CN111032731B

CN111032731B - Method for producing fluorine-containing ether compound, and method for producing article

Info

Publication number: CN111032731B
Application number: CN201880053389.2A
Authority: CN
Inventors: 高尾清贵; 青山元志; 富依勇佑
Original assignee: Asahi Glass Co Ltd
Current assignee: AGC Inc
Priority date: 2017-08-18
Filing date: 2018-07-06
Publication date: 2022-06-24
Anticipated expiration: 2038-07-06
Also published as: CN111032731A; JP2020045498A; WO2019035288A1; JPWO2019035288A1; JP6635229B2

Abstract

A method for producing a fluorine-containing ether compound and a method for producing an article, which can form a surface layer having excellent abrasion resistance and in which the generation of particulate matter is suppressed. A process for producing a fluorine-containing ether compound, characterized by reacting a compound having a poly (oxyperfluoroalkylene) chain and an omega-alkenyl group with a compound having a hydrogen atom bonded to a silicon atom and having at least one of a hydrolyzable group bonded to a silicon atom and a hydroxyl group bonded to a silicon atom in the presence of a hydrosilylation catalyst to produce a fluorine-containing ether compound having a poly (oxyperfluoroalkylene) chain and having at least one of a hydrolyzable group bonded to a silicon atom and a hydroxyl group bonded to a silicon atom, 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 mass% or less, or is reacted in the presence of a hydrosilylation catalyst and an adsorbent having a water content of 1.0 mass% or less.

Description

Method for producing fluorine-containing ether compound, and method for producing article

Technical Field

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

Background

The fluorine-containing compound exhibits high lubricity, water/oil repellency, and the like, and is therefore suitably used for a surface treatment agent. When the surface treatment agent imparts water-and oil-repellency to the surface of the substrate, stains on the surface of the substrate can be easily wiped off, and the stain 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-) exists in a perfluoroalkylene chain is a compound having excellent flexibility, and particularly excellent in stain removal properties such as fats and oils.

The surface treatment agent containing the fluorine-containing ether compound is required to be used for applications in which the following properties are maintained for a long period of time, for example, a surface treatment agent used as a member constituting a finger touch surface of a touch panel: the performance (rub resistance) that the water-and oil-repellency is not easily reduced even by repeated rubbing with a finger, and the performance (fingerprint stain removability) that fingerprints adhering to the surface can be easily removed by wiping.

As the above-mentioned fluorine-containing ether compound, a compound having a poly (oxyperfluoroalkylene) chain and having a hydrolyzable group bonded to a silicon atom at the terminal, which is obtained by reacting a compound having a poly (oxyperfluoroalkylene) chain with an alkoxysilane, is widely used (patent document 1).

Documents of the prior art

Patent document

Patent document 1: international publication No. 2014/163004

Disclosure of Invention

Problems to be solved by the invention

In recent years, the physical properties required for a surface layer formed using a surface treatment agent containing a fluorine-containing ether compound have been further improved.

The present inventors have found that, when a surface layer is formed on the surface of a base material using the surface treatment agent containing a fluorine-containing ether compound described in patent document 1, the rubbing resistance of the surface layer may be insufficient, or particulate matter derived from aggregates may be generated, and the appearance characteristics of the surface layer may be poor.

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 are capable of forming a surface layer having excellent abrasion resistance and in which the generation of particulate matter is suppressed.

Means for solving the problems

The present invention provides a method for producing a fluorine-containing ether compound having the following configurations [1] to [10], and a method for producing an article.

[1] A process for producing a fluorine-containing ether compound, characterized by reacting a compound having a poly (oxyperfluoroalkylene) chain and an omega-alkenyl group with a compound having a hydrogen atom bonded to a silicon atom and having at least one of a hydrolyzable group bonded to the silicon atom and a hydroxyl group bonded to the silicon atom in the presence of a hydrosilylation catalyst to produce a fluorine-containing ether compound having a poly (oxyperfluoroalkylene) chain and having at least one of a hydrolyzable group bonded to the silicon atom and a hydroxyl group bonded to the silicon atom,

in the method, 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,

The reaction is carried out in the presence of the hydrosilylation catalyst and the adsorbent having a water content of 1.0 mass% or less.

[2] The production method according to item [1], wherein the water content of the adsorbent is 0.1 mass% or less.

[3] The production method according to [1] or [2], wherein the adsorbent is activated carbon, a molecular sieve, silica gel, or diatomaceous earth.

[4] The production process according to any one of [1] to [3], wherein the hydrosilylation catalyst is a group 8 to group 10 transition metal catalyst.

[5] The production 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).

[A¹-O-Z¹-(R^fO)_m-]_jZ²[-CH＝CH₂]_q (1)

Wherein A is¹Is perfluoroalkyl or-Q [ -CH ═ CH-₂]_k，A¹is-Q [ -CH ═ CH₂]_kWhen the number of the adjacent groups is j is 1,

q is a (k +1) -valent linking group, k is an integer of 1 to 10,

Z¹a C1-20 oxyfluoroalkylene group in which 1 or more hydrogen atoms are replaced with a fluorine atom (excluding oxyperfluoroalkylene groups, the oxygen atom in the oxyfluoroalkylene group and (R)^fO)_mAnd (4) bonding. ) Or poly (oxyfluoroalkylene) having 1 to 20 carbon atoms in which 1 or more hydrogen atoms are replaced by fluorine atoms (and (R)^fO)_mOxygen atom of bonded oxyfluoroalkylene group with (R)^fO)_mAnd (4) bonding. And (R)^fO)_mThe bonded oxyfluoroalkylene group contains 1 or more hydrogen atoms. Poly (oxyfluoroalkylene) optionally comprising: both oxyperfluoroalkylene groups in which all hydrogen atoms are replaced with fluorine atoms and oxyfluoroalkylene groups containing 1 or more hydrogen atoms. ),

R^fis a perfluoroalkylene group, m is an integer of 2 to 200, (R)^fO)_mIn which 2 or more kinds of R having different carbon numbers are present^fWhen O is present, each R^fThe bonding order of O is not limited,

Z²is a linking group having a valence of (j + q), and j and q are each an integer of 1 or more.

[6] The production method according to any one of [1] to [5], wherein the compound having a hydrogen atom bonded to a silicon atom and at least one of 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).

H-SiR_nL_3-n(3)

Wherein R is a 1-valent hydrocarbon group, L is a hydrolyzable group or a hydroxyl group, n is an integer of 0 to 2, when n is 0 or 1, a plurality of L's present in 1 molecule are optionally the same or different from each other, and when n is 2, 2R's present in 1 molecule are optionally the same or different from each other.

[7] The production method according to [6], wherein n is 0 or 1, and L's are each a hydrolyzable group.

[8] The production method according to any one of [1] to [7], wherein the adsorbent is used in an amount of 1 to 30% by mass based on the total mass of the compound having a poly (oxyperfluoroalkylene) chain and an ω -alkenyl group.

[9] The production method according to any one of [1] to [8], wherein the fluorine-containing ether compound is obtained and then the fluorine-containing ether compound is brought into contact with an adsorbent having a water content of 1.0 mass% or less in a liquid medium.

[10] A method for producing an article, characterized in that a surface layer is formed 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 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a method for producing a fluorine-containing ether compound and a method for producing an article, which can form a surface layer having excellent abrasion resistance and in which the generation of particulate matter is suppressed, can be provided.

Detailed Description

In the present specification, the compound represented by formula (1) is referred to as compound 1. The compounds represented by the other formulae are also described in the same manner. The group represented by formula (1) is designated as group 1. Groups represented by other formulae are also described similarly.

In the present specification, "alkylene group optionally has group A" means that an alkylene group optionally has group A between carbon atoms in the alkylene group and carbon atoms, and optionally has group A at the terminal as in the case of alkylene-A group-.

The terms used in the present invention have the following meanings.

"etheric oxygen atom" means an oxygen atom forming an ether bond (-O-) between carbon atoms.

