JPWO2019035288A1 - Method for producing fluorine-containing ether compound and method for producing article - Google Patents

Abstract

A method for producing a fluorine-containing ether compound and a method for producing an article capable of forming a surface layer having excellent friction resistance and suppressing generation of particulate matter. In the presence of a hydrosilylation catalyst, a compound having a poly (oxyperfluoroalkylene) chain and an ω-alkenyl group and at least a hydrogen atom bonded to a silicon atom and a hydrolyzable group bonded to the silicon atom and a hydroxyl group bonded to the silicon atom Reacting with a compound having one of them to produce a fluorine-containing ether compound having a poly (oxyperfluoroalkylene) chain and at least one of a hydrolyzable group bonded to a silicon atom and a hydroxyl group bonded to a silicon atom. A method for producing a compound, wherein after obtaining a fluorinated ether compound, the fluorinated ether compound is brought into contact with an adsorbent having a water content of 1.0% by mass or less, or a hydrosilylation catalyst and a water content of 1% by mass. The reaction is carried out in the presence of not more than 0.0% by mass of an adsorbent. Process for producing a fluorinated ether compound.

Description

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

  Since the fluorine-containing compound exhibits high lubricity, water / oil repellency, and the like, it is preferably used as a surface treatment agent. When the surface treatment agent imparts water and oil repellency to the surface of the base material, it becomes easy to wipe off the dirt on the surface of the base material, and the removability of the dirt is improved. Among the fluorine-containing compounds, the fluorine-containing ether compound having a poly (oxyperfluoroalkylene) chain in which an ether bond (—O—) is present in the middle of the perfluoroalkylene chain is a compound having excellent flexibility. Excellent dirt removal.

The surface treatment agent containing the above-mentioned fluorine-containing ether compound has the ability to prevent water and oil repellency from being lowered even when repeatedly rubbed with a finger (friction resistance) and the ability to easily remove fingerprints attached to the surface by wiping (fingerprint stains) For example, it is used as a surface treatment agent for a member constituting a surface touched by a finger of a touch panel.
Examples of the fluorine-containing ether compound include a poly (oxyperfluoroalkylene) chain obtained by reacting a compound having a poly (oxyperfluoroalkylene) chain with an alkoxysilane, and having a poly (oxyperfluoroalkylene) chain bonded to a silicon atom at the end. A compound having a decomposable group is widely used (Patent Document 1).

International Publication No. 2014/163004

In recent years, physical properties required for a surface layer formed using a surface treatment agent containing a fluorine-containing ether compound have been further improved.
When the present inventors formed a surface layer on the surface of the substrate using the surface treating agent containing the fluorine-containing ether compound described in Patent Document 1, when the surface layer has insufficient friction resistance, or It has been found that there are cases where the granular material resulting from the aggregates is generated and the appearance characteristics of the surface layer are inferior.

  An object of this invention is to provide the manufacturing method of the fluorine-containing ether compound which can form the surface layer which was excellent in abrasion resistance and the generation | occurrence | production of the granular material was suppressed in view of the said subject, and the manufacturing method of articles | goods.

The present invention provides a method for producing a fluorine-containing ether compound and a method for producing an article having the following configurations [1] to [10].
[1] A compound having a poly (oxyperfluoroalkylene) chain and an ω-alkenyl group, a hydrogen atom bonded to a silicon atom, a hydrolyzable group bonded to a silicon atom, and a silicon atom in the presence of a hydrosilylation catalyst Reacting with a compound having at least one of hydroxyl groups to produce a fluorinated ether compound having at least one of a poly (oxyperfluoroalkylene) chain, a hydrolyzable group bonded to a silicon atom, and a hydroxyl group bonded to a silicon atom; A method for producing a fluorine-containing ether compound, comprising:
After obtaining the fluorine-containing ether compound, the fluorine-containing ether compound is contacted with an adsorbent having a water content of 1.0% by mass or less, or
A method for producing a fluorinated ether compound, wherein the reaction is carried out in the presence of the hydrosilylation catalyst and an adsorbent having a water content of 1.0% by mass or less.

[2] The method according to [1], wherein the moisture content of the adsorbent is 0.1% by mass or less.
[3] The method according to [1] or [2], wherein the adsorbent is activated carbon, molecular sieve, silica gel, or celite.
[4] The method according to any one of [1] to [3], wherein the hydrosilylation catalyst is a Group 8 to Group 10 transition metal catalyst.

[5] The production method of any one of [1] to [4], wherein the compound having a poly (oxyperfluoroalkylene) chain and an ω-alkenyl group is a compound represented by the following formula (1).
_{^{[A 1 -O-Z 1 -}} (R f O) m -] j Z 2 [-CH = CH 2] q (1)
However, ^{A 1} is a perfluoroalkyl group or a _{-Q [-CH = CH 2] k} , if ^{A 1} is _{-Q [-CH = CH 2] k} j is 1,
Q is a (k + 1) -valent linking group, k is an integer of 1 to 10,
Z ¹ is a single bond, an oxyfluoroalkylene group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom (excluding an oxyperfluoroalkylene group. The oxygen atom in the oxyfluoroalkylene group is , (R ^f O) _m .), Or a poly (oxyfluoroalkylene) group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms (bonded to (R ^f O) _m oxygen atoms in the oxy-fluoroalkylene group is (R f ^O) binds to _m. oxyfluoroalkylene group bonded to (R f ^O) _m is. poly (oxy-fluoroalkylene comprising one or more hydrogen atoms ) Group includes both an oxyperfluoroalkylene group in which all hydrogen atoms are substituted with fluorine atoms and an oxyfluoroalkylene group containing one or more hydrogen atoms. May be included.)
R ^f is a perfluoroalkylene group, m is an integer of 2 to 200, and when two or more types of R ^f O having different carbon numbers are present in (R ^f O) _m , the bonding order of each R ^f O Is not limited,
Z ² is a (j + q) -valent linking group, and j and q are each an integer of 1 or more.

[6] The compound having at least one of a hydrogen atom bonded to the silicon atom, a hydrolyzable group bonded to the silicon atom, and a hydroxyl group bonded to the silicon atom is a compound represented by the following formula (3): 1]-[5] any manufacturing method.
_{H-SiR n L 3-n} (3)
However, R is a monovalent hydrocarbon group, L is a hydrolyzable group or a hydroxyl group, n is an integer of 0 to 2, and when n is 0 or 1, a plurality of molecules present in one molecule L may be the same as or different from each other. When n is 2, two Rs present in one molecule may be the same as or different from each other.
[7] The production method of [6], wherein n is 0 or 1, and a plurality of L are all hydrolyzable groups.

[8] The amount of the adsorbent used is 1 to 30% by mass based on the total mass of the compound having a poly (oxyperfluoroalkylene) chain and an ω-alkenyl group. Either manufacturing method.
[9] After obtaining the fluorine-containing ether compound, any one of [1] to [8], wherein the fluorine-containing ether compound and an adsorbent having a water content of 1.0% by mass or less are contacted in a liquid medium. Manufacturing method.
[10] A method for producing an article, wherein a surface layer is formed on the surface of a substrate using the fluorine-containing ether compound obtained by the production method of any one of [1] to [9].

  ADVANTAGE OF THE INVENTION According to this invention, it can provide the manufacturing method of the fluorine-containing ether compound which can form the surface layer which was excellent in friction resistance and the generation | occurrence | production of the granular material was suppressed, and the manufacturing method of articles | goods.

In the present specification, the compound represented by the formula (1) is referred to as Compound 1. The same applies to compounds represented by other formulas. A group represented by formula (1) is referred to as group 1. Groups represented by other formulas are also described in the same manner.
In the present specification, “an alkylene group may have an A group” and “an alkylene group which may have an A group” mean an A group between a carbon atom and a carbon atom in the alkylene group. It may have, and it means that you may have A group at the terminal like alkylene group -A group-.
The meanings of terms in the present invention are as follows.
The “etheric oxygen atom” means an oxygen atom that forms an ether bond (—O—) between a carbon atom and a carbon atom.
The “divalent organopolysiloxane residue” is a group represented by the following formula. R ^a in the following formula is an alkyl group (preferably having a carbon number of 1 to 10) or a phenyl group. Moreover, g1 is an integer greater than or equal to 1, the integer of 1-9 is preferable and the integer of 1-4 is especially preferable.

