CN115867595A

CN115867595A - Fluorine-containing ether compound, fluorine-containing ether composition, coating liquid, article, and method for producing article

Info

Publication number: CN115867595A
Application number: CN202180050421.3A
Authority: CN
Inventors: 富依勇佑; 远田丰和; 渡边弘毅
Original assignee: Asahi Glass Co Ltd
Current assignee: AGC Inc
Priority date: 2020-08-17
Filing date: 2021-08-17
Publication date: 2023-03-28
Also published as: WO2022039172A1; JPWO2022039172A1

Abstract

The present invention aims to provide a fluorinated ether compound, a fluorinated ether composition, a coating liquid, and an article having a surface layer excellent in fingerprint stain removability and finger slipperiness, which can form a surface layer excellent in fingerprint stain removability and finger slipperiness, and a method for producing the same. A fluorine-containing ether compound represented by the following formula (1) or the following formula (2). { (R) ^f1 ‑A ¹ ‑) _p1 Si(‑R ¹ ) _3‑p1 } _q1 ‑Q ¹ (‑T) _n1 (‑R ^f2 ) _r1 Formula (1). { (R) ^f1 ‑A ¹ ‑) _p2 Si(‑R ¹ ) _3‑p2 } _q2 ‑Q ² (‑T) _n2 ‑R ^f3 ‑Q ³ (‑T) _n3 {‑Si(‑R ² ) _3‑p3 (‑A ² ‑R ^f1 ) _p3 } _q3 Formula (2). Wherein each symbol in the formula is as described in the specification.

Description

Fluorine-containing ether compound, fluorine-containing ether composition, coating liquid, article, and method for producing article

Technical Field

The present invention relates to a fluorinated ether compound, a fluorinated ether composition, a coating liquid, an article, and a method for producing an article.

Background

Fluorine-containing ether compounds having a fluoropolyether chain and a hydrolyzable silyl group have attracted attention because they can impart excellent water-and oil-repellency, abrasion resistance, low fingerprint-adhesion property, fingerprint stain-removing property and finger-slipping property to the surface of a substrate. Since a surface layer such as a display can be formed on the surface of the substrate, it is suitable for use as a surface treatment agent.

For example, patent document 1 proposes a fluorine-containing ether compound having a perfluoropolyether chain and a hydrolyzable silyl group as a fluorine-containing ether compound capable of forming a durable surface layer having excellent fingerprint stain removability on the surface of a substrate.

Documents of the prior art

Patent literature

Patent document 1: international publication No. 2017/038832

Disclosure of Invention

Problems to be solved by the invention

The present invention aims to provide a fluorinated ether compound, a fluorinated ether composition, a coating liquid, and an article having a surface layer excellent in fingerprint stain removability and finger slipperiness, which can form a surface layer excellent in fingerprint stain removability and finger slipperiness, and a method for producing the same.

Means for solving the problems

The present invention provides a fluorine-containing compound having the following configurations [1] to [9], a method for producing the same, a composition containing the fluorine-containing compound, a coating liquid, an article, and a method for producing the same.

[1] A fluorine-containing ether compound represented by the following formula (1) or the following formula (2).

{(R ^f1 -A ¹ -) _p1 Si(-R ¹ ) _3-p1 } _q1 -Q ¹ (-T) _n1 (-R ^f2 ) _r1 Formula (1)

{(R ^f1 -A ¹ -) _p2 Si(-R ¹ ) _3-p2 } _q2 -Q ² (-T) _n2 -R ^f3 -Q ³ (-T) _n3 {-Si(-R ² ) _3-p3 (-A ² -R ^f1 ) _p3 } _q3 Formula (2)

Wherein the content of the first and second substances,

R ^f1 is a 1-valent polyfluoropolyether chain optionally having substituents, a plurality of R being present ^f1 Are optionally the same as or different from each other,

R ^f2 is a 1-valent polyfluoropolyether chain, a plurality of R being present ^f2 Are optionally the same as or different from each other,