The "2-valent organopolysiloxane residue" is a group represented by the following formula. R in the formula^aIs an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group. G1 is an integer of 1 or more, preferably an integer of 1 to 9, and particularly preferably an integer of 1 to 4.

"Siliphenylene backbone" is-Si (R)^b)₂PhSi(R^b)₂- (wherein Ph is phenylene, R)^bIs a 1-valent organic group. ) The radicals shown. As R^bPreferably an alkyl group (preferably having 1 to 10 carbon atoms).

"Dialkylsilylene" is-Si (R)^c)₂- (wherein, R)^cIs an alkyl group (preferably having 1 to 10 carbon atoms). ) The groups shown.

The "hydrolyzable silyl group" is a group formed by a silicon atom to which a hydrolyzable group is bonded.

"silanol group" is a hydroxyl group bonded to a silicon atom.

The "surface layer" refers to a layer formed on the surface of the substrate.

The "number average molecular weight" of the fluorine-containing ether compound was calculated by the following method using NMR analysis.

By using¹H-NMR and¹⁹F-NMR was calculated by obtaining the number (average value) of oxyperfluoroalkylene groups based on the terminal groups.

The production method of the present invention (hereinafter, also referred to as "the present production method") is characterized by using an adsorbent having a predetermined water content.

The present inventors have found that water is involved in the reason why a desired effect cannot be obtained by using a fluorine-containing ether compound obtained by a conventional production method. More specifically, in the method described in patent document 1, after the production of the fluorine-containing ether compound, the fluorine-containing ether compound is brought into contact with an adsorbent such as activated carbon. When the water content in the adsorbent is high, the hydrolyzable group bonded to the silicon atom in the fluorine-containing ether compound undergoes a hydrolysis reaction, and then undergoes a condensation reaction to form an aggregate. As a result, particulates were observed on the formed surface layer to deteriorate the appearance characteristics, and the rubbing resistance was also deteriorated. The present inventors have solved the above problems by controlling the water content of the adsorbent based on the above findings.

The present production method is characterized by being a method for producing compound C as follows: a compound having a poly (oxyperfluoroalkylene) chain and an ω -alkenyl group (hereinafter, also referred to as "compound a") and a compound having a hydrogen atom bonded to a silicon atom and at least one of a hydrolyzable group bonded to a silicon atom and a hydroxyl group bonded to a silicon atom (hereinafter, also referred to as "compound B") are reacted with each other in the presence of a hydrosilylation catalyst to produce a fluorine-containing ether compound having a poly (oxyperfluoroalkylene) chain and at least one of a hydrolyzable silyl group and a silanol group (hereinafter, also referred to as "compound C"), and the compound C is obtained, the compound C is brought into contact with an adsorbent having a water content of 1.0 mass% or less (hereinafter, also referred to as "specific adsorbent"), or the reaction is carried out in the presence of a hydrosilylation catalyst and the specific adsorbent.

That is, as the 1 st aspect of the present manufacturing method, the following can be mentioned: compound a and compound B are reacted in the presence of a hydrosilylation catalyst to produce compound C, and the obtained compound C is brought into contact with a specific adsorbent.

As the 2 nd aspect of the present production method, the following aspects can be mentioned: compound a and compound B are reacted in the presence of a hydrosilylation catalyst and a specific adsorbent to produce compound C.

Hereinafter, the materials used in the present manufacturing method will be described in detail first, and the steps of each embodiment will be described in detail later.

[ Compound A ]

The poly (oxyperfluoroalkylene) chain of the compound A is preferably (R) in that the water-and oil-repellency of the surface layer is more excellent^fO)_m(wherein, R^fIs a perfluoroalkylene group, m is an integer of 2 to 200, and R may be 2 or more kinds of R having different carbon numbers^fAnd O. ).

(R^fO)_mThe definitions of (c) are described in detail in the following paragraphs.

Compound a may have multiple omega-alkenyl groups. The number of ω -alkenyl groups in the compound A is preferably 1 to 10, more preferably 1 to 6, particularly preferably 1 to 3.

Examples of the ω -alkenyl group include an allyl group, a vinyl group, and a 3-butenyl group.

The compound a is preferably the compound 1 in that the water-and oil-repellency of the surface layer is more excellent.

[A¹-O-Z¹-(R^fO)_m-]_jZ²[-CH＝CH₂]_q (1)

A¹Is perfluoroalkyl or-Q [ -CH ═ CH₂]_k。

The number of carbons 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.

Wherein A is¹is-Q [ -CH ═ CH₂]_kWhen j is 1.

As the perfluoroalkyl group, CF is mentioned₃-、CF₃CF₂-、CF₃CF₂CF₂-、CF₃CF₂CF₂CF₂-、CF₃CF₂CF₂CF₂CF₂-、CF₃CF₂CF₂CF₂CF₂CF₂-、CF₃CF(CF₃) -and the like.

The perfluoroalkyl group is preferably CF in view of more excellent water and oil repellency of the surface layer₃-、CF₃CF₂-、CF₃CF₂CF₂-。

Q is a (k +1) -valent linking group. k is an integer of 1 to 10. Therefore, examples of Q include a linking group having a valence of 2 to 11.

Examples of Q include an alkylene group optionally having an etheric oxygen atom or a 2-valent organopolysiloxane residue, a carbon atom, a nitrogen atom, a silicon atom, a 2-to 8-valent organopolysiloxane residue, and a compound obtained by removing-CH ═ CH from the following formulae (2-1), (2-2), and (2-1-1) to (2-1-6)₂A group of (1).

Z¹A C1-20 oxyfluoroalkylene group in which 1 or more hydrogen atoms are replaced with a fluorine atom (excluding oxyperfluoroalkylene groups, the oxygen atom in the oxyfluoroalkylene group and (R)^fO)_mAnd (4) bonding. ) Or poly (oxygen) having 1 to 20 carbon atoms wherein 1 or more hydrogen atoms are replaced by fluorine atomsFluoroalkylene) (and (R)^fO)_mOxygen atom of bonded oxyfluoroalkylene group with (R)^fO)_mAnd (4) bonding. And (R)^fO)_mThe bonded oxyfluoroalkylene group contains 1 or more hydrogen atoms. Poly (oxyfluoroalkylene) optionally comprising: both oxyperfluoroalkylene groups in which all hydrogen atoms are replaced with fluorine atoms and oxyfluoroalkylene groups containing 1 or more hydrogen atoms. ). The number of carbon atoms of the oxyfluoroalkylene group or poly (oxyfluoroalkylene) group is preferably 1 to 10.

As Z¹From the viewpoint of ease of production of the compound, a single bond, -CHFCF is preferred₂OCH₂CF₂O-、-CF₂CHFCF₂OCH₂CF₂CF₂O-、-CF₂CF₂CHFCF₂OCH₂CF₂O-、-CF₂CF₂OCHFCF₂OCH₂CF₂O-、-CF₂CF₂OCF₂CF₂OCHFCF₂OCH₂CF₂O-、-CF₂CH₂OCH₂CF₂O-、-CF₂CF₂OCF₂CH₂OCH₂CF₂O- (in the above formula, the left side is represented by the formula A)¹-O bonding. ). As Z¹Particularly preferred is a single bond, -CHFCF₂OCH₂CF₂O-。

R^fIs a perfluoroalkylene group.

The number of carbon atoms of the perfluoroalkylene group is preferably 1 to 6 in terms of more excellent water and oil repellency of the surface layer.

The perfluoroalkylene group may be linear or branched, and is preferably linear in view of further improving the water-and oil-repellency of the surface layer.

In addition, a plurality of R^fMay be the same or different. That is, (R)^fO)_mCan be composed of more than 2 kinds of R with different carbon numbers^fAnd O.

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

(R^fO)_mIn (B), 2 or more kinds of R having different carbon numbers are present^fWhen O is present, each R^fThe bonding order of O is not limited. For example, there are 2R^fIn the case of O, 2 kinds of R^fO may be arranged randomly, alternately, or in blocks.