The “silphenylene skeleton group” is a group represented by —Si (R ^b ) ₂ PhSi (R ^b ) ₂ — (wherein Ph is a phenylene group and R ^b is a monovalent organic group). It is. R ^b is preferably an alkyl group (preferably having 1 to 10 carbon atoms).
The “dialkylsilylene group” is a group represented by —Si (R ^c ) ₂ — (wherein R ^c is an alkyl group (preferably having 1 to 10 carbon atoms)).
The “hydrolyzable silyl group” is a group consisting of a silicon atom to which a hydrolyzable group is bonded.
The “silanol group” is a hydroxyl group bonded to a silicon atom.
“Surface layer” means a layer formed on the surface of a substrate.
The “number average molecular weight” of the fluorine-containing ether compound is calculated by the following method using NMR analysis.
It is calculated by determining the number (average value) of oxyperfluoroalkylene groups based on terminal groups by ¹ H-NMR and ¹⁹ F-NMR.

The production method of the present invention (hereinafter also referred to as “the present production method”) is characterized in that an adsorbent exhibiting a predetermined moisture content is used.
When the fluorine-containing ether compound obtained by the manufacturing method of the prior art is used, the present inventors know that water is related as a reason why the desired effect cannot be obtained. More specifically, in the method described in Patent Document 1, the fluorine-containing ether compound is brought into contact with an adsorbent such as activated carbon after production. When the moisture content in the adsorbent is high, a hydrolysis reaction of a hydrolyzable group bonded to a silicon atom in the fluorine-containing ether compound proceeds, and then an aggregate is formed through a condensation reaction. As a result, particulate matter is observed on the surface layer to be formed, the appearance characteristics are deteriorated, and the friction resistance is also deteriorated. Based on the above findings, the present inventors have solved the above problems by controlling the moisture content of the adsorbent.

This production method comprises a compound having a poly (oxyperfluoroalkylene) chain and an ω-alkenyl group (hereinafter also referred to as “compound A”), a hydrogen atom bonded to a silicon atom, and a silicon atom in the presence of a hydrosilylation catalyst. By reacting with a compound having at least one of a hydrolyzable group bonded to silicon and a hydroxyl group bonded to a silicon atom (hereinafter also referred to as “compound B”) to produce a poly (oxyperfluoroalkylene) chain and a hydrolyzable silyl group. And a method for producing compound C, which comprises producing a fluorine-containing ether compound having at least one of silanol groups (hereinafter also referred to as “compound C”). 1.0 mass% or less of adsorbent (hereinafter also referred to as “specific adsorbent”) or hydrosilyl Presence of a catalyst and a particular adsorbent, perform the above reaction, wherein the.
That is, as the first aspect of the production method, there is an aspect in which compound A is produced by reacting compound A and compound B in the presence of a hydrosilylation catalyst, and the obtained compound C and the specific adsorbent are brought into contact with each other. Can be mentioned.
Moreover, as a 2nd aspect of this manufacturing method, the aspect which reacts the compound A and the compound B in presence of a hydrosilylation catalyst and a specific adsorbent, and manufactures the compound C is mentioned.
Below, the material used by this manufacturing method is explained in full detail first, and the procedure of each aspect is explained in full detail after that.

[Compound A]
The poly (oxyperfluoroalkylene) chain of compound A is (R ^f O) _m (where R ^f is a perfluoroalkylene group, and m is from 2 to 200, since the water and oil repellency of the surface layer is more excellent. And may be composed of two or more types of R ^f O having different carbon numbers.
The definition of (R ^f O) _m will be described in detail later.

Compound A may have a plurality of ω-alkenyl groups. 1-10 are preferable, as for the number of the omega-alkenyl group in the compound A, 1-6 are more preferable, and 1-3 are especially preferable.
Examples of the ω-alkenyl group include allyl group, vinyl group, and 3-butenyl group.

As compound A, compound 1 is preferable in that the water and oil repellency of the surface layer is more excellent.
_{^{[A 1 -O-Z 1 -}} (R f O) m -] j Z 2 [-CH = CH 2] q (1)

A ¹ is a perfluoroalkyl group or a _{-Q [-CH = CH 2] k} .
The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, and particularly preferably 1 to 3, from the viewpoint that the friction resistance of the surface layer is more excellent.
The perfluoroalkyl group may be linear or branched.
However, if ^{A 1} is _{-Q [-CH = CH 2] k} , j is 1.

As perfluoroalkyl groups, 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.
As the perfluoroalkyl group, CF ₃ —, CF ₃ CF ₂ —, and CF ₃ CF ₂ CF ₂ — are preferable because the water and oil repellency of the surface layer is more excellent.

Q is a (k + 1) -valent linking group. k is an integer of 1-10. Therefore, examples of Q include a 2-11 valent linking group.
As Q, for example, an alkylene group optionally having an etheric oxygen atom or a divalent organopolysiloxane residue, a carbon atom, a nitrogen atom, a silicon atom, a divalent to octavalent organopolysiloxane residue, and And a group obtained by removing —CH═CH ₂ from formula (2-1), formula (2-2), and formulas (2-1-1) to (2-1-6) described later.

Z ¹ is a single bond, an oxyfluoroalkylene group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom (excluding an oxyperfluoroalkylene group. The oxygen atom in the oxyfluoroalkylene group is , (R ^f O) _m .), Or a poly (oxyfluoroalkylene) group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms (bonded to (R ^f O) _m oxygen atoms in the oxy-fluoroalkylene group is (R f ^O) binds to _m. oxyfluoroalkylene group bonded to (R f ^O) _m is. poly (oxy-fluoroalkylene comprising one or more hydrogen atoms ) Group includes both an oxyperfluoroalkylene group in which all hydrogen atoms are substituted with fluorine atoms and an oxyfluoroalkylene group containing one or more hydrogen atoms. May be included.) The oxyfluoroalkylene group or poly (oxyfluoroalkylene) group preferably has 1 to 10 carbon atoms.

Z ¹ may be a single bond, —CHFCF ₂ OCH ₂ CF ₂ O—, —CF ₂ CHFCF ₂ OCH ₂ CF ₂ CF ₂ O—, —CF ₂ CF ₂ CHFCF ₂ OCH ₂ CF because it is easy to produce a compound. ₂ O—, —CF ₂ CF ₂ OCHFCF ₂ OCH ₂ CF ₂ O—, —CF ₂ CF ₂ OCF ₂ CF ₂ OCHFCF ₂ OCH ₂ CF ₂ O—, —CF ₂ CH ₂ OCH ₂ CF ₂ O—, —CF _{2 CF 2 OCF 2 CH 2 OCH} 2 CF 2 O- are preferred (in the formula, the left side is bound to ^a 1 -O.). Z ¹ is particularly preferably a single bond or —CHFCF ₂ OCH ₂ CF ₂ O—.

R ^f is a perfluoroalkylene group.
The number of carbon atoms of the perfluoroalkylene group is preferably 1 to 6 because the water and oil repellency of the surface layer is more excellent.
The perfluoroalkylene group may be linear or branched, but is preferably linear because it is more excellent in water and oil repellency of the surface layer.
The plurality of R ^f may be the same or different. That is, (R ^f O) _m may be composed of two or more types of R ^f O having different carbon numbers.

  m is an integer of 2 to 200, an integer of 5 to 150 is preferable, and an integer of 10 to 100 is particularly preferable. When m is not less than the lower limit of the above range, the water and oil repellency of the surface layer is more excellent. If m is not more than the upper limit of the above range, the friction resistance of the surface layer is more excellent.

