WO2019035288A1 - Production method for fluorine-containing ether compound and production method for article - Google Patents

Abstract

A production method for a fluorine-containing ether compound that makes it possible to form a surface layer that has excellent abrasion resistance and suppressed particle generation; and a production method for an article. A production method for a fluorine-containing ether compound, the production method involving reacting, in the presence of a hydrosilylation catalyst, a compound that has a poly(oxyperfluoroalkylene) chain and a ω-alkenyl group and a compound that has a hydrogen atom that is bonded to a silicon atom and also has a hydrolyzable group that is bonded to a silicon atom and/or a hydroxyl group that is bonded to a silicon atom to produce a fluorine-containing ether compound that has a poly(oxyperfluoroalkylene) chain and also has a hydrolyzable group that is bonded to a silicon atom and/or a hydroxyl group that is bonded to a silicon atom. The production method is characterized in that, after the fluorine-containing ether compound has been obtained, the fluorine-containing ether compound is brought into contact with an adsorbent that has a water content of no more than 1.0 mass%, or a reaction is performed in the presence of a hydrosilylation catalyst and an adsorbent that has a water content of no more than 1.0 mass%.

Description

METHOD FOR PRODUCING FLUORINE-CONTAINING ETHER COMPOUND, AND METHOD FOR PRODUCING ARTICLE

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

Since a fluorine-containing compound exhibits high lubricity, water and oil repellency, etc., it is suitably used as a surface treatment agent. When the surface treatment agent imparts water and oil repellency to the surface of the substrate, the dirt on the surface of the substrate can be easily wiped off, and the dirt removability is improved. Among the above-mentioned fluorine-containing compounds, a 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 removability.

The surface treatment agent containing the above-mentioned fluorine-containing ether compound has a performance (friction resistance) in which water and oil repellency hardly decreases even if it is repeatedly rubbed with a finger (friction resistance) and a performance capable of easily removing fingerprints attached to the surface by wiping (fingerprint stain It is used as a surface treatment agent of the member which comprises the surface touched by the finger of a touch panel, for example for which the removal property is required to be maintained for a long time.
As the above-mentioned fluorine-containing ether compound, a compound having a poly (oxyperfluoroalkylene) chain and an alkoxysilane, which is obtained by reacting a compound having a poly (oxyperfluoroalkylene) chain and having a terminal bonded to a silicon atom A compound having a degradable 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 are further improved.
When the present inventors formed a surface layer on the surface of a substrate using the surface treatment agent containing a fluorine-containing ether compound described in Patent Document 1, when the abrasion resistance of the surface layer is insufficient, or It has been found that particulates resulting from aggregates may be generated and the appearance characteristics of the surface layer may be inferior.

This invention aims at provision of the manufacturing method of the fluorine-containing ether compound which can form the surface layer which was excellent in abrasion resistance and in which generation | occurrence | production of the granular material was suppressed in view of the said subject, and the manufacturing method of articles.

The present invention provides a method for producing a fluorine-containing ether compound having the following constitutions [1] to [10] and a method for producing an article.
[1] A compound having a poly (oxyperfluoroalkylene) chain and an ω-alkenyl group in the presence of a hydrosilylation catalyst, and a hydrogen atom bonded to a silicon atom and a hydrolyzable group bonded to a silicon atom and a silicon atom 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 is produced by reacting the compound with at least one hydroxyl group. A method for producing a fluorine-containing ether compound,
After the fluorine-containing ether compound is obtained, the fluorine-containing ether compound is brought into contact with an adsorbent having a water content of 1.0% by mass or less, or
A process for producing a fluorine-containing 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 production method of [1], wherein the moisture content of the adsorbent is 0.1 mass% or less.
[3] The production method of [1] or [2], wherein the adsorbent is activated carbon, molecular sieve, silica gel or celite.
[4] The process according to any one of [1] to [3], wherein the hydrosilylation catalyst is a Group 8 to 10 transition metal catalyst.

[5] The process according to 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, when A ¹ is a perfluoroalkyl group or -Q [-CH = CH ₂ ] _k and A ¹ is -Q [-CH = CH ₂ ] _k , j is 1;
Q is a (k + 1) -valent linking group, and k is an integer of 1 to 10,
Z ¹ is a single bond or an oxyfluoroalkylene group having 1 to 20 carbon atoms in which one or more hydrogen atoms have been substituted by a fluorine atom (however, the oxyperfluoroalkylene group is excluded. 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 by a fluorine atom (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 ) Groups include both oxyperfluoroalkylene groups in which all hydrogen atoms have been substituted by fluorine atoms, and oxyfluoroalkylene groups 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 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 a silicon atom, a hydrolyzable group bonded to a silicon atom, and a hydroxyl group bonded to a silicon atom is a compound represented by the following formula (3): The manufacturing method in any one of 1]-[5].
H-SiR _n L _3-n (3)
However, R is a monovalent hydrocarbon group, L is a hydrolysable group or a hydroxyl group, n is an integer of 0 to 2, and when n is 0 or 1, a plurality of molecules exist in one molecule. L may be the same as or different from each other, and when n is 2, two R present in one molecule may be the same as or different from each other.
[7] The production method of [6], wherein the n is 0 or 1 and the plurality of Ls are all hydrolyzable groups.

[8] [1] to [7], wherein the amount of the adsorbent used is 1 to 30% by mass with respect to the total mass of the compound having the poly (oxyperfluoroalkylene) chain and the ω-alkenyl group Any manufacturing method.
[9] After obtaining the fluorine-containing ether compound, the fluorine-containing ether compound is brought into contact with an adsorbent having a water content of 1.0% by mass or less in a liquid medium, any one of [1] to [8] Manufacturing method.
[10] A method for producing an article, comprising forming a surface layer on the surface of a substrate using the fluorine-containing ether compound obtained by the production method according to any one of the above [1] to [9].

