JP2020158779A - Method for producing fluorine-containing ether compound and method for producing article - Google Patents

Abstract

To provide a method for producing a fluorine-containing ether compound capable of forming a surface layer having excellent initial water repellency even under any production condition of dry-coating and wet-coating.SOLUTION: There is provided a method for producing a fluorine-containing ether compound in which a fluorine-containing ether compound having either one or both of a hydrolyzable group bonded to a poly (oxyperfluoroalkylene) chain and a silicon atom and a hydroxyl group bonded to a silicon atom is obtained by reacting a compound having a poly (oxyperfluoroalkylene) chain and an ω-alkenyl group and a compound having either one or both of a hydrolyzable group bonded to a hydrogen atom bonded to a silicon atom and a silicon atom and a hydroxyl group bonded to a silicon atom in the presence of a hydrosilylation catalyst and then the fluorine-containing ether compound is filtered using a filter having a water content of 2.5 g/m2 or less.SELECTED DRAWING: None

Description

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

Fluorine-containing compounds are preferably used as surface treatment agents because they exhibit high lubricity, water and oil repellency, and the like. When water and oil repellency is imparted to the surface of the base material by the surface treatment agent, it becomes easy to wipe off the dirt on the surface of the base material, and the dirt removal property is improved. Among the above-mentioned 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, and particularly, such as fats and oils. Excellent in removing dirt.

The surface treatment agent containing the fluorine-containing ether compound has a performance that the water and oil repellency does not easily decrease even if it is repeatedly rubbed with a finger (friction resistance) and a performance that can easily remove fingerprints adhering to the surface by wiping (fingerprint stains). (Removability) is required to be maintained for a long time, for example, it is used as a surface treatment agent for a member constituting a surface touched by a finger of a touch panel.
As a method for producing the above-mentioned fluorine-containing ether compound, a method of reacting a compound having a poly (oxyperfluoroalkylene) chain with acetoxysilane or the like in the presence of a platinum complex as a hydrosilylation catalyst is known (Patent Document 1). ..

International Publication No. 2017/022437

In recent years, the physical properties required for a surface layer formed by using a surface treatment agent containing a fluorine-containing ether compound have been further improved, and specifically, a surface layer having excellent initial water repellency is required. ..
When the present inventors formed a surface layer on the surface of the base material using the fluorine-containing ether compound obtained by the production method described in Patent Document 1, the surface was subjected to either dry coating or wet coating production conditions. It was found that the initial water repellency of the layer may be insufficient.

In view of the above problems, an object of the present invention is to provide a method for producing a fluorine-containing ether compound and a method for producing an article, which can form a surface layer having excellent initial water repellency under any production conditions of dry coating and wet coating. To do.

The present invention provides a method for producing a fluorine-containing ether compound having the following configurations [1] to [8] and a method for producing an article.
[1] In the presence of a hydrosilylation catalyst, a compound having a poly (oxyperfluoroalkylene) chain and an ω-alkenyl group was bonded to a hydrogen atom bonded to a silicon atom, a hydrolyzable group bonded to the silicon atom, and a silicon atom. By reacting with a compound having either one or both of the hydroxyl groups, a poly (oxyperfluoroalkylene) chain and a hydrolyzable group bonded to a silicon atom and a fluorine-containing compound having one or both of the hydroxyl groups bonded to a silicon atom A method for producing a fluorine-containing ether compound, which comprises filtering the fluorine-containing ether compound using a filter having a water content of 2.5 g / m ² or less after obtaining the ether compound.
[2] The production method of [1], wherein the material constituting the filter is polytetrafluoroethylene.
[3] The production method of [1] or [2], wherein the filter is a filter that has been subjected to a drying treatment.
[4] The production method according to any one of [1] to [3], wherein the drying treatment includes a treatment for passing nitrogen gas.
[5] The production method according to any one of [1] to [4], wherein the drying treatment includes a heating treatment.
[6] The production method according to any one of [1] to [5], wherein the water content of the filter is 1.5 g / m ² or less.
[7] The production method according to any one of [1] to [6], wherein the water content of the filter is 1.0 g / m ² or less.
[8] An article characterized in that a surface layer is formed on the surface of a base material using the fluorine-containing ether compound obtained by the method for producing a fluorine-containing ether compound according to any one of the above [1] to [7]. Manufacturing method.

According to the present invention, it is possible to provide a method for producing a fluorine-containing ether compound and a method for producing an article, which can form an initial surface layer having excellent water repellency under any production conditions of dry coating and wet coating.

In the present specification, the compound represented by the formula (1) is referred to as compound 1. Compounds represented by other formulas are also described in the same manner. The group represented by the formula (1) is referred to as group 1. The groups represented by other formulas are also described in the same manner.
In the present specification, "the alkylene group may have an A group" and "the alkylene group which may have an A group" means an A group between carbon atoms in the alkylene group. It may have, or may have an A group at the end such as an alkylene group-A group.
The meanings of the terms in the present invention are as follows.
The "ethery oxygen atom" means an oxygen atom that forms an ether bond (-O-) between carbon atoms.
The "divalent organopolysiloxane residue" is a group represented by the following formula. ^Ra in the following formula is an alkyl group (preferably 1 to 10 carbon atoms) 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- (where Ph is a phenylene group and R ^b is a monovalent organic group). Is. As R ^b , an alkyl group (preferably 1 to 10 carbon atoms) is preferable.
A "dialkylsilylene group" is a group represented by −Si (R ^c ) _2- (where R ^c is an alkyl group (preferably having 1 to 10 carbon atoms)).
"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 an NMR analysis method.
¹ Calculated by ¹ H-NMR and ¹⁹ F-NMR by determining the number (average value) of oxyperfluoroalkylene groups with reference to the terminal groups.