In (R ^f O) _m , when two or more types of R ^f O having different carbon numbers are present, the bonding order of each R ^f O is not limited. For example, when two types of R ^f O are present, the two types of R ^f O may be randomly, alternately, and arranged in blocks.
^(R f _O) as the _m, from the viewpoint of water and oil repellency of the surface layer is more _{excellent, {(CF 2 O) m11} (CF 2 CF 2 O) m12 (CF 2 CF 2 CF 2 O) m13 (CF 2 _{CF 2 CF 2 CF 2 O)} m14}, (CF 2 CF 2 O) m16, (CF 2 CF 2 CF 2 O) m17, (CF 2 CF 2 O-CF 2 CF 2 CF 2 CF 2 O) m15 ( _{CF 2 CF 2 O), (} CF 2 O-CF 2 CF 2 CF 2 CF 2 CF 2 O) m18 (CF 2 O) or _{(CF 2 CF 2 O-CF} 2 CF 2 CF 2 CF 2 CF 2 CF 2 _{O) m19 (CF 2 CF 2} O) are _{preferred, {(CF 2 O) m11} (CF 2 CF 2 O) m12 (CF 2 CF 2 CF 2 O) m13 (CF 2 CF 2 CF 2 CF 2 O) m14 } _{(CF 2 CF 2 O-CF} 2 CF 2 CF 2 CF 2 O) m15 (CF 2 CF 2 O), (CF 2 O-CF 2 CF 2 CF 2 CF 2 CF 2 O) m18 (CF 2 O), (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) _m19 (CF ₂ CF ₂ O) is particularly preferred.
However, m11 and m12 are each an integer of 1 or more, m13 and m14 are each an integer of 0 or 1, and m11 + m12 + m13 + m14 is an integer of 2 to 200, m11 CF ₂ O, m12 The bonding order of CF ₂ CF ₂ O, m13 CF ₂ CF ₂ CF ₂ O, and m14 CF ₂ CF ₂ CF ₂ CF ₂ O is not limited. m16 and m17 are each an integer of 2 to 200, and m15, m18 and m19 are integers of 1 to 99.

Z ² is a (j + q) -valent linking group.
Z ² is, for example, an ethereal oxygen atom or an alkylene group optionally having a divalent organopolysiloxane residue, a carbon atom, a nitrogen atom, a silicon atom, a divalent to octavalent organopolysiloxane residue, and And a group obtained by removing —CH═CH ₂ from formula (2-1), formula (2-2), and formulas (2-1-1) to (2-1-6) described later.

j is an integer of 1 or more, an integer of 1 to 5 is preferable from the viewpoint of better water and oil repellency of the surface layer, and 1 is particularly preferable from the viewpoint of easy production of the compound.
q is an integer of 1 or more, and is preferably an integer of 2 to 4, more preferably 2 or 3, and particularly preferably 3, from the viewpoint of better water / oil repellency of the surface layer.

As compound 1, compound 1-1 is preferable because the water and oil repellency of the surface layer is more excellent. _{^{A 1 -O-Z 1 - (}} R f O) m -Z 3 (1-1)
In formula (1-1), the definitions of A ¹ , Z ¹ , R ^f and m are the same as the definitions of each group in formula (1).

Z ³ is group 2-1 or group 2-2.
_{^{-R f7 -Q a -X (-Q b}} -CH = CH 2) h (-R 7) i (2-1)
_{^{-R f7 -Q 71 - [CH 2}} C (R 71) (- Q 72 -CH = CH 2)] y -R 72 (2-2)

R ^f7 is a perfluoroalkylene group.
1-30 are preferable and, as for carbon number of a perfluoroalkylene group, 1-6 are especially preferable.
The perfluoroalkylene group may be linear or branched.
R ^f7 is preferably —CF ₂ CF ₂ CF ₂ CF ₂ — or —CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ — from the viewpoint of easy production of the compound.

Q ^a is a single bond or a divalent linking group.
Examples of the divalent linking group include a divalent hydrocarbon group (a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, an alkenylene group, and an alkynylene group. A divalent saturated carbonization group. The hydrogen group may be linear, branched or cyclic and includes, for example, an alkylene group, preferably having 1 to 20 carbon atoms, and a divalent aromatic hydrocarbon group having carbon atoms. 5 to 20 are preferable, and examples thereof include a phenylene group, and may be an alkenylene group having 2 to 20 carbon atoms or an alkynylene group having 2 to 20 carbon atoms. , —O—, —S—, —SO ₂ —, —N (R ^d ) —, —C (O) —, —Si (R ^a ) ₂ —, and groups in which two or more of these are combined. . Here, R ^a is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group. R ^d is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
Examples of the group in which two or more of these are combined include, for example, —OC (O) —, —C (O) N (R ^d ) —, an alkylene group —O-alkylene group, and an alkylene group —OC (O). - an alkylene group, an alkylene group -Si ^(R _{a) 2} - phenylene group -Si ^(R _{a) 2} and the like.

X is a single bond, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom, or a divalent to octavalent organopolysiloxane residue.
The alkylene group may have —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue, or a dialkylsilylene group. The alkylene group may have a plurality of groups selected from the group consisting of —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue, and a dialkylsilylene group.
1-20 are preferable and, as for carbon number of the alkylene group represented by X, 1-10 are especially preferable. Examples of the divalent to octavalent organopolysiloxane residue include a divalent organopolysiloxane residue and a (w + 1) valent organopolysiloxane residue described later.

Q ^b is a single bond or a divalent linking group.
Definition of the divalent linking group are the same as those defined as described in the above-described Q ^a.

R ⁷ is a hydroxyl group or an alkyl group.
1-5 are preferable, as for carbon number of an alkyl group, 1-3 are more preferable, and 1 is especially preferable.

When X is a single bond or an alkylene group, h is 1, i is 0,
When X is a nitrogen atom, h is an integer of 1 to 2, i is an integer of 0 to 1, and satisfies h + i = 2.
When X is a carbon atom or a silicon atom, h is an integer of 1 to 3, i is an integer of 0 to 2, and satisfies h + i = 3,
When X is a divalent to octavalent organopolysiloxane residue, h is an integer of 1 to 7, i is an integer of 0 to 6, and h + i = 1 to 7 is satisfied.
If ^(-Q b -CH = CH ₂₎ there are two or more, two or more ^(-Q b -CH = CH ₂₎ may be be the same or different. When two or more R ⁷ are present, two or more (—R ⁷ ) may be the same or different.

Q ⁷¹ is a single bond, an alkylene group, or a group having an etheric oxygen atom between carbon atoms and carbon atoms of an alkylene group having 2 or more carbon atoms, and is preferably a single bond from the viewpoint of easy production of a compound.
1-10 are preferable and, as for carbon number of an alkylene group, 2-6 are especially preferable.
2-10 are preferable and, as for carbon number of the group which has an etheric oxygen atom between carbon atoms-carbon atoms of a C2-C2 or more alkylene group, 2-6 are especially preferable.

R ⁷¹ is 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 a compound.
As the alkyl group, a methyl group is preferable.

Q ⁷² is a single bond or an alkylene group. 1-10 are preferable and, as for carbon number of an alkylene group, 1-6 are especially preferable. Q ⁷² is preferably a single bond or —CH ₂ — from the viewpoint of easy production of the compound.

R ⁷² is a hydrogen atom or a halogen atom, and is preferably a hydrogen atom from the viewpoint of easy production of a compound.

y is an integer of 1 to 10, and an integer of 1 to 6 is preferable.
Two or more [CH ₂ C (R ⁷¹ ) (— Q ⁷² —CH═CH ₂ )] may be the same or different.

As the group 2-1, groups 2-1 to 2-1-6 are preferable.
_{^{-R f7 - (X 1) p}} -Q 1 -CH = CH 2 (2-1-1)
_{^{-R f7 - (X 2) r1}} -Q 21 -N [- (Q 22) r2 -CH = CH 2] 2 (2-1-2)
^{-R f7 -Q 31 -G (R 3} ) [- (Q 32) c -CH = CH 2] 2 (2-1-3)
_{^{-R f7 - [C (O)}} N (R d)] s -Q 41 - (O) t -C [- (O) u1 - (Q 42) u2 -CH = CH 2] 3 (2-1- 4)
_{^{-R f7 -Q 51 -Si [- (}} Q 52) e -CH = CH 2] 3 (2-1-5)
_{^{-R f7 - [C (O)}} N (R d)] v1 -Q 61 -Z 3 [- (Q 62) v2 -CH = CH 2] w (2-1-6)
The definition of ^{R f7} in the formula (2-1-1) - (2-1-6) are as described above.

X ¹ is —O— or —C (O) N (R ^d ) — (wherein N binds to Q ¹ ).
The definition of R ^d is as described above.
p is 0 or 1.