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

In the present specification, the compound represented by Formula (1) is referred to as Compound 1. The compounds represented by other formulas are similarly described. The group represented by formula (1) is referred to as group 1. The same applies to groups represented by other formulas.
In the present specification, “an alkylene group may have an A group” and “an alkylene group optionally having an A group” mean an A group between carbon atoms and carbon atoms in the alkylene group. It means that it may have, and it may have an A group at its end like an alkylene group -A group-.
The meanings of the terms in the present invention are as follows.
The "etheric oxygen atom" means an oxygen atom which forms an ether bond (-O-) between carbon atom and 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. Further, g1 is an integer of 1 or more, preferably an integer of 1 to 9, and particularly preferably an integer of 1 to 4.

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. As R ^b , an alkyl group (preferably having a carbon number of 1 to 10) is preferable.
The “dialkylsilylene group” is a group represented by —Si (R ^c ) ₂ — in which R ^c is an alkyl group (preferably having a carbon number of 1 to 10).
The "hydrolyzable silyl group" is a group composed 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 the end 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 by using an adsorbent exhibiting a predetermined moisture content.
The present inventors have found that water is related as a reason why a desired effect can not be obtained when using a fluorine-containing ether compound obtained by the production method of the prior art. More specifically, in the method described in Patent Document 1, a fluorine-containing ether compound is produced and then brought into contact with an adsorbent such as activated carbon. When the water content in the adsorbent is high, the hydrolysis reaction of the hydrolyzable group bonded to the silicon atom in the fluorine-containing ether compound proceeds, and then an aggregate is formed through a condensation reaction. Granules are observed in the surface layer formed as a result, the appearance characteristics deteriorate, and the abrasion resistance also deteriorates. The present inventors solve the above-mentioned subject by controlling the moisture content of adsorption material based on the above-mentioned knowledge.

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 one another and a hydroxyl group bonded to a silicon atom (hereinafter also referred to as “compound B”), a poly (oxyperfluoroalkylene) chain and a hydrolyzable silyl group And a fluorine-containing ether compound having at least one of silanol groups (hereinafter, also referred to as “compound C”), which is a method for producing compound C, wherein after the compound C is obtained, the compound C and water content are Contact with 1.0% by mass or less of an adsorbent (hereinafter, also referred to as “specific adsorbent”), or hydrosilylation Presence of a catalyst and a particular adsorbent, perform the above reaction, wherein the.
That is, as a first embodiment of the present production method, compound C is produced by reacting compound A with compound B in the presence of a hydrosilylation catalyst, and the obtained compound C is brought into contact with a specific adsorbent. It can be mentioned.
In addition, as a second embodiment of the present production method, a compound C can be produced by reacting compound A with compound B in the presence of a hydrosilylation catalyst and a specific adsorbent.
In the following, first, the materials used in the present manufacturing method will be described in detail, and then the procedures of each embodiment will be described in detail.

[Compound A]
As the poly (oxyperfluoroalkylene) chain possessed by the compound A, (R ^f O) _m (where R ^f is a perfluoroalkylene group and m is 2 to 200) from the viewpoint that the water and oil repellency of the surface layer is more excellent. And may consist of two or more kinds of R ^f O different in carbon number).
The definition of (R ^f O) _m will be described in detail later.

The compound A may have a plurality of ω-alkenyl groups. The number of ω-alkenyl groups in compound A is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 3.
Examples of the ω-alkenyl group include an allyl group, a vinyl group and a 3-butenyl group.

As the compound A, the 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 -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 because the friction resistance of the surface layer is more excellent.
The perfluoroalkyl group may be linear or branched.
However, j is 1 when A ¹ is -Q [-CH = CH ₂ ] _k .

As a perfluoroalkyl group, 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 from the viewpoint that 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 to 10. Thus, examples of Q include di- to 11-valent linking groups.
As Q, for example, an alkylene group which may have 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 groups obtained by removing —CH = CH ₂ from formulas (2-1), (2-2) and formulas (2-1-1) to (2-1-6) described later.

Z ¹ is a single bond or an oxyfluoroalkylene group having 1 to 20 carbon atoms in which one or more hydrogen atoms have been substituted by a fluorine atom (however, the oxyperfluoroalkylene group is excluded. 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 by a fluorine atom (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 ) Groups include both oxyperfluoroalkylene groups in which all hydrogen atoms have been substituted by fluorine atoms, and oxyfluoroalkylene groups containing one or more hydrogen atoms. May be included)). The carbon number of the oxyfluoroalkylene group or the poly (oxyfluoroalkylene) group is preferably 1 to 10.

As Z ¹ , 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 from the viewpoint of easy production of the 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— is preferable (in the above formula, the left side is bonded to A ¹ -O). As Z ¹ , a single bond, —CHFCF ₂ OCH ₂ CF ₂ O— is particularly preferable.

R ^f is a perfluoroalkylene group.
The carbon number of the perfluoroalkylene group is preferably 1 to 6 from the viewpoint that the water and oil repellency of the surface layer is more excellent.
The perfluoroalkylene group may be linear or branched, but is preferably linear from the viewpoint of being 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 different in carbon number.

M is an integer of 2 to 200, preferably an integer of 5 to 150, and particularly preferably an integer of 10 to 100. If m is at least the lower limit value of the above range, the water and oil repellency of the surface layer is more excellent. If m is below the upper limit of the said range, the abrasion resistance of a surface layer will be more excellent.

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. For example, if two R ^f O are present, two R ^f O may be arranged randomly, alternately, in a block.
^(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) _{m 14} }, (CF ₂ CF ₂ O) _{m 16,} (CF ₂ CF ₂ CF ₂ O) _{m 17} , (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) _{m 15} ( CF ₂ CF ₂ O), (CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) _{m 18} (CF ₂ O) or (CF ₂ CF ₂ O-CF ₂ 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) _{m 19} (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, and m11 CF ₂ O, m12 CF ₂ CF ₂ O, bond order of m13 amino _{CF 2 CF 2 CF 2 O,} m14 amino _{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 an integer of 1 to 99.

Z ² is a (j + q) -valent linking group.
Z ² represents, for example, an alkylene group which may have 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 groups obtained by removing —CH = CH ₂ from formulas (2-1), (2-2) and formulas (2-1-1) to (2-1-6) described later.

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

As Compound 1, Compound 1-1 is preferable from the viewpoint that 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 the respective groups in formula (1).

Z ³ is a group 2-1 or a 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.
The carbon number of the perfluoroalkylene group is preferably 1 to 30, and particularly preferably 1 to 6.
The perfluoroalkylene group may be linear or branched.
As R ^f7 , —CF ₂ CF ₂ CF ₂ CF ₂ — or —CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ — is preferable from the viewpoint of easy production of the compound.

Q ^a is a single bond or a divalent linking group.
The bivalent linking group may be, for example, a bivalent hydrocarbon group (a bivalent saturated hydrocarbon group, a bivalent aromatic hydrocarbon group, an alkenylene group, an alkynylene group). The hydrogen group may be linear, branched or cyclic, and includes, for example, an alkylene group, preferably from 1 to 20 carbon atoms, and from the divalent aromatic hydrocarbon group, from carbon atoms 5 to 20 are preferable, and examples thereof include a phenylene group, and may also be an alkenylene group having 2 to 20 carbon atoms or an alkynylene group having 2 to 20 carbon atoms), and a divalent heterocyclic group And -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 a carbon number of 1 to 10) or a phenyl group. R ^d is a hydrogen atom or an alkyl group (preferably having a carbon number of 1 to 10).
Examples of the combination of two or more of the above include, for example, -OC (O)-, -C (O) N (R ^d )-, an alkylene group -O-alkylene group, and an alkylene group -OC (O) And-alkylene group and alkylene group -Si (R ^a ) ₂ -phenylene group -Si (R ^a ) ₂ can be mentioned.

X is a single bond, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom or a di- to octa-valent organopolysiloxane residue.
The above-mentioned 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.
The carbon number of the alkylene group represented by X is preferably 1 to 20, and particularly preferably 1 to 10. Examples of the divalent to octavalent organopolysiloxane residue include divalent organopolysiloxane residues and (w + 1) -valent organopolysiloxane residues described later.

Q ^b is a single bond or a divalent linking group.
The definition of the divalent linking group is the same as the definition described for Q ^a above.

R ⁷ is a hydroxyl group or an alkyl group.
The carbon number of the alkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1.

When X is a single bond or an alkylene group, h is 1 and 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 h + i = 2 is satisfied,
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 h + i = 3 is satisfied,
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.
When (-Q ^b -CH = CH ₂ ) is two or more, two or more (-Q ^b -CH = CH ₂ ) may be the same or different. When two or more R ^{7 s} are present, two or more (-R ^{7 s} ) may be the same as or different from each other.

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 a single bond is preferable from the viewpoint of easily producing a compound.
The carbon number of the alkylene group is preferably 1 to 10, and particularly preferably 2 to 6.
The carbon number of the group having an etheric oxygen atom between carbon atoms and carbon atoms of the alkylene group having 2 or more carbon atoms is preferably 2 to 10, and particularly preferably 2 to 6.

R ⁷¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a hydrogen atom is preferable from the viewpoint of easily producing a compound.
As an alkyl group, a methyl group is preferable.

Q ⁷² is a single bond or an alkylene group. The carbon number of the alkylene group is preferably 1 to 10, and particularly preferably 1 to 6. In terms of easy production of the compound, Q ⁷² is preferably a single bond or -CH _2- .

R ⁷² is a hydrogen atom or a halogen atom, and a hydrogen atom is preferable from the viewpoint of easily producing a compound.

y is an integer of 1 to 10, preferably an integer of 1 to 6.
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 2-1-1 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 formulas (2-1-1) to (2-1-6) is as described above.

X ¹ is —O— or —C (O) N (R ^d ) — (wherein N is bonded 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.
When the alkylene group has —O—, it is preferable to have —O— between carbon atoms and carbon atoms. In addition, when the alkylene group has a silphenylene skeleton group, a bivalent organopolysiloxane residue or a dialkylsilylene group, it is at the end opposite to the carbon atom-carbon atom or the side to be bonded to (X ¹ ) _p It is preferable to have these groups.

The carbon number of the alkylene group represented by Q ¹ is preferably 1 to 10, and particularly preferably 1 to 6.