As (R)^fO)_mFrom the viewpoint of more excellent water-and oil-repellency of the surface layer, { (CF) is preferred₂O)_m11(CF₂CF₂O)_m12(CF₂CF₂CF₂O)_m13(CF₂CF₂CF₂CF₂O)_m14}、(CF₂CF₂O)_m16、(CF₂CF₂CF₂O)_m17、(CF₂CF₂O-CF₂CF₂CF₂CF₂O)_m15(CF₂CF₂O)、(CF₂O-CF₂CF₂CF₂CF₂CF₂O)_m18(CF₂O) or (CF)₂CF₂O-CF₂CF₂CF₂CF₂CF₂CF₂O)_m19(CF₂CF₂O), particularly preferably { (CF)₂O)_m11(CF₂CF₂O)_m12(CF₂CF₂CF₂O)_m13(CF₂CF₂CF₂CF₂O)_m14}、(CF₂CF₂O-CF₂CF₂CF₂CF₂O)_m15(CF₂CF₂O)、(CF₂O-CF₂CF₂CF₂CF₂CF₂O)_m18(CF₂O)、(CF₂CF₂O-CF₂CF₂CF₂CF₂CF₂CF₂O)_m19(CF₂CF₂O)。

Wherein m11 and m12 are each an integer of 1 or more, m13 and m14 are each an integer of 0 or 1 or more, and m11+ m12+ m13+ m14 is 2 to 20Integer of 0, m11 CF₂O, m12 CF₂CF₂O, m13 CF₂CF₂CF₂O, m14 CF₂CF₂CF₂CF₂The bonding order of O is not limited. m16 and m17 are each an integer of 2 to 200, and m15, m18 and m19 are each an integer of 1 to 99.

Z²Is a (j + q) -valent linking group.

Z²Examples thereof include alkylene groups optionally having an etheric oxygen atom or a 2-valent organopolysiloxane residue, carbon atoms, nitrogen atoms, silicon atoms, and 2 to 8-valent organopolysiloxane residues, and those obtained by removing-CH-CH from the following formulae (2-1), formulae (2-2), and formulae (2-1-1) to (2-1-6)₂A group of (1).

j is an integer of 1 or more, and is preferably an integer of 1 to 5 from the viewpoint of more excellent water-and oil-repellency of the surface layer, and particularly preferably 1 from the viewpoint of ease of production of the compound.

q is an integer of 1 or more, and is preferably an integer of 2 to 4, more preferably 2 or 3, and particularly preferably 3, from the viewpoint of further improving water and oil repellency of the surface layer.

The compound 1 is preferably a compound 1-1 in that the water-and oil-repellency of the surface layer is more excellent. A. the¹-O-Z¹-(R^fO)_m-Z³(1-1)

In the formula (1-1), A¹、Z¹、R^fAnd m is as defined for each group in formula (1).

Z³Is a group 2-1 or a group 2-2.

-R^f7-Q^a-X(-Q^b-CH＝CH₂)_h(-R⁷)_i (2-1)

-R^f7-Q⁷¹-[CH₂C(R⁷¹)(-Q⁷²-CH＝CH₂)]_y-R⁷² (2-2)

R^f7Is a perfluoroalkylene group.

The number of carbon atoms of the perfluoroalkylene group is preferably 1 to 30, particularly preferably 1 to 6.

The perfluoroalkylene group may be linear or branched.

As R^f7From the viewpoint of ease of production of the compound, -CF is preferred₂CF₂CF₂CF₂-or-CF₂CF₂CF₂CF₂CF₂-。

Q^aIs a single bond or a 2-valent linking group.

The connecting group having a valence of 2 includes, for example, a hydrocarbon group having a valence of 2 (which may be a saturated hydrocarbon group having a valence of 2, an aromatic hydrocarbon group having a valence of 2, an alkenylene group, or an alkynylene group, the saturated hydrocarbon group having a valence of 2 may be linear, branched, or cyclic, and may include, for example, an alkylene group having a carbon number of preferably 1 to 20, and the aromatic hydrocarbon group having a valence of 2 may preferably have a carbon number of 5 to 20, and may include, for example, a phenylene group, and may further include, in addition to the alkenylene group having a carbon number of 2 to 20, the alkynylene group having a carbon number of 2 to 20), a heterocyclic group having a valence of 2, -O-, -S-, -SO-, -₂-、-N(R^d)-、-C(O)-、-Si(R^a)₂And a group obtained by combining 2 or more of them. Here, R^aIs an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group. R^dIs a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).

Examples of the group obtained by combining 2 or more of the above groups include-OC- (O) -and-C (O) N (R)^d) -, alkylene-O-alkylene, alkylene-OC (O) -alkylene, alkylene-Si (R)^a)₂-phenylene-Si (R)^a)₂。

X is a single bond, alkylene, carbon atom, nitrogen atom, silicon atom or 2-8 valent organopolysiloxane residue.

The alkylene group may have an-O-, silylene skeleton group, a 2-valent organopolysiloxane residue, or a dialkylsilylene group. The alkylene group may have a plurality of groups selected from the group consisting of-O-, a silylene skeleton group, a 2-valent organopolysiloxane residue, and a dialkylsilylene group.

The number of carbon atoms of the alkylene group represented by X is preferably 1 to 20, particularly preferably 1 to 10. Examples of the 2 to 8-valent organopolysiloxane residue include a 2-valent organopolysiloxane residue and a (w +1) -valent organopolysiloxane residue described later.

Q^bIs a single bond or a 2-valent linking group.

Definition of linking group having valences 2 to Q above^aThe definitions described in (1) are synonymous.

R⁷Is hydroxyl or alkyl.

The number of carbon atoms in 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, 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, h + i is 2,

when X is a carbon atom or a silicon atom, h is an integer of 1 to 3, i is an integer of 0 to 2, h + i is 3,

when X is a 2-8 valent organopolysiloxane residue, h is an integer of 1-7, i is an integer of 0-6, and h + i is 1-7.

(-Q^b-CH＝CH₂) In the case of 2 or more (-Q), 2 or more (-Q)^b-CH＝CH₂) May be the same or different. R is⁷In the case of 2 or more (-R), 2 or more (-R)⁷) May be the same or different.

Q⁷¹The single bond is preferred in terms of ease of production of the compound, because the single bond is a single bond, an alkylene group, or a group having an etheric oxygen atom between carbon atoms of an alkylene group having 2 or more carbon atoms.

The number of carbon atoms of the alkylene group is preferably 1 to 10, particularly preferably 2 to 6.

The number of carbon atoms of the group having an etheric oxygen atom between carbon atoms of the alkylene group having 2 or more carbon atoms is preferably 2 to 10, and particularly preferably 2 to 6.

R⁷¹The alkyl group is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and is preferably a hydrogen atom from the viewpoint of easy production of the compound.

As the alkyl group, a methyl group is preferable.

Q⁷²Is a single bond or alkylene. The number of carbon atoms of the alkylene group is preferably 1 to 10, particularly preferably 1 to 6. Is made from easilyAspect of the production of the Compound, Q⁷²Preferably a single bond or-CH₂-。

R⁷²The hydrogen atom or halogen atom is preferred in that the compound is easily produced.

y is an integer of 1 to 10, preferably 1 to 6.

More than 2 of [ CH₂C(R⁷¹)(-Q⁷²-CH＝CH₂)]May be the same or different.

As the group 2-1, groups 2-1-1 to 2-1-6 are preferable.

-R^f7-(X¹)_p-Q¹-CH＝CH₂(2-1-1)

-R^f7-(X²)_r1-Q²¹-N[-(Q²²)_r2-CH＝CH₂]₂(2-1-2)

-R^f7-Q³¹-G(R³)[-(Q³²)_c-CH＝CH₂]₂(2-1-3)

-R^f7-[C(O)N(R^d)]_s-Q⁴¹-(O)_t-C[-(O)_u1-(Q⁴²)_u2-CH＝CH₂]₃(2-1-4)

-R^f7-Q⁵¹-Si[-(Q⁵²)_e-CH＝CH₂]₃(2-1-5)

-R^f7-[C(O)N(R^d)]_v1-Q⁶¹-Z³[-(Q⁶²)_v2-CH＝CH₂]_w(2-1-6)

R in the formulae (2-1-1) to (2-1-6)^f7As defined above.

X¹is-O-, or, -C (O) N (R)^d) - (wherein, N and Q in the formula¹Bonding).

R^dAs defined above.

p is 0 or 1.

Q¹Is a single bond or alkylene. The alkylene group may have an-O-, a silaphenylene skeleton group, or a 2-valent organopolysiloxane residueA radical or a dialkylsilylene radical. The alkylene group may have a plurality of groups selected from the group consisting of-O-, a silylphenylene skeleton group, a 2-valent organopolysiloxane residue, and a dialkylsilylene group.

When the alkylene group has-O-, it is preferable to have-O-between carbon atoms. In addition, in the case where the alkylene group has a silylphenylene skeleton group, a 2-valent organopolysiloxane residue, or a dialkylsilylene group, it is preferable that the alkylene group is bonded to (X) at a carbon atom-carbon atom interval or at a position corresponding to the bond¹)_pThe side of (b) on the opposite side terminates with these groups.

Q¹The number of carbon atoms of the alkylene group is preferably 1 to 10, particularly preferably 1 to 6.

As Q¹When p is 0, a single bond, -CH is preferred₂OCH₂-、-CH₂OCH₂CH₂OCH₂-、-CH₂CH₂-、-CH₂-、-CH₂OCH₂CH₂CH₂Si(CH₃)₂OSi(CH₃)₂-。(X¹)_p1In the case of-O-, it is preferably-CH₂-、-CH₂CH₂OCH₂-。(X¹)_p1is-C (O) N (R)^d) In the case of (A), an alkylene group having 1 to 6 carbon atoms (wherein N and Q in the formula)¹Bonding). Q¹When the group is mentioned above, the compound can be easily produced.

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

X²is-O-, -NH-, or-C (O) N (R)^d)-。

R^dAs defined above.

Q²¹A single bond, an alkylene group, or a group having an etheric oxygen atom, -C (O) -, -C (O) O-, -OC (O) -, or-NH-between carbon atoms-carbon atoms of an alkylene group having 2 or more carbon atoms.

Q²¹The number of carbon atoms of the alkylene group is preferably 1 to 10, particularly preferably 1 to 6.

Q²¹The alkylene group having 2 or more carbon atoms has preferably 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms in the group having an etheric oxygen atom, -C (O) -, -C (O) O-, -OC (O) -, or-NH-between carbon atoms.

As Q²¹From the viewpoint of ease of production of the compound, -CH is preferred₂-、-CH₂CH₂-、-CH₂CH₂CH₂-、-CH₂OCH₂CH₂-、-CH₂NHCH₂CH₂-、-CH₂CH₂OC(O)CH₂CH₂- (wherein the right side is bonded to N.).

r1 is 0 or 1 (wherein, Q)²¹And 0 in the case of a single bond. ). From the viewpoint of ease of production of the compound, 0 is preferred.

r2 is 0 or 1.

Q²²Is an alkylene group optionally having a 2-valent organopolysiloxane residue, or a group having an etheric oxygen atom or-NH-between carbon atoms of an alkylene group having 2 or more carbon atoms.

In the case where the alkylene group has an organopolysiloxane residue having a valence of 2, it is preferable to have the group at a carbon atom-carbon atom or at a terminal on the side opposite to the side bonded to N.

Q²²The number of carbon atoms of the alkylene group optionally having a 2-valent organopolysiloxane residue is preferably 1 to 10, and particularly preferably 1 to 6.

Q²²The number of carbon atoms of the group having an etheric oxygen atom or-NH-between carbon atoms of the alkylene group having 2 or more carbon atoms is preferably 2 to 10, and particularly preferably 2 to 6.

As Q²²From the viewpoint of ease of production of the compound, -CH is preferred₂-、-CH₂CH₂OCH₂- (wherein the right side is associated with-CH ═ CH₂And (4) bonding. ).

2 [ - (Q)²²)_r2-CH＝CH₂]May be the same or different.

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

Q³¹The single bond is preferred in terms of ease of production of the compound, because the single bond is a single bond, an alkylene group, or a group having an etheric oxygen atom between carbon atoms of an alkylene group having 2 or more carbon atoms.

Q³¹The number of carbon atoms of the alkylene group is preferably 1 to 10, particularly preferably 2 to 6.

Q³¹The number of carbon atoms of the group having an etheric oxygen atom between carbon atoms of the alkylene group having 2 or more carbon atoms is preferably 2 to 10, and particularly preferably 2 to 6.

G is a carbon atom or a silicon atom.

R³Is hydroxyl or alkyl. R³The number of carbon atoms in the alkyl group is preferably 1 to 4.

c is 0 or 1.

As G (R)³) From the viewpoint of easy production of the compound, C (OH) or Si (R) is preferred^3a) (wherein, R^3aIs an alkyl group. The carbon number of the alkyl group is preferably 1 to 10, and a methyl group is particularly preferred. ).

Q³²Is an alkylene group optionally having a 2-valent organopolysiloxane residue, or a group having an etheric oxygen atom between carbon atoms of an alkylene group having 2 or more carbon atoms.

When the alkylene group has an organopolysiloxane residue having a valence of 2, it is preferable to have the group at a carbon atom-carbon atom or at the end opposite to the side bonded to G.

Q³²The number of carbon atoms of the alkylene group optionally having a 2-valent organopolysiloxane residue is preferably 1 to 10, and particularly preferably 1 to 6.

Q³²The number of carbon atoms of the group having an etheric oxygen atom between carbon atoms of the alkylene group having 2 or more carbon atoms is preferably 2 to 10, and particularly preferably 2 to 6.

As Q³²From the viewpoint of ease of production of the compound, -CH is preferred₂-、-CH₂CH₂CH₂CH₂CH₂CH₂-。

2 [ - (Q)³²)_c-CH＝CH₂]May be the same or different.

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

R in the formula (2-1-4)^dAs defined above.

s is 0 or 1.

Q⁴¹Is a single bond, an alkylene group, or a group having an etheric oxygen atom between carbon atoms of an alkylene group having 2 or more carbon atoms.

Q⁴¹The number of carbon atoms of the alkylene group is preferably 1 to 10, particularly preferably 2 to 6.

Q⁴¹The number of carbon atoms of the group having an etheric oxygen atom between carbon atoms of the alkylene group having 2 or more carbon atoms is preferably 2 to 10, and particularly preferably 2 to 6.

t is 0 or 1 (wherein, Q)⁴¹And 0 in the case of a single bond. ).

as-Q⁴¹-(O)_tWhen s is 0, a single bond, -CH is preferred in view of easy production of the compound₂O-、-CH₂OCH₂-、-CH₂OCH₂CH₂O-、-CH₂OCH₂CH₂OCH₂-、-CH₂OCH₂CH₂CH₂CH₂OCH₂- (wherein, left side and R)^f7And (4) bonding. ) When s is 1, a single bond, -CH is preferred₂-、-CH₂CH₂-。

Q⁴²Is alkylene, 2-valent organopolysiloxane residue or dialkylsilylene, the alkylene can have-O-, -C (O) N (R)^d)-〔R^dAs defined above.A silylene skeleton group, a 2-valent organopolysiloxane residue, or a dialkylsilylene group.

When the alkylene group has-O-, it is preferable to have-O-between carbon atoms. In addition, the alkylene group has a structure of-C (O) N (R)^d) In the case of residues of dialkylsilylene or 2-valent organopolysiloxanes, preference is given to residues on a carbon atom-carbon atom basis or bonded to (O)_u1The end of one side of (a) has these groups. When the alkylene group has a silylene skeleton group, it is preferably bonded to (O) at a carbon atom-carbon atom interval_u1The end of the side of (A) on the opposite side has these groups.

Q⁴²The number of carbon atoms of the alkylene group is preferably 1 to 10, particularly preferably 1 to 6.

u1 is 0 or 1.

u2 is 0 or 1.