Q ¹ is a single bond or an alkylene group. The alkylene group may have —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue, or a dialkylsilylene group. The alkylene group may have a plurality of groups selected from the group consisting of —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue, and a dialkylsilylene group.
In addition, when an alkylene group has -O-, it is preferable to have -O- between a carbon atom and a carbon atom. Further, when the alkylene group has a silphenylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group, the carbon atom-to-carbon atom or the terminal opposite to the side bonded to (X ¹ ) _p It is preferable to have these groups.

The alkylene group represented by Q ¹ is 1 to 10 are preferred, 1-6 being particularly preferred.

As Q ¹ , when p is 0, a single bond, —CH ₂ OCH ₂ —, —CH ₂ OCH ₂ CH ₂ OCH ₂ —, —CH ₂ CH ₂ —, —CH ₂ —, —CH ₂ OCH _{2 CH 2 CH 2 Si (CH 3} ) 2 OSi (CH 3) 2 - are preferred. (X ¹ ) When _p1 is —O—, —CH ₂ — and —CH ₂ CH ₂ OCH ₂ — are preferable. (X ¹ ) When _p1 is —C (O) N (R ^d ) —, an alkylene group having 1 to 6 carbon atoms is preferable (where N in the formula is bonded to Q ¹ ). Q ¹ is the compound is likely to manufacture and is these groups.

  Specific examples of the group 2-1-1 include the following groups.

X ² is —O—, —NH—, or —C (O) N (R ^d ) —.
The definition of R ^d is as described above.

Q ²¹ represents a single bond, an alkylene group, or an etheric oxygen atom, —C (O) —, —C (O) O—, —OC (between a carbon atom and a carbon atom of an alkylene group having 2 or more carbon atoms. A group having O)-or -NH-.
The alkylene group represented by Q ²¹ is 1 to 10 preferably 1 to 6 is particularly preferred.
Carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ²¹ - etheric oxygen atom between carbon atoms, -C (O) -, - C (O) O -, - OC (O) - or -NH 2-10 are preferable and, as for carbon number of group which has-, 2-6 are especially preferable.

The Q ^21, from the viewpoint of easily producing the _{compound, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH 2 -, - CH 2 OCH 2 CH 2 -, - CH 2 NHCH 2 CH 2 _{-, - CH 2 CH 2 OC} (O) CH 2 CH 2 - is preferred (but the right side is attached to the N.).

r1 is 0 or 1 (provided that 0 when Q ²¹ is a single bond). From the viewpoint of easy production of the compound, 0 is preferable.
r2 is 0 or 1.

Q ²² represents an alkylene group which may have a divalent organopolysiloxane residue, or a group having an etheric oxygen atom or —NH— between the carbon atoms and the carbon atoms of the alkylene group having 2 or more carbon atoms. It is.
In addition, when an alkylene group has a bivalent organopolysiloxane residue, it is preferable to have this group at the terminal of the opposite side to the side couple | bonded between carbon atom-carbon atoms or N.
Q ²² 2 divalent carbon number of an alkylene group which may contain an organopolysiloxane residue represented by the 1-10 preferably 1-6 being particularly preferred.
Q carbon atoms in the alkylene group having 2 or more carbon atoms represented by ²² - number of carbon atoms of the group having an etheric oxygen atom or -NH- between carbon atoms is preferably 2 to 10, 2 to 6 is particularly preferred.

The Q ^22, from the viewpoint of easily producing the _{compound, -CH 2 -, - CH 2} CH 2 OCH 2 - is preferred (but the right side is attached to the -CH = CH _2.).

Two [— (Q ²² ) _r2 —CH═CH ₂ ] may be the same or different.

  Specific examples of the group 2-1-2 include the following groups.

Q ³¹ is a single bond, an alkylene group, or a group having an etheric oxygen atom between carbon atoms and carbon atoms of an alkylene group having 2 or more carbon atoms, and is preferably a single bond from the viewpoint of easy production of a compound.
The alkylene group represented by Q ³¹ is 1 to 10 preferably 2 to 6 is particularly preferred.
Carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ³¹ - number of carbon atoms of the group having an etheric oxygen atom between carbon atoms, preferably 2 to 10, 2 to 6 is particularly preferred.

G is a carbon atom or a silicon atom.
R ³ is a hydroxyl group or an alkyl group. As for carbon number of the alkyl group represented by R < ³ >, 1-4 are preferable.
c is 0 or 1.
G (R ³ ) is C (OH) or Si (R ^3a ) (provided that R ^3a is an alkyl group. The alkyl group preferably has 1 to 10 carbon atoms, and is preferably methyl. Group is particularly preferred.).

Q ³² is an alkylene group which may have a divalent organopolysiloxane residue, or a group having an etheric oxygen atom between the carbon atoms of the alkylene group having 2 or more carbon atoms.
In addition, when an alkylene group has a bivalent organopolysiloxane residue, it is preferable to have this group at the terminal on the side opposite to the side bonded to G or between carbon atoms or G.
Q ³² 2 divalent carbon number of an alkylene group which may contain an organopolysiloxane residue represented by the 1-10 preferably 1-6 being particularly preferred.
Carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ³² - number of carbon atoms of the group having an etheric oxygen atom between carbon atoms, preferably 2 to 10, 2 to 6 is particularly preferred.
Q ³² is preferably —CH ₂ — or —CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ — from the viewpoint of easy production of the compound.

Two [— (Q ³² ) _c —CH═CH ₂ ] may be the same or different.

  Specific examples of the group 2-1-3 include the following groups.

The definition of R ^d in formula (2-1-4) is as described above.
s is 0 or 1.
Q ⁴¹ is a single bond, an alkylene group, or a group having an etheric oxygen atom between carbon atoms of a C 2 or more alkylene group.
The alkylene group represented by Q ⁴¹ is 1 to 10 preferably 2 to 6 is particularly preferred.
Carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ⁴¹ - number of carbon atoms of the group having an etheric oxygen atom between carbon atoms, preferably 2 to 10, 2 to 6 is particularly preferred.
t is 0 or 1 (provided that 0 when Q ⁴¹ is a single bond).
-Q ⁴¹ - _{(O) t} - as is from the viewpoint of easily producing the compound, if s is 0, a single _{bond, -CH 2 O -, - CH} 2 OCH 2 -, - CH 2 OCH 2 CH 2 O—, —CH ₂ OCH ₂ CH ₂ OCH ₂ —, —CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ — are preferred (where the left side is bonded to R ^f7 ), and when s is 1, single _{bond, -CH 2 -, - CH 2} CH 2 - is preferred.

Q ⁴² is an alkylene group, a divalent organopolysiloxane residue or dialkyl silylene group, the alkylene group -O -, - C (O) N (R d) - [in ^{R d} definition described above Street. ], May have a silphenylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group.
In addition, when an alkylene group has -O-, it is preferable to have -O- between a carbon atom and a carbon atom. Further, when the alkylene group has —C (O) N (R ^d ) —, a dialkylsilylene group or a divalent organopolysiloxane residue, the terminal on the side bonded to the carbon atom-carbon atom or (O) _u1 side. It is preferable to have these groups. Moreover, when an alkylene group has a silphenylene skeleton group, it is preferable to have these groups at the terminal on the opposite side from the side couple _| bonded with carbon atom-carbon atom or (O) _u1 .
The alkylene group represented by Q ⁴² is 1 to 10 preferably 1 to 6 is particularly preferred.

u1 is 0 or 1.
u2 is 0 or 1.
— (O) _u1 — (Q ⁴² ) _u2 — is a single bond, —CH ₂ —, —CH ₂ OCH ₂ —, —CH ₂ OCH ₂ CH ₂ CH ₂ —, — _{OCH 2 -, - OSi (CH} 3) 2 CH 2 -, - OSi (CH 3) 2 OSi (CH 3) 2 CH 2 -, - CH 2 CH 2 CH 2 Si (CH 3) 2 PhSi (CH 3) _2- is preferred (however, the right side is bonded to —CH═CH ₂ ).

Three ^{_{[- (O) u1 - (}} Q 42) u2 -CH = CH 2] may be be the same or different.

  Specific examples of the group 2-1-4 include the following groups.

Q ⁵¹ is an alkylene group or a group having an etheric oxygen atom between carbon atoms of a C 2 or more alkylene group.
The alkylene group represented by Q ⁵¹ is 1 to 10 preferably 1 to 6 is particularly preferred.
Carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ⁵¹ - number of carbon atoms of the group having an etheric oxygen atom between carbon atoms, preferably 2 to 10, 2 to 6 is particularly preferred.
The Q ^51, from the viewpoint of easily producing the _{compound, -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 — is preferred (however, the right side is bonded to Si).

  e is 0 or 1.