R ^f3 is a 2-valent polyfluoropolyether chain,

A ¹ and A ² A plurality of A's each independently being-O-or C (= O) -O-, present ¹ And A ² Each independently of the other optionally being the same or different,

R ¹ and R ² A plurality of R's present as alkyl groups, hydrolyzable groups or hydroxyl groups ¹ And R ² Are optionally the same as or different from each other,

Q ¹ a linking group having a valence of q1+ n1+ r1,

Q ² a q2+ n2+1 valent linking group,

Q ³ a q3+ n3+1 valent linking group,

t is-Si (-R) _3-a (-L) _a And when there are more than 2 Ts, the more than 2 Ts are optionally the same or different,

r is an alkyl group, and R is a substituted alkyl group,

l is a hydrolyzable group or a hydroxyl group, and at least 2 of L in each T are the same or different,

a is 2 or 3, and a is,

q1 is an integer of 1 or more,

when q1 is 1, p1 is 1 or 2,

when q1 is 2 or more, p1 is an integer of 0 to 3, at least one of the plural p1 s present is 1 or 2, the plural p1 s present are optionally the same or different from each other,

n1 is an integer of 0 or more, r1 is an integer of 1 or more,

q2 is an integer of 1 or more,

when q2 is 1, p2 is 1 or 2,

when q2 is 2 or more, p2 is an integer of 0 to 3, at least one of the plural p2 s present is 1 or 2, and the plural p2 s present are optionally the same or different from each other,

n2 is an integer of 0 or more,

q3 is an integer of 0 or more,

when q3 is 1 or more, p3 is an integer of 0 to 3, and when a plurality of p3 exist, the p3 s are optionally the same or different from each other,

n3 is an integer of 0 or more, and q3+ n3 is an integer of 1 or more.

[2]According to [1]Wherein R is the same as R ^f1 Represented by the following formula (3A).

L ¹ -R ^f11a -(OR ^f12 ) _m1 -(CH ₂ ) _s1 -formula (3A)

L ¹ Is hydrogen atom, fluorine atom, hydroxyl, -C (O) X, -C (O) OR ¹⁰ 、-C(O)N(R ¹⁰ )2，

X is a hydrogen atom or a halogen atom,

R ¹⁰ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and optionally having a fluorine atom, or a phenyl group optionally having a fluorine atom, and a plurality of R's are present ¹⁰ When a plurality of R is present ¹⁰ Are optionally the same as or different from each other,

R ^f11a a fluoroalkylene group having 1 to 20 carbon atoms,

R ^f12 a fluoroalkylene group having 1 to 6 carbon atoms,

m1 is an integer of 0 to 500, and when m1 is 2 or more, the compound is presentPlural R of ^f12 Optionally the same or different, and optionally,

s1 is an integer of 0 to 20.

[3]According to [1]Or [ 2]]Wherein R is the same as R ^f2 This is represented by the following formula (3).

R ^f11 -(OR ^f12 ) _m1 -formula (3)

Wherein the content of the first and second substances,

R ^f11 is a fluoroalkyl group having 1 to 20 carbon atoms,

R ^f12 a fluoroalkylene group having 1 to 6 carbon atoms,

m1 is an integer of 0 to 500, and when m1 is 2 or more, a plurality of R's are present ^f12 Optionally the same or different.

[4]According to [1]～[3]Wherein R is the same as R ^f3 This is represented by the following formula (4).

-R ^f13 -(OR ^f13 ) _m2 -formula (4)

Wherein, the first and the second end of the pipe are connected with each other,

R ^f13 a fluoroalkylene group having 1 to 6 carbon atoms, a plurality of R being present ^f13 Optionally the same or different, and optionally,

m2 is an integer of 0 to 500.

[5]According to [1]～[4]Wherein Q is a fluorine-containing ether compound of (1) ¹ 、Q ² And Q ³ Each independently represented by any one of the following formulae (5-1) to (5-7).