As- (O)_u1-(Q⁴²)_u2From the viewpoint of ease of production of the compound, a single bond, -CH is preferred₂-、-CH₂OCH₂-、-CH₂OCH₂CH₂CH₂-、-OCH₂-、-OSi(CH₃)₂CH₂-、-OSi(CH₃)₂OSi(CH₃)₂CH₂-、-CH₂CH₂CH₂Si(CH₃)₂PhSi(CH₃)₂- (wherein right side and-CH ═ CH)₂And (4) bonding. )

3 [ - (O)_u1-(Q⁴²)_u2-CH＝CH₂]May be the same or different.

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

Q⁵¹The alkylene group or the alkylene group having 2 or more carbon atoms has an etheric oxygen atom between carbon atoms.

Q⁵¹The number of carbon atoms of the alkylene group is preferably 1 to 10, particularly preferably 1 to 6.

Q⁵¹The number of carbon atoms of the group having an etheric oxygen atom between carbon atoms of the alkylene group having 2 or more carbon atoms is preferably 2 to 10, and particularly preferably 2 to 6.

As Q⁵¹From the viewpoint of ease of production of the compound, -CH is preferred₂OCH₂CH₂CH₂-、-CH₂OCH₂CH₂OCH₂CH₂CH₂-、-CH₂CH₂-、-CH₂CH₂CH₂- (where the right side is bonded to Si).

e is 0 or 1.

Q⁵²Is an alkylene group optionally having a 2-valent organopolysiloxane residue, or a group having an etheric oxygen atom between carbon atoms of an alkylene group having 2 or more carbon atoms.

In the case where the alkylene group has an organopolysiloxane residue having a valence of 2, it is preferable to have the group at a carbon atom-carbon atom or at a terminal on the side opposite to the side bonded to Si.

Q⁵²The number of carbon atoms of the alkylene group is preferably 1 to 10, particularly preferably 1 to 6.

Q⁵²The number of carbon atoms of the group having an etheric oxygen atom between carbon atoms of the alkylene group having 2 or more carbon atoms is preferably 2 to 10, and particularly preferably 2 to 6.

As Q⁵²From the viewpoint of ease of production of the compound, -CH is preferred₂-、-CH₂CH₂OCH₂- (wherein the right side is associated with-CH ═ CH₂And (6) bonding. ).

3 [ - (Q)⁵²)_e-CH＝CH₂]May be the same or different.

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

R in the formula (2-1-6)^dAs defined above.

v1 is 0 or 1.

Q⁶¹Is an alkylene group or a group having an etheric oxygen atom between carbon atoms of an alkylene group having 2 or more carbon atoms.

Q⁶¹The alkylene group preferably has 1 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.

Q⁶¹The number of carbon atoms of the group having an etheric oxygen atom between carbon atoms of the alkylene group having 2 or more carbon atoms is preferably 2 to 10, and particularly preferably 2 to 6.

As Q⁶¹From the viewpoint of ease of production of the compound, -CH is preferred₂OCH₂CH₂CH₂-、-CH₂OCH₂CH₂OCH₂CH₂CH₂-、-CH₂CH₂-、-CH₂CH₂CH₂- (therein, right side and Z)³And (4) bonding. ).

Z³Is a (w +1) -valent organopolysiloxane residue.

w is an integer of 2 to 7.

The (w +1) -valent organopolysiloxane residue includes the following groups. Wherein R in the formula^aAs described above.

v2 is 0 or 1.

Q⁶²Is an alkylene group optionally having a 2-valent organopolysiloxane residue, or a group having an etheric oxygen atom between carbon atoms of an alkylene group having 2 or more carbon atoms.

In the case of an organopolysiloxane residue having an alkylene group with a valence of 2, it is preferable that the alkylene group is bonded to Z at a carbon atom-carbon atom interval³The group is present at the end of the side of the substrate opposite to the side of the substrate.

Q⁶²The number of carbon atoms of the alkylene group is preferably 1 to 10, particularly preferably 1 to 6.

Q⁶²The number of carbon atoms of the group having an etheric oxygen atom between carbon atoms of the alkylene group having 2 or more carbon atoms is preferably 2 to 10, and particularly preferably 2 to 6.

As Q⁶²From the viewpoint of ease of production of the compound, -CH is preferred₂-。

w [ - (Q)⁶²)_v2-CH＝CH₂]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, particularly preferably 1.

As compound B, compound 3 is preferred.

H-SiR_nL_3-n (3)

R is a hydrocarbyl group having a valence of 1, preferably a saturated hydrocarbyl group having a valence of 1. 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 in turn react among the silanol groups to form Si-O-Si bonds. In addition, the silanol group and the hydroxyl group on the surface of the substrate (substrate-OH) undergo a dehydration condensation reaction, and a chemical bond (substrate-O-Si) can be formed.

The hydrolyzable group is preferable as L, and examples of the hydrolyzable group include an alkoxy group, a halogen atom, an acyl group, and an isocyanate group (-NCO). The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms. The halogen atom is preferably a chlorine atom.

L is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom, because it is easy to industrially produce. L is preferably an alkoxy group having 1 to 4 carbon atoms, from the viewpoint of less outgassing during coating and more excellent storage stability of compound 3, and particularly preferably an ethoxy group when long-term storage stability of compound 3 is required, and particularly preferably a methoxy group when the reaction time after coating is short.

n is an integer of 0 to 2.

n is preferably 0 or 1, particularly preferably 0. The presence of a plurality of L makes the adhesion of the surface layer to the substrate stronger.

In the case where n is 0 or 1, L's present in 1 molecule are optionally the same or different from each other. From the viewpoint of availability of raw materials and ease of production, they are preferably the same. In the case where n is 2, 2R's present in 1 molecule are optionally the same or different from each other.

As the compound 3, H-Si (OCH) is preferable₃)₃、H-SiCH₃(OCH₃)₂、H-Si(OCH₂CH₃)₃、H-SiCl₃、H-Si(OC(O)CH₃)₃、H-Si(NCO)₃。

[ Compound C ]

The compound C preferably has a hydrolyzable silyl group, because it is more excellent in storage stability.

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. When the number average molecular weight is within this range, the surface layer is excellent in friction resistance.

As compound C, compound 4 is preferred.

[A²-O-Z¹-(R^fO)_m-]_jZ²[-C₂H₄-SiR_nL_3-n]_q (4)

In the formula (4), A²Is perfluoroalkyl or-Q [ -C [ ]₂H₄-SiR_nL_3-n]_k。

Wherein A is²is-Q [ -C₂H₄-SiR_nL_3-n]_kIn the case of (3), j is 1.

The other groups are as defined above.

As the compound 4, the compound 4-1 is preferred.

A²-O-Z¹-(R^fO)_m-Z⁴ (4-1)

In the formula (4-1), A²、Z¹、R^fAnd m is as defined above.

Z⁴Is a group 5-1 or a group 5-2.

-R^f7-Q^a-X(-Q^b-C₂H₄-SiR_nL_3-n)_h(-R⁷)_I (5-1)

-R^f7-Q⁷¹-[CH₂C(R⁷¹)(-Q⁷²-C₂H₄-SiR_nL_3-n)]_y-R⁷² (5-2)

The groups in the formulae (5-1) and (5-2) are as defined above.

Further, the group 5-1 is preferably a group 5-1-1 to 5-1-6.

-R^f7-(X¹)_p-Q¹-C₂H₄-SiR_nL_3-n (5-1-1)

-R^f7-(X²)_r1-Q²¹-N[-(Q²²)_r2-C₂H₄-SiR_nL_3-n]₂ (5-1-2)

-R^f7-Q³¹-G(R³)[-(Q³²)_c-C₂H₄-SiR_nL_3-n]₂ (5-1-3)

-R^f7-[C(O)N(R^d)]_s-Q⁴¹-(O)_t-C[-(O)_u1-(Q⁴²)_u2-C₂H₄-SiR_nL_3-n]₃(5-1-4)

-R^f7-Q⁵¹-Si[-(Q⁵²)_e-C₂H₄-SiR_nL_3-n]₃ (5-1-5)

-R^f7-[C(O)N(R^d)]_v1-Q⁶¹-Z³[-(Q⁶²)_v2-C₂H₄-SiR_nL_3-n]_w (5-1-6)

The groups in the formulae (5-1-1) and (5-1-6) are as defined above.