Q ⁵² is an alkylene group which may have a divalent organopolysiloxane residue, or a group having an etheric oxygen atom between carbon atoms of the alkylene group having 2 or more carbon atoms.
In addition, when an alkylene group has a bivalent organopolysiloxane residue, it is preferable to have this group at the terminal of the side opposite to the side couple | bonded between carbon atoms or between carbon atoms or Si.
The alkylene group represented by Q ⁵² is 1 to 10 preferably 1 to 6 is particularly preferred.
Carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ⁵² - number of carbon atoms of the group having an etheric oxygen atom between carbon atoms, preferably 2 to 10, 2 to 6 is particularly preferred.
The Q ^52, from the viewpoint of easily producing the _{compound, -CH 2 -, - CH 2} CH 2 OCH 2 - is preferred (but the right side is attached to the -CH = CH _2.).

Three [— (Q ⁵² ) _e —CH═CH ₂ ] may be the same or different.

  Specific examples of the group 2-1-5 include the following groups.

The definition of R ^d in formula (2-1-6) is as described above.
v1 is 0 or 1.

Q ⁶¹ is an alkylene group or a group having an etheric oxygen atom between carbon atoms of a C 2 or more alkylene group.
The alkylene group represented by Q ⁶¹ is 1 to 10 preferably 2 to 6 is particularly preferred.
Carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ⁶¹ - number of carbon atoms of the group having an etheric oxygen atom between carbon atoms, preferably 2 to 10, 2 to 6 is particularly preferred.
The Q ^61, from the viewpoint of easily producing the _{compound, -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 — is preferred (however, the right side is bonded to Z ³ ).

Z ³ is a (w + 1) valent organopolysiloxane residue.
w is an integer of 2-7.
Examples of the (w + 1) -valent organopolysiloxane residue include the following groups. However, R ^a in the following formula is as described above.

  v2 is 0 or 1.

Q ⁶² is a divalent organopolysiloxane residue alkylene group which may have, or the carbon atoms of the alkylene group having 2 or more carbon atoms - a group having an etheric oxygen atom between carbon atoms.
In the case where the alkylene group having a divalent organopolysiloxane residue, carbon atoms - preferably has the group at the opposite side to the side to be bonded to a carbon atom or between Z ^3.
The alkylene group represented by Q ⁶² is 1 to 10 preferably 1 to 6 is particularly preferred.
Carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ⁶² - number of carbon atoms of the group having an etheric oxygen atom between carbon atoms, preferably 2 to 10, 2 to 6 is particularly preferred.
Q ⁶² is preferably —CH ₂ — from the viewpoint of easy production of the compound.

of w number _{^{[- (Q 62) v2 -CH}} = CH 2] may also be the same or different.

[Compound B]
1-3 are preferable and, as for the number of the hydrogen atoms couple | bonded with the silicon atom in the compound B, 1 is especially preferable.

As compound B, compound 3 is preferable.
_{H-SiR n L 3-n} (3)

  R is a monovalent hydrocarbon group, preferably a monovalent saturated hydrocarbon group. 1-6 are preferable, as for carbon number, 1-3 are more preferable, and 1-2 are especially preferable.

L is a hydrolyzable group or a hydroxyl group.
The hydrolyzable group of L is a group that becomes a hydroxyl group by a hydrolysis reaction. That is, a silanol group is formed from a hydrolyzable silyl group by a hydrolysis reaction. Silanol groups further react between the silanol groups to form Si-O-Si bonds. Further, the silanol group can form a chemical bond (base material-O-Si) by dehydration condensation reaction with a hydroxyl group (base material-OH) on the surface of the base material.

L is preferably a hydrolyzable group, and examples of the hydrolyzable group include an alkoxy group, a halogen atom, an acyl group, an isocyanate group (—NCO) and the like. As an alkoxy group, a C1-C4 alkoxy group is preferable. As the halogen atom, a chlorine atom is preferable.
L is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom from the viewpoint of easy industrial production. L is preferably an alkoxy group having 1 to 4 carbon atoms from the viewpoint that the outgassing during coating is small and the storage stability of compound 3 is more excellent. When long-term storage stability of compound 3 is required, an ethoxy group is required. Is particularly preferred, and a methoxy group is particularly preferred when the reaction time after coating is short.

n is an integer of 0-2.
n is preferably 0 or 1, particularly preferably 0. By the presence of a plurality of L, the adhesion of the surface layer to the substrate becomes stronger.
When n is 0 or 1, a plurality of L present in one molecule may be the same as or different from each other. From the viewpoint of availability of raw materials and ease of production, it is preferable that they are the same. When n is 2, two Rs present in one molecule may be the same or different from each other.

The compound _{3, H-Si (OCH 3} ) 3, H-SiCH 3 (OCH 3) 2, H-Si (OCH 2 CH 3) 3, H-SiCl 3, H-Si (OC (O) CH 3 ) ₃ and H—Si (NCO) ₃ are preferred.

[Compound C]
Compound C preferably has a hydrolyzable silyl group from the viewpoint that the storage stability of the compound is more excellent.

  The number average molecular weight of Compound C is preferably 500 to 20,000, more preferably 800 to 10,000, and particularly preferably 1,000 to 8,000. When the number average molecular weight is within this range, the surface layer is excellent in friction resistance.

As compound C, compound 4 is preferred.
_{^{[A 2 -O-Z 1 -}} (R f O) m -] j Z 2 [-C 2 H 4 -SiR n L 3-n] q (4)
Wherein (4), ^{A 2} is a perfluoroalkyl group or a _{-Q [-C 2 H 4 -SiR n} L 3-n] k.
However, if ^{A 2} is _{-Q [-C 2 H 4 -SiR n} L 3-n] k, j is 1.
The definition of each other group is as described above.

As the compound 4, the compound 4-1 is preferable.
_{^{A 2 -O-Z 1 - (}} R f O) m -Z 4 (4-1)
In formula (4-1), the definitions of A ² , Z ¹ , R ^f , and m are as described above.

Z ⁴ is group 5-1 or group 5-2.
_{^{-R f7 -Q a -X (-Q b}} -C 2 H 4 -SiR n L 3-n) h (-R 7) i (5-1)
_{^{-R f7 -Q 71 - [CH 2}} C (R 71) (- Q 72 -C 2 H 4 -SiR n L 3-n)] y -R 72 (5-2)
In addition, the definition of each group in Formula (5-1) and (5-2) is as having mentioned above.

Further, the group 5-1 is preferably a group 5-1 to 5-1-6.
_{^{-R f7 - (X 1) p}} -Q 1 -C 2 H 4 -SiR n L 3-n (5-1-1)
_{^{-R f7 - (X 2) r1}} -Q 21 -N [- (Q 22) r2 -C 2 H 4 -SiR n L 3-n] 2 (5-1-2)
^{-R f7 -Q 31 -G (R 3} ) [- (Q 32) c -C 2 H 4 -SiR n L 3-n] 2 (5-1-3) -R f7 - [C (O) N _{^{(R d)] s -Q 41}} - (O) t -C [- (O) u1 - (Q 42) u2 -C 2 H 4 -SiR n L 3-n] 3 (5-1-4)
_{^{-R f7 -Q 51 -Si [- (}} Q 52) e -C 2 H 4 -SiR n L 3-n] 3 (5-1-5)
_{^{-R f7 - [C (O)}} N (R d)] v1 -Q 61 -Z 3 [- (Q 62) v2 -C 2 H 4 -SiR n L 3-n] w (5-1-6)
In addition, the definition of each group in Formula (5-1-1) and (5-1-6) is as having mentioned above.

[Hydrosilylation catalyst]
The hydrosilylation catalyst is preferably a transition metal catalyst, more preferably a Group 8 to Group 10 transition metal catalyst, further a platinum (Pt) catalyst, a ruthenium (Ru) catalyst, a rhodium (Rh) catalyst, or an iron (Fe) catalyst. A platinum catalyst and an iron catalyst are particularly preferable from the viewpoint that the hydrosilylation reaction further proceeds. Group 8 to Group 10 are group numbers according to the revised IUPAC inorganic chemical nomenclature (1989).
Specific examples of the platinum catalyst include a Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, a Pt complex of divinyltetramethyldisiloxane, a Pt complex of tetramethyltetravinylcyclotetrasiloxane, Examples include chloroplatinic acid and platinum oxide.
Specific examples of the iron catalyst include hydrosilylated iron catalysts described in International Publication No. 2016/027819.