The method for producing a fluorine-containing ether compound of the present invention (hereinafter, also referred to as “the present production method”) is a compound having a poly (oxyperfluoroalkylene) chain and an ω-alkenyl group in the presence of a hydrosilylation catalyst (hereinafter, “the production method”). (Also also referred to as “Compound A”) and a compound having either or both of a hydrogen atom bonded to a silicon atom, a hydrolyzable group bonded to the silicon atom, and a hydroxyl group bonded to the silicon atom (hereinafter, also referred to as “Compound B”). A fluorine-containing ether compound having one or both of a poly (oxyperfluoroalkylene) chain, a hydrolyzable group bonded to a silicon atom, and a hydroxyl group bonded to a silicon atom (hereinafter, "compound"). After obtaining (also referred to as C ”), compound C is filtered using a filter having a water content of 2.5 g / m ² or less.
In the present specification, the step of reacting compound A with compound B in the presence of a hydrosilylation catalyst to obtain compound C is referred to as a "synthesis step". Further, a step of filtering compound C using the above filter having a water content of 2.5 g / m ² or less is referred to as a “filtration step”.

According to the filtered compound C obtained by this production method, a surface layer having excellent initial water repellency can be formed under any production conditions of dry coating and wet coating. The details of this reason have not been clarified yet, but it is presumed that it is due to the following reasons.
In the production of compound C, an adsorbent such as activated carbon may be used to remove impurities from the target product (fluorine-containing ether compound). In addition, dust, dust, and other dust may be mixed in during the production of compound C. In order to remove such adsorbents and dust, the target product is filtered using a filter.
Here, when the hydrolysis reaction of compound C proceeds due to the water brought in from the filter, and the hydroxyl groups bonded to the silicon atoms generated from compound C are dehydrated and condensed between the molecules to form a Si—O—Si bond. There is. Then, since the hydroxyl group bonded to the silicon atom generated by the hydrolysis of the compound C is consumed before the surface treatment of the base material is performed, the reaction points between the compound C and the base material are reduced, and the surface layer and the base are reduced. It is presumed that the adhesion with the material is reduced. As a result, it is presumed that the initial water repellency was lowered as a result of the surface layer not being able to sufficiently cover the surface of the base material.
In response to this problem, according to this production method, since a filter having a water content of a predetermined value or less is used, hydrolysis of compound C can be suppressed. As a result, it is considered that the surface layer having excellent initial water repellency could be formed under both the dry coating and wet coating production conditions by using the filtered compound C obtained by this production method.

[Synthesis process]
(Compound A)
As the poly (oxyperfluoroalkylene) chain contained in compound A, (R ^f O) _m (where R ^f is a perfluoroalkylene group and m is 2 to 200) because the surface layer has more excellent water and oil repellency. It is an integer of, and may consist of two or more types of R ^f O having different carbon atoms.) Is preferable.
The definition of (R ^f O) _m will be described in detail later.

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 because the surface layer has more excellent water and oil repellency.
[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, further preferably 1 to 6, and particularly preferably 1 to 3 from the viewpoint of more excellent abrasion resistance of the surface layer.
The perfluoroalkyl group may be linear or branched.
However, when A ¹ is −Q [−CH = CH ₂ ] _k , j is 1.

Perfluoroalkyl groups include 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 )-etc.
As the perfluoroalkyl group, CF ₃ −, CF ₃ CF ₂ −, and CF ₃ CF ₂ CF ₂ − are preferable because the surface layer has more excellent water and oil repellency.

Q is a linking group of (k + 1) valence. As will be described later, k is an integer of 1 to 10. Therefore, as Q, a linking group having a valence of 2 to 11 can be mentioned.
Q includes, for example, an alkylene group which may have an ethereal oxygen atom or a divalent organopolysiloxane residue, a carbon atom, a nitrogen atom, a silicon atom, a 2-8 valent organopolysiloxane residue, and , A group obtained by removing −CH = CH ₂ from the formulas (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 replaced with 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 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 ) The group may contain both an oxyperfluoroalkylene group in which all hydrogen atoms are substituted with fluorine atoms and an oxyfluoroalkylene group containing one or more hydrogen atoms.) The oxyfluoroalkylene group or poly (oxyfluoroalkylene) group preferably has 1 to 10 carbon atoms.

As Z ¹ , 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 compounds. 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.). As Z ¹ , a single bond, −CHFCF ₂ OCH ₂ CF ₂ O−, is particularly preferable.

R ^f is a perfluoroalkylene group.
The number of carbon atoms of the perfluoroalkylene group is preferably 1 to 6 from the viewpoint of more excellent water and oil repellency of the surface layer.
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 ^fs 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 atoms.

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

When two or more kinds of R ^f O having different carbon atoms are present in (R ^f O) _m , 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, or arranged in blocks.
As (R ^f O) _m , {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 (CF ₂ CF ₂ CF ₂ O) _m13 (CF ₂ ) because the surface layer has more excellent water and oil repellency. 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) is preferable, {(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 preferable.
However, m11 and m12, each an integer of 1 or more, m13 and m14 are each 0 or an integer of 1 or more, m11 + m12 + m13 + m14 is an integer of 2 to 200, m11 amino _CF 2 O, m12 amino 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 integers of 2 to 200, respectively, and m15, m18 and m19 are integers of 1 to 99, respectively.

Z ² is a (j + q) valence linking group.
Z ² may have, for example, an etheric oxygen atom or a divalent organopolysiloxane residue, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom, a 2-8 valent organopolysiloxane residue, and , A group obtained by removing −CH = CH ₂ from the formulas (2-1), formula (2-2), and formulas (2-1-1) to (2-1-6) described later.

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

As the compound 1, the compound 1-1 is preferable because the surface layer has more excellent water and oil repellency.
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 synonymous with 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.
The number of carbon atoms of the perfluoroalkylene group is preferably 1 to 30, and particularly preferably 1 to 6.
The perfluoroalkylene group may be linear or branched.
The R ^f7, from the viewpoint of easily producing the _{compound, -CF 2 CF 2 CF 2 CF} 2 - or _{-CF 2 CF 2 CF 2 CF 2} CF 2 - is preferred.

Q ^a is a single bond or divalent linking group.
The divalent linking group may be, for example, a divalent hydrocarbon group (a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, an alkenylene group, or an alkynylene group. Divalent saturated hydrocarbon group. The hydrogen group may be linear, branched or cyclic, and examples thereof include an alkylene group. The carbon number is preferably 1 to 20, and the divalent aromatic hydrocarbon group has a carbon number of carbon. 5 to 20 is preferable, and examples thereof include a phenylene group. In addition, an alkenylene group having 2 to 20 carbon atoms and an alkynylene group having 2 to 20 carbon atoms may be used.) A divalent heterocyclic group. , -O-, -S-, -SO _2- , -N (R ^d )-, -C (O)-, -Si ( ^Ra ) _2-, and a group combining two or more of these. .. Here, ^Ra is an alkyl group (preferably 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 -OC (O)-, -C (O) N (R ^d )-, an alkylene group having an etheric oxygen atom, and -OC (O)-. Examples thereof include an alkylene group having an alkylene group, an alkylene group-Si ( ^Ra ) ₂ -phenylene group-Si ( ^Ra ) ₂ .

X is a single bond, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom or a 2-8 valent organopolysiloxane residue.
The alkylene group may have an —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 2 to 8-valent organopolysiloxane residue include a divalent organopolysiloxane residue and a (w + 1) -valent organopolysiloxane residue described later.

Q ^b is a single bond or 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.
The number of carbon atoms 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 2-8 valent 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. If R ⁷ is two or more, two or more (-R ⁷⁾ may be be the same or different.

Q ⁷¹ is a single bond or an alkylene group which may have an ethereal oxygen atom, and a single bond is preferable from the viewpoint of easy production of a compound.
The number of carbon atoms of the alkylene group which may have an ethereal oxygen atom is preferably 1 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 easy production of a compound.
As the alkyl group, a methyl group is preferable.

Q ⁷² is a single bond or an alkylene group. The alkylene group preferably has 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms. From the viewpoint of easy production of a 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 because it is easy to produce 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.

The group 2-1 is preferably a group 2-1 to 2-1-6.
−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 formulas (2-1-1) to (2-1-6) is as described above.

X ¹ is -O- or -C (O) N (R ^d )-(where N in the equation is bound 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 an —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. When the alkylene group has a silphenylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group, it is located between carbon atoms or at the end 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.

The Q ^1, if 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 preferable. (X ¹ ) When _p1 is an etheric oxygen atom, −CH ₂ − and −CH ₂ CH ₂ OCH ₂ − are preferable. ^(X _{1) p1} is ^{-C (O) N (R d} ) - in the case of, preferably an alkylene group having 1 to 6 carbon atoms (provided that, N in the formula is bound to ^{Q 1).} If Q ¹ is these groups, the compound can be easily produced.

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 an alkylene group which may have a single bond or an ethereal oxygen atom, -C (O)-, -C (O) O-, -OC (O)-, or -NH-. is there.
Etheric oxygen atom represented by ^{Q 21, -C (O) -} , - C (O) O -, - OC (O) -, or the number of carbon atoms of the alkylene group which may have a -NH- in 1 to 10 are preferable, and 1 to 6 are particularly 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 preferable (however, the right side binds to N).

r1 is 0 or 1 (however, 0 when Q ²¹ is a single bond). 0 is preferable from the viewpoint that the compound can be easily produced.
r2 is 0 or 1.

Q ²² is an alkylene group that may have a divalent organopolysiloxane residue, an ethereal oxygen atom or -NH-.
When the alkylene group has a divalent organopolysiloxane residue, it is preferable to have this group between carbon atoms or at the end opposite to the side where N is bonded.
Divalent organopolysiloxane residue represented by Q ^22, the carbon number of etheric oxygen atom or an alkylene group which may -NH- a have the 1 to 10 preferably 1 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.).

The 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 or an alkylene group which may have an ethereal oxygen atom, and a single bond is preferable from the viewpoint of easy production of a compound.
The number of carbon atoms of the alkylene group which may have an etheric oxygen atom represented by Q ³¹ is 1 to 10 preferably 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. The alkyl group represented by R ³ preferably has 1 to 4 carbon atoms.
c is 0 or 1.
As G (R ³ ), C (OH) or Si (R ^3a ) (however, R ^3a is an alkyl group. The alkyl group preferably has 1 to 10 carbon atoms, preferably methyl, from the viewpoint of easy production of a compound. The group is particularly preferable.) Is preferable.

Q ³² 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.
When the alkylene group has a divalent organopolysiloxane residue, it is preferable to have this group at the end between carbon atoms or the side opposite to the side where G is bonded.
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.
The Q ^32, from the viewpoint of easily producing the _{compound, -CH 2 -, - CH 2} CH 2 CH 2 CH 2 CH 2 CH 2 - is preferred.

The 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 an alkylene group which may have a single bond or an ethereal oxygen atom.
The number of carbon atoms of the alkylene group which may have an etheric oxygen atom represented by Q ⁴¹ is 1 to 10 preferably 2 to 6 is particularly preferred.
t is 0 or 1 (however, 0 when Q ⁴¹ is a single bond).
As for −Q ⁴¹ − (O) _t −, when s is 0, it is a single bond, −CH ₂ O−, −CH ₂ OCH ₂ −, −CH ₂ OCH ₂ CH _{2 because} it is easy to produce a compound. O-, -CH ₂ OCH ₂ CH ₂ OCH _2- , -CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH _2- is preferable (however, the left side is bound 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 It's a street. ], It 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. When the alkylene group has a -C (O) N (R ^d )-, dialkylsilylene group or a divalent organopolysiloxane residue, it is between carbon atoms or the end on the side that bonds with (O) _u1. It is preferable to have these groups in. When the alkylene group has a silphenylene skeleton group, it is preferable to have these groups between carbon atoms or at the end opposite to the side bonded to (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 -,-, because it is easy to produce 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 binds to -CH = CH ₂ ).

The 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 which may have an ethereal oxygen atom.
The number of carbon atoms of the alkylene group which may have an etheric oxygen atom represented by Q ⁵¹ is 1 to 10 preferably 1 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 preferable (however, the right side is bonded to Si).

e is 0 or 1.

Q ⁵² 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.
When the alkylene group has a divalent organopolysiloxane residue, it is preferable to have this group at the end between carbon atoms or the side opposite to the side where Si is bonded.
The carbon number of the alkylene group represented by Q ⁵² is preferably 1 to 10, and particularly preferably 1 to 6.
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.).

The three [-(Q ⁵² ) _e -CH = CH ₂ ] may be the same or different.

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

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

Q ⁶¹ is a alkylene group which may have an etheric oxygen atom.
The number of carbon atoms of the alkylene group which may have an etheric oxygen atom represented by Q ⁶¹ is 1 to 10 preferably 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 binds to Z ³ ).

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

v2 is 0 or 1.