[ hydrosilylation catalyst ]

The hydrosilylation catalyst is preferably a transition metal catalyst, more preferably a group 8 to group 10 transition metal catalyst, still more preferably a platinum (Pt) catalyst, a ruthenium (Ru) catalyst, a rhodium (Rh) catalyst, or an iron (Fe) catalyst, and particularly preferably a platinum catalyst or an iron catalyst from the viewpoint of further progressing the hydrosilylation reaction. The groups 8 to 10 are group numbers based on the revised IUPAC inorganic chemical nomenclature (1989).

Specific examples of the platinum catalyst include a Pt complex of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane, a Pt complex of divinyltetramethyldisiloxane, a Pt complex of tetramethyltetravinylcyclotetrasiloxane, chloroplatinic acid, and platinum oxide.

Specific examples of the iron catalyst include iron hydrosilylated catalysts described in International publication No. 2016/027819.

[ adsorbing Material ]

The water content of the adsorbent is 1.0 mass% or less, and is preferably 0.5 mass% or less, and particularly preferably 0.1 mass% or less, from the viewpoint of obtaining at least one of the point that generation of particulate matter in the surface layer is further suppressed and the point that the friction resistance is more excellent (hereinafter, also referred to as "the point that the effect of the present invention is more excellent"). The water content of the adsorbent is usually 0.001 mass% or more.

The water content of the adsorbent is a mass ratio of water in the total amount of the adsorbent, and can be measured by a dry-weight reduction method or the like.

The adsorbent may have a water content outside the above range (for example, 2 to 3 mass%) before use, such as storage, as long as the adsorbent satisfies the above range of water content when used in the present production method.

When the adsorbent is used, for example, an adsorbent having a water content exceeding the above range (exceeding 1.0 mass%) is subjected to dehydration treatment to obtain an adsorbent having a predetermined water content, and then the adsorbent is applied to the present production method.

Examples of the dehydration treatment include a method of blowing a gas having a low water content (for example, nitrogen gas having a dew point of 0 ℃ or lower) to the adsorbent, and a method of heating the adsorbent.

Specific examples of the adsorbent include activated carbon, molecular sieves, silica gel, and diatomaceous earth, and among these, activated carbon is preferable in terms of further improving the effect of the present invention.

The activated carbon is a material mainly composed of carbon atoms, and may be, for example, activated carbon obtained by firing natural materials such as a woody material, coconut shell, and coal, or activated carbon obtained by firing artificial materials such as a synthetic organic polymer compound.

The particle size of the activated carbon is preferably 5 to 50 meshes, and particularly preferably 10 to 30 meshes. Particle size of activated carbon was measured according to JIS K1474: 2014.

The activated carbon may be commercially available, and examples thereof include aigret G2c, aigret GM2x, aigret GH2x, aigret WH2C, KURARAY co.

[ other ingredients ]

In the present production method, components other than the above-described components may be used.

For example, in the present production method, a liquid medium such as a solvent can be used. That is, the reaction of compound a with compound B can be carried out in the presence of a liquid medium. The liquid medium is preferably a solvent capable of dissolving the compound a, the compound B, and the compound C.

Examples of the solvent include organic solvents. Specific examples of the organic solvent include a fluorine-containing organic solvent and a non-fluorine-containing organic solvent.

The organic solvent may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The water content of the organic solvent is preferably 100ppm or less, more preferably 20ppm or less.

Specific examples of the fluorine-containing organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluorinated alkyl ethers, fluorinated alkylamines, and fluorinated alcohols.

The fluorinated alkane is preferably a C4-8 compound, and examples thereof include C₆F₁₃H (AC-2000: manufactured by Asahi glass Co., Ltd.), C₆F₁₃C₂H₅(AC-6000, product name, manufactured by Asahi glass Co., Ltd.), C₂F₅CHFCHFCF₃(Vertrel: 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, and examples thereof include CF₃CH₂OCF₂CF₂H (AE-3000: manufactured by Asahi glass Co., Ltd.), C₄F₉OCH₃(Novec-7100, product name, 3M Co., Ltd.), C₄F₉OC₂H₅(Novec-7200, product name, 3M Co., Ltd.), C₂F₅CF(OCH₃)C₃F₇(Novec-7300: product name, 3M).

Specific examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.

Specific examples of the fluoroalcohol include 2,2,3, 3-tetrafluoropropanol, 2,2, 2-trifluoroethanol, and hexafluoroisopropanol.

The non-fluorine-containing organic solvent is preferably a compound formed only of hydrogen atoms and carbon atoms, or a compound formed only of hydrogen atoms, carbon atoms, and oxygen atoms, and specifically, a hydrocarbon-based organic solvent, a ketone-based organic solvent, an ether-based organic solvent, and an ester-based organic solvent are exemplified.

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.

Specific examples of the ester-based organic solvent include ethyl acetate and butyl acetate.

In addition, in the present production method, a rearrangement 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 rearrangement inhibitor, a compound described in paragraph 0115 of WO2014/069592 can be cited.

[1 st mode ]

The 1 st aspect of the present manufacturing method is as follows: 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 is reacted with the compound B, a hydrosilylation catalyst, the compound a, and the compound B are mixed, and heat treatment is performed as necessary to perform the reaction.

The hydrosilylation catalyst, compound a, and compound B may be mixed together or in portions.

The order of mixing the components is not particularly limited.

The amount of the hydrosilylation catalyst is preferably 0.00001 to 0.1% by mass, and particularly preferably 0.001 to 0.02% by mass, based on the total amount of the compound a and the compound B.

The mixing ratio of the compound A and the compound B is selected to be an optimum ratio depending on the structure of the compound, and the ratio of the number of moles of hydrogen atoms bonded to silicon atoms in the compound B to the number of moles of omega-alkenyl groups in the compound A (hydrogen atoms/omega-alkenyl groups) is preferably 1.0 to 3.0.

The reaction temperature in the reaction of the compound A and the compound B is preferably 0 to 100 ℃ and particularly preferably 50 to 80 ℃. The reaction time is preferably 30 to 600 minutes, and particularly preferably 60 to 300 minutes.

After the compound a and the compound B are reacted, the following reaction may be carried out as necessary: the kind of the hydrolyzable group in the compound C obtained was changed. For example, after the compound C having a halogen atom as a hydrolyzable group is obtained by reacting the compound a and the compound B, a reaction of changing the halogen atom to an alkoxy group may be carried out.

Next, the obtained compound C is brought into contact with a specific adsorbent.

Examples of the method of contact include a method of mixing the compound C with a specific adsorbent, and a method of passing the compound C through a filter filled with a specific adsorbent.

When the compound C is brought into contact with the specific adsorbent, the compound C may be brought into direct contact with the specific adsorbent, or a solution obtained by dissolving the compound C in a solvent or a dispersion obtained by dispersing the compound C in a dispersion medium may be prepared, and the obtained solution or dispersion may be brought into contact with the specific adsorbent. Preferably, a solution obtained by dissolving the compound C in a solvent is brought into contact with the specific adsorbent.

The solvent or dispersion medium used is not particularly limited as long as it is a liquid medium capable of dissolving or dispersing the compound C, and an organic solvent is preferred, and a fluorine-based organic solvent is particularly preferred. Specific examples of the fluorine-containing organic solvent are as described above.

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

The contact time is preferably 0.1 to 180 minutes, and particularly preferably 1 to 60 minutes, from the viewpoint of further improving the effect of the present invention.

The temperature at the time of contact is preferably 0 to 40 ℃, and particularly preferably 10 to 30 ℃ from the viewpoint of further improving the effect of the present invention.

[ means 2]

The 2 nd embodiment of the present production method includes the following embodiments: compound a and compound B are reacted in the presence of a hydrosilylation catalyst and a specific adsorbent to produce compound C.