[Adsorbent]
The moisture content of the adsorbent is 1.0% by mass or less, and at least one of the point that the generation of particulate matter in the surface layer is further suppressed and the point that the friction resistance is more excellent is obtained (hereinafter referred to as “the present invention”). In other words, it is also preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less. Moreover, the moisture content of the adsorbent is often 0.001% by mass or more.
The moisture content of the adsorbent is a mass ratio of water in the total mass of the adsorbent, and can be measured by a loss on drying method or the like.

The adsorbent only needs to satisfy the above moisture content range when using this production method, and the moisture content of the adsorbent is outside the above range (for example, 2 to 3% by mass) before use such as storage. ).
When the adsorbent is used, for example, the adsorbent having a moisture content exceeding the above range (over 1.0 mass%) is subjected to dehydration treatment to obtain an adsorbent having a predetermined moisture content. You may apply to the method.
Examples of the dehydration method include a method of spraying a gas having a low water content (for example, nitrogen having a dew point of 0 ° C. or less) and a method of heating the adsorbent.

Specific examples of the adsorbent include activated carbon, molecular sieve, silica gel, and celite. Among them, activated carbon is preferable in that the effect of the present invention is more excellent.
Activated carbon is a material mainly composed of carbon atoms. For example, activated carbon obtained by firing natural materials such as wood, coconut shells, and coal may be used, or artificial materials such as synthetic organic polymer compounds may be fired. Activated carbon obtained in this way may be used.
The particle size of the activated carbon is preferably 5 to 50 mesh, particularly preferably 10 to 30 mesh. The particle size of the activated carbon is determined according to the method described in JIS K1474: 2014.
The activated carbon may be a commercially available product, and examples thereof include Hakuho G2c, Hakuho GM2x, Hakuho GH2x, Hakuho WH2C, and Kuraray Co., manufactured by Kuraray.

[Other ingredients]
In this manufacturing method, you may use components other than the component mentioned above.
For example, in this manufacturing method, a liquid medium such as a solvent may be used. That is, the reaction between Compound A and Compound B may be performed in the presence of a liquid medium. As the liquid medium, a solvent capable of dissolving Compound A, Compound B, and Compound C is preferable.
Examples of the solvent include organic solvents. Specific examples of the organic solvent include fluorinated organic solvents and non-fluorinated organic solvents.
An organic solvent may be used individually by 1 type, and may use 2 or more types together.
The water content of the organic solvent is preferably 100 ppm or less, and more preferably 20 ppm or less.

Specific examples of the fluorinated organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.
The fluorinated alkane is preferably a compound having 4 to 8 carbon atoms. For example, C ₆ F ₁₃ H (AC-2000: product name, manufactured by Asahi Glass Co., Ltd.), C ₆ F ₁₃ C ₂ H ₅ (AC-6000: product name). And Asahi Glass Co., Ltd.) and C ₂ F ₅ CHFCHFCF ₃ (Bertrel: product name, manufactured by DuPont).
Specific examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, 1,3-bis (trifluoromethyl) benzene, and 1,4-bis (trifluoromethyl) benzene.
The fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms. For example, CF ₃ CH ₂ OCF ₂ CF ₂ H (AE-3000: product name, manufactured by Asahi Glass Co., Ltd.), C ₄ F ₉ OCH ₃ (Novec-7100: product name, 3M _{Co.), C 4 F 9 OC 2} H 5 ( Novec -7200: product name, manufactured by 3M _{Co.), C 2 F 5 CF (} OCH 3) C 3 F 7 ( Novec -7300: product name, 3M).
Specific examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
Specific examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.

As the non-fluorine-based organic solvent, a compound consisting only of a hydrogen atom and a carbon atom, and a compound consisting only of a hydrogen atom, a carbon atom and an oxygen atom are preferable. Specifically, a hydrocarbon-based organic solvent, a ketone-based organic solvent , Ether organic solvents and ester organic solvents.
Specific examples of the hydrocarbon organic solvent include hexane, heptane, and cyclohexane.
Specific examples of the ketone organic solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
Specific examples of the ether organic solvent include diethyl ether, tetrahydrofuran, and tetraethylene glycol dimethyl ether.
Specific examples of the ester organic solvent include ethyl acetate and butyl acetate.

  In this production method, a dislocation inhibitor may be used. That is, the reaction between Compound A and Compound B may be carried out in the presence of a rearrangement inhibitor. Examples of the dislocation inhibitor include the compounds described in paragraph 0115 of WO2014 / 069592.

[First aspect]
The first aspect of this production method is an aspect in which compound A is produced by reacting compound A and compound B in the presence of a hydrosilylation catalyst, and the resulting compound C and a specific adsorbent are brought into contact with each other.
First, when the compound A and the compound B are reacted, the hydrosilylation catalyst, the compound A and the compound B are mixed and subjected to a heat treatment as necessary to carry out the reaction.
As a method for mixing the hydrosilylation catalyst, the compound A, and the compound B, the respective components may be mixed at once, or the respective components may be mixed separately.
The order of mixing the components is not particularly limited.

The amount of the hydrosilylation catalyst used is preferably 0.00001 to 0.1% by mass, particularly preferably 0.001 to 0.02% by mass, based on the total amount of Compound A and Compound B.
As the mixing ratio of Compound A and Compound B, an optimum ratio is selected depending on the structure of the compound, but the moles of hydrogen atoms bonded to silicon atoms in Compound B with respect to the moles of ω-alkenyl groups in Compound A are as follows. The number ratio (hydrogen atom / ω-alkenyl group) is preferably 1.0 to 3.0.

  As reaction temperature at the time of making compound A and compound B react, 0-100 degreeC is preferable and 50-80 degreeC is especially preferable. The reaction time is preferably 30 to 600 minutes, particularly preferably 60 to 300 minutes.

  In addition, after making the compound A and the compound B react, you may implement reaction which changes the kind of hydrolysable group in the obtained compound C as needed. For example, after reacting compound A and compound B to obtain compound C having a halogen atom as a hydrolyzable group, a reaction in which the halogen atom is changed to an alkoxy group may be carried out.

Next, the obtained compound C and a specific adsorbent are brought into contact with each other.
Examples of the contacting method include a method of mixing the compound C and the specific adsorbent, and a method of circulating the compound C through a filter filled with the specific adsorbent.
When the compound C and the specific adsorbent are brought into contact with each other, the compound C and the specific adsorbent may be brought into direct contact, or a solution in which the compound C is dissolved in a solvent or a dispersion liquid in which the dispersion is dispersed in a dispersion medium is prepared. Then, the obtained solution or dispersion may be brought into contact with the specific adsorbent. Preferably, a solution in which compound C is dissolved in a solvent is brought into contact with the specific adsorbent.
The solvent or dispersion medium used may be a liquid medium that can dissolve or disperse the compound C, preferably an organic solvent, and particularly preferably a fluorinated organic solvent. Specific examples of the fluorinated organic solvent are as described above.

  When the compound C and the specific adsorbent are brought into contact, the amount of the specific adsorbent used is preferably 1 to 30% by mass, particularly preferably 5 to 25% by mass with respect to the total mass of the compound C.

The contact time is preferably from 0.1 to 180 minutes, and particularly preferably from 1 to 60 minutes, in that the effect of the present invention is more excellent.
As temperature at the time of contact, 0-40 degreeC is preferable and 10-30 degreeC is especially preferable at the point which the effect of this invention is more excellent.

[Second embodiment]
A second embodiment of this production method includes an embodiment in which compound C is produced by reacting compound A and compound B in the presence of a hydrosilylation catalyst and a specific adsorbent.
As a procedure of this embodiment, a hydrosilylation catalyst, a specific adsorbent, compound A and compound B are mixed and subjected to a heat treatment as necessary to carry out the reaction.
As a method for mixing the hydrosilylation catalyst, the specific adsorbent, the compound A and the compound B, the respective components may be mixed at once, or the respective components may be mixed separately.
The order of mixing the components is not particularly limited.
Moreover, the reaction conditions (amount used, reaction temperature, reaction time, etc.) between compound A and compound B are the same as in the first embodiment.

1-30 mass% is preferable with respect to the total mass of the compound A and the compound B, and, as for the usage-amount of a specific adsorbent, 5-25 mass% is especially preferable.
The contact time is preferably from 0.1 to 180 minutes, and particularly preferably from 1 to 60 minutes, in that the effect of the present invention is more excellent.
As temperature at the time of contact, 0-40 degreeC is preferable and 10-30 degreeC is especially preferable at the point which the effect of this invention is more excellent.

You may manufacture the composition by mixing the compound C (compound C after contact with a specific adsorption material) obtained by the method of the said 1st aspect or the 2nd aspect, and a liquid medium.
Specific examples of the liquid medium include organic solvents. Specific examples of the organic solvent include the fluorinated organic solvent and the non-fluorinated organic solvent. An organic solvent may be used individually by 1 type, and may use 2 or more types together.
Specific examples of the fluorinated organic solvent and the non-fluorinated organic solvent are as described above.
Moreover, the composition containing the compound C and the liquid medium obtained by using the liquid medium in the method of the first aspect or the second aspect may be the above composition. Further, a new composition may be prepared by adjusting the concentration of the compound C from the obtained composition containing the compound C and the liquid medium, and the liquid medium used in the method of the first aspect or the second aspect may be different. It is good also as a new composition by converting into this liquid medium.

0.01-50.00 mass% is preferable with respect to the total mass of a composition, and, as for content of the compound C in a composition, 1.00-30.00 mass is especially preferable.
The content of the liquid medium in the composition is preferably 50.00 to 99.99% by mass, particularly preferably 70.00 to 99.00% by mass, based on the total mass of the composition.

A surface layer can be formed on the surface of the substrate using Compound C obtained by the present production method.
More specifically, by using the compound C or composition, a surface layer having excellent friction resistance and suppressing generation of particulates can be formed on the surface of the substrate. That is, an article having a base material and a surface layer formed from the compound C or composition arranged on the surface of the base material can be produced.

The substrate is not particularly limited as long as it is required to impart water and oil repellency. Specific examples of the base material include metals, resins, glass, sapphire, ceramics, stones, and composite materials thereof. The glass may be chemically strengthened. The base material may be surface-treated with SiO ₂ or the like.
As a base material, the base material for touchscreens and a display base material are preferable, and the base material for touchscreens is especially preferable. It is preferable that the base material for touch panels has translucency. “Having translucency” means that a normal incidence visible light transmittance according to JIS R3106: 1998 (ISO 9050: 1990) is 25% or more. As a material of the base material for touch panels, glass or transparent resin is preferable.

The article can be manufactured, for example, by the following method.
-The method of obtaining the said article | item by processing the surface of a base material by the dry-coating method using the compound C or a composition.
A method in which the composition is applied to the surface of a substrate by a wet coating method and dried to obtain the article.

Specific examples of the dry coating method include a vacuum deposition method, a CVD method, and a sputtering method. Among these, the vacuum vapor deposition method is preferable from the viewpoint of suppressing the decomposition of the compound C and the simplicity of the apparatus. At the time of vacuum deposition, a pellet-like material obtained by impregnating a metal porous body such as iron or steel with the compound C or the composition may be used.
Specific examples of the wet coating method include spin coating method, wipe coating method, spray coating method, squeegee coating method, dip coating method, die coating method, ink jet method, flow coating method, roll coating method, casting method, Langmuir-Blodget Method and gravure coating method.

The surface layer formed by the above procedure contains a compound obtained through the hydrolysis reaction and condensation reaction of Compound C.
1-100 nm is preferable and, as for the film thickness of a surface layer, 1-50 nm is especially preferable. The film thickness of the surface layer is determined by obtaining an interference pattern of reflected X-rays by an X-ray reflectivity method using an X-ray diffractometer for thin film analysis (manufactured by RIGAKU, ATX-G). It can be calculated.

  Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these examples. In addition, the usage-amount of each component shows a mass reference | standard. Among Examples 1-7, Examples 1-4 and 6-7 are Examples, and Example 5 is a comparative example.

[Evaluation methods]
(Moisture content of adsorbent)
The sample was heated in an oven (180 ° C., 2 hours), and the mass before and after heating was measured and calculated.
(Appearance characteristics)
The surface layer of the evaluation sample was visually confirmed, and appearance characteristics were evaluated based on the presence or absence of particulate matter in the surface layer. The evaluation criteria are as follows.
A: There is no granular material of about 100 μm on the surface layer.
B: The surface layer has a granular material of about 100 μm.

(Abrasion resistance)
The water contact angle was measured for the evaluation samples before and after the friction resistance test. The smaller the decrease in water contact angle after friction, the smaller the decrease in performance due to friction and the better the friction resistance.
<Measurement method of water contact angle>
The contact angle (water contact angle) of about 2 μL of distilled water placed on the surface of the surface layer was measured using a contact angle measuring device (DM-500, manufactured by Kyowa Interface Science Co., Ltd.). Measurements were made at five different locations on the surface of the surface layer, and the average value was calculated. The 2θ method was used to calculate the contact angle.
<Abrasion resistance test method>
For the surface layer, using a reciprocating traverse tester (manufactured by KE NTE Co., Ltd.) in accordance with JIS L0849: 2013 (ISO 105-X12: 2001), a steel wool bonster (# 0000) is pressure: 98.07 kPa, speed: 320 cm. It was reciprocated 10,000 times per minute.

[Synthesis Example 1]
Compound C-1 was synthesized according to the method described in Synthesis Example 15 of WO2014 / 069592. Specifically, a compound having a poly (oxyperfluoroalkylene) chain and an ω-alkenyl group (perfluoropolyether group-containing allyl compound represented by the following formula (5)) and a hydrolyzable group bonded to a silicon atom Is reacted with trichlorosilane, which is a compound having a hydrogen atom, in the presence of a Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, which is a hydrosilylation catalyst, and then the chlorine atom of the obtained compound Was substituted with a methoxy group to obtain a compound C-1 represented by the following formula (6). The obtained compound C-1 was dissolved in Novec-7200 (manufactured by 3M) (water content: 10 ppm) so as to have a concentration of 20% by mass to prepare 100 g of composition 1.

In the above compound C-1, as the average _composition, the repeating units of _{(CF 2 CF 2 CF 2 CF} 2 O) recurring units 0.17 units and _{(CF 2 CF 2 CF 2 O} ) 0. Although 18 were included, they were omitted due to the small amount.

[Synthesis Example 2]
Compound C-2 was synthesized according to the method described in Synthesis Example 3 of WO2017 / 022437. Specifically, a compound having a poly (oxyperfluoroalkylene) chain and an ω-alkenyl group (perfluoropolyether group-containing allyloxy compound represented by the following formula (7)) and a hydrolyzable group bonded to a silicon atom Is reacted with trichlorosilane, which is a compound having a hydrogen atom, in the presence of a Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, which is a hydrosilylation catalyst, and then the chlorine atom of the obtained compound Was substituted with a methoxy group to obtain a compound C-2 represented by the following formula (8). The obtained compound C-2 was dissolved in Novec-7200 (manufactured by 3M) (water content: 10 ppm) so as to have a concentration of 20% by mass to prepare 100 g of composition 2.

[Example 1]
5 g of activated carbon (manufactured by Kuraray Co., Ltd., Kuraray Coal GLC, standard particle size: 10 to 30 mesh) was packed in a filter, and nitrogen having a dew point of −20 ° C. was circulated for 1 minute. The water content of the activated carbon after nitrogen circulation was 0.9 mass%.
Next, the obtained activated carbon was added to 100 g of the composition 1 and stirred at 25 ° C. for 5 minutes, and then the activated carbon was filtered off to obtain a composition 11.
Using the composition 11 thus obtained, a surface layer was formed on the surface of the base material (chemically tempered glass) by the following dry coating method. First, 0.5 g of the composition 11 was filled in a molybdenum board in a vacuum vapor deposition apparatus (manufactured by ULVAC, VTR-350M), and the inside of the vacuum vapor deposition apparatus was evacuated to 1 × 10 ⁻³ Pa or less. The board on which the composition 11 is arranged is heated at a rate of temperature rise of 10 ° C./min or less, and when the deposition rate by the crystal oscillation type film thickness meter exceeds 1 nm / second, the shutter is opened and applied to the surface of the substrate. Film formation was started. When the film thickness reached 50 nm, the shutter was closed to complete film formation on the surface of the substrate. The obtained base material was heat-treated at 200 ° C. for 30 minutes and washed with Asahi Clin AK-225 (trade name, Asahi Glass Co., Ltd.) to obtain an article having a surface layer disposed on the surface of the base material. . The appearance characteristics and friction resistance of the article were evaluated, and the results are shown in Table 1.