(-A ¹¹ -Q ¹² -)C(-R ^e2 ) _2-d3 (-Q ³² -)(-Q ²² -) _d3 Formula (5-2)

(-A ¹¹ -Q ¹³ -)N(-Q ³³ -)(-Q ²³ -) formula (5-3)

(-A ¹¹ -Q ¹⁴ -)Z(-Q ³⁴ -)(-Q ²⁴ -) _d4 Formula (5-4)

(-A ¹¹ -Q ¹⁵ -)Si(-R ^e3 ) _2-d5 (-Q ³⁵ -)(-Q ²⁵ -) _d5 Formula (5-5)

-A ¹¹ -Q ¹² -CH(-Q ³² -)-Si(R ^e3 ) _3-d6 (-Q ²⁵ -) _d6 Formula (5-6)

-A ¹¹ -Q ¹² -CH(-Q ²² -)-Si(R ^e3 ) _2-d7 (-Q ³⁵ -)(-Q ²⁵ -) _d7 Formula (5-7)

Wherein, in the formulae (5-1) to (5-7), A ¹¹ Side and R ^f2 Or R ^f3 Connection, Q ²² 、Q ²³ 、Q ²⁴ Or Q ²⁵ Side to T, Q ³² 、Q ³³ 、Q ³⁴ Or Q ³⁵ By means of Si and R ^f1 The connection is carried out by connecting the two parts,

A ¹¹ is a single bond, -C (O) NR ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ -，

Q ¹¹ Is a single bond, -C (O) NR ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ -, alkylene, or alkylene having 2 or more carbon atoms and having-C (O) NR between carbon-carbon atoms ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ -a group of (a) or (b),

Q ¹² is a single bond, alkylene, or has-C (O) NR between carbon-carbon atoms of alkylene having 2 or more carbon atoms ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ -a group of (a) or (b),

Q ¹³ is a single bond (wherein, A is-C (O) -), alkylene; having-C (O) NR between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ -a group of (a); or, on the N-side of the alkylene radicalA group having-C (O) -at the terminal,

at Q ¹⁴ When the atom in Z bonded thereto is a carbon atom, Q ¹⁴ Is Q ¹² At Q ¹⁴ When the atom in Z bonded thereto is a nitrogen atom, Q ¹⁴ Is Q ¹³ ，

Q ¹⁵ Is an alkylene group; or having-C (O) NR between carbon atoms of an alkylene group having 2 or more carbon atoms ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ -a group of (a) or (b),

Q ²² and Q ³² Each independently an alkylene group; having-C (O) NR between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ -a group of (a); having-C (O) NR at the end of the alkylene group on the side not bonded to Si ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ -a group of (a); or having-C (O) NR between carbon atoms of an alkylene group having 2 or more carbon atoms ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ And has-C (O) NR at the end of the side not bonded to Si ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ A group of (A) in which a plurality of Q's are present ²² A plurality of Q's present ²² Optionally the same or different, and optionally,

Q ²³ and Q ³³ Each independently is an alkylene group; or having-C (O) NR between carbon atoms of an alkylene group having 2 or more carbon atoms ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ -a group of (a) or (b),

at Q ²⁴ Or Q ³⁴ When the atom in Z bonded thereto is a carbon atom, Q ²⁴ And Q ³⁴ Each independently is Q ²² Or Q ³² At Q ²⁴ Or Q ³⁴ When the atom in Z bonded thereto is a nitrogen atom, Q ²⁴ And Q ³⁴ Each independently is Q ²³ Or Q ³³ There are a plurality of Q ²⁴ A plurality of Q's present ²⁴ Optionally the same or different, and optionally,

Q ²⁵ and Q ³⁵ Each independently is an alkylene group; or having-C (O) NR between carbon atoms of an alkylene group having 2 or more carbon atoms ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ A group of (A) in which a plurality of Q's are present ²⁵ A plurality of Q's present ²⁵ Optionally the same or different, and optionally,

z is a group having a d4+2 valent ring structure having a valence of Q ¹⁴ 、Q ²⁴ And Q ³⁴ A directly bonded carbon atom or nitrogen atom,