Q ⁶² is a divalent organopolysiloxane residue, or a alkylene group which may have an etheric oxygen atom.
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.
The Q ^62, from the viewpoint of easily producing the compound, -CH ₂ - are preferred.

The w [-(Q ⁶² ) _v2 -CH = CH ₂ ] may be the same or different.

(Compound B)
The number of hydrogen atoms bonded to silicon atoms in compound B is preferably 1 to 3, particularly preferably 1.

Compound B is preferably compound 3.
H-SiR _n L _3-n (3)

R is a monovalent hydrocarbon group, and a monovalent saturated hydrocarbon group is preferable. The number of carbon atoms 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 that becomes a hydroxyl group by the hydrolysis reaction. That is, the hydrolyzable group becomes a hydroxyl group by the hydrolysis reaction. The hydroxyl groups bonded to the silicon atom further react between the hydroxyl groups bonded to the silicon atom to form a Si—O—Si bond. Further, the hydroxyl group bonded to the silicon atom can form a chemical bond (base material-O-Si) by dehydration condensation reaction with the hydroxyl group (base material-OH) on the surface of the base material.

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

n is an integer from 0 to 2.
n is preferably 0 or 1, and 0 is particularly preferable. The presence of a plurality of L makes the adhesion of the surface layer to the base material stronger.
When n is 1 or less, the plurality of Ls present in one molecule may be the same or different from each other. From the viewpoint of availability of raw materials and ease of production, they are preferably the same.

Compound 3 includes 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 preferable.

(Compound C)
Compound C preferably has a hydrolyzable group bonded to a silicon atom because 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 has excellent abrasion resistance.

As compound C, compound 4 is preferable.
[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, when A ² is −Q [−C ₂ H _{4 −} SiR _n L _3-n ] _k , j is 1.
The definitions of the other groups are as described above.

As the compound 4, 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 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 definitions of each group in the formulas (5-1) and (5-2) are as described above.

Further, 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 definitions of each group in the formulas (5-1-1) and (5-1-6) are as described above.

(Hydrosilylation catalyst)
As the hydrosilylation catalyst, a transition metal catalyst is preferable, a group 8 to group 10 transition metal catalyst is more preferable, and a platinum (Pt) catalyst, a ruthenium (Ru) catalyst, a rhodium (Rh) catalyst, and an iron (Fe) catalyst are further preferable. Platinum catalysts and iron catalysts are particularly preferred, preferably because the hydrosilylation reaction proceeds more. The 8th to 10th groups are group numbers according to the revised version of the 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, and a Pt complex of tetramethyltetravinylcyclotetrasiloxane. Examples thereof include platinum chloride acid and platinum oxide.
Specific examples of the iron catalyst include the hydrosilylated iron catalyst described in International Publication No. 2016/027819.
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.

(Other ingredients)
In the synthesis step, components other than the above-mentioned components may be used.
For example, a liquid medium may be used in the synthesis step. That is, the reaction of compound A and compound B may be carried out in the presence of a liquid medium.
Examples of the liquid medium include water and an organic solvent. Specific examples of the organic solvent include a fluorine-based organic solvent and a non-fluorine-based organic solvent.
The organic solvent may be used alone or in combination of two or more.

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 (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, 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, (Made by 3M).
Specific examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
Specific examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.

As the non-fluorine-based organic solvent, a compound consisting of only hydrogen atoms and carbon atoms and a compound consisting of only hydrogen atoms, carbon atoms and oxygen atoms are preferable, and specifically, a hydrocarbon-based organic solvent and a ketone-based organic solvent are used. , Ether-based organic solvent, ester-based organic solvent can be mentioned.
As the hydrocarbon-based organic solvent, hexane, heptane, cyclohexane and the like are preferable.
As the ketone-based organic solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone and the like are preferable.
As the ether-based organic solvent, diethyl ether, tetrahydrofuran, tetraethylene glycol dimethyl ether and the like are preferable.
As the ester-based organic solvent, ethyl acetate, butyl acetate and the like are preferable.

In addition, a dislocation inhibitor may be used in the synthesis step. That is, the reaction of compound A and compound B may be carried out in the presence of a dislocation inhibitor. Examples of the dislocation inhibitor include the compounds described in paragraph 0115 of WO2014 / 069592.

[Filtration process]
(filter)
The water content of the filter is a 2.5 g / ^{m 2} or less, from the viewpoint of the initial water repellency of the surface layer is further improved, preferably 1.5 g / ^{m 2} or less, more preferably 1.0 g / ^{m 2} or less , 0.5 g / m ² or less is more preferable, and 0 g / m ² is particularly preferable.

The water content (g / m ² ) of the filter in the present invention is calculated based on the filter mass before and after the following water content measurement process is performed.
First, a filter used for filtration in this production method (hereinafter, also referred to as “filter A”) is prepared. Next, after passing nitrogen gas through the filter A and replacing the gas held in the filter A with nitrogen gas, water vapor is detected from the gas detector tube (manufactured by Gastec, product name "No. 6L"). Filter A is heated at 100 ° C. (water content measurement treatment) until no more, and filter B is obtained.
Then, based on the masses of the filter A and the filter B, the water content of the filter is calculated by the following formula. In the following equation, the “filtration area” means the surface area of the filter at the portion where the object to be filtered comes into contact with the filter during filtration. The masses of the filter A and the filter B are arithmetic mean values obtained by weighing each filter three times.
Water content of filter (g / m ² ) = [{mass of filter A (g)}-{mass of filter B (g)}] / filtration area (m ² )
The water content of the filter during drying can be calculated based on the mass and water content of the filter A and the mass of the filter B.

Specific examples of the materials constituting the filter include metal, carbon, glass, cellulose, polyamide, polyester, polycarbonate, polyolefin (for example, polyethylene (PE), polypropylene (PP)), polytetrafluoroethylene (PTFE), and polyvinylidene fluoride. Includes floride (PVDF) and polychlorotrifluoroethylene (PCTFE). PTFE and PVDF are preferable because they have a low water content without performing treatments such as heat treatment and nitrogen substitution treatment, which will be described later, and they are not easily deteriorated even when they come into contact with compound C or a liquid medium, and also have an impurity removal performance. PTFE is particularly preferred because of its superiority.
Specific examples of the filter include paper, cloth (for example, non-woven fabric, woven fabric, knitted fabric), metal filter, sintered filter, membrane (membrane), hollow fiber membrane, and paper, which is excellent in removing impurities. Membranes and hollow fiber membranes are preferable.
The pore diameter (opening diameter) of the filter is preferably 0.01 to 1,000 μm, more preferably 0.05 to 100 μm, and particularly 0.1 to 10 μm, from the viewpoint of excellent balance between impurity removal performance and filtration efficiency. preferable.