In the step of this embodiment, the hydrosilylation catalyst, the specific adsorbent, the compound a, and the compound B are mixed, and heat treatment is performed as necessary to cause a reaction.

As a method for mixing the hydrosilylation catalyst, the specific adsorbent, the compound a, and the compound B, the components may be mixed together, or the components may be mixed in portions.

The order of mixing the components is not particularly limited.

The reaction conditions (amount, reaction temperature, reaction time, etc.) of the compound a and the compound B are the same as in embodiment 1.

The amount of the specific adsorbent to be used is preferably 1 to 30% by mass, and particularly preferably 5 to 25% by mass, based on the total mass of the compound a and the compound B.

The compound C (the specific adsorbent and the compound C after contact) obtained by the method according to embodiment 1 or 2 above may be mixed with a liquid medium to produce a composition.

Specific examples of the liquid medium include organic solvents. Specific examples of the organic solvent include the fluorine-containing organic solvent and the non-fluorine-containing organic solvent. The organic solvent may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Specific examples of the fluorine-containing organic solvent and the non-fluorine-containing organic solvent are as described above.

In addition, a composition containing the compound C and a liquid medium obtained by using a liquid medium in the method of embodiment 1 or 2 may be used as the composition. Further, the concentration of the compound C may be adjusted to prepare a new composition from the obtained composition containing the compound C and the liquid medium, or the liquid medium used in the method of the above-described 1 st or 2 nd aspect may be changed to another liquid medium to prepare 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 amount of the composition.

The content of the liquid medium in the composition is preferably 50.00 to 99.99% by mass, and particularly preferably 70.00 to 99.00% by mass, based on the total amount of the composition.

By using the compound C obtained by the present production method, a surface layer can be formed on the surface of the substrate.

More specifically, by using the compound C or the composition, a surface layer having excellent abrasion resistance and suppressed generation of particulates can be formed on the surface of the base material. That is, the following article can be manufactured, the article having: a substrate, and a surface layer formed of the compound C or the composition, which is disposed on the surface of the substrate.

The substrate is not particularly limited as long as it is a substrate to which water-and oil-repellency is required to be imparted. Specific examples of the material of the substrate include metals, resins, glass, sapphire, ceramics, stones, and composite materials thereof. The glass may be chemically strengthened. The substrate may be made of SiO₂Etc. are subjected to surface treatment.

As the substrate, a substrate for a touch panel and a substrate for a display are preferable, and a substrate for a touch panel is particularly preferable. The substrate for a touch panel preferably has light transmittance. "having light transmittance" means that the composition has a light transmittance according to JIS R3106: 1998(ISO 9050: 1990) has a visible light transmittance of 25% or more in the vertical incidence type. As a material of the substrate for a touch panel, glass or a transparent resin is preferable.

The article can be produced, for example, by the following method.

A method of obtaining the above-mentioned article by treating the surface of the base material by a dry coating method using the compound C or the composition.

A method of obtaining the above article by applying the composition to the surface of a substrate by a wet coating method and drying the composition.

Specific examples of the dry coating method include a vacuum deposition method, a CVD method, and a sputtering method. Among these, the vacuum deposition method is preferable from the viewpoint of suppressing the decomposition of the compound C and the viewpoint of the simplicity of the apparatus. In the case of vacuum deposition, a granular material obtained by impregnating a porous metal body such as iron or steel with the compound C or the composition can be used.

Specific examples of the wet coating method include a spin coating method, a wipe coating method, a spray coating method, an extrusion coating method, a dip coating method, a die coating method, an ink jet method, a flow coating method, a roll coating method, a casting method, a Langmuir-Blodgett method, and a gravure coating method.

The surface layer formed by the above steps contains a compound obtained by hydrolysis and condensation of the compound C.

The film thickness of the surface layer is preferably 1 to 100nm, particularly preferably 1 to 50 nm. The thickness of the surface layer can be calculated from the oscillation period of an interference pattern reflecting X-rays obtained by an X-ray reflectance method using an X-ray diffractometer for thin film analysis (ATX-G, manufactured by RIGAKU).

Examples

The present invention will be described in detail below with reference to examples. However, the present invention is not limited to these examples. The amounts of the respective components used represent mass references. Of examples 1 to 7, examples 1 to 4 and 6 to 7 are examples, and example 5 is a comparative example.

[ evaluation method ]

(moisture content of adsorbent)

The sample was heated in an oven (180 ℃ C., 2 hours), and the mass before and after heating was measured to calculate the mass.

(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 the particulate matter in the surface layer. The evaluation criteria are as follows.

A: the surface layer had no particles of about 100 μm.

B: the surface layer has particles of about 100 μm.

(Friction resistance)

The water contact angle was measured for the evaluation samples before and after the abrasion resistance test. The smaller the decrease in water contact angle after rubbing, the smaller the decrease in performance due to rubbing, and the more excellent the rub resistance.

< method for measuring Water contact Angle >

The contact angle (water contact angle) of about 2. mu.L of distilled water placed on the surface of the surface layer was measured using a contact angle measuring apparatus (DM-500, manufactured by Kyowa Kagaku Co., Ltd.). The measurement was performed at 5 different sites on the surface of the surface layer, and the average value thereof was calculated. The contact angle was calculated by the 2 θ method.

< method for testing Friction resistance >

For the surface layer, the thickness was measured in accordance with JIS L0849: 2013(ISO 105-X12: 2001), a reciprocating traverse tester (manufactured by ケイエヌテー) was used to measure the pressure: 98.07kPa, speed: steel wool BONSTAR (#0000) was shuttled 1 ten thousand times at 320 cm/min.

[ Synthesis example 1]

Compound C-1 was synthesized according to the method described in synthetic example 15 of WO 2014/069592. Specifically, a compound having a poly (oxyperfluoroalkylene) chain and an ω -alkenyl group (a perfluoropolyether group-containing allyl compound represented by the following formula (5)) and trichlorosilane as a compound having a hydrolyzable group bonded to a silicon atom are reacted in the presence of a Pt complex of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane as a hydrosilylation catalyst, and then a chlorine atom of the obtained compound is substituted with a methoxy group to obtain a compound C-1 represented by the following formula (6). The obtained compound C-1 was dissolved in Novec-7200 (manufactured by 3M) (water content: 10ppm) so that the concentration became 20% by mass, to prepare 100g of composition 1.

CF₃O(CF₂CF₂O)₁₅(CF₂O)₁₆CF₂CH₂OCH₂CH₂CH₂Si(CH₂CH＝CH₂)₃ (5)

CF₃O(CF₂CF₂O)₁₅(CF₂O)₁₆CF₂CH₂OCH₂CH₂CH₂Si[CH₂CH₂CH₂Si(OCH₃)₃]₃ (6)

In the compound C-1, 0.17 (CF) was contained as an average composition₂CF₂CF₂CF₂Heavy of O)Complex unit and 0.18 (CF)₂CF₂CF₂O) is omitted because the repeating unit is a trace amount.

[ Synthesis example 2]

Compound C-2 was synthesized according to the method described in synthetic example 3 of WO 2017/022437. Specifically, a compound having a poly (oxyperfluoroalkylene) chain and an ω -alkenyl group (a perfluoropolyether group-containing allyloxy compound represented by the following formula (7)) and trichlorosilane as a compound having a hydrolyzable group bonded to a silicon atom are reacted in the presence of a Pt complex of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane as a hydrosilylation catalyst, and then a chlorine atom of the obtained compound is 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: 10ppm) so that the concentration thereof became 20% by mass, to prepare 100g of composition 2.

CF₃O(CF₂CF₂O)₂₀(CF₂O)₁₆CF₂CH₂OCH₂CH₂CH₂CH₂OCH₂C(CH₂OCH₂CH＝CH₂)₃ (7)

CF₃O(CF₂CF₂O)₂₀(CF₂O)₁₆CF₂CH₂OCH₂CH₂CH₂CH₂OCH₂C[CH₂OCH₂CH₂CH₂Si(OCH₃)₃]₃ (8)

[ example 1]

5g of activated carbon (KURARAAY CO., LTD, KURAAY COAL GLC, standard particle size: 10-30 mesh) was charged into a filter, and nitrogen gas having a dew point of-20 ℃ was passed through the filter for 1 minute. The water content of the activated carbon after the nitrogen gas had flowed through was 0.9 mass%.