R ^e1 is a hydrogen atom or an alkyl group, in which plural R's are present ¹ When a plurality of R is present ¹ Optionally the same or different, and optionally,

R ^e2 is a hydrogen atom, a hydroxyl group, an alkyl group or an acyloxy group,

R ^e3 is an alkyl group, and is,

R ⁶ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group,

d1 is an integer of 0 to 3, d2 is an integer of 0 to 3, d1+ d2 is an integer of 1 to 6,

d3 is 1 or 2 and is,

d4 is an integer of 1 or more,

d5 is 1 or 2, and the compound has the following structure,

d6 is an integer of 1 to 3,

d7 is 1 or 2.

[6] A fluorine-containing ether composition comprising the fluorine-containing ether compound of [1] to [5] and another fluorine-containing ether compound.

[7] A coating liquid comprising the fluorine-containing ether compound according to [1] to [5] or the fluorine-containing ether composition according to [6], and a liquid medium.

[8] An article having a surface layer comprising the fluorine-containing ether compound according to [1] to [5] or the fluorine-containing ether composition according to [6] on the surface of a substrate.

[9] A method for producing an article, wherein a surface layer is formed by a dry coating method or a wet coating method using the fluorine-containing ether compound according to [1] to [5], the fluorine-containing ether composition according to [6], or the coating liquid according to [7 ].

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention provides a fluorinated ether compound, a fluorinated ether composition, and a coating liquid capable of forming a surface layer excellent in fingerprint stain removability and finger slipperiness, and an article having a surface layer excellent in fingerprint stain removability and finger slipperiness, and a method for producing the same.

Drawings

Fig. 1 is a schematic cross-sectional view showing an example of an article of the present invention.

Detailed Description

In the present specification, the compound represented by the formula (1) is referred to as compound (1). Other compounds represented by the formulae and the like are also based on this.

The following terms in the present specification have the following meanings.

"reactive silyl group" refers to a generic name of a hydrolyzable silyl group and a silanol group (Si-OH). Reactive silyl refers to: in, for example, formula (1) or formula (2) — Si (-R) _3-a (-L) _a and-Si (-R) ¹ ) Or Si (-R) ² ) In, R ¹ Or R ² In the case of a hydrolyzable group or a hydroxyl group.

"hydrolyzable silyl" refers to: a group capable of undergoing a hydrolysis reaction to form a silanol group.

"surface layer" means: a layer formed on the surface of the substrate.

When the fluorine-containing ether compound is a mixture of plural kinds of fluorine-containing ether compounds having different chain lengths of the polyfluoropolyether chain, the "molecular weight" of the polyfluoropolyether chain is determined by ¹ H-NMR and ¹⁹ F-NMR was carried out to obtain the number average molecular weight calculated from the number (average value) of oxyfluoroalkylene units.

The fluorine-containing ether compound is fluorine-containing polyether chain with single chain lengthIn the case of ether compounds, the "molecular weight" of the polyfluoropolyether chain is determined by ¹ H-NMR and ¹⁹ determination of R by F-NMR ^f Molecular weight calculated from the structure of (1).

"to" indicating a numerical range means: the numerical values recited before and after the description are included as the lower limit value and the upper limit value.

[ fluorine-containing ether Compound ]

The fluorine-containing ether compound of the present invention (hereinafter also referred to as "the present compound") is a compound represented by the following formula (1) or the following formula (2).

Wherein the content of the first and second substances,

R ^f3 is a 2-valent polyfluoropolyether chain,

Q ¹ a linking group having a valence of q1+ n1+ r1,

Q ² is a q2+ n2+1 valent linking group,

Q ³ is a q3+ n3+1 valent linking group,

r is an alkyl group, and R is a substituted alkyl group,

a is 2 or 3, and a is,

q1 is an integer of 1 or more,

when q1 is 1, p1 is 1 or 2,

n1 is an integer of 0 or more, r1 is an integer of 1 or more,

q2 is an integer of 1 or more,

when q2 is 1, p2 is 1 or 2,

when q2 is 2 or more, p2 is an integer of 0 to 3, at least one of the plural p2 s present is 1 or 2, the plural p2 s present are optionally the same or different from each other,

n2 is an integer of 0 or more,

q3 is an integer of 0 or more,

n3 is an integer of 0 or more, and q3+ n3 is an integer of 1 or more.