The filtration pressure is preferably 0 to 2.0 MPa, particularly preferably 0.05 to 0.5 MPa, from the viewpoint of excellent productivity and handling.

The filter may satisfy the above range of water content when the present production method is used, and the water content of the filter may be outside the above range before use such as during storage.
As a method of adjusting the water content of the filter within the above range, for example, a method of subjecting the filter to a drying treatment can be mentioned. The drying treatment of the filter is preferably carried out when the water content of the filter is outside the above range, but is carried out even when the water content of the filter is within the above range for the purpose of further reducing the water content of the filter. May be done.
The drying treatment may be carried out before the filtration step, and specifically, it may be carried out at any timing before the synthesis step, during the synthesis step, or after the synthesis step.
Specific examples of the drying treatment include a nitrogen substitution treatment in which nitrogen gas is passed through the filter and a heat treatment in which the filter is heated. As a result, the water content of the filter can be reduced, so that the initial water repellency of the surface layer is further improved.
Specifically, if the nitrogen substitution treatment of the filter is carried out, the gas held in the filter (for example, air containing water vapor) is replaced with nitrogen gas, so that the water content of the filter can be reduced. Further, the nitrogen substitution treatment can remove the dust held in the filter, so that the filtration efficiency of the filter is improved.
Further, if the heat treatment of the filter is carried out, the water content retained in the filter evaporates, so that the water content of the filter can be reduced.
From the viewpoint that the effect of the present invention is more exerted, the filter after the drying treatment is immediately (for example, until the difference in water content of the filter before and after the nitrogen substitution treatment becomes 1.5 g / m ² ). It is preferably used for filtration of compound C.

Either one of the nitrogen substitution treatment and the heat treatment may be carried out, or both may be carried out, but it is preferable to carry out both treatments from the viewpoint of more exerting the effects of the present invention.
When both treatments are carried out, the order of carrying out the nitrogen substitution treatment and the heat treatment is not particularly limited, and the heat treatment may be carried out after the nitrogen substitution treatment, or the nitrogen substitution treatment may be carried out after the heat treatment. , Both processes may be carried out at the same time.

Compound C used in the filtration step may be used as a filtration solution containing compound C.
When a liquid medium is used in the step of synthesizing compound C, the filtration solution may be a mixed solution containing the synthesized compound C and the liquid medium as it is. A liquid medium may be further added to the mixed solution for use. When a liquid medium is not used in the step of synthesizing compound C, the liquid medium may be added to the mixture containing the compound C after synthesis.
Specific examples of the liquid medium are the same as those of the liquid medium in the above synthesis step, and thus the description thereof will be omitted. The liquid medium may be used alone or in combination of two or more.

The content of the liquid medium is preferably 30 to 99% by mass, particularly preferably 40 to 95% by mass, based on the total mass of the filtration solution.
The content of compound C is preferably 1 to 70% by mass, particularly preferably 5 to 60% by mass, based on the total mass of the filtration solution.

[Other processes]
In the present production method, the compound C may be brought into contact with the adsorbent after the synthesis step of the compound C and before the filtration step. By adsorption, the catalyst and the like present together with compound C can be removed.
Specific examples of the adsorbent include activated carbon, molecular sieve, and zeolite.

[Manufacturing method of goods]
Compound C obtained by this production method (that is, compound C after filtration) can be used to form a surface layer on the surface of the substrate.
More specifically, by using the above-mentioned compound C or a composition containing the compound C and a liquid medium (hereinafter, also referred to as “composition”), the base material can be used under any production conditions of dry coating and wet coating. A surface layer having excellent initial water repellency can be formed on the surface of the surface. That is, an article having a base material and a surface layer formed from the compound C or the composition arranged on the surface of the base material can be produced.
The content of compound C in the composition is preferably 0.01 to 50.00% by mass, particularly preferably 1.0 to 30.00% by mass, based on 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, based on the total mass of the composition.

The base material is not particularly limited as long as it is a base material that is required to be provided with water and oil repellency. Specific examples of the material of the base material include metal, resin, glass, sapphire, ceramic, stone, and composite materials thereof. The glass may be chemically strengthened. The base material may be surface-treated with SiO ₂ or the like.
As the base material, a touch panel base material and a display base material are preferable, and a touch panel base material is more preferable. The base material for the touch panel preferably has translucency. “Having translucency” means that the vertically incident visible light transmittance according to JIS R3106: 1998 (ISO 9050: 1990) is 25% or more. As the material of the base material for the touch panel, glass or a transparent resin is preferable.

The article can be manufactured, for example, by the following method.
A method for obtaining the above-mentioned article by treating the surface of a base material by a dry coating method using compound C or a composition.
-A method in which the composition is applied to the surface of a base material by a wet coating method and dried to obtain the above-mentioned 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 compound C and the simplicity of the apparatus. At the time of vacuum deposition, a pellet-like substance obtained by impregnating a metal porous body such as iron or steel with compound C or a 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, inkjet method, flow coating method, roll coating method, casting method, Langmuir Brodget. The method and the gravure coat method can be mentioned.

The surface layer formed by the above procedure contains a compound obtained through a hydrolysis reaction and a condensation reaction of compound C.
The film thickness of the surface layer is preferably 1 to 100 nm, particularly preferably 1 to 50 nm. The thickness of the surface layer is determined by obtaining an interference pattern of reflected X-rays by the X-ray reflectivity method using an X-ray diffractometer for thin film analysis (ATX-G manufactured by RIGAKU), and from the vibration cycle of this interference pattern. 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. The blending amount of each component indicates the mass standard. Of Examples 1 to 8, Examples 3 to 8 are Examples, and Examples 1 to 2 are Comparative Examples. Further, among Examples 9A, 9B, 10A, 10B, 11A, 11B, 12A and 12B, Examples 9B, 10B, 11B and 12B are Examples, and Examples 9A, 10A, 11A and 12A are Comparative Examples.

〔Evaluation method〕
(Measurement method of contact angle)
The contact angle of about 2 μL of distilled water or n-hexadecane placed on the surface of the surface layer was measured using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., product name “DM-500”). Measurements were made at five different points on the surface of the surface layer, and the average value was calculated. The 2θ method was used to calculate the contact angle.

<Initial contact angle>
For the surface layer, the initial contact angles of water and n-hexadecane were measured by the above measuring method. The evaluation criteria are as follows.
<< Initial contact angle of water >>
◎ (excellent): 115 degrees or more ○ (good): 110 degrees or more and less than 115 degrees △ (possible): 100 degrees or more and less than 110 degrees × (impossible): less than 100 degrees << initial contact angle of n-hexadecane >>
◎ (excellent): 66 degrees or more ○ (good): 65 degrees or more and less than 66 degrees △ (possible): 63 degrees or more and less than 65 degrees × (impossible): less than 63 degrees

(Abrasion resistance)
For the surface layer, use a reciprocating traverse tester (manufactured by KNT) in accordance with JIS L0849: 2013 (ISO 105-X12: 2001), and use a steel wool bonster (# 0000) with a pressure of 98.07 kPa and a speed of 320 cm. After reciprocating 10,000 times at / minute, the contact angle of water was measured. The smaller the decrease in the contact angle of water after rubbing, the smaller the decrease in performance due to friction, and the better the friction resistance.
◎ (Excellent): Change in water contact angle after 10,000 round trips is 5 degrees or less ○ (Good): Change in water contact angle after 10,000 round trips is more than 5 degrees and 10 degrees or less △ (Yes): 10,000 Change in water contact angle after round trip is more than 10 degrees and less than 20 degrees × (impossible): Change in water contact angle after 10,000 round trips is more than 20 degrees

(chemical resistance)
<Alkali resistance>
The article was immersed in a 1N aqueous NaOH solution (pH = 14) for 5 hours, washed with water, air-dried, and the water contact angle was measured by the above method. The smaller the decrease in water contact angle after the test, the smaller the decrease in performance due to alkali, and the better the alkali resistance. The evaluation criteria are as follows.
◎ (Excellent): Change in water contact angle after alkali resistance test is 5 degrees or less 〇 (Good): Change in water contact angle after alkali resistance test is more than 5 degrees and 10 degrees or less △ (Yes): After alkali resistance test The change in water contact angle is more than 10 degrees and less than 20 degrees × (impossible): The change in water contact angle after alkali resistance test is more than 20 degrees <salt water resistance>
A salt spray test was conducted in accordance with JIS H8502. That is, after the article was exposed to a salt water atmosphere in a salt spray tester (manufactured by Suga Test Instruments Co., Ltd.) for 300 hours, the water contact angle was measured by the above method. The smaller the decrease in the water contact angle after the test, the smaller the decrease in performance due to salt water, and the better the salt water resistance. The evaluation criteria are as follows.
◎ (Excellent): Change in water contact angle after salt spray test is 5 degrees or less ○ (Good): Change in water contact angle after salt spray test is more than 5 degrees and 10 degrees or less △ (Yes): After salt spray test Change in water contact angle is more than 10 degrees and less than 20 degrees × (impossible): Change in water contact angle after salt spray test is more than 20 degrees

(Fingerprint stain removal property)
After adhering an artificial fingerprint liquid (a liquid consisting of oleic acid and squalene) to the flat surface of a silicon rubber stopper, wipe off excess oil with a non-woven fabric (Bencot (registered trademark) M-3 manufactured by Asahi Kasei Corporation). I prepared a fingerprint stamp. The fingerprint stamp was placed on the surface layer and pressed under a load of 9.8 N for 10 seconds. The haze at the place where the fingerprint was attached was measured with a haze meter and used as the initial value. Next, the portion to which the fingerprint was attached was wiped off with a load of 4.9 N using a reciprocating traverse tester (manufactured by KNT) equipped with tissue paper. The value of haze was measured for each round trip of wiping, and the number of times of wiping that haze became 10% or less from the initial value was measured. The smaller the number of wipes, the easier it is to remove fingerprint stains, and the better the fingerprint stain wiping performance. The evaluation criteria are as follows.
◎ (Excellent): The number of wipes is 3 or less ○ (Good): The number of wipes is 4 to 5 △ (Yes): The number of wipes is 6 to 8 × (No): The number of wipes is 9 or more

[Example 1]
Compound C-1 was synthesized according to the method described in Synthesis Example 3 of WO2017 / 022437. Specifically, it is a compound having a poly (oxyperfluoroalkylene) chain and an ω-alkenyl group (the following perfluoropolyether group-containing allyloxy compound (B)) and a compound having a hydrolyzable group bonded to a silicon atom. A certain trichlorosilane was reacted 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 used as a methoxy group. Substitution gave compound C-1. The obtained compound C-1 was dissolved in Novell 7200 (manufactured by 3M Ltd.) so as to have a concentration of 10% by mass to prepare 100 g of a filtration solution.

Next, the filtration solution was filtered using an untreated filter paper (manufactured by Advantech, product name "No. 5C") to obtain a filtrate containing the filtered compound C-1 and Novec-7200. In this way, compound C-1 (after filtration) according to Example 1 was obtained.
The filtration area of the filter paper was 13.84 cm ² , and the water content of the untreated filter paper was calculated according to the above method and found to be 5.8 g / m ² .

[Examples 2 to 5]
Nitrogen gas was passed through the untreated filter paper used in Example 1 (nitrogen substitution treatment), and the water content was 2.8 g / m ² , 1.5 g / m ² , 0.7 g / m ² , and 0 g / m, respectively. ² filter papers were prepared. Compound C-1 (after filtration) was obtained in the same manner as in Example 1 except that the filter paper having the adjusted water content was used.
The filtration area of the filter paper used in Examples 2 to 5 is the same as that of Example 1, the supply amount of nitrogen gas in the nitrogen substitution treatment is 0.42 m ³ / hour, and the dew point of nitrogen gas is −55 ° C. ..
Here, the water content of the filter paper used in Examples 2 to 5 was calculated according to the following formula. In the following formula, the filter A means untreated filter paper. Further, the filter B means a completely dried filter paper, and specifically, a filter paper dried until water vapor is no longer detected by the gas detector tube described above. Further, the filter C means a filter paper that has been subjected to a nitrogen substitution treatment and partially dried (that is, the filter paper used in Examples 2 to 5).
Water content of filter C (g / cm ² ) = {Water content of filter A (g / cm ² )} × [{Mass of filter C (g)}-{Mass of filter B (g)}] / [{ Filter A mass (g)}-{Filter B mass (g)}]

[Examples 6 to 8]
First, untreated PTFE membrane filter (manufactured by Advantech, trade name "T050A", pore diameter 0.5 μm), untreated PTFE filter paper (manufactured by Advantech, trade name "PF050", pore diameter 0.5 μm), untreated. A PP filter cloth (manufactured by Philis, trade name "filter cloth") was prepared.
Next, nitrogen gas is passed through each filter (nitrogen substitution treatment), and each filter having a water content of 0 g / m ² (meaning a completely dried filter, specifically the above-mentioned gas detector tube). A filter that was dried until no water vapor was detected) was obtained.
Compound C-1 (after filtration) was obtained in the same manner as in Example 1 except that each filter having an adjusted water content was used.

[Preparation of evaluation sample]
Using the compound C-1 (after filtration) obtained in each example, the surface treatment of the base material was performed by the following dry coating method or wet coating method, and a surface layer was formed on the surface of the base material (chemically tempered glass). An evaluation sample formed was obtained.
The following evaluation test was carried out using the obtained evaluation sample, and the results are shown in Table 1.

(Dry coating method)
Dry coating on the substrate was performed using a vacuum vapor deposition apparatus (VTR-350M, manufactured by ULVAC, Inc.). Specifically, first, 0.5 g of the compound C-1 (after filtration) obtained in each example was filled in a molybdenum-based boat in the vacuum vapor deposition apparatus, and the inside of the vacuum vapor deposition apparatus was 1 × 10 ^-3 Pa or less. Exhausted to. The boat on which compound C-1 is placed is heated at a heating rate of 10 ° C./min or less, and when the vapor deposition rate by the crystal oscillation type film thickness meter exceeds 1 nm / sec, the shutter is opened to the surface of the substrate. Film formation was started. When the film thickness reached about 50 nm, the shutter was closed to complete the film formation on the surface of the substrate. The base material on which compound C-1 is deposited is heat-treated at 200 ° C. for 30 minutes and then washed with Asahiclean AK-225 (trade name, manufactured by Asahi Glass Co., Ltd.) to evaluate having a surface layer on the surface of the base material. A sample (article) was obtained.

(Wet coating method)
The filtrate of the example was mixed with Novec-7200 to obtain a composition for wet coating in which the concentration of compound C-1 was 0.05% by mass.
The base material was dipped into each composition, left for 30 minutes, and then the base material was pulled up (dip coating method). The coating film was dried at 200 ° C. for 30 minutes and washed with AK-225 to obtain an evaluation sample (article) having a surface layer on the surface of the substrate.

As shown in Table 1, by using a fluorine-containing ether compound filtered using a filter having a water content of 2.5 g / m ² or less, a surface layer having excellent initial water repellency under both dry coating and wet coating production conditions. Was shown to be able to form (Examples 3-8).
On the other hand, when a fluorine-containing ether compound filtered using a filter having a water content of more than 2.5 g / m ² is used, the initial water repellency of the surface layer obtained under either the dry coating or wet coating production condition is inferior. Was shown (Examples 1 and 2).

[Example 9]
The following compound C-2 was synthesized according to the method described in Example 3 of WO2017 / 038832. However, the average value of the number of units x3 was 13, and the number average molecular weight of compound C-2 was 4,780.
C-2: CF _3- O- (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _x3 (CF ₂ CF ₂ O) -CF ₂ CF ₂ CF ₂ CH _2- N [CH ₂ CH ₂ CH _2- Si (OCH ₃ ) ₃ ] ₂
The obtained compound C-2 was dissolved in Novell 7200 (manufactured by 3M Ltd.) so as to have a concentration of 10% by mass to prepare 100 g of a filtration solution.
Similar to Example 1, the filtration solution is filtered using untreated filter paper (manufactured by Advantech, product name “No. 5C”) to obtain a filtrate containing the filtered compound C-2 and Novec-7200. It was. In this way, compound C-2 (after filtration) according to Example 9A was obtained. The water content of the filter paper was 8.2 g / m ² .
Further, nitrogen gas was passed through an untreated PTFE membrane filter (manufactured by Advantech, trade name "T050A", pore size 0.5 μm) to obtain a filter having a water content of 0 g / m ² . Compound C-2 (after filtration) according to Example 9B was obtained in the same manner as in Example 9A except that a filter having an adjusted water content was used.

[Example 10]
The following compound C-3 was synthesized according to the methods described in Synthesis Example 2 and Synthesis Example 4 of Japanese Patent No. 5761305.
_{C-3: CF 3 CF 2} CF 2 -O- (CF 2 CF 2 CF 2 O) 20 -CF 2 CF 2 CH 2 OCH 2 CH 2 CH 2 -Si [CH 2 CH 2 CH 2 -Si (OCH 3 ) ₃ ] ₃
The obtained compound C-3 was dissolved in Novell 7200 (manufactured by 3M Ltd.) so as to have a concentration of 10% by mass to prepare 100 g of a filtration solution.
As in Example 1, the filtration solution is filtered using untreated filter paper (manufactured by Advantech, product name “No. 5C”) to obtain a filtrate containing the filtered compound C-3 and Novec-7200. It was. In this way, compound C-3 (after filtration) according to Example 10A was obtained. The water content of the filter paper was 5.5 g / m ² .
Further, nitrogen gas was passed through an untreated PTFE membrane filter (manufactured by Advantech, trade name "T050A", pore size 0.5 μm) to obtain a filter having a water content of 0 g / m ² . Compound C-3 (after filtration) according to Example 10B was obtained in the same manner as in Example 10A except that a filter having an adjusted water content was used.

[Example 11]
The following compound C-4 was synthesized according to the method described in Example 1 of JP-A-2015-199906. However, p1: q1 = 47: 53, and p1 + q1 was about 43.
C-4: CF ₃ O- (CF ₂ O) _p1- (CF ₂ CF ₂ O) _q1- CF ₂ C (OH) [CH ₂ CH ₂ CH _2- Si (OCH ₃ ) ₃ ] ₂
The obtained compound C-4 was dissolved in Novell 7200 (manufactured by 3M Ltd.) so as to have a concentration of 10% by mass to prepare 100 g of a filtration solution.
As in Example 1, the filtration solution is filtered using untreated filter paper (manufactured by Advantech, product name “No. 5C”) to obtain a filtrate containing the filtered compound C-4 and Novec-7200. It was. In this way, compound C-4 (after filtration) according to Example 11A was obtained. The water content of the filter paper was 4.5 g / m ² .
Further, nitrogen gas was passed through an untreated PTFE membrane filter (manufactured by Advantech, trade name "T050A", pore size 0.5 μm) to obtain a filter having a water content of 0 g / m ² . Compound C-4 (after filtration) according to Example 11B was obtained in the same manner as in Example 11A except that a filter having an adjusted water content was used.

[Example 12]
The following compound C-5 was synthesized according to the method described in Example 7 of WO2017 / 038832. However, the average value of the number of units x1 was 21, and the average value of the number of units x2 was 20.
C-5: [(CH ₃ O) ₃ Si-CH ₂ CH ₂ CH ₂ ] ₂ N-CH _2- (CF ₂ O) {(CF ₂ O) _{X 1} (CF ₂ CF ₂ O) _{X 2} } CF ₂ − CH _2- N [CH ₂ CH ₂ CH _2- Si (OCH ₃ ) ₃ ] ₂
The obtained compound C-5 was dissolved in Novell 7200 (manufactured by 3M Ltd.) so as to have a concentration of 10% by mass to prepare 100 g of a filtration solution.
As in Example 1, the filtration solution is filtered using untreated filter paper (manufactured by Advantech, product name “No. 5C”) to obtain a filtrate containing the filtered compound C-5 and Novec-7200. It was. In this way, compound C-5 (after filtration) according to Example 12A was obtained. The water content of the filter paper was 6.0 g / m ² .
Further, nitrogen gas was passed through an untreated PTFE membrane filter (manufactured by Advantech, trade name "T050A", pore size 0.5 μm) to obtain a filter having a water content of 0 g / m ² . Compound C-5 (after filtration) according to Example 12B was obtained in the same manner as in Example 12A except that a filter having an adjusted water content was used.

[Preparation of evaluation sample]
Using the compounds C-2 to 5 (after filtration) obtained in each example, the surface treatment of the base material was performed by the dry coating method or the wet coating method in the same manner as in Example 1, and the base material (chemically tempered glass) was subjected to surface treatment. An evaluation sample was obtained in which a surface layer was formed on the surface of the glass. An evaluation test was carried out using the obtained evaluation sample. The results are shown in Table 2.

As shown in Table 2, by using a fluorine-containing ether compound filtered using a filter having a water content of 2.5 g / m ² or less, a surface layer having excellent initial water repellency under both dry coating and wet coating production conditions. Was shown to be able to form (Examples 9B, 10B, 11B, 12B).
On the other hand, when a fluorine-containing ether compound filtered using a filter having a water content of more than 2.5 g / m ² is used, the initial water repellency of the surface layer obtained under either the dry coating or wet coating production condition is inferior. Was shown (Examples 9A, 10A, 11A, 12A).

The fluorine-containing ether compound obtained by this production method can be used in various applications in which lubricity and water / oil repellency are required. For example, a coat for display input devices such as touch panels; a surface protective coat for transparent glass or transparent plastic members, an antifouling coat for kitchens; a water-repellent and moisture-proof coat for electronic devices, heat exchangers, batteries, etc. Antifouling coat for toiletries; Coat for members that require liquid repellency while conducting; Water-repellent / waterproof / water-sliding coat for heat exchangers; Can be used for vibration sieving, low-friction coating on the surface of cylinders, etc. More specific examples of use include a display front protective plate, an antireflection plate, a polarizing plate, an antiglare plate, or a surface of which an antireflection film treatment is applied, and a touch panel of a device such as a mobile phone or a mobile information terminal. Coats of various devices that have display input devices such as sheets and touch panel displays that operate on the screen with human fingers or palms, coats of decorative building materials around water such as toilets, baths, washrooms, kitchens, waterproofing for wiring boards Coating, water-repellent / waterproof / sliding coat for heat exchangers, water-repellent coat for solar cells, waterproof / water-repellent coat for printed wiring boards, waterproof / water-repellent coat for electronic device housings and electronic parts, insulation of power transmission lines Performance improvement coat, waterproof / water repellent coat for various filters, waterproof coat for radio wave absorbers and sound absorbing materials, antifouling coat for baths, kitchen equipment, toiletries, surface low friction coat for vibration sieves and cylinder interiors, mechanical parts, etc. Examples include surface protective coatings for vacuum equipment parts, bearing parts, automobile parts, tools and the like.

Claims (8)

Either 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, or a hydroxyl group bonded to a silicon atom in the presence of a hydrosilylation catalyst. By reacting with a compound having one or both, a fluorine-containing ether compound having either one or both of a poly (oxyperfluoroalkylene) chain and a hydrolyzable group bonded to a silicon atom and a hydroxyl group bonded to a silicon atom is obtained. A method for producing a fluorine-containing ether compound, which comprises filtering the fluorine-containing ether compound using a filter having a water content of 2.5 g / m ² or less after obtaining the compound. The production method according to claim 1, wherein the material constituting the filter is polytetrafluoroethylene. The manufacturing method according to claim 1 or 2, wherein the filter is a filter that has been subjected to a drying treatment. The production method according to claim 3, wherein the drying treatment includes a treatment for passing nitrogen gas. The production method according to claim 3 or 4, wherein the drying treatment includes a heating treatment. The production method according to any one of claims 1 to 5, wherein the water content of the filter is 1.5 g / m ² or less. The production method according to any one of claims 1 to 6, wherein the water content of the filter is 1.0 g / m ² or less. Production of an article characterized by forming a surface layer on the surface of a substrate by using the fluorine-containing ether compound obtained by the method for producing a fluorine-containing ether compound according to any one of claims 1 to 7. Method.