[Examples 2 to 5]
A surface layer was formed according to the same procedure as in Example 1 except that the flow time of nitrogen and the type of composition were changed. The appearance characteristics and friction resistance of the article were evaluated, and the results are shown in Table 1.
[Example 6]
A surface layer was formed according to the same procedure as in Example 1 except that molecular sieve 4A (manufactured by Junsei Chemical Co., Ltd.) was used instead of activated carbon. The appearance characteristics and friction resistance of the article were evaluated, and the results are shown in Table 1.
[Example 7]
The same as Example 1 except that silica gel (MS GEL (model number: D-75-60A (N) average particle diameter 75 microns, average pore diameter 60 angstrom) manufactured by AGC Sitech) was used instead of activated carbon. A surface layer was formed according to the procedure, and the appearance characteristics and friction resistance of the article were evaluated, and the results are shown in Table 1.

As shown in Table 1, in Examples 1 to 4 and 6 to 7 using an adsorbent having a water content of 1.0% by mass or less, no particulate matter is generated and the appearance is excellent and the initial water repellency and friction resistance are high. A surface layer having excellent properties was obtained.
Moreover, from the comparison of Examples 1-3, when the moisture content of the adsorbent was 0.1% by mass or less, it was confirmed that the effect was more excellent.
On the other hand, in the case of Example 5 using an adsorbent having a moisture content of more than 1.0% by mass, a granular material was generated, the appearance was insufficient, and a surface layer with insufficient friction resistance was obtained. .

  When the compound C-2 was synthesized according to the method described in Synthesis Example 3 of WO2017 / 022437, the activated carbon having a water content of 0.9% by mass used in Example 4 was further used to In the presence, compound C-2 was obtained by reacting the perfluoropolyether group-containing allyloxy compound represented by the above formula (7) used in Synthesis Example 3 of WO2017 / 022437 with trichlorosilane. . Using the obtained compound C-2, a surface layer was formed according to the same procedure as in Example 4. As a result, the same results (appearance characteristics and abrasion resistance) as in Example 4 were obtained.

The fluorine-containing ether compound obtained by this production method can be used for various applications that require lubricity and water / oil repellency. For example, coats for display input devices such as touch panels, surface protective coats made of transparent glass or transparent plastic parts, antifouling coats for kitchens, electronic equipment, heat exchangers, batteries, etc. It can be used for antifouling coatings for toiletries, coatings for members that require liquid repellency while conducting, water repellency / waterproofing / sliding coatings for heat exchangers, vibration screens, surface friction coatings inside cylinders, and the like. More specific examples of use include a front protective plate of a display, an antireflection plate, a polarizing plate, an antiglare plate, or an antireflection coating on the surface thereof, a touch panel of a device such as a mobile phone or a portable information terminal. Coats for various devices with display input devices that operate on the screen with human fingers or palms such as sheets and touch panel displays, coats of decorative building materials around water such as toilets, baths, washrooms, and kitchens, waterproofing for wiring boards Coating, water repellent / waterproof / slidable coat for heat exchangers, water repellent coat for solar cells, waterproof / water repellent coat for printed wiring boards, waterproof / water repellent coat for electronic equipment casings and electronic parts, insulation of power transmission lines Coatings, waterproof / water-repellent coatings for various filters, waterproof coatings for radio wave absorbers and sound absorbing materials, antifouling coatings for baths, kitchen equipment, toiletries, vibration sieves and screens Surface low friction coating of Sunda internal like, mechanical parts, vacuum equipment parts, bearing parts, automobile parts, surface protection coating such as a tool and the like.
In addition, the entire content of the specification, claims and abstract of Japanese Patent Application No. 2017-157902 filed on Aug. 18, 2017 is incorporated herein as a disclosure of the specification of the present invention. It is.

Claims (10)

In the presence of a hydrosilylation catalyst, at least a compound having a poly (oxyperfluoroalkylene) chain and an ω-alkenyl group, a hydrogen atom bonded to a silicon atom, a hydrolyzable group bonded to a silicon atom, and a hydroxyl group bonded to a silicon atom Fluorine-containing ether for producing a fluorine-containing ether compound having at least one of a poly (oxyperfluoroalkylene) chain, a hydrolyzable group bonded to a silicon atom, and a hydroxyl group bonded to a silicon atom by reacting with a compound having one A method for producing a compound comprising:
After obtaining the fluorine-containing ether compound, the fluorine-containing ether compound is contacted with an adsorbent having a water content of 1.0% by mass or less, or
A method for producing a fluorinated ether compound, wherein the reaction is carried out in the presence of the hydrosilylation catalyst and an adsorbent having a water content of 1.0% by mass or less.   The manufacturing method of Claim 1 whose moisture content of the said adsorbent is 0.1 mass% or less.   The production method according to claim 1 or 2, wherein the adsorbent is activated carbon, molecular sieve, silica gel, or celite.   The manufacturing method according to any one of claims 1 to 3, wherein the hydrosilylation catalyst is a Group 8 to Group 10 transition metal catalyst. The production method according to any one of claims 1 to 4, wherein the compound having a poly (oxyperfluoroalkylene) chain and an ω-alkenyl group is a compound represented by the following formula (1).
_{^{[A 1 -O-Z 1 -}} (R f O) m -] j Z 2 [-CH = CH 2] q (1)
However, ^{A 1} is a perfluoroalkyl group or a _{-Q [-CH = CH 2] k} , if ^{A 1} is _{-Q [-CH = CH 2] k} j is 1,
Q is a (k + 1) -valent linking group, k is an integer of 1 to 10,
Z ¹ is a single bond, an oxyfluoroalkylene group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom (excluding an oxyperfluoroalkylene group. The oxygen atom in the oxyfluoroalkylene group is , (R ^f O) _m .), Or a poly (oxyfluoroalkylene) group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms (bonded to (R ^f O) _m oxygen atoms in the oxy-fluoroalkylene group is (R f ^O) binds to _m. oxyfluoroalkylene group bonded to (R f ^O) _m is. poly (oxy-fluoroalkylene comprising one or more hydrogen atoms ) Group includes both an oxyperfluoroalkylene group in which all hydrogen atoms are substituted with fluorine atoms and an oxyfluoroalkylene group containing one or more hydrogen atoms. May be included.)
R ^f is a perfluoroalkylene group, m is an integer of 2 to 200, and when two or more types of R ^f O having different carbon numbers are present in (R ^f O) _m , the bonding order of each R ^f O Is not limited,
Z ² is a (j + q) -valent linking group, and j and q are each an integer of 1 or more. The compound having at least one of the hydrogen atom bonded to the silicon atom, the hydrolyzable group bonded to the silicon atom, and the hydroxyl group bonded to the silicon atom is a compound represented by the following formula (3). 6. The production method according to any one of 5 above.
_{H-SiR n L 3-n} (3)
However, R is a monovalent hydrocarbon group, L is a hydrolyzable group or a hydroxyl group, n is an integer of 0 to 2, and when n is 0 or 1, a plurality of molecules present in one molecule L may be the same as or different from each other. When n is 2, two Rs present in one molecule may be the same as or different from each other.   The production method according to claim 6, wherein n is 0 or 1, and a plurality of L are all hydrolyzable groups.   The amount of the adsorbent used is 1 to 30% by mass with respect to the total mass of the compound having a poly (oxyperfluoroalkylene) chain and an ω-alkenyl group. The manufacturing method as described.   After obtaining the said fluorine-containing ether compound, the said fluorine-containing ether compound and the adsorbent whose water content is 1.0 mass% or less are made to contact in a liquid medium. Production method.   A method for producing an article, wherein a surface layer is formed on a surface of a substrate using the fluorine-containing ether compound obtained by the production method according to any one of claims 1 to 9.