The compound (1) has two polyfluoropolyether chains, a reactive silyl group, and a specific linking group [ A ] for linking the polyfluoropolyether chain and the reactive silyl group ¹ -Si(R ¹ )-Q ¹ ]。

Further, the compound (2) has three polyfluoropolyether chains, a reactive silyl group, and a specific linking group [ A ] for linking the polyfluoropolyether chain to the reactive silyl group ¹ -Si(R ¹ )-Q ² ]And [ Q ] ³ -Si(R ² )-A ² ]。

The compound has a polyfluoropolyether chain. The present compound having a polyfluoropolyether chain has excellent fingerprint soil removability on the surface layer. In addition, the compoundsHaving at least one reactive silyl group [ T ]]While [ Si (R) in the linker group ¹ )]And [ Si (R) ] ² )]Also functions as a reactive silyl group. In the present compound, a reactive silyl group [ T ]]And is arranged at [ T ] with the]At slightly spaced apart positions [ Si (R) ] ¹ )]And [ Si (R) ] ² )]Each of which is firmly chemically bonded to the base material. In this case, in the compound (1), two polyfluoropolyether chains [ R ] ^f1 ]And [ R ] ^f2 ]Arranged at remote locations, in the compound (2), two polyfluoropolyether chains [ R ] ^f1 ]And [ R ] ^f1 ]Are arranged at remote locations. As a result, a surface layer having excellent abrasion resistance and excellent fingerprint stain removability and finger slip property is formed.

Further, the present compound can be easily introduced into the compound (1) by the following production method to form two polyfluoropolyether chains [ R ] ^f1 ]And [ R ] ^f2 ]Two polyfluoropolyether chains [ R ] can be easily introduced into the compound (2) ^f1 ]And [ R ] ^f3 ]Thus, different polyfluoropolyether chains can be easily introduced, and the degree of freedom in molecular design increases. Therefore, the present compound also has an advantage that it is easy to design a molecular structure in accordance with physical properties required for the surface layer of an article. The different polyfluoropolyether chains include polyfluoropolyether chains having different numbers of carbon atoms in the oxyfluoroalkyl groups constituting the polyfluoropolyether chain, polyfluoropolyether chains having different molecular weights, and the like.

R ^f1 And R ^f2 Is a 1-valent polyfluoropolyether chain.

As R ^f1 The polyfluoropolyether chain (b) has a fluorination rate represented by the following formula (1) of preferably 60% or more, more preferably 80% or more, and even more preferably substantially 100%, from the viewpoint of further improving the abrasion resistance of the surface layer and the fingerprint stain removability. When the fluorination rate is not less than the lower limit, the amount of fluorine in the polyfluoropolyether chain increases, and the slidability and fingerprint removability are improved.

Mathematical formula (1): fluorination rate (%) = (number of fluorine atoms)/{ (number of fluorine atoms) + (number of hydrogen atoms) } × 100

From the viewpoint of satisfying both of the fingerprint stain removability and the sliding resistance of the surface layerEvery 1 polyfluoropolyether chain (R) ^f1 Or R ^f2 ) The molecular weight of (A) is preferably 1000 to 20000, more preferably 2500 to 15000, and still more preferably 3000 to 10000. When the molecular weight of the polyfluoropolyether chain is not less than the lower limit, the flexibility of the polyfluoropolyether chain is improved, the amount of fluorine in the molecule is increased, and the finger sliding property and fingerprint removability are improved. On the other hand, if the molecular weight of the polyfluoropolyether chain is not more than the above upper limit, the friction resistance of the surