (HSPiP)) can be used to easily estimate Hansen solubility parameters from their chemical structures. In the present invention, the value is used for the liquid medium registered in the database, and the estimated value by HSPiP version 3 is used for the liquid medium not registered. For the mixed liquid medium, the volume-averaged value of the Hansen solubility parameter of each liquid medium is used.
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 oxyfluoroalkylene groups based on the terminal groups by ¹ H-NMR and ¹⁹ F-NMR. The end group is, for example, a perfluoroalkyl group for A ² or SiR _n L _3-n for B ² in Formula 2.

[Method for producing fluorine-containing ether compound]
In the method for producing a fluorine-containing ether compound of the present invention, an object to be treated containing a liquid fluorine-containing ether compound (however, the object to be treated does not contain a liquid medium) is treated with a part of the liquid fluorine-containing ether compound. In this method, a dissolving liquid medium capable of dissolving the fluorine-containing ether compound is used, and the material dissolved in the dissolving liquid medium is separated from the material not dissolved therein.

As a method for producing the fluorine-containing ether compound of the present invention, an object to be treated and a liquid medium for dissolution are mixed, and a part of the fluorine-containing ether compound is dissolved in the liquid medium for dissolution and dissolved in the liquid medium for dissolution. A method of separating a part of the fluorine-containing ether compound from the object to be treated by separating the rest of the object to be treated that has not been treated is preferred.

FIG. 1 is a flow diagram showing an example of the method for producing a fluorine-containing ether compound of the present invention. In addition, the method for producing a fluorine-containing ether compound of the present invention is not limited to the flow method shown in the drawings.
An object to be treated containing a liquid fluorine-containing ether compound and a liquid medium for dissolution are placed in a stirring vessel 1 and stirred with a stirrer or the like to mix the object to be treated and the liquid medium for dissolution. Additives such as surfactants may be added during mixing.
After the object to be treated and the liquid medium for dissolution are mixed, the mixture is transferred to the separation tank 2, and a solution in which a part of the fluorine-containing ether compounds among the liquid fluorine-containing ether compounds are dissolved in the liquid medium for dissolution and the object to be treated are separated. Allow to stand until the remainder of the mixture separates into two layers. After separation into two layers, the solution and the rest of the material to be treated are recovered respectively.
The collected solution is transferred to the distillation apparatus 3 and separated into a portion of the fluorine-containing ether compound and the liquid medium for dissolution by distillation. The recovered dissolving liquid medium may be returned to the stirring vessel 1 for reuse. A portion of the collected fluorine-containing ether compound may be returned to the stirring vessel 1 as a treatment object, if necessary.
The rest of the collected objects to be treated may be returned to the stirring vessel 1 as objects to be treated as needed.

The time for mixing the object to be treated and the liquid medium for dissolution by stirring may be appropriately determined according to the type of the liquid medium for dissolution, the type or molecular weight of a part of the fluorine-containing ether compound, and the like.
The temperature at which the object to be treated and the liquid medium for dissolution are mixed (hereinafter referred to as the "temperature at the time of mixing") may be any temperature at which the liquid fluorine-containing ether compound and the liquid medium for dissolution can remain liquid. .
The ratio between the object to be treated and the liquid medium for dissolution may be appropriately determined according to the type of the liquid medium for dissolution, the type or molecular weight of a part of the fluorine-containing ether compound, and the like.
The temperature at which the solution and the remainder of the object to be treated are separated (hereinafter referred to as the "separation temperature") may be any temperature at which the liquid fluorine-containing ether compound and the liquid medium for dissolution can remain liquid.
When recovering a portion of the fluorine-containing ether compound and the liquid medium for dissolution from the solution, one or a combination of two or more of distillation, column chromatography, membrane separation, permeation through an adsorbent, filtration, etc. may be employed. .

(Object to be processed)
The object to be treated contains a liquid fluorine-containing ether compound. The object to be treated may contain components other than the liquid fluorine-containing ether compound (hereinafter also referred to as “other components”). However, the object to be processed does not contain a liquid medium.
Other components include raw materials other than the fluorine-containing ether compound used when synthesizing the liquid fluorine-containing ether compound (metal salts derived from metal compounds used in catalysts, etc.), and liquid fluorine-containing ether compounds. and other by-products other than the fluorine-containing ether compound, which are by-produced during the synthesis of.

The liquid fluorine-containing ether compound is liquid at the temperature of mixing and the temperature of separation. If the liquid fluorine-containing ether compound is liquid at the temperature at the time of mixing and the temperature at the time of separation, the object to be treated and the liquid medium for dissolution are mixed, and a solution in which a part of the fluorine-containing ether compound is dissolved in the liquid medium for dissolution is used. Separation from the rest of the object to be processed is facilitated.

The liquid fluorine-containing ether compound is a linear or branched molecule having a fluorine-containing polyether chain, and is a fluorine-containing ether compound that does not have a cyclic structure in which the ends of the molecular chains are bonded intramolecularly (hereinafter referred to as (also referred to as a "chain fluorine-containing ether compound"). The fluorine-containing polyether chain may be a polyfluoropolyether chain having one or more hydrogen atoms, or a PFPE chain in which all hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms.
The liquid fluorine-containing ether compound may contain a fluorine-containing ether compound other than the linear fluorine-containing ether compound (hereinafter also referred to as "another fluorine-containing ether compound").

The details of the chain fluorine-containing ether compound will be described later.
Other fluorine-containing ether compounds include fluorine-containing ether compounds that are by-produced when synthesizing liquid fluorine-containing ether compounds (hereinafter also referred to as "by-product fluorine-containing ether compounds"), and liquid fluorine-containing ether compounds. Examples thereof include fluorine-containing ether compounds (monomers, etc.) used as raw materials in the synthesis, and fluorine-containing ether compounds remaining when the monomers are synthesized.
By-product fluorine-containing ether compounds include cyclized products obtained by condensing multiple raw material monomers (e.g., dimers and decamers), and raw material monomers with hydrogen atoms or fluorine atoms in the unsaturated groups. Added saturates and the like can be mentioned.

When the raw material monomer is CF ₂ =CFOCF ₂ CF ₂ CF ₂ CH ₂ OH, examples of the cyclized product include compounds represented by the following formulae.

When the raw material monomer is CF ₂ =CFOCF ₂ CF ₂ CF ₂ CH ₂ OH, examples of the saturates include compounds represented by the following formula.
_{CHF2CF2OCF2CF2CF2CH2OH , _ _ _ _
CHF2CHFOCF2CF2CF2CH2OH . _ _ _}

When the raw material monomer is CF ₂ =CFOCF ₂ CF ₂ CF ₂ CH ₂ OH, the fluorine-containing ether compound remaining when the monomer is synthesized includes the compound represented by the following formula.
_{CHF2CF2CF2OCF ( CF3 ) CH2OH} ,
_{CHF2CF2CF2OCF2CH2OH . _ _ _}

(Target fluorine-containing ether compound)
Examples of the fluorine-containing ether compound to be obtained from the object to be treated in the production method of the present invention include the following.
・Separation of a solution in which some of the liquid fluorine-containing ether compounds contained in the object to be treated are dissolved in the liquid medium for dissolution, and the remaining part of the object to be treated that is not dissolved in the liquid medium for dissolution liquid fluorine-containing ether compound contained in the remainder of the object to be treated obtained by
・Separation of a solution in which some of the liquid fluorine-containing ether compounds contained in the object to be treated are dissolved in the liquid medium for dissolution, and the remaining part of the object to be treated that is not dissolved in the liquid medium for dissolution part of the fluorine-containing ether compound contained in the solution obtained by

Regarding which of these fluorine-containing ether compounds to use as the target fluorine-containing ether compound, the treatment conditions (type of liquid medium for dissolution, temperature during mixing, temperature during separation, mixing time, separation time, etc.), target inclusion It may be appropriately determined according to the molecular weight, purity, etc. required for the fluorine ether compound.

(Some fluorine-containing ether compounds)
As the partial fluorine-containing ether compound to be dissolved in the liquid medium for dissolution, either one or both of a by-product fluorine-containing ether compound and a fluorine-containing ether compound in a partial molecular weight range contained in the liquid fluorine-containing ether compound is mentioned.
A cyclized form is preferable as the by-produced fluorine-containing ether compound dissolved in the liquid medium for dissolution as a part of the fluorine-containing ether compound.

The fluorine-containing ether compound having a partial molecular weight range is a component of the liquid fluorine-containing ether compound that dissolves in the liquid medium for dissolution. The molecular weight range of the fluorine-containing ether compound in a partial molecular weight range varies depending on the type of liquid medium for dissolution, temperature during mixing, temperature during separation, mixing time, separation time, and the like. The molecular weight range of the fluorine-containing ether compound in a partial molecular weight range may be appropriately set according to the molecular weight of the target fluorine-containing ether compound.
A fluorine-containing ether compound having a partial molecular weight range may be a low-molecular-weight compound, a high-molecular-weight compound, or a fluorine-containing ether compound having a desired molecular weight.

When a part of the fluorine-containing ether compound is a cyclized compound, the method for producing the fluorine-containing ether compound of the present invention includes Method I below.
Method I: A method of separating the cyclized form from the object to be treated using a dissolving liquid medium capable of dissolving the cyclized form.

When a part of the fluorine-containing ether compound is a fluorine-containing ether compound in a part of the molecular weight range, the method for producing the fluorine-containing ether compound of the present invention includes Method II below.
Method II: A method of separating a fluorine-containing ether compound having a partial molecular weight range from an object to be treated using a dissolving liquid medium capable of dissolving a fluorine-containing ether compound having a partial molecular weight range.

Method II specifically includes the following method.
Method IIa: A method of using a dissolving liquid medium capable of dissolving a low molecular weight substance to separate a solution containing the low molecular weight substance from the remainder of the object to be treated containing fluorine-containing ether compounds other than the low molecular weight substance.
Method IIb: A method of separating a solution containing a high-molecular weight substance from the rest of the object to be treated containing a fluorine-containing ether compound other than the high-molecular weight substance using a dissolving liquid medium capable of dissolving the high-molecular weight substance.
Method IIc: A solution containing a fluorine-containing ether compound other than a high-molecular weight compound and the remainder of the object to be treated containing a high-molecular-weight substance, using a dissolving liquid medium capable of dissolving a fluorine-containing ether compound other than a high-molecular weight compound. how to get
Method IId: A solution containing a fluorine-containing ether compound other than a low-molecular-weight compound and the remainder of the object to be treated containing a low-molecular-weight compound, using a dissolving liquid medium capable of dissolving a fluorine-containing ether compound other than a low-molecular-weight compound. how to get

When a low-molecular-weight compound and a high-molecular-weight compound are separated from an object to be treated to obtain a fluorine-containing ether compound having a desired molecular weight, two of the following methods IIa to IId are used in combination.
- Obtain the remainder of the object to be treated containing the fluorine-containing ether compound of the desired molecular weight by Method IIb from the remainder of the object to be treated containing the high molecular weight compound and the fluorine-containing ether compound of the desired molecular weight obtained by Method IIa.
Obtain the remainder of the solution containing the fluorine-containing ether compound of the target molecular weight by Method IIc from the remainder of the object to be treated containing the high molecular weight compound and the target molecular weight of the fluorine-containing ether compound obtained by Method IIa.
Obtain the remainder of the object to be treated containing the fluorine-containing ether compound of the desired molecular weight by Method IIa from the remainder of the object to be treated containing the low-molecular-weight compound and the fluorine-containing ether compound of the desired molecular weight obtained by Method IIb.
A solution containing a fluorine-containing ether compound with a target molecular weight is obtained by Method IId from the remainder of the object to be treated containing the low-molecular-weight compound and the target molecular weight fluorine-containing ether compound obtained by Method IIb.
- Removal of the liquid medium for dissolution from the solution containing the low-molecular-weight substance and the target molecular weight fluorine-containing ether compound obtained by Method IIc, and then the treatment object containing the target molecular weight fluorine-containing ether compound by Method IIa. get the remainder of
- Remove the liquid medium for dissolution from the solution containing the low molecular weight compound and the target molecular weight fluorine-containing ether compound obtained by Method IIc, and then obtain a solution containing the target molecular weight fluorine-containing ether compound by Method IId. .
- Removal of the liquid medium for dissolution from the solution containing the high molecular weight substance and the target molecular weight fluorine-containing ether compound obtained by Method IId, and then the treatment object containing the target molecular weight fluorine-containing ether compound by Method IIb. get the remainder of
- Remove the liquid medium for dissolution from the solution containing the high molecular weight compound and the target molecular weight fluorine-containing ether compound obtained by Method IId, and then obtain the solution containing the target molecular weight fluorine-containing ether compound by Method IIc. .

When a part of the fluorine-containing ether compound is a cyclized product or a fluorine-containing ether compound having a partial molecular weight range, the method for producing the fluorine-containing ether compound of the present invention includes Method III below.
Method III: Using a dissolving liquid medium capable of dissolving the cyclized form and a fluorine-containing ether compound other than the cyclized form and having a partial molecular weight range, the cyclized form and the A method for separating a fluorine-containing ether compound having a molecular weight range of
Depending on the molecular weight of the cyclized product and the molecular weight of the fluorine-containing ether compound in a part of the molecular weight range, normally the cyclized product and the low molecular weight product can be separated from the material to be processed by Method III.

(liquid medium)
The dissolving liquid medium is liquid at the temperature of mixing and the temperature of separation. If the liquid medium for dissolution is liquid at the temperature at the time of mixing and the temperature at the time of separation, the object to be treated and the liquid medium for dissolution are mixed, and a solution in which a part of the fluorine-containing ether compound is dissolved in the liquid medium for dissolution and the object to be treated Separation from the rest of the object is facilitated.

Liquid media include water and organic solvents. The organic solvent may be a fluorine-containing organic solvent or a non-fluorine organic solvent.
Examples of fluorine-containing organic solvents include fluorinated alkanes, chlorinated 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 C ₆ F ₁₃ H (manufactured by Asahi Glass Co., Ltd., Asahiklin (registered trademark) AC-2000), C ₆ F ₁₃ C ₂ H ₅ (manufactured by Asahi Glass Co., Ltd., Asahiklin (registered trademark) AC-6000), C ₂ F ₅ CHFCHFCF ₃ (Vertrel (registered trademark) XF manufactured by Chemours) and the like.
Examples of chlorinated fluorinated alkanes include dichloropentafluoropropane (Asahiclin (registered trademark) AK-225, manufactured by Asahi Glass Co., Ltd.) and the like.
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 Company, Novec (registered trademark) 7100), C _{4F9OC2H5 (} manufactured by 3M, Novec (registered trademark) 7200) _{, C2F5CF (} OCH3) _{C3F7 (} manufactured by 3M _{, Novec} (registered trademark) 7300), and the like.
Fluorinated alkylamines include perfluorotripropylamine, perfluorotributylamine, and the like.
Fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol and the like.

Non-fluorine organic solvents include chlorinated alkanes, hydrocarbons, alcohols, ketones, ethers, esters, nitrogen-containing compounds, sulfur-containing compounds, and the like.
Chlorinated alkanes include chloroform, methylene chloride, carbon tetrachloride, 1,1,1-trichloroethylene and the like.
Hydrocarbons include hexane, pentane, heptane, cyclohexane, decane, benzene, toluene, and the like.
Alcohols include methanol, ethanol, isopropyl alcohol, benzoyl alcohol, and the like.
Ketones include acetone, ethyl methyl ketone, and the like.
Ethers include tetrahydrofuran (hereinafter also referred to as "THF"), diethyl ether, isopropyl ether and the like.
Esters include methyl acetate, ethyl acetate, butyl acetate and the like.
Nitrogen-containing compounds include N,N-dimethylformamide, acetonitrile, triethylamine and the like.
Examples of sulfur-containing compounds include ethyl methyl sulfide and dimethyl sulfoxide.

The liquid medium for dissolution is preferably a liquid medium having a Hansen Solubility Parameter dispersion term dD of 12 to 20 and a hydrogen bonding term dH of 0 to 28, and a dispersion term dD of 14 to 18 and a hydrogen bonding term dH. is from 0 to 25 is particularly preferred. If the dispersion term dD and the hydrogen bonding term dH of the Hansen solubility parameter are within the above ranges, the target fluorine-containing ether compound can be obtained. The polarity term dP of the liquid medium for dissolution is preferably 0-10.
Table 1 shows the dispersion term dD, the hydrogen bonding term dH and the polarity term dP of major liquid media.

The liquid medium for dissolution may be appropriately selected according to a portion of the fluorine-containing ether compound to be dissolved in the liquid medium for dissolution. The liquid medium for dissolution may be used singly or in combination of two or more.

When a part of the fluorine-containing ether compound is a cyclized form, the dissolving liquid medium is preferably a liquid medium in which the cyclized form is relatively easily dissolved in comparison with fluorine-containing ether compounds other than the cyclized form. When some of the fluorine-containing ether compounds are cyclized, chloroform, carbon tetrachloride, hexane, heptane, chloroform, carbon tetrachloride, hexane, heptane, Cyclohexane, benzene, 1,1,1-tetrachloroethylene, AK-225, or a mixed liquid medium of two or more of these is preferred. A mixed liquid medium of hexane and acetone, a mixed liquid medium of hexane and toluene, and a mixed liquid medium of cyclohexane and 1,4-dioxane are also preferred. The volume ratio of hexane and acetone is preferably 99:1 to 60:40. The volume ratio of hexane and toluene is preferably 99:1 to 30:70. The volume ratio of cyclohexane and 1,4-dioxane is preferably 99:1 to 60:40.
Dispersion term dD of the liquid medium for dissolution when a part of the fluorine-containing ether compound is a cyclized form is preferably 14 to 20 from the viewpoint that the cyclized form contained in the object to be treated can be selectively reduced. The coupling term dH is preferably 0-6. The polarity term dP is preferably 0-5.

When some of the fluorine-containing ether compounds are low-molecular-weight, the dissolution liquid medium is preferably a liquid medium in which the low-molecular-weight compounds are relatively easily dissolved in comparison with fluorine-containing ether compounds other than low-molecular-weight compounds. When the liquid medium is a low-molecular-weight substance, hexane, chloroform, methanol, ethanol, 1-propanol, butanol, or A mixed liquid medium of two or more of these is preferred. A mixed liquid medium of cyclohexane and water, a mixed liquid medium of xylene and 1-propanol, a mixed liquid medium of heptane and ethanol, and a mixed liquid medium of n-hexane and benzyl alcohol are also preferred. The volume ratio of cyclohexane and water is preferably 60:40 to 80:20. The volume ratio of xylene and 1-propanol is preferably 40:60 to 55:45. The volume ratio of heptane to ethanol is preferably 40:60 to 55:45. The volume ratio of n-hexane and benzyl alcohol is preferably 70:30 to 40:60.
Dispersion term dD of the liquid medium for dissolution when a part of the fluorine-containing ether compound is a low molecular weight compound is preferably 14 to 18 from the viewpoint that low molecular weight compounds contained in the object to be treated can be selectively reduced. The bond term dH is preferably 0-25, particularly preferably 0-23. The polarity term dP is preferably 3.5-9.

When some of the fluorine-containing ether compounds are high-molecular-weight, the dissolution liquid medium is preferably a liquid medium in which low-molecular-weight compounds are relatively easily dissolved in comparison with fluorine-containing ether compounds other than low-molecular-weight compounds. As the liquid medium for dissolution when the liquid medium is low-molecular-weight substances, a mixed liquid medium of chloroform and acetone is preferable because the low-molecular-weight substances contained in the object to be treated can be selectively reduced. The volume ratio of chloroform and acetone is preferably 60:40 to 40:60.
Dispersion term dD of the liquid medium for dissolution when part of the fluorine-containing ether compound is a high molecular weight compound is preferably 15 to 20 from the viewpoint that low molecular weight substances contained in the object to be treated can be selectively reduced. The binding term dH is preferably 0-25. The polarity term dP is preferably 5-8.

When some fluorine-containing ether compounds are cyclized and low-molecular-weight compounds, methylene chloride is used as the dissolution liquid medium because it can selectively reduce the cyclized and low-molecular-weight compounds contained in the object to be treated. , chloroform, 1,1-dichloroethane, 1,2-dichloroethane, or a mixed liquid medium of two or more of these is preferred. Mixed liquid media of heptane and benzoyl alcohol, cyclohexane and 2-butanol, THF and methyl acetate are also preferred. The volume ratio of heptane to benzoyl alcohol is preferably 40:60 to 60:40. The volume ratio of cyclohexane and 2-butanol is preferably 70:30 to 90:10. The volume ratio of THF and methyl acetate is preferably 60:40 to 40:60.
Dispersion term dD of the liquid medium for dissolution when a part of the fluorine-containing ether compound is a cyclized form and a low molecular weight form can selectively reduce the cyclized form and low molecular weight form contained in the object to be treated. , 14-18, and the hydrogen bond term dH is preferably 0-10. The polar term dP is preferably 2-8.

When the dissolving liquid medium capable of dissolving the cyclized product is different from the dissolving liquid medium capable of dissolving the fluorine-containing ether compound having a partial molecular weight range, and the part of the fluorine-containing ether compound is the cyclized product and In the case of a fluorine-containing ether compound having a partial molecular weight range, it is preferable to carry out Method II after carrying out Method I, or to carry out Method I after carrying out Method II.
When the dissolving liquid medium capable of dissolving the cyclized product and the dissolving liquid medium capable of dissolving the fluorine-containing ether compound having a partial molecular weight range are the same, and the part of the fluorine-containing ether compound is the cyclized product and When the fluorine-containing ether compound has a partial molecular weight range, method II may be performed after method I, method I may be performed after method II, or only method III may be performed.

(Mechanism of action)
In the method for producing a fluorine-containing ether compound of the present invention described above, an object to be treated (however, the object to be treated does not contain a liquid medium) containing a liquid fluorine-containing ether compound is treated with a liquid fluorine-containing ether compound. A dissolution liquid medium capable of dissolving a portion of the fluorine-containing ether compound among the compounds is used to separate those dissolved in the dissolution liquid medium and those that are not dissolved. Compared to chromatography, it is easier to separate the target fluorine-containing ether compound from other fluorine-containing ether compounds.
In addition, compared with conventional chromatography using silica gel, separation of the target fluorine-containing ether compound from other fluorine-containing ether compounds does not take much time, resulting in good productivity.
In addition, compared with conventional chromatography using silica gel, the amount of liquid medium used can be reduced, and since silica gel is not used, production costs are low.
In addition, since silica gel is not used, loss of the target fluorine-containing ether compound is small and the yield of the target fluorine-containing ether compound is high as compared with conventional chromatography using silica gel.

[A chain fluorine-containing ether compound]
Examples of chain fluorine-containing ether compounds include polar group-containing fluorine-containing ether compounds described later and hydrolyzable silyl group-containing fluorine-containing ether compounds described later. As the chain fluorine-containing ether compound contained in the object to be treated, a polar group-containing fluorine-containing ether compound is useful as an intermediate of a hydrolyzable silyl group-containing fluorine-containing ether compound, and the effect of the present invention is likely to be exhibited. Ether compounds are preferred.

(Polar group-containing fluorine-containing ether compound)
A polar group-containing fluorine-containing ether compound has -OR ² , -C(O)OR ² , -C(O)N(R ² ) ₂ or -C(O)X (where R ² is a hydrogen atom or is an alkyl group having 1 to 10 carbon atoms, and X is a halogen atom) (hereinafter, these groups are also collectively referred to as a "polar group").

The polar group-containing fluorine-containing ether compound may have a polar group at one end of the fluorine-containing polyether chain via a linking group, and may have a polar group at both ends of the fluorine-containing polyether chain via a linking group. You may have a group. As the polar group-containing fluorine-containing ether compound, a compound having a polar group only at one end of the fluorine-containing polyether chain is preferable.

As the polar group-containing fluorine-containing ether compound, one end of the fluorine-containing polyether chain is an alkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 20 carbon atoms, and the other end of the fluorine-containing polyether chain is a linking group. A compound in which a polar group is bonded via is preferred.

Examples of the linking group include known linking groups that connect the fluorine-containing polyether chain and the polar group in a known fluorine-containing ether compound. A known linking group may be structurally modified. A group having a structure to be adopted as a linking group may be appropriately determined within the scope of the technical common sense of those skilled in the art.

The polar group-containing fluorine-containing ether compound may be a single compound or a mixture of two or more different fluorine-containing polyether chains, terminal groups, linking groups, and the like.
The number average molecular weight of the polar group-containing fluorine-containing ether compound is preferably 2,000 to 10,000, more preferably 2,100 to 9,000, and particularly preferably 2,400 to 8,000.

As the polar group-containing fluorine-containing ether compound, compound 1 is preferable because it is useful as an intermediate for a hydrolyzable silyl group-containing fluorine-containing ether compound.
A ¹ -O-[(R ^f1 O) _m1 (R ¹ O) _m2 ]-B ¹ Formula 1
provided that A ¹ is an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms or B ¹ ; R ^f1 is a fluoroalkylene group having ¹ to 6 carbon atoms; an alkylene group having 1 to 6 carbon atoms; _m1 is an integer of 2 or more; m2 is an integer of 0 or more; ^m1 +m2 is an integer of 2 to 200; (R ¹ O) ^m2 may consist of two or more R ¹ O when _m2 is an integer of 2 or more; B ¹ is -R ^f2 CH ₂ -OR ² , -R ^f2 -C(O)OR ² , -R ^f2 -C(O)N(R ² ) ₂ or -R ^f2 -C(O)X; R ^f2 is an alkylene group having 1 to 6 carbon atoms or a fluoroalkylene group having 1 to 6 carbon atoms; R ² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; X is a halogen atom .

In [(R ^f1 O) _m1 (R ¹ O) _m2 ], the bonding order of m1 (R ^f1 O) and m2 (R ¹ O) is not limited, and may be random, block or alternating. may be placed.
m1+m2 is preferably an integer of 5-150, particularly preferably an integer of 10-100.

As [(R ^f1 O) _m1 (R ¹ O) _m2 ], the following are preferable from the viewpoint of easy production of compound 1.
CHFCF ₂ O—CH ₂ CF ₂ O {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 },
CF ₂ CF ₂ O—CF ₂ CF ₂ O {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 },
_{( CF2CHFO - CF2CF2CF2CH2O} ) _{x3 CF2CHFO ,
( CF2CF2O - CF2CF2CF2CF2O ) x3 CF2CF2O , _
( CF2CF2O} ) _x4 ,
_{( CF2CF2CF2O ) x5 ,
( CH2O - CH2CF2CF2CF2CH2O ) x6 CH2O ,
( CF2CHFO - CF2CF2CF2CF2CF2CH2O ) x7 CF2CHFO , _
( CF2O - CF2CF2CF2CF2CF2O ) x6 CF2O ,
( CF2CF2O - CF2CF2CF2CF2CF2CF2O ) x7 CF2CF2O . _ _ _}
provided that x1 and x2 are each an integer of 1 or more, x1+x2 is an integer of 2 to 198, x3, x6 and x7 are each an integer of 1 to 199, and x4 and x5 are each an integer of 2 to 200 integers.

A ¹ is preferably an alkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 20 carbon atoms. Alkyl groups and fluoroalkyl groups may be linear or branched. When A ¹ is an alkyl group or a fluoroalkyl group, the number of carbon atoms in A ¹ is preferably 1-10, more preferably 1-6, and particularly preferably 1-3.

When there are two ^B1 's in the molecule, they may be the same or different.
R ^f2 may be linear or branched. R ^f2 is preferably —CF ₂ CF ₂ CF ₂ —, —CF ₂ —, or —CF ₂ CF ₂ — from the viewpoint of easy production of compound 1.
When R ² is an alkyl group, the alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1-3.
X includes a fluorine atom, a chlorine atom, a bromine atom, a chlorine atom and the like, and a fluorine atom is preferred.

Hereinafter, compound 1 in which B ¹ is —R ^f2 CH ₂ —OR ² is compound 1a, compound 1 in which B ¹ is —R ^f2 —C(O)OR ² is compound 1b, and B ¹ is —R ^f2 —C Compound 1 in which (O)N(R ² ) ₂ is represented as compound 1c, and compound 1 in which B ¹ is —R ^f2 —C(O)X is referred to as compound 1d.
A ¹ —O—[(R ^f1 O) _m1 (R ¹ O) _m2 ]—R ^f2 CH ₂ —OR ² Formula 1a,
A ¹ —O—[(R ^f1 O) _m1 (R ¹ O) _m2 ]—R ^f2 —C(O)OR ² Formula 1b,
A ¹ —O—[(R ^f1 O) _m1 (R ¹ O) _m2 ]—R ^f2 —C(O)N(R ² ) ₂ Formula 1c,
A ¹ —O—[(R ^f1 O) _m1 (R ¹ O) _m2 ]—R ^f2 —C(O)X Formula 1d.

A polar group-containing fluorine-containing ether compound can be produced by the same production method as that for a known intermediate of a fluorine-containing ether compound used as a surface treatment agent.

[(R ^f1 O) _m1 (R ¹ O) _m2 ] is (CF ₂ CHFOCF ₂ CF ₂ CF ₂ CH ₂ O) _x 3 CF ₂ CHFO, or (CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) _x 3 Compounds 1a to 1d, which are CF ₂ CF ₂ O, can be produced, for example, as follows.

Compound 1a-1 can be produced by the method described in Patent Document 1 using R ⁸ OH and CF ₂ =CFOCF ₂ CF ₂ CF ₂ CH ₂ OH as starting materials. However, R ⁸ is an alkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 20 carbon atoms.
R ⁸ —O—(CF ₂ CHFO—CF ₂ CF ₂ CF ₂ CH ₂ O)×3 CF _{2 CHFO} —CF ₂ CF ₂ CF ₂ CH ₂ —OH Formula 1a-1

Compound 1b-1 is obtained by reacting compound 1a-1 with FC(O)R ^F9 according to the method described in Patent Document 1 to protect the terminal hydroxyl group and then fluorinating with fluorine gas to give compound 1e. After obtaining -1, it can be produced by reacting compound 1e-1 with an alcohol (HOR ^2a ) in the presence of a metal fluoride. However, R ^F8 is a perfluoroalkyl group having 1 to 20 carbon atoms, and R ^F9 is a perfluoroalkyl group (preferably 1 to 20 carbon atoms) or a perfluoroalkyl group having 2 or more carbon atoms (preferably 2 to 2 carbon atoms). 20) having an etheric oxygen atom between carbon atoms, and R ^2a is an alkyl group having 1 to 10 carbon atoms.
R ^F8 —O—(CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _× 3 CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ —OC(O)R ^F9 Formula 1e-1
R ^F8 —O—(CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _× 3 CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ —C(O)OR ^2a Formula 1b-1

Compound 1a-2 can be produced by hydrogen reduction of compound 1b-1.
R ^F8 —O—(CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _× 3 CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CH ₂ —OH Formula 1a-2

Compound 1c-1 can be produced by reacting compound 1b-1 with ammonia, a primary amine or a secondary amine.
R ^F8 —O—(CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _× 3 CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ —C(O)N(R ² ) ₂ Formula 1c-1

Compound 1d-1 can be produced by reacting compound 1e-1 with a metal fluoride (NaF, CsF, KF, AgF, etc.) according to the method described in Patent Document 1.
R ^F8 —O—(CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _× 3 CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ —C(O)F Formula 1d-1

As the polar group-containing fluorine-containing ether compound contained in the object to be treated, by-products such as cyclized products that inhibit subsequent reactions (esterification reaction, amidation reaction, halogenation reaction, hydrosilylation reaction, etc.) Compound 1a-1 is preferred because it can be removed at an early stage in a series of reaction steps.

[(R ^f1 O) _{m1 (} R ¹ O) _m2 ] is _{CHFCF2OCH2CF2O { ( CF2O} ) _{x1 ( CF2CF2O} ) _{x2 }} , or _{CF2CF2OCF2CF2O {} (CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } Compounds 1a to 1d can be obtained or produced, for example, as follows.

Compound 1a-3 is available as FLUOROLINK® D4000 from Solvay Solexis.
HO—CH ₂ CF ₂ —O{(CF ₂ O) _× 1 (CF ₂ CF ₂ O) _×2 }—CF ₂ CH ₂ —OH Formula 1a-3

Compound 1a-4 can be produced by reacting compound 1a-3 with R ^F8 —O—CF=CF ₂ according to the method described in WO2017/038832.
R ^F8 —O—CHFCF ₂ OCH ₂ CF ₂ O{(CF ₂ O) _× 1 (CF ₂ CF ₂ O) _×2 }—CF ₂ CH ₂ —OH Formula 1a-4

Compound 1b-2 is obtained by reacting compound 1a-4 with FC(O)R ^F9 according to the method described in International Publication No. 2017/038832, protecting the terminal hydroxyl group, and then fluorinating with fluorine gas. After carrying out to obtain compound 1e-2, it can be produced by reacting compound 1e-2 with an alcohol (HOR ^2a ) in the presence of a metal fluoride.
R ^F8 —O—CF ₂ CF ₂ OCF ₂ CF ₂ O{(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 }—CF ₂ CF ₂ —OC(O)R ^F9 Formula 1e-2
R ^F8 —O—CF ₂ CF ₂ OCF ₂ CF ₂ O{(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 }—CF ₂ —C(O)OR ^2a Formula 1b-2

Compound 1a-5 can be produced by hydrogen reduction of compound 1b-2.
R ^F8 —O—CF ₂ CF ₂ OCF ₂ CF ₂ O{(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 }—CF ₂ CH ₂ —OH Formula 1a-5

Compound 1c-2 can be produced by reacting compound 1b-2 with ammonia, a primary amine or a secondary amine.
R ^F8 —O—CF ₂ CF ₂ OCF ₂ CF ₂ O{(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 }—CF ₂ —C(O)N(R ² ) ₂ Formula 1c-2

Compound 1d-2 can be produced by reacting compound 1e-2 with a metal fluoride (NaF, CsF, KF, AgF, etc.).
R ^F8 —O—CF ₂ CF ₂ OCF ₂ CF ₂ O{(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 }—CF ₂ —C(O)F Formula 1d-2

(Hydrolyzable silyl group-containing fluorine-containing ether compound)
The hydrolyzable silyl group-containing fluorine-containing ether compound is a polar group-containing fluorine-containing ether compound —OR ² , —C(O)OR ² , —C(O)N(R ² ) ₂ or —C(O)X A hydrolyzable silyl group is introduced via a linking group to the end having

The hydrolyzable silyl group-containing fluorine-containing ether compound may have a hydrolyzable silyl group at one end of the fluorine-containing polyether chain via a linking group, and may have a hydrolyzable silyl group at both ends of the fluorine-containing polyether chain. It may have a hydrolyzable silyl group via a linking group. The hydrolyzable silyl group-containing fluorine-containing ether compound preferably has a hydrolyzable silyl group only at one end of the fluorine-containing polyether chain from the viewpoint of further improving the abrasion resistance of the surface layer.

The fluorine-containing polyether chain in the hydrolyzable silyl group-containing fluorine-containing ether compound is preferably a PFPE chain from the viewpoint that the initial water/oil repellency and fingerprint stain removability of the surface layer are more excellent.
As the hydrolyzable silyl group-containing fluorine-containing ether compound, a perfluoroalkyl compound having 1 to 20 carbon atoms at one end of the PFPE chain is used because the initial water and oil repellency, abrasion resistance, and fingerprint stain removability of the surface layer are further excellent. and a hydrolyzable silyl group is bonded to the other end of the PFPE chain via a linking group.

Examples of the linking group include known linking groups that connect PFPE chains and hydrolyzable silyl groups in known hydrolyzable silyl group-containing fluorine-containing ether compounds used as surface treatment agents. A known linking group may be structurally modified. A group having a structure to be adopted as a linking group may be appropriately determined within the scope of the technical common sense of those skilled in the art.
The number of hydrolyzable silyl groups bonded to the linking group is preferably 1 to 10, more preferably 1 to 3, and particularly preferably 2 or 3, from the viewpoint that the effects of the present invention can be sufficiently exhibited.

The hydrolyzable silyl group-containing fluorine-containing ether compound may be a single compound or a mixture of two or more different fluorine-containing polyether chains, terminal groups, linking groups, and the like.
The hydrolyzable silyl group-containing fluorine-containing ether compound preferably has a number average molecular weight of 2,000 to 10,000. If the number average molecular weight is within the above range, the abrasion resistance of the surface layer is further improved. The number average molecular weight of the hydrolyzable silyl group-containing fluorine-containing ether compound is more preferably 2,100 to 9,000, particularly preferably 2,400 to 8,000.

Since the hydrolyzable silyl group-containing fluorine-containing ether compound has a fluorine-containing polyether chain, the content of fluorine atoms is large. Therefore, the hydrolyzable silyl group-containing fluorine-containing ether compound has high initial water and oil repellency, and can form a surface layer excellent in abrasion resistance and fingerprint stain removability.

In surface treatment with a hydrolyzable silyl group-containing fluorine-containing ether compound, the hydrolyzable silyl group (SiR _n L _3-n ) in the hydrolyzable silyl group-containing fluorine-containing ether compound undergoes a hydrolysis reaction to form a silanol group. (Si—OH) is formed, and the silanol groups react intermolecularly to form Si—O—Si bonds, or the silanol groups undergo a dehydration condensation reaction with hydroxyl groups on the surface of the substrate (substrate —OH). A chemical bond (substrate-O-Si) is formed. That is, the surface layer in the present invention is formed by hydrolyzing a hydrolyzable silyl group-containing fluorine-containing ether compound, part or all of the hydrolyzable silyl groups of the hydrolyzable silyl group-containing fluorine-containing ether compound, and performing dehydration condensation. Contain in the reacted state.

As the hydrolyzable silyl group-containing fluorine-containing ether compound, compound 2 is preferred because it has high initial water and oil repellency and can form a surface layer with even better abrasion resistance and fingerprint stain removability.
A ² —O—(R ^F1 O) _m —B ² Formula 2
with the proviso that A ² is a perfluoroalkyl group having 1 to 20 carbon atoms or B ² ; R ^F1 is a perfluoroalkylene group having 1 to 20 carbon atoms; m is an integer of 2 to 200; ^F1 O) _m may consist of two or more R ^F1 O; B ² is any of groups g1 to g7.
—R ^F2 —(X ¹ ) _p —Q ¹ —SiR _n L _3-n Formula g1
—R ^F2 —(X ² ) _r —Q ²¹ —N[—Q ²² —SiR _n L _3-n ] ₂ formula g2
—R ^F2 —[C(O)N(R ³¹ )] _s —Q ³¹ —(O) _t —C[—(O) _u —Q ³² —SiR _n L _3-n ] ₃ formula g3
—R ^F2 —Q ⁴¹ —Si[—Q ⁴² —SiR _n L _3-n ] ₃ formula g4
-R ^F2 -[C(O)N(R ⁵ )] _v -Q ⁵¹ -Z[-Q ⁵² -SiR _n L _3-n ] _w formula g5
-R ^F2 -Q ⁶¹ -G(R ⁶ )[-Q ⁶² -SiR _n L _3-n ] ₂ formula g6
—R ^F2 —Q ⁷¹ —[CH ₂ C(R ⁷¹ )(-Q ⁷² —SiR _n L _3-n )] _y —R ⁷² formula g7
provided that R ^F2 is a perfluoroalkylene group having 1 to 6 carbon atoms; R is a hydrogen atom or a monovalent hydrocarbon group; L is a hydrolyzable group; is an integer.
In formula g1, X ¹ is an etheric oxygen atom or -C(O)N(R ¹ )- (where N is bonded to Q ¹ ), and R ¹ is a hydrogen atom or an alkyl group. , p is 0 or 1, Q ¹ is an alkylene group, a group having an etheric oxygen atom or a silphenylene skeleton between the carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or an alkylene group having 2 or more carbon atoms It is a group having a divalent organopolysiloxane residue or a dialkylsilylene group between the carbon atoms of the group or at the end of the side that bonds to (X ¹ ) _p .
In formula g2, X ² is an etheric oxygen atom, —NH— or —C(O)N(R ² )— (where N is bonded to Q ²¹ ), and R ² is a hydrogen atom or an alkyl group, r is 0 or ^{1 (} however, it is 0 when Q21 is a single bond), Q21 is a single bond, an alkylene group, or a carbon atom of an alkylene group having 2 or more carbon atoms - is a group having an etheric oxygen atom, -NH-, -C(O)-, -C(O)O- or -OC(O)- between carbon atoms, and Q ²² is an alkylene group or a carbon A group having an etheric oxygen atom, —NH— or a divalent organopolysiloxane residue between the carbon-carbon atoms of an alkylene group having a number of 2 or more, and having two [—Q ²² —SiR _n L _3-n ] may be the same or different.
In formula g3, R ³¹ is a hydrogen atom or an alkyl group, s is 0 or 1, and Q ³¹ is a single bond, an alkylene group, or between carbon atoms of an alkylene group having 2 or more carbon atoms. a group having an etheric oxygen atom, t is 0 or 1 (however, it is 0 when ^Q31 is a single bond), u is 0 or 1, and ^Q32 is an alkylene group , a group having an etheric oxygen atom or a silphenylene skeleton between the carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or between the carbon-carbon atoms of an alkylene group having 2 or more carbon atoms or the side that binds to (O) _u is a group having -C(O)N(R ³² )-, a divalent organopolysiloxane residue or a dialkylsilylene group at the terminal of R ³² is a hydrogen atom or an alkyl group, and three [- (O) _u —Q ³² —SiR _n L _3-n ] may be the same or different.
In formula g4, Q ⁴¹ is an alkylene group or a group having an etheric oxygen atom between the carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, and Q ⁴² is an alkylene group or an alkylene group having 2 or more carbon atoms. A group having an etheric oxygen atom or a divalent organopolysiloxane residue between the carbon-carbon atoms of the group, and three [-Q ⁴² -SiR _n L _3-n ] may be the same or different. may be
In formula g5, R ⁵ is a hydrogen atom or an alkyl group, v is 0 or 1, Q ⁵¹ is an alkylene group, or an etheric oxygen between the carbon-carbon atoms of an alkylene group having 2 or more carbon atoms is a group having atoms, Z is a (w+1)-valent organopolysiloxane residue, Q ⁵² is an alkylene group, or an etheric oxygen atom or a group having a divalent organopolysiloxane residue, w is an integer of 2 to 7, and w [-Q ⁵² -SiR _n L _3-n ] may be the same or different; good too.
In formula g6, Q ⁶¹ is a single bond, an alkylene group, or a group having an etheric oxygen atom between the carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, G is a carbon atom or a silicon atom, R ⁶ is a hydroxyl group or an alkyl group, and Q ⁶² is an alkylene group or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between the carbon-carbon atoms of an alkylene group having 2 or more carbon atoms. and two [-Q ⁶² -SiR _n L _3-n ] may be the same or different.
In formula g7, Q ⁷¹ is a single bond, an alkylene group, or a group having an etheric oxygen atom between the carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, and R ⁷¹ is a hydrogen atom or an alkyl group. , Q ⁷² is a single bond or an alkylene group, R ⁷² is a hydrogen atom or a halogen atom, y is an integer of 1 to 10, and 2 to 10 [-Q ⁷² -SiR _n L _{3 -n} ] may be the same or different.

In (R ^F1 O) _m , the bonding order of m (R ^F1 O)s is not limited, and may be arranged randomly, in blocks, or alternately.
m is preferably an integer of 5 to 150, particularly preferably an integer of 10 to 100.

As (R ^F1 O) _m , the following are preferable from the viewpoint that the initial water and oil repellency, abrasion resistance, and fingerprint stain removability of the surface layer are more excellent.
CF ₂ CF ₂ O—CF ₂ CF ₂ O {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 },
_{( CF2CF2O - CF2CF2CF2CF2O ) x3 CF2CF2O , _
( CF2CF2O} ) _x4 ,
_{( CF2CF2CF2O ) x5 ,
( CF2O - CF2CF2CF2CF2CF2O ) x6 CF2O ,
( CF2CF2O - CF2CF2CF2CF2CF2CF2O ) x7 CF2CF2O . _ _ _}
provided that x1 and x2 are each an integer of 1 or more, x1+x2 is an integer of 2 to 198, x3, x6 and x7 are each an integer of 1 to 199, and x4 and x5 are each an integer of 2 to 200 integers.

A ² is a C 1-20 perfluoroalkyl group or B ² . A perfluoroalkyl group having 1 to 20 carbon atoms is preferred from the viewpoint of further improving the abrasion resistance of the surface layer. A perfluoroalkyl group may be linear or branched. When A ² is a perfluoroalkyl group, A ² preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
A ² includes CF ₃ -, CF ₃ CF ₂ -, CF ₃ CF ₂ CF ₂ -, CF ₃ CF ₂ CF ₂ CF ₂ -, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ -, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ -, CF ₃ CF(CF ₃ )- and the like.
A ² is preferably CF ₃ —, CF ₃ CF ₂ —, or CF ₃ CF ₂ CF ₂ — from the viewpoint that the initial water/oil repellency, abrasion resistance, and fingerprint stain removability of the surface layer are more excellent.

When there are ^two B2's in the molecule, they may be the same or different.
R ^F2 may be linear or branched. R ^F2 is preferably -CF ₂ CF ₂ CF ₂ -, -CF ₂ -, or -CF 2 CF ₂ - from the viewpoint of easy production of compound ₂ .

The hydrolyzable group of L is a group that becomes a hydroxyl group by a hydrolysis reaction.
Examples of L 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.
L is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom from the viewpoint of ease of industrial production. 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 2, and an ethoxy group when long-term storage stability of compound 2 is required. A methoxy group is particularly preferred when the reaction time after coating is shortened.

Examples of the monovalent hydrocarbon group for R include an alkyl group, an aryl group, a cycloalkyl group, an alkenyl group, and groups in which two or more of these groups are combined.
R 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.
As R, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and an alkyl group having 1 to 2 carbon atoms is particularly preferable, from the viewpoint of simplicity of synthesis.

n is preferably 0 or 1, particularly preferably 0. By having multiple Ls in the molecule, the bonding with the surface of the substrate becomes stronger.
When n is 1 or less, multiple Ls present in one molecule may be the same or different. From the standpoint of availability of raw materials and ease of manufacture, they are preferably the same.

Hydrolyzable silyl groups (SiR _n L _3-n ) include -Si(OCH ₃ ) ₃ , -SiCH ₃ (OCH ₃ ) ₂ , -Si(OCH ₂ CH ₃ ) ₃ , -SiCl ₃ , -Si( OC(O)CH ₃ ) ₃ and —Si(NCO) ₃ are preferred. —Si(OCH ₃ ) ₃ is particularly preferred from the viewpoint of ease of handling in industrial production.

Hereinafter, compound ² in which B2 is group g1 is compound 2a, compound ² in which B2 is group g2 is compound 2b, compound ² in which B2 is group g3 is compound 2c, and compound ² in which B2 is group g4 is compound 2d, compound ² in which B2 is group g5 is referred to as compound 2e, compound ² in which B2 is group g6 is referred to as compound 2f, and compound ² in which B2 is group g2 is referred to as compound 2g.
A ² —O—(R ^F1 O) _m —R ^F2 —(X ¹ ) _p —Q ¹ —SiR _n L _3-n Formula 2a,
A ² —O—(R ^F1 O) _m —R ^F2 —(X ² ) _r —Q ²¹ —N[—Q ²² —SiR _n L _3-n ] ₂ formula 2b,
A ² —O—(R ^F1 O) _m —R ^F2 —[C(O)N(R ³¹ )] _s —Q ³¹ —(O) _t —C[—(O) _u —Q ³² —SiR _n L _3-n ] ₃ formula 2c,
A ² —O—(R ^F1 O) _m —R ^F2 —Q ⁴¹ —Si[—Q ⁴² —SiR _n L _3-n ] ₃ formula 2d,
A ² —O—(R ^F1 O) _m —R ^F2 —[C(O)N(R ⁵ )] _v —Q ⁵¹ —Z[—Q ⁵² —SiR _n L _3-n ] _w formula 2e,
A ² —O—(R ^F1 O) _m —R ^F2 —Q ⁶¹ —G(R ⁶ )[—Q ⁶² —SiR _n L _3-n ] ₂ formula 2f,
A ² —O—(R ^F1 O) _m —R ^F2 —Q ⁷¹ —[CH ₂ C(R ⁷¹ )(—Q ⁷² —SiR _n L _3-n )] _y —R ⁷² formula 2g.

Examples of divalent organopolysiloxane residues in groups g1 to g6 include groups of the following formulae. However, Ra in the following formula is ^a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. The number of carbon atoms in the alkyl group and alkoxy group of R ^a is preferably 1 to 10, particularly preferably 1.

The silphenylene skeleton in groups g1 and g3 is represented by —Si(R ^b ) ₂ PhSi(R ^b ) ₂ — (where Ph is a phenylene group and R ^b is a monovalent organic group). is a group. R ^b is preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably a methyl group.
The dialkylsilylene groups in groups g1 and g3 are groups represented by —Si(R ^c ) ₂ — (where R ^c is an alkyl group). R ^c is preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably a methyl group.

R ¹ in compound 2a is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom from the viewpoint of easy production of compound 2a.
Q ¹ is an alkylene group having 1 to 10 carbon atoms, a group having an etheric oxygen atom or a silphenylene skeleton between the carbon atoms of the alkylene group having 2 to 10 carbon atoms, or an alkylene group having 2 to 10 carbon atoms. is preferably a group having a divalent organopolysiloxane residue or a dialkylsilylene group between the carbon atoms of or at the terminal on the side bonding to (X ¹ ) _p . Q ¹ is -CH ₂ OCH ₂ CH ₂ CH ₂ -, -CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ when (X ¹ ) _p is a single bond because of the ease of producing compound 2a. -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ OCH ₂ CH ₂ CH ₂ Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ CH ₂ CH ₂ - is preferred, and (X ¹ ) When _p is -O-, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ - is preferable, and (X ¹ ) _p is -C(O)N(R ¹ ) In the case of -, an alkylene group having 2 to 6 carbon atoms is preferable (however, the right side is bonded to Si).

Specific examples of compound 2a include the following compounds. provided that PFPE is A ² —O—(R ^F1 O) _m —R ^F2 — if it has a B ² at one end of the PFPE chain, ie —O—(R ^F1 O) _m —, and —O—( When R ^F1 O) _m - has B ² at both ends, it is -R ^F2 -O-(R ^F1 O) _m -R ^F2 -. A preferred form of PFPE would be a combination of the preferred A ² , (R ^F1 O) _m and R ^F2 described above.

(X ² ) _r in compound 2b is preferably a single bond from the viewpoint of easy production of compound 2b.
R ² is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom from the viewpoint of facilitating production of compound 2b.
Q ²¹ is, when (X ² ) _r is a single bond, an alkylene group having 1 to 10 carbon atoms, or an etheric oxygen atom or —NH— -CH ₂ -, -CH ₂ CH _{2 -, -CH 2 CH 2 CH 2 -, -CH 2 OCH 2 CH 2 -, -CH 2 NHCH 2 from the viewpoint of easy production} of compound 2b. CH ₂ — is particularly preferred (provided that the right side is attached to N).
Q ²² is preferably an alkylene group having 1 to 10 carbon atoms, or a group having an etheric oxygen atom or —NH— between the carbon-carbon atoms of an alkylene group having 2 to 10 carbon atoms, which facilitates the production of compound 2b. From this point of view, -CH ₂ CH ₂ CH ₂ - and -CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ - are particularly preferable (provided that the right side is bonded to Si).

Specific examples of compound 2b include the following compounds. However, the PFPE is the same as the PFPE of compound 2a, and the preferred forms are also the same.

As R ³¹ in compound 2c, a hydrogen atom is preferable from the viewpoint of easy production of compound 2c. The alkyl group for R ³¹ is preferably an alkyl group having 1 to 4 carbon atoms.
-Q ³¹ - is preferably an alkylene group having 1 to 10 carbon atoms, or a group having an etheric oxygen atom between carbon atoms of an alkylene group having 2 to 10 carbon atoms. —Q ³¹ —(O) _t — is a single bond, —CH ₂ O—, —CH ₂ OCH ₂ —, —CH ₂ when s is 0 from the viewpoint of ease of production of compound 2c. OCH ₂ CH ₂ O— and —CH ₂ OCH ₂ CH ₂ OCH ₂ — are preferred (where the left side is bonded to R ^f7 ), and when s is 1, a single bond, —CH ₂ —, —CH ₂ CH ₂ — is preferred.
R ³² is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom from the viewpoint of easy production of compound 2c.
Q ³² is an alkylene group having 1 to 10 carbon atoms, a group having an etheric oxygen atom or silphenylene skeleton between the carbon atoms of the alkylene group having 2 to 10 carbon atoms, or an alkylene group having 2 to 10 carbon atoms. or a group having —C(O)N(R ³² )—, a divalent organopolysiloxane residue or a dialkylsilylene group between the carbon atoms of or at the terminal on the side bonding to (O) _u . —(O) _u —Q ³² — is —CH _{2 CH 2 —, —CH 2 CH 2 CH 2} —, —CH ₂ OCH ₂ CH ₂ CH ₂ — from the viewpoint of ease of production of compound 2c. , —CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —, —OCH ₂ CH ₂ CH ₂ —, —OSi(CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ —, —OSi(CH ₃ ) ₂ OSi(CH ₃ ) 2CH ₂ CH ₂ CH ₂ - and -CH ₂ CH ₂ CH ₂ Si(CH ₃ ) ₂ PhSi(CH ₃ ) ₂ CH ₂ CH ₂ - _are preferred (where the right side is bonded to Si).

Specific examples of compound 2c include the following compounds. However, the PFPE is the same as the PFPE of compound 2a, and the preferred forms are also the same.

Q ⁴¹ in compound 2d is preferably an alkylene group having 1 to 10 carbon atoms, or a group having an etheric oxygen atom between the carbon-carbon atoms of an alkylene group having 2 to 10 carbon atoms, which facilitates the production of compound 2d. _{From the viewpoint of the _ _ _ _ _ _ _ _ _ _} bonds to Si).
Q ⁴² is preferably an alkylene group having 1 to 10 carbon atoms, or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between the carbon-carbon atoms of an alkylene group having 2 to 10 carbon atoms, —CH ₂ CH ₂ CH ₂ — and —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ — are preferred from the viewpoint of easy production of compound 2d (where the right side is bonded to SiR _n L _3-n ).

Specific examples of compound 2d include the following compounds. However, the PFPE is the same as the PFPE of compound 2a, and the preferred forms are also the same.

R ⁵ in compound 2e is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom from the viewpoint of easy production of compound 2e.
Q ⁵¹ is preferably an alkylene group having 1 to 10 carbon atoms, or a group having an etheric oxygen atom between the carbon-carbon atoms of an alkylene group having 2 to 10 carbon atoms. -CH ₂ OCH ₂ CH ₂ CH ₂ -, -CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ - are preferred (however, the right side is Z Join.).
Q ⁵² is preferably an alkylene group having 1 to 10 carbon atoms, or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between the carbon-carbon atoms of an alkylene group having 2 to 10 carbon atoms, -CH ₂ CH ₂ - and -CH ₂ CH ₂ CH ₂ - are preferred from the viewpoint of easy production of compound 2e.
The (w+1)-valent organopolysiloxane residue of Z includes the following groups. However, Ra in the following formula is ^a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. The number of carbon atoms in the alkyl group and alkoxy group of R ^a is preferably 1 to 10, particularly preferably 1.

Q ⁶¹ in compound 2f is preferably a single bond, an alkylene group having 1 to 10 carbon atoms, or a group having an etheric oxygen atom between the carbon-carbon atoms of an alkylene group having 2 to 10 carbon atoms to produce compound 2f. A single bond is preferred because it is easy to bond.
G(R ⁶ ) is C(OH) or Si(R ^6a ) (where R ^6a is an alkyl group. The number of carbon atoms is preferably 1 to 10, and 1 is particularly preferred.) is preferred.
Q ⁶² is preferably an alkylene group having 1 to 10 carbon atoms, or a group having an etheric oxygen atom between the carbon-carbon atoms of an alkylene group having 2 to 10 carbon atoms, and from the viewpoint of easy production of compound 2f, - CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ - are preferred.

Specific examples of compound 2f include the following compounds. However, the PFPE is the same as the PFPE of compound 2a, and the preferred forms are also the same.

Q ⁷¹ in compound 2g is preferably a single bond, an alkylene group having 1 to 10 carbon atoms, or a group having an etheric oxygen atom between the carbon-carbon atoms of an alkylene group having 2 to 10 carbon atoms, and compound 2g is produced. A single bond is preferred because it is easy to bond.
R ⁷¹ is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and is preferably a hydrogen atom from the viewpoint of easy production of compound 2g. A methyl group is preferred as the alkyl group for R ⁷¹ .
Q ⁷² is preferably a single bond or an alkylene group having 1 to 10 carbon atoms, and is preferably a single bond or —CH ₂ — from the viewpoint of easy production of compound 2g.
R ⁷² is preferably a hydrogen atom from the viewpoint of facilitating production of compound 2g.

Specific examples of compound 2g include the following compounds. However, the PFPE is the same as the PFPE of compound 2a, and the preferred forms are also the same.

The hydrolyzable silyl group-containing fluorine-containing ether compound can be produced by the same production method as that for known hydrolyzable silyl group-containing fluorine-containing ether compounds used as surface treatment agents.
Known production methods include, for example, the following methods.
- A polar group-containing fluorine-containing ether compound having -OR ² , -C(O)OR ² , -C(O)N(R ² ) ₂ or -C(O)X at the end is attached by a known method. After introducing a carbon-carbon unsaturated double bond to obtain an unsaturated double bond-terminated fluorine-containing ether compound, the unsaturated double bond-terminated fluorine-containing ether compound and HSiR _n L _3-n are subjected to a hydrosilylation reaction. Method.
• A method of polymerizing CH ₂ ═CH—SiR _n L _3-n , CH ₂ ═CHCH ₂ —SiR _n L _3-n , etc. using an iodine-terminated fluorine-containing ether compound as an initiator.

Compounds 2a to 2g can be produced, for example, as follows.
Compound 2a, for example, according to the method described in Patent Document 1 or JP-A-2012-072272, compound 1a-2, compound 1a-5, compound 1b-1, compound 1b-2, compound 1d-1, compound 1d-2 and the like can be prepared as starting materials.
Compound 2b can be produced, for example, according to the method described in WO 2017/038832, using compound 1a-2, compound 1a-5, etc. as starting materials.

Compound 2c shown in Chemical Formula 5 can be produced, for example, according to the method described in International Publication No. 2017/038830, using compound 1a-2, compound 1a-5, etc. as starting materials.
Compound 2c shown in Chemical Formula 6 can be produced, for example, according to the method described in JP-A-2016-204656, using compound 1b-1, compound 1b-2 and the like as starting materials.
Compound 2c shown in Chemical Formula 7 can be produced, for example, according to the method described in International Publication No. 2017/038830, using compound 1b-1, compound 1b-2, etc. as starting materials.

Compound 2d can be produced, for example, according to the method described in JP-A-2016-037541 or WO 2016/121211, using compounds 1a-2, 1a-5 and the like as starting materials.
Compound 2e can be produced, for example, according to the method described in JP-A-2012-072272, using compounds 1a-2, 1a-5 and the like as starting materials.
Compound 2f in which G(R ⁶ ) is C(OH) can be produced, for example, according to the method described in JP-A-2016-037541, using compounds 1b-1, 1b-2, etc. as starting materials.

Compound 2g is prepared by, for example, compound 1d-1, compound 1d-2, etc. after iodination using an iodinating agent (LiI, iodine/potassium carbonate, etc.) to convert terminal —C(O)F to —I. , according to the method described in International Publication No. 2016/121211, using an iodine-terminated fluorine-containing ether compound as an initiator, CH ₂ ═CHSi(OCH ₃ ) ₃ , CH ₂ ═CHCH ₂ Si(OCH ₃ ) ₃ and the like are polymerized. It can be manufactured by

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.
Example 1 is a production example, and Example 2-1, Example 2-3, Example 2-4, Example 3-1, Example 3-4, Example 3-6, and Examples 4 to 6 are examples. 2-2, Example 3-2, Example 3-3, Example 3-5, and Example 7 are reference examples.

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

(Content of cyclized form)
The cyclized product content in the treated material or the remainder of the treated material was determined by gas chromatography (GC). In addition, the cyclized products in Examples 2 and 3 are the compounds shown in Formula 1.

(Molecular weight distribution)
The molecular weight distribution of the object to be treated, the recovered solution, and the remainder of the object to be treated was determined in terms of polystyrene by the GPC method.

[Example 1]
CF ₂ ═CFOCF ₂ CF ₂ CF ₂ CH ₂ OH was obtained in the same manner as in Example 1-1 of Patent Document 1. Using this, an object to be treated containing compound 1-1 and by-products was obtained with reference to Example 6-1 of Patent Document 1. The object to be treated was obtained by performing a reaction to obtain compound 1-1, followed by liquid separation treatment, washing with water, recovering the organic phase, and concentrating with an evaporator. The object to be processed does not contain a liquid medium.
CH ₃ —O—(CF ₂ CHFO—CF ₂ CF ₂ CF ₂ CH ₂ O)×3 CF _{2 CHFO} —CF ₂ CF ₂ CF ₂ CH ₂ —OH Formula 1-1
Average value of number of units x3: 15, number average molecular weight of compound 1-1: 4,480.

[Example 2]
(Example 2-1)
10 mL of the object to be treated and 50 mL of chloroform were placed in a vial and stirred at 400 rpm with a mechanical stirrer at a temperature of 25° C. for 30 seconds. The mixture was allowed to stand and separated into two layers, an upper layer consisting of a solution in which a part of the object to be treated was dissolved in chloroform and a lower layer consisting of the remainder of the object to be treated that was not dissolved in chloroform. The remainder of the object to be treated was collected, and the collected remainder of the object to be treated was analyzed by GC to determine the content of the cyclized form in the remainder of the object to be treated.
The remaining portion of the recovered object to be treated was used again as the object to be treated, and the same purification operation was repeated five times in total. Table 2 shows the content of the cyclized form in the object to be treated before the purification operation and the content of the cyclized form in the remainder of the object to be treated after each purification operation.

(Example 2-2 to Example 2-4)
Purification was carried out in the same manner as in Example 2-1, except that chloroform was changed to the following liquid medium. Example 2-2: n-hexane, Example 2-3: carbon tetrachloride, Example 2-4: AK-225. Table 2 shows the results.

The cyclized form contained in the remainder of the object to be treated could be reduced by the purification operation.
However, since n-hexane in Example 2-2 has low solubility of the cyclized product, it is necessary to repeat the purification operation more times. In AK-225 of Example 2-4, the desired fluorine-containing ether compound and the cyclized product thereof are highly soluble, so that the yield of the desired fluorine-containing ether compound is slightly reduced.

[Example 3]
The remainder of the object to be treated obtained in the fifth purification operation of Example 2-4 was used as the object to be treated.
A molecular weight distribution of the object to be treated was obtained. Table 3 shows the molecular weight at the peak top of the molecular weight distribution.
A device with the flow shown in FIG. 1 was assembled. Using this apparatus, the target molecular weight compound 1-1 and the low molecular weight compounds were separated from the object to be treated in which the cyclized product was below the detection limit.

(Example 3-1)
10 mL of the object to be treated and 300 mL of chloroform were placed in a stirring vessel and stirred at 50 revolutions per minute at a temperature of 25° C. for 6 hours. The mixture is transferred to a separation tank and allowed to stand still to separate into two layers: an upper layer consisting of a solution in which part of the object to be treated is dissolved in chloroform and a lower layer consisting of the remaining part of the object to be treated that is not dissolved in chloroform. rice field. The remainder of the solution and the object to be treated were collected, and the molecular weight distribution of each was determined. Also, the ratio of the dissolved matter in the solution to the object to be treated and the ratio of the remainder of the object to be treated to the object to be treated were obtained. Table 3 shows the results.

(Example 3-2 to Example 3-4)
Purification was carried out in the same manner as in Example 3-1, except that chloroform was changed to the following liquid medium. Example 3-2: methanol, Example 3-3: n-hexane, Example 3-4: n-hexane:benzyl alcohol=52:48 (volume ratio). Table 3 shows the results.

[Example 4]
The remainder of the object to be treated obtained in the fifth purification operation of Example 2-4 was used as the object to be treated. Using the same apparatus as in Example 3, the compound 1-1 having the target molecular weight and the high molecular weight compound were separated from the object to be treated in which the cyclized product was below the detection limit.
Purification was carried out in the same manner as in Example 3-1, except that chloroform was changed to chloroform:acetone=50:50 (volume ratio). Table 3 shows the results.

(Example 3-5)
Similar to Example 3-3 (n-hexane) using the average composition CF ₃ O(CF ₂ CF ₂ O) ₁₅ (CF ₂ O) ₁₆ CF ₂ CH ₂ OH described in Synthesis Example 11 of Japanese Patent No. 5761305 operation was performed. As a result, the lysate in solution/process of interest was 18% with a peak top molecular weight of 1,100, and the remainder of the process/process of interest was 82% with a peak top molecular weight of 2,980. separated into

(Example 3-6)
_{Example 3-4 ( n - hexane _ _ _ _} and benzyl alcohol mixed liquid medium). As a result, the lysate in solution/process of interest was 24% with a peak top molecular weight of 1,550, and the remainder of the process/process of interest was 76% with a peak top molecular weight of 2,850. separated into

In Examples 3-1 to 3-4, it was possible to separate the remainder of the object to be treated containing compound 1-1 of the desired molecular weight from the solution containing low molecular weight compounds by the purification operation.
When it is desired to narrow the molecular weight distribution, Example 3-1 is most preferred, followed by Examples 3-4, 3-2 and 3-3 in that order. Since n-hexane of Example 3-3 has low solubility of low molecular weight substances, the amount of reduction of low molecular weight substances is slightly small.
In Examples 3-5 and 3-6, it was possible to separate the remainder of the object to be treated containing the compound of the desired molecular weight from the solution containing the low molecular weight compound by the purification operation.
In Example 4, it was possible to separate the remainder of the object to be treated containing Compound 1-1 of the desired molecular weight from the solution containing the high molecular weight substance by the purification operation.

[Example 5]
Compound 2-1 was obtained in the same manner as in Example 11 of WO 2017/38830 using the remainder of the object to be treated obtained in the fifth purification operation of Example 2-4.
_{CF3 -} O- _{( CF2CF2O - CF2CF2CF2CF2O} ) _{x3 CF2CF2O - CF2CF2CF2 - C (} O)NH _{- CH2 -} C[CH2CH ₂ CH ₂ —Si(OCH ₃ ) ₃ ] ₃ Formula 2-1
Average value of number of units x3: 15, number average molecular weight of compound 2-1: 5,570.

[Example 6]
Compound 2-2 was obtained in the same manner as in Example 3 of WO 2017/38832 using the remainder of the object to be treated obtained in the fifth purification operation of Example 2-4.
_{CF3 -} O- _{( CF2CF2O - CF2CF2CF2CF2O} ) _{x3 CF2CF2O - CF2CF2CF2 - CH2 - N [ CH2CH2CH2 -} Si ₍ OCH ₃ ) ₃ ] ₂ Formula 2-2
Average value of number of units x3: 15, number average molecular weight of compound 2-2: 4,780.

[Example 7]
CF ₃ O(CF ₂ CF ₂ O) ₁₅ (CF ₂ O) ₁₆ CF from the remainder of the object to be treated obtained in Example 3-5 with reference to the method described in [0110] of WO 2015/087902 _{2CH2OCH2CH = CH2} was obtained and _{CF3O ( CF2CF2O} ) _{15 ( CF2O} ) with a molecular weight of 3,560 was obtained using the procedure of Synthesis Example 15 of Japanese Patent No. 5761305. _{16CF2CH2OCH2CH2CH2Si [ CH2CH2CH2Si ( OCH3 ) 3 ] 3 was synthesized .}

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 made of transparent glass or transparent plastic members, an antifouling coating for kitchens; It can be used for antifouling coating; coating on members that require liquid repellency while conducting; water-repellent, water-proof, and water-sliding coating for heat exchangers; More specific examples of use include front protective plates for displays, anti-reflection plates, polarizing plates, anti-glare plates, or those with anti-reflection coatings on their surfaces, and touch panels for devices such as mobile phones and personal digital assistants. Various devices with display input devices that operate on the screen with fingers or palms such as seats and touch panel displays, decorative building materials around water such as toilets, baths, washrooms, kitchens, waterproof coating for circuit boards Repellent of heat exchangers Water/waterproof coatings, water-repellent coatings for solar cells, waterproof/water-repellent coatings for printed wiring boards, waterproof/water-repellent coatings for electronic device housings and electronic components, insulation-enhancing coatings for transmission lines, waterproofing/water-repellent coatings for various filters Water-repellent coating, waterproof coating for radio-wave absorbing and sound-absorbing materials, antifouling coating for bathrooms, kitchen equipment, toiletries, water-repellent, waterproof, and sliding coating for heat exchangers, surface low-friction coating for vibrating screens and inside cylinders, etc. Examples include surface protective coatings for machine parts, vacuum equipment parts, bearing parts, automobile parts, tools, and the like.

1 stirring vessel, 2 separating vessel, 3 distillation apparatus.

Claims (9)

For dissolving an object to be treated containing a liquid fluorine-containing ether compound (however, said object to be treated does not contain a liquid medium), which is capable of dissolving a part of the fluorine-containing ether compound among the liquid fluorine-containing ether compounds. A liquid medium is used to separate substances dissolved in the liquid medium for dissolution and substances not dissolved in the liquid medium for dissolution, and the substances not dissolved in the liquid medium for dissolution are recovered,
The fluorine-containing ether compound is a compound represented by the following formula 1,
The dispersion term dD of the Hansen solubility parameter of the liquid medium for dissolution is 14 to 18, the hydrogen bonding term dH is 0 to 10, the polar term dP is 2 to 8 ,
A method for producing a fluorine-containing ether compound , wherein the peak top molecular weight of the compound dissolved in the dissolving liquid medium is 88.14% or less of the peak top molecular weight of the compound not dissolved in the dissolving liquid medium .
A ¹ -O-[(R ^f1 O) _m1 (R ¹ O) _m2 ]-B ¹ Formula 1
provided that A ¹ is an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms or B ¹ ; R ^f1 is a fluoroalkylene group having ¹ to 6 carbon atoms; an alkylene group having 1 to 6 carbon atoms; _m1 is an integer of 2 or more; m2 is an integer of 0 or more; ^m1 +m2 is an integer of 2 to 200; (R ¹ O) ^m2 may consist of two or more R ¹ O when _m2 is an integer of 2 or more; B ¹ is -R ^f2 CH ₂ -OR ² , -R ^f2 -C(O)OR ² , -R ^f2 -C(O)N(R ² ) ₂ or -R ^f2 -C(O)X; R ^f2 is an alkylene group having 1 to 6 carbon atoms or a fluoroalkylene group having 1 to 6 carbon atoms; R ² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; X is a halogen atom . The object to be treated and the liquid medium for dissolution are mixed, and a solution in which the part of the fluorine-containing ether compound is dissolved in the liquid medium for dissolution and the object to be treated that is not dissolved in the liquid medium for dissolution 2. The production method according to claim 1, wherein the part of the fluorine-containing ether compound is separated from the object to be treated by separating the remaining portion and recovering the portion not dissolved in the dissolving liquid medium. The liquid fluorine-containing ether compound contains a cyclic fluorine-containing ether compound as one of the liquid fluorine-containing ether compounds,
3. The production method according to claim 1, wherein the cyclic fluorine-containing ether compound is separated from the object to be treated using a dissolving liquid medium capable of dissolving the cyclic fluorine-containing ether compound. Using a dissolving liquid medium capable of dissolving the fluorine-containing ether compound in the partial molecular weight range among the liquid fluorine-containing ether compounds, the fluorine-containing ether compound in the partial molecular weight range is separated from the object to be treated. , The manufacturing method according to claim 1 or 2. The liquid fluorine-containing ether compound contains a cyclic fluorine-containing ether compound as one of the liquid fluorine-containing ether compounds,
Using a dissolving liquid medium capable of dissolving the cyclic fluorine-containing ether compound and a fluorine-containing ether compound in a partial molecular weight range among the fluorine-containing ether compounds other than the cyclic fluorine-containing ether compound, the above-mentioned 3. The production method according to claim 1, wherein the cyclic fluorine-containing ether compound and the fluorine-containing ether compound in the partial molecular weight range are separated. 6. The production method according to claim 4 or 5, wherein the fluorine-containing ether compound having a partial molecular weight range is a fluorine-containing ether compound having a low molecular weight range. The production method according to any one of claims 1 to 6, wherein the liquid fluorine-containing ether compound comprises a cyclic fluorine-containing ether compound. From the fluorine-containing ether compound having —OR ² , —C(O)OR ² , —C(O)N(R ² ) ₂ or —C(O)X at the terminal, hydration via a linking group at the terminal 8. The production method according to any one of claims 1 to 7, wherein a hydrolyzable silyl group-containing fluorine-containing ether compound having a degradable silyl group is obtained. 9. The production method according to claim 8, wherein the hydrolyzable silyl group-containing fluorine-containing ether compound is a compound represented by the following formula 2.
A ² —O—(R ^F1 O) _m —B ² Formula 2
however,
A ² is a C 1-20 perfluoroalkyl group or B ² ,
R ^F1 is a perfluoroalkylene group having 1 to 6 carbon atoms,
m is an integer from 2 to 200,
(R ^F1 O) _m may consist of two or more R ^F1 O,
B2 is a group represented by any ^one of the following formulas g1 to g7.
—R ^F2 —(X ¹ ) _p —Q ¹ —SiR _n L _3-n Formula g1
—R ^F2 —(X ² ) _r —Q ²¹ —N[—Q ²² —SiR _n L _3-n ] ₂ formula g2
—R ^F2 —[C(O)N(R ³¹ )] _s —Q ³¹ —(O) _t —C[—(O) _u —Q ³² —SiR _n L _3-n ] ₃ formula g3
—R ^F2 —Q ⁴¹ —Si[—Q ⁴² —SiR _n L _3-n ] ₃ formula g4
-R ^F2 -[C(O)N(R ⁵ )] _v -Q ⁵¹ -Z[-Q ⁵² -SiR _n L _3-n ] _w formula g5
-R ^F2 -Q ⁶¹ -G(R ⁶ )[-Q ⁶² -SiR _n L _3-n ] ₂ formula g6
—R ^F2 —Q ⁷¹ —[CH ₂ C(R ⁷¹ )(-Q ⁷² —SiR _n L _3-n )] _y —R ⁷² formula g7
however,
R ^F2 is a perfluoroalkylene group having 1 to 6 carbon atoms,
R is a hydrogen atom or a monovalent hydrocarbon group,
L is a hydrolyzable group,
n is an integer of 0-2.
In formula g1,
X ¹ is an etheric oxygen atom or -C(O)N(R ¹ )- (wherein N is bonded to Q ¹ ),
R ¹ is a hydrogen atom or an alkyl group,
p is 0 or 1;
Q ¹ is an alkylene group, a group having an etheric oxygen atom or a silphenylene skeleton between the carbon-carbon atoms of an alkylene group with 2 or more carbon atoms, or between the carbon-carbon atoms of an alkylene group with 2 or more carbon atoms or (X ¹ ) A group having a divalent organopolysiloxane residue or a dialkylsilylene group at the terminal on the side bonded to _p .
In formula g2,
X ² is an etheric oxygen atom, -NH- or -C(O)N(R ² )- (where N is bonded to Q ²¹ );
^R2 is a hydrogen atom or an alkyl group,
r is 0 or 1 (provided that it is 0 when Q ²¹ is a single bond);
Q ²¹ is a single bond, an alkylene group, or an etheric oxygen atom, —NH—, —C(O)—, —C(O)O— or — between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms OC(O)— is a group having
Q ²² is an alkylene group or a group having an etheric oxygen atom, -NH- or a divalent organopolysiloxane residue between the carbon-carbon atoms of an alkylene group having 2 or more carbon atoms,
Two [-Q ²² -SiR _n L _3-n ] may be the same or different.
In formula g3,
R ³¹ is a hydrogen atom or an alkyl group,
s is 0 or 1;
Q ³¹ is a single bond, an alkylene group, or a group having an etheric oxygen atom between carbon atoms of an alkylene group having 2 or more carbon atoms,
t is 0 or 1 (however, it is 0 when Q ³¹ is a single bond);
u is 0 or 1,
Q ³² is an alkylene group, a group having an etheric oxygen atom or silphenylene skeleton between the carbon-carbon atoms of an alkylene group with 2 or more carbon atoms, or between the carbon-carbon atoms of an alkylene group with 2 or more carbon atoms or (O ) is a group having —C(O)N(R ³² )—, a divalent organopolysiloxane residue or a dialkylsilylene group at the terminal on the side that bonds to _u ,
R ³² is a hydrogen atom or an alkyl group,
Three [-(O) _u -Q ³² -SiR _n L _3-n ] may be the same or different.
In formula g4,
Q ⁴¹ is an alkylene group or a group having an etheric oxygen atom between the carbon-carbon atoms of an alkylene group having 2 or more carbon atoms,
Q ⁴² is an alkylene group or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between the carbon-carbon atoms of an alkylene group having 2 or more carbon atoms,
Three [-Q ⁴² -SiR _n L _3-n ] may be the same or different.
In formula g5,
^R5 is a hydrogen atom or an alkyl group,
v is 0 or 1;
Q ⁵¹ is an alkylene group or a group having an etheric oxygen atom between the carbon-carbon atoms of an alkylene group having 2 or more carbon atoms,
Z is a (w+1) valent organopolysiloxane residue,
Q ⁵² is an alkylene group or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between the carbon-carbon atoms of an alkylene group having 2 or more carbon atoms,
w is an integer from 2 to 7;
The w [-Q ⁵² -SiR _n L _3-n ] may be the same or different.
In formula g6,
Q ⁶¹ is a single bond, an alkylene group, or a group having an etheric oxygen atom between carbon atoms of an alkylene group having 2 or more carbon atoms,
G is a carbon atom or a silicon atom,
^R6 is a hydroxyl group or an alkyl group,
Q ⁶² is an alkylene group or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between the carbon-carbon atoms of an alkylene group having 2 or more carbon atoms,
Two [-Q ⁶² -SiR _n L _3-n ] may be the same or different.
In formula g7,
Q ⁷¹ is a single bond, an alkylene group, or a group having an etheric oxygen atom between carbon atoms of an alkylene group having 2 or more carbon atoms,
R ⁷¹ is a hydrogen atom or an alkyl group,
Q ⁷² is a single bond or an alkylene group,
R ⁷² is a hydrogen atom or a halogen atom,
y is an integer from 1 to 10,
2 to 10 [-Q ⁷² -SiR _n L _3-n ] may be the same or different.

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