Subsequently, the obtained activated carbon was added to 100g of composition 1, and after stirring at 25 ℃ for 5 minutes, the activated carbon was filtered to obtain composition 11.

Using the obtained composition 11, a substrate was subjected to the following dry coating method (chemical)Strengthened glass) forms a surface layer. First, 0.5g of composition 11 was charged into a molybdenum plate in a vacuum deposition apparatus (VTR-350M manufactured by ULVAC), and the interior of the vacuum deposition apparatus was evacuated to 1X 10^-3Pa or less. The plate on which the composition 11 was placed was heated at a temperature rise rate of 10 ℃/min or less, and at a time when the deposition rate based on the quartz oscillation film thickness exceeded 1 nm/sec, a shutter (shutter) was opened to start film formation on the surface of the substrate. The shutter was closed at the time when the film thickness became 50nm, and the film formation on the surface of the substrate was completed. The obtained substrate was subjected to heat treatment at 200 ℃ for 30 minutes and washed with ASAHIKLIN AK-225 (trade name, Asahi glass company, Ltd.), thereby obtaining an article having a surface layer disposed on the surface of the substrate. The appearance characteristics and abrasion resistance of the article were evaluated, and the results are shown in table 1.

[ examples 2 to 5]

A surface layer was formed in the same manner as in example 1, except that the nitrogen gas flow time and the type of the composition were changed. The appearance characteristics and abrasion resistance of the article were evaluated, and the results are shown in table 1.

[ example 6]

A surface layer was formed in the same manner as in example 1, except that molecular sieve 4A (manufactured by seiko chemical corporation) was used instead of activated carbon. The appearance characteristics and abrasion resistance of the article were evaluated, and the results are shown in table 1.

[ example 7]

A surface layer was formed in the same manner as in example 1 except that silica gel (model: D-75-60a (n) average particle diameter 75 μm, average pore diameter 60 a) was used instead of activated carbon (model: m.s. gel manufactured by AGC Sitech corporation), and evaluation of appearance characteristics and abrasion resistance of the article was performed, and the results are shown in table 1.

[ Table 1]

As shown in Table 1, in the case of examples 1 to 4 and 6 to 7 using the adsorbent having a water content of 1.0 mass% or less, the surface layer was obtained which did not generate granular matters, had excellent appearance, and had excellent initial water repellency and abrasion resistance.

Further, comparison of examples 1 to 3 confirmed that the adsorbent had a water content of 0.1 mass% or less and was more excellent.

On the other hand, in the case of example 5 in which the adsorbent having a water content of more than 1.0 mass% was used, a surface layer having an insufficient appearance due to generation of granular matters and having insufficient abrasion resistance was obtained.

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

Industrial applicability

The fluorine-containing ether compound obtained by the production method can be used for various applications requiring lubricity, water repellency and oil repellency. For example, the coating composition can be used for a coating layer of a display input device such as a touch panel, a surface protective coating layer of a transparent glass or transparent plastic member, an antifouling coating layer for kitchens, a water-repellent and moisture-proof coating layer of electronic devices, heat exchangers, batteries, etc., an antifouling coating layer for washing products, a coating layer on a member which is conductive and requires liquid repellency, a water-repellent, water-repellent and water-slip coating layer of heat exchangers, a vibrating screen, a surface low-friction coating layer in a cylinder, etc. More specific examples of the use include front protective plates, antireflection plates, polarizing plates, antiglare plates for displays, coatings for various devices having display input devices for performing operations on screens with human fingers or hands, such as touch panel sheets and touch panel displays for devices such as mobile phones and portable information terminals, which are treated with antireflection films on their surfaces, coatings for decorative building materials for water-use places such as toilets, bathrooms, toilets and kitchens, wiring boards, water-repellent and water-slip coatings for heat exchangers, water-repellent coatings for solar cells, water-repellent and water-repellent coatings for printed wiring boards, housings for electronic devices, water-repellent and water-repellent coatings for electronic components, insulation-improving coatings for power transmission lines, water-repellent and water-repellent coatings for various filters, radio wave absorbing materials, coatings for sound-absorbing materials, and the like, Antifouling coatings for bathrooms, kitchen equipment, washing and care products, low-friction coatings for surfaces of vibrating screens, cylinder interiors and the like, surface protective coatings for machine parts, vacuum equipment parts, bearing parts, automobile parts, tools and the like, and the like.

The entire contents of the specification, claims and abstract of japanese patent application No. 2017-157902, filed on 2017, 08, month and 18, are incorporated herein as the disclosure of the specification of the present invention.

Claims

1. A process for producing a fluorine-containing ether compound, characterized by reacting a compound having a poly (oxyperfluoroalkylene) chain and an omega-alkenyl group with a compound having a hydrogen atom bonded to a silicon atom and having at least one of a hydrolyzable group bonded to the silicon atom and a hydroxyl group bonded to the silicon atom in the presence of a hydrosilylation catalyst to produce a fluorine-containing ether compound having a poly (oxyperfluoroalkylene) chain and having at least one of a hydrolyzable group bonded to the silicon atom and a hydroxyl group bonded to the silicon atom,

in the method, 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 mass% or less, or

The reaction is carried out in the presence of the hydrosilylation catalyst and an adsorbent having a water content of 1.0 mass% or less.

2. The production method according to claim 1, wherein the water content of the adsorbent is 0.1 mass% or less.

3. The production method according to claim 1 or 2, wherein the adsorbent is activated carbon, a molecular sieve, silica gel, or diatomaceous earth.

4. The production method according to claim 1 or 2, wherein the hydrosilylation catalyst is a group 8 to group 10 transition metal catalyst.

5. The production process according to claim 1 or 2, wherein the compound having a poly (oxyperfluoroalkylene) chain and an ω -alkenyl group is a compound represented by the following formula (1),

[A¹-O-Z¹-(R^fO)_m-]_jZ²[-CH＝CH₂]_q (1)

wherein A is¹Is perfluoroalkyl or-Q [ -CH ═ CH-₂]_k，A¹is-Q [ -CH ═ CH₂]_kWhen the value of j is 1, the value of j is,

q is a (k +1) -valent linking group, k is an integer of 1 to 10,

Z¹a single bond, a C1-20 oxyfluoroalkylene group in which 1 or more hydrogen atoms are replaced with fluorine atoms, or a C1-20 poly (oxyfluoroalkylene group) in which 1 or more hydrogen atoms are replaced with fluorine atoms; the oxyfluoroalkylene group does not include an oxyperfluoroalkylene group in which the oxygen atom is in contact with (R)^fO)_mBonding; in the poly (oxyfluoroalkylene) with (R)^fO)_mOxygen atom of bonded oxyfluoroalkylene group with (R)^fO)_mIs bonded with (R)^fO)_mThe bonded oxyfluoroalkylene group contains 1 or more hydrogen atoms, and the poly (oxyfluoroalkylene group) optionally contains: both oxyperfluoroalkylene groups in which all hydrogen atoms are replaced with fluorine atoms and oxyfluoroalkylene groups containing 1 or more hydrogen atoms,

6. The production method according to claim 1 or 2, wherein the compound having a hydrogen atom bonded to a silicon atom and at least one of 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),

H-SiR_nL_3-n(3)

7. The production method according to claim 6, wherein n is 0 or 1, and each of L is a hydrolyzable group.

8. The production method according to claim 1 or 2, wherein the amount of the adsorbent is 1 to 30% by mass based on the total mass of the compound having a poly (oxyperfluoroalkylene) chain and an ω -alkenyl group.

9. The production method according to claim 1 or 2, 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 mass% or less in a liquid medium.

10. A method for producing an article, characterized in that a surface layer is formed 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.