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 -is preferred. When (X ¹ ) _p1 is —O—, —CH ₂ — or —CH ₂ CH ₂ OCH ₂ — is preferable. When (X ¹ ) _p1 is —C (O) N (R ^d ) —, an alkylene group having 1 to 6 carbon atoms is preferable (however, N in the formula is bonded to Q ¹ ). A compound is easy to manufacture as Q ¹ 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 is a single bond, an alkylene group, or an etheric oxygen atom, —C (O) —, —C (O) O— or —OC (between carbon atom and carbon atom of alkylene group having 2 or more carbon atoms) O) a group having-or -NH-.
The carbon number of the alkylene group represented by Q ²¹ is preferably 1 to 10, and particularly preferably 1 to 6.
An etheric oxygen atom, -C (O)-, -C (O) O-, -OC (O)-or -NH, between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ²¹ 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 (provided that the right side is bound to N).

r1 is 0 or 1 (however, it is 0 when Q ²¹ is a single bond). In terms of easy production of the compound, 0 is preferable.
r2 is 0 or 1;

Q ²² is an alkylene group which may have a bivalent organopolysiloxane residue, or a group having an etheric oxygen atom or —NH— between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms It is.
When the alkylene group has a bivalent organopolysiloxane residue, it is preferable to have this group at the end opposite to the carbon atom-carbon atom side or the side bonded to N.
The carbon number of the alkylene group which may have a divalent organopolysiloxane residue represented by Q ²² is preferably 1 to 10, and particularly preferably 1 to 6.
The carbon number of the group having an etheric oxygen atom or —NH— between carbon atoms and carbon atoms of the alkylene group having 2 or more carbon atoms represented by Q ²² is preferably 2 to 10, and particularly preferably 2 to 6.

As Q ²² , —CH ₂ — and —CH ₂ CH ₂ OCH ₂ — are preferable from the viewpoint of easily producing a compound (however, the right side is bonded to —CH = CH ₂ ).

Two [-(Q ²² ) _{r 2} -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 a single bond is preferable from the viewpoint of easy production of the compound.
The alkylene group represented by Q ³¹ is preferably 1-10, 2-6 being particularly preferred.
The carbon number of the group having an etheric oxygen atom between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ³¹ is preferably 2 to 10, and particularly preferably 2 to 6.

G is a carbon atom or a silicon atom.
R ³ is a hydroxyl group or an alkyl group. The carbon number of the alkyl group represented by R ³ is preferably 1 to 4.
c is 0 or 1;
As G (R ³ ), C (OH) or Si (R ^3a ) (wherein R ^3a is an alkyl group) from the viewpoint of easy production of the compound, wherein the alkyl group preferably has 1 to 10 carbon atoms, and methyl Groups are particularly preferred).

Q ³² is an alkylene group which may have a divalent organopolysiloxane residue, or a group having an etheric oxygen atom between carbon atoms and carbon atoms of an alkylene group having 2 or more carbon atoms.
When the alkylene group has a bivalent organopolysiloxane residue, it is preferable to have this group at the end opposite to the carbon atom-carbon atom side or the side bonded to G.
The carbon number of the alkylene group which may have a divalent organopolysiloxane residue represented by Q ³² is preferably 1 to 10, and particularly preferably 1 to 6.
The carbon number of the group having an etheric oxygen atom between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ³² is preferably 2 to 10, and particularly preferably 2 to 6.
From the viewpoint of easy production of the compound, Q ³² is preferably —CH ₂ — or —CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —.

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 the 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 and carbon atoms of an alkylene group having 2 or more carbon atoms.
The alkylene group represented by Q ⁴¹ is preferably 1-10, 2-6 being particularly preferred.
The carbon number of the group having an etheric oxygen atom between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ⁴¹ is preferably 2 to 10, and particularly preferably 2 to 6.
t is 0 or 1 (however, it is 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 -is preferable (provided that 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 represents an alkylene group, a divalent organopolysiloxane residue or a dialkylsilylene group, and the above-mentioned alkylene group is —O—, —C (O) N (R ^d ) — [R ^{d is} as defined above] It is street. And may have a silphenylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group.
When the alkylene group has —O—, it is preferable to have —O— between carbon atoms and carbon atoms. Further, the alkylene group is -C (O) N (R d ) -, when having a dialkyl silylene or a divalent organopolysiloxane residue, carbon atoms - a terminal of a side that binds between carbon atoms or (O) _u1 Preferably have these groups. In addition, when the alkylene group has a silphenylene skeleton group, it is preferable to have these groups at the end opposite to the side to be bonded to a carbon atom-carbon atom or (O) _u1 .
The carbon number of the alkylene group represented by Q ⁴² is preferably 1 to 10, and particularly preferably 1 to 6.

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 -,-as-from the point which is easy to manufacture a compound. 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 preferable (however, the right side is bonded to -CH = CH ₂ ).

Three [-(O) _u1- (Q ⁴² ) _u2 -CH = CH ₂ ] may 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 and carbon atoms of an alkylene group having 2 or more carbon atoms.
The carbon number of the alkylene group represented by Q ⁵¹ is preferably 1 to 10, and particularly preferably 1 to 6.
The carbon number of the group having an etheric oxygen atom between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ⁵¹ is preferably 2 to 10, and particularly preferably 2 to 6.
As Q ⁵¹ , from the viewpoint of easy production of 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 (but 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 and carbon atoms of an alkylene group having 2 or more carbon atoms.
When the alkylene group has a bivalent organopolysiloxane residue, it is preferable to have this group at the end opposite to the carbon atom-carbon atom side or the side bonded to Si.
The carbon number of the alkylene group represented by Q ⁵² is preferably 1 to 10, and particularly preferably 1 to 6.
The carbon number of the group having an etheric oxygen atom between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ⁵² is preferably 2 to 10, and particularly preferably 2 to 6.
Q ⁵² is preferably —CH ₂ — or —CH ₂ CH ₂ OCH ₂ — as far as it is easy to produce a compound (provided that the right side is bonded to —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 and carbon atoms of an alkylene group having 2 or more carbon atoms.
The alkylene group represented by Q ⁶¹ is preferably 1-10, 2-6 being particularly preferred.
The carbon number of the group having an etheric oxygen atom between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ⁶¹ is preferably 2 to 10, and particularly preferably 2 to 6.
As Q ⁶¹ , in view of easy production of 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 (but the right side is bound to Z ³ ).

Z ³ is an organopolysiloxane residue of (w + 1) valence.
w is an integer of 2 to 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 an alkylene group which may have a divalent organopolysiloxane residue, or a group having an etheric oxygen atom between carbon atoms and a carbon atom of an alkylene group having 2 or more carbon atoms.
When the alkylene group has a bivalent organopolysiloxane residue, it is preferable to have this group at the end opposite to the carbon atom-carbon atom side or the side bonded to Z ³ .
The carbon number of the alkylene group represented by Q ⁶² is preferably 1 to 10, and particularly preferably 1 to 6.
The carbon number of the group having an etheric oxygen atom between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ⁶² is preferably 2 to 10, and particularly preferably 2 to 6.
As Q ⁶² , -CH ₂ -is preferable from the viewpoint of easy production of the compound.

The w [-(Q ⁶² ) _{v 2} -CH = CH ₂ ] may be the same or different.

[Compound B]
The number of hydrogen atoms bonded to silicon atoms in the compound B is preferably 1 to 3, and 1 is particularly preferred.

As compound B, compound 3 is preferred.
H-SiR _n L _3-n (3)

R is a monovalent hydrocarbon group, preferably a monovalent saturated hydrocarbon group. The carbon number is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2.

L is a hydrolyzable group or a hydroxyl group.
The hydrolyzable group of L is a group which becomes a hydroxyl group by a hydrolysis reaction. That is, a silanol group is formed from a hydrolyzable silyl group by a hydrolysis reaction. The silanol groups further react between silanol groups to form Si-O-Si bonds. In addition, the silanol group can be subjected to a dehydration condensation reaction with a hydroxyl group (substrate -OH) on the surface of the substrate to form a chemical bond (substrate -O-Si).

As L, a hydrolyzable group is preferable, and as the hydrolyzable group, an alkoxy group, a halogen atom, an acyl group, an isocyanate group (-NCO) and the like can be mentioned. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms. As a halogen atom, a chlorine atom is preferable.
As L, an alkoxy group having 1 to 4 carbon atoms or a halogen atom is preferable from the viewpoint of easy industrial production. L is preferably an alkoxy group having a carbon number of 1 to 4 from the viewpoint of little outgassing at the time of application and the storage stability of the compound 3 being more excellent, and an ethoxy group when long-term storage stability of the compound 3 is required. In particular, when the reaction time after coating is to be short, a methoxy group is particularly preferable.

n is an integer of 0 to 2.
n is preferably 0 or 1, and particularly preferably 0. The presence of a plurality of L makes the adhesion of the surface layer to the substrate 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 as each other. When n is 2, two R present in one molecule may be the same as 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 ) H-Si (NCO) ₃ is preferred.

[Compound C]
It is preferable that the compound C has a hydrolysable silyl group from the point which the storage stability of a compound is more excellent.

The number average molecular weight of the compound C is preferably 500 to 20,000, more preferably 800 to 10,000, and particularly preferably 1,000 to 8,000. If the number average molecular weight is within the above range, the abrasion resistance of the surface layer is excellent.

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)
In formula (4), A ² is a perfluoroalkyl group or -Q [-C ₂ H ₄ -SiR _n L _3-n ] _k .
However, j is 1 when A ² is —Q [—C ₂ H ₄ —SiR _n L _3-n ] _k .
The definition of each other group is as described above.

As compound 4, compound 4-1 is preferred.
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 a group 5-1 or a 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)
The definition of each group in the formulas (5-1) and (5-2) is as described above.

Furthermore, as the group 5-1, groups 5-1-1 to 5-1-6 are preferable.
-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)
The definition of each group in the formulas (5-1-1) and (5-1-6) is as described above.

[Hydrosilylation catalyst]
The hydrosilylation catalyst is preferably a transition metal catalyst, more preferably a group 8 to 10 transition metal catalyst, and further a platinum (Pt) catalyst, a ruthenium (Ru) catalyst, a rhodium (Rh) catalyst, an iron (Fe) catalyst Preferably, a platinum catalyst and an iron catalyst are particularly preferred in view of the progress of the hydrosilylation reaction. Groups 8 to 10 are group numbers according to the IUPAC Inorganic Chemical Nomenclature, Revised Edition (1989).
Specific examples of platinum catalysts include Pt complexes of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, Pt complexes of divinyltetramethyldisiloxane, and Pt complexes of tetramethyltetravinylcyclotetrasiloxane, There may be mentioned chloroplatinic acid and platinum oxide.
Specific examples of the iron catalyst include the hydrosilylated iron catalyst described in WO 2016/027819.

[Adsorbent]
The moisture content of the adsorbent is 1.0% by mass or less, and at least one of a point where generation of particulates in the surface layer is further suppressed and a point where friction resistance is more excellent (hereinafter referred to as “in In addition, 0.5 mass% or less is preferable, and 0.1 mass% or less is especially preferable. Further, the moisture content of the adsorbent is often 0.001% by mass or more.
The moisture content of the adsorbent is the mass ratio of water in the total mass of the adsorbent, and can be measured by the loss on drying method or the like.

The adsorbent should satisfy the above range of moisture content when using the present manufacturing method, and the moisture content of the adsorbent is out of the above range (for example, 2 to 3% by mass before storage, etc.) ) May be.
When using an adsorbent, for example, the adsorbent having a water content exceeding the above range (more than 1.0% by mass) is subjected to a dehydration treatment to form an adsorbent having a predetermined water content, and then this production is performed. It may be applied to the method.
As the method of the said dehydration process, the method of spraying the gas (for example, nitrogen whose dew point is 0 degrees C or less) with small water content with respect to an adsorbent, the method of heating an adsorbent, etc. are mentioned, for example.

Specific examples of the adsorbent include activated carbon, molecular sieves, 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, and may be, for example, activated carbon obtained by firing a natural material such as wood material, coconut shell, coal or the like, or firing an artificial material such as a synthetic organic polymer compound It is also possible to use activated carbon obtained by
The particle size of the activated carbon is preferably 5 to 50 mesh, and particularly preferably 10 to 30 mesh. The particle size of the activated carbon can be determined according to the method described in JIS K1474: 2014.
The activated carbon may be a commercially available product, and examples thereof include Shirasu G2c, Shirasu GM2x, Shirasu GH2x, Shirasu WH2C, Kuraray Co., Ltd., manufactured by Nippon EnviroChemical.

[Other ingredients]
In the present production method, components other than the components described above may be used.
For example, in the present production method, a liquid medium such as a solvent may be used. That is, the reaction of Compound A with Compound B may be carried out in the presence of a liquid medium. As a liquid medium, a solvent capable of dissolving Compound A, Compound B and Compound C is preferable.
The solvent includes an organic solvent. Specific examples of the organic solvent include fluorine-based organic solvents and non-fluorine-based organic solvents.
The organic solvents may be used alone or in combination of two or more.
100 ppm or less is preferable and, as for the water content of the organic solvent, 20 ppm or less is more preferable.

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) Asahi Glass Co., Ltd., C ₂ F ₅ CHFCHFCF ₃ (Bartrel: 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, manufactured by 3M), C ₄ F ₉ OC ₂ H ₅ (Novec-7200: product name, manufactured by 3M), C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ (Novec-7300: product name, 3M company).
Specific examples of fluorinated alkylamines include perfluorotripropylamine and perfluorotributylamine.
Specific examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol and hexafluoroisopropanol.

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

Further, in the present production method, a dislocation inhibitor may be used. That is, the reaction of Compound A with Compound B may be carried out in the presence of a rearrangement inhibitor. As the anti-rearrangement agent, the compounds described in paragraph 0115 of WO2014 / 069592 can be mentioned.

[First aspect]
The first aspect of the present production method is an aspect in which compound C is produced by reacting compound A with compound B in the presence of a hydrosilylation catalyst, and the obtained compound C is brought into contact with a specific adsorbent.
First, when the compound A and the compound B are reacted, the hydrosilylation catalyst, the compound A and the compound B are mixed, and if necessary, heat treatment is performed to carry out a reaction.
In the method of mixing the hydrosilylation catalyst, the compound A and the compound B, the respective components may be mixed at once, or the components may be mixed and divided.
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 the compound A and the compound B.
As the mixing ratio of the compound A and the compound B, an optimum ratio is selected depending on the structure of the compound, but the mole of the hydrogen atom bonded to the silicon atom in the compound B with respect to the mole number of the ω-alkenyl group in the compound A The ratio of the numbers (hydrogen atom / ω-alkenyl group) is preferably 1.0 to 3.0.

The reaction temperature for reacting the compound A with the compound B is preferably 0 to 100 ° C., particularly preferably 50 to 80 ° C. 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 compound A and compound B are reacted to obtain compound C having a halogen atom as a hydrolysable group, a reaction of changing a halogen atom to an alkoxy group may be carried out.

Next, the obtained compound C is brought into contact with a specific adsorbent.
As a method of contacting, there is a method of mixing the compound C and the specific adsorbent, and a method of distributing 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 dispersion in which the compound C is dissolved in a solvent or a dispersion medium is prepared. And the obtained solution or dispersion may be brought into contact with the specific adsorbent. Preferably, a solution of compound C dissolved in a solvent is brought into contact with a specific adsorbent.
The solvent or dispersion medium to be used may be a liquid medium capable of dissolving or dispersing Compound C, preferably an organic solvent, particularly preferably a fluorine-based organic solvent. Specific examples of the fluorine-based organic solvent are as described above.

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

The contact time is preferably 0.1 to 180 minutes, particularly preferably 1 to 60 minutes, in that the effect of the present invention is more excellent.
The temperature at the time of contact is preferably 0 to 40 ° C., particularly preferably 10 to 30 ° C., in that the effect of the present invention is more excellent.

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

The amount of the specific adsorbent used is preferably 1 to 30% by mass, particularly preferably 5 to 25% by mass, based on the total mass of the compound A and the compound B.
The contact time is preferably 0.1 to 180 minutes, particularly preferably 1 to 60 minutes, in that the effect of the present invention is more excellent.
The temperature at the time of contact is preferably 0 to 40 ° C., particularly preferably 10 to 30 ° C., in that the effect of the present invention is more excellent.

The composition may be produced by mixing the compound C (the compound C after contacting with the specific adsorbent) obtained by the method of the first aspect or the second aspect and a liquid medium.
An organic solvent is mentioned as a specific example of a liquid medium. Specific examples of the organic solvent include the fluorine-based organic solvent and the non-fluorine-based organic solvent. The organic solvents may be used alone or in combination of two or more.
Specific examples of the fluorine-based organic solvent and the non-fluorine-based organic solvent are as described above.
In addition, a composition containing Compound C and a liquid medium, which is obtained by using a liquid medium in the method of the first aspect or the second aspect, can also be the above composition. Furthermore, the concentration of compound C may be adjusted from the composition containing the compound C and the liquid medium to obtain a new composition, and the liquid medium used in the method of the first or second aspect may be different. It may be converted to a liquid medium of the following to form a new composition.

The content of the compound C in the composition is preferably 0.01 to 50.00 mass%, particularly preferably 1.00 to 30.00 mass, with respect to the total mass of the composition.
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, with respect to the total mass of the composition.

A surface layer can be formed on the surface of a substrate using Compound C obtained by the present production method.
More specifically, by using the compound C or the composition, it is possible to form on the surface of the substrate a surface layer which is excellent in abrasion resistance and in which the generation of particles is suppressed. That is, an article having a substrate and a surface layer formed of the compound C or the composition disposed on the surface of the substrate can be manufactured.

The substrate is not particularly limited as long as the substrate is required to be imparted with water and oil repellency. Specific examples of the material of the substrate include metals, resins, glasses, sapphires, ceramics, stones, and composite materials of these. The glass may be chemically strengthened. The substrate 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. The touch panel substrate preferably has a light transmitting property. “Having light transmittance” means that the vertical incident visible light transmittance according to JIS R 3106: 1998 (ISO 9050: 1990) is 25% or more. As a material of the base material for touchscreens, glass or transparent resin is preferable.

The above-mentioned article can be manufactured, for example, by the following method.
-A method of treating the surface of a substrate by a dry coating method using Compound C or a composition to obtain the above-mentioned article.
-A method of applying the composition to the surface of a substrate by a wet coating method and drying it to obtain the above-mentioned article.

Specific examples of the dry coating method include a vacuum evaporation method, a CVD method, and a sputtering method. Among these, the vacuum evaporation method is preferable in terms of suppressing the decomposition of the compound C and the simplicity of the apparatus. At the time of vacuum deposition, a pellet-like substance in which a metal porous body such as iron or steel is impregnated 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-Blodgett And gravure coating.

The surface layer formed by the above procedure includes the compound obtained through the hydrolysis reaction and condensation reaction of compound C.
The thickness of the surface layer is preferably 1 to 100 nm, particularly preferably 1 to 50 nm. The film thickness of the surface layer is obtained by obtaining the interference pattern of the reflected X-ray by the X-ray reflectance method using an X-ray diffractometer for thin film analysis (manufactured by RIGAKU, ATX-G), and from the vibration period of this interference pattern It can be calculated.

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

[Evaluation method]
(Water content of adsorbent)
The sample was heated by 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 the appearance characteristics were evaluated based on the presence or absence of particulate matter in the surface layer. Evaluation criteria are as follows.
A: There are no particles of about 100 μm in the surface layer.
B: There are particles of about 100 μm in the surface layer.

(Anti-friction)
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 measurement device (DM-500, manufactured by Kyowa Interface Science Co., Ltd.). It measured in five different places in the surface of a surface layer, and computed the average value. The 2θ method was used to calculate the contact angle.
<Test method of abrasion resistance>
With respect to the surface layer, using a reciprocating traverse tester (manufactured by Kei Ente Co., Ltd.) in accordance with JIS L 0849: 2013 (ISO 105-X 12: 2001), a steel wool Bonstar (# 0000) pressure: 98.07 kPa, speed: 320 cm It reciprocated 10,000 times a 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 the following formula, 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 by 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) to a concentration of 20% by mass to prepare 100 g of Composition 1.

In the above compound C-1, as an average composition, 0.17 repeating units of (CF ₂ CF ₂ CF ₂ CF ₂ O) and 0.10 (CF ₂ CF ₂ CF ₂ O) of repeating units are used. Although 18 pieces were included, it was omitted because of a small amount.

Synthesis Example 2
Compound C-2 was synthesized according to the method described in Synthesis Example 3 of WO 2017/022437. Specifically, a compound having a poly (oxyperfluoroalkylene) chain and an ω-alkenyl group (perfluoropolyether group-containing allyloxy body represented by the following formula (7)) and a hydrolyzable group bonded to a silicon atom Is reacted with trichlorosilane, which is a compound having the following formula, 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) to a concentration of 20% by mass to prepare 100 g of Composition 2.

[Example 1]
5 g of activated carbon (Kuraray Co., Ltd., KURARECOL GLC, standard particle size: 10 to 30 mesh) was charged in a filter, and nitrogen having a dew point of −20 ° C. was circulated for 1 minute. The moisture content of the activated carbon after nitrogen flow was 0.9% by 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 obtained composition 11, a surface layer was formed on the surface of a substrate (chemically strengthened glass) by the following dry coating method. First, 0.5 g of the composition 11 was filled in a molybdenum board in a vacuum deposition apparatus (VTR-350M, manufactured by ULVAC), and the inside of the vacuum deposition apparatus was evacuated to 1 × 10 ⁻³ Pa or less. The board on which the composition 11 is disposed is heated at a heating rate of 10 ° C./min or less, and the shutter is opened when the deposition rate by a quartz crystal oscillator thickness meter exceeds 1 nm / sec. Film formation was started. When the film thickness reached 50 nm, the shutter was closed to complete the film formation on the surface of the substrate. The resulting substrate was heat-treated at 200 ° C. for 30 minutes, and washed with Asahi Clean AK-225 (trade name, Asahi Glass Co., Ltd.) to obtain an article having a surface layer disposed on the surface of the substrate. . The appearance characteristics and abrasion resistance of the articles were evaluated, and the results are shown in Table 1.

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

As shown in Table 1 above, in the cases of 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, the appearance is excellent, and the initial water repellency and friction resistance are obtained. An excellent surface layer was obtained.
Further, from the comparison of Examples 1 to 3, it was confirmed that the effect is more excellent when the moisture content of the adsorbent is 0.1 mass% or less.
On the other hand, in the case of Example 5 using an adsorbent having a moisture content of more than 1.0% by mass, particulate matter was generated and the appearance was insufficient, and a surface layer having insufficient abrasion resistance was obtained. .

In the synthesis of Compound C-2 according to the method described in Synthesis Example 3 of WO 2017/022437, the activated carbon having a water content of 0.9% by mass used in Example 4 is further used to obtain the activated carbon and the hydrosilylation catalyst. The perfluoropolyether group-containing allyloxy compound represented by the above formula (7) used in Synthesis Example 3 of WO 2017/022437 was reacted with trichlorosilane in the presence to obtain Compound C-2 . The surface layer was formed according to the same procedure as Example 4 using the obtained compound C-2, and the same result (appearance characteristics and abrasion resistance) as Example 4 was obtained.

The fluorine-containing ether compound obtained by the present production method can be used in various applications where it is required to impart lubricity and water and oil repellency. For example, a coat of a display input device such as a touch panel, a surface protection coat of a transparent glass or transparent plastic member, an antifouling coat for a kitchen, a water repellent moistureproof coat or an antifouling coat such as an electronic device, a heat exchanger, or a battery It can be used as an antifouling coat for toiletries, a coat on a member that needs to be liquid repellent while conducting, a water repellent / waterproof / sliding water coat of a heat exchanger, a surface low friction coat such as a vibrating screen or the inside of a cylinder. More specific examples of use include front protective plate of display, anti-reflection plate, polarizing plate, anti-glare plate, or those with anti-reflection film treatment on their surface, touch panel of devices such as mobile phones and portable information terminals Coats of various devices that have display input devices that operate on the screen with a finger or palm of a person such as a sheet or touch panel display, coats of decorative building materials around water such as toilets, baths, washrooms and kitchens, waterproofing for wiring boards Coatings, heat and water repellant water-repellent / water-sliding coatings, solar cell water-repellent coatings, printed wiring board waterproof / water-repellent coatings, electronic equipment housings and electronic components waterproof / water-repellent coatings, transmission line insulation Performance improvement coat, waterproof / water repellent coat of various filters, waterproof coat of radio wave absorbing material and sound absorbing material, bath, kitchen equipment, antifouling coat for toiletries, vibrating sieve and sieve 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.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2017-157902 filed on Aug. 18, 2017 are incorporated herein by reference and incorporated as disclosure of the specification of the present invention. It is.

Claims (10)

1. A compound having a poly (oxyperfluoroalkylene) chain and an ω-alkenyl group in the presence of a hydrosilylation catalyst, a hydrogen atom bonded to a silicon atom, a hydrolyzable group bonded to a silicon atom, and at least a hydroxyl group bonded to a silicon atom A fluorine-containing ether which reacts with a compound having one side to produce a fluorine-containing ether compound having a poly (oxyperfluoroalkylene) chain and a hydrolyzable group bonded to a silicon atom and at least one hydroxyl group bonded to a silicon atom. A method of producing a compound,
   After the fluorine-containing ether compound is obtained, the fluorine-containing ether compound is brought into contact with an adsorbent having a water content of 1.0% by mass or less, or
   A process for producing a fluorine-containing 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 manufacturing method according to claim 1, wherein a moisture content of the adsorbent is 0.1 mass% or less.
3. The manufacturing method according to claim 1 or 2, wherein the adsorbent is activated carbon, molecular sieve, silica gel or celite.
4. The method according to any one of claims 1 to 3, wherein the hydrosilylation catalyst is a Group 8 to 10 transition metal catalyst.
5. 5. The 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, when A ¹ is a perfluoroalkyl group or -Q [-CH = CH ₂ ] _k and A ¹ is -Q [-CH = CH ₂ ] _k , j is 1;
   Q is a (k + 1) -valent linking group, and k is an integer of 1 to 10,
   Z ¹ is a single bond or an oxyfluoroalkylene group having 1 to 20 carbon atoms in which one or more hydrogen atoms have been substituted by a fluorine atom (however, the oxyperfluoroalkylene group is excluded. 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 by a fluorine atom (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 ) Groups include both oxyperfluoroalkylene groups in which all hydrogen atoms have been substituted by fluorine atoms, and oxyfluoroalkylene groups 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 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 a silicon atom, a hydrolyzable group bonded to a silicon atom, and a hydroxyl group bonded to a silicon atom is a compound represented by the following formula (3): The manufacturing method according to any one of 5.
   H-SiR _n L _3-n (3)
   However, R is a monovalent hydrocarbon group, L is a hydrolysable group or a hydroxyl group, n is an integer of 0 to 2, and when n is 0 or 1, a plurality of molecules exist in one molecule. L may be the same as or different from each other, and when n is 2, two R present in one molecule may be the same as or different from each other.
7. The method according to claim 6, wherein n is 0 or 1 and each of a plurality of L is a hydrolyzable group.
8. The amount of the adsorbent used is 1 to 30% by mass with respect to the total mass of the compound having the poly (oxyperfluoroalkylene) chain and the ω-alkenyl group. Manufacturing method described.
9. The method according to any one of claims 1 to 8, wherein after the fluorine-containing ether compound is obtained, the fluorine-containing ether compound is brought into contact with an adsorbent having a water content of 1.0% by mass or less in a liquid medium. Production method.
10. A method for producing an article, comprising forming a surface layer on the surface of a substrate using the fluorine-containing ether compound obtained by the production method according to any one of claims 1 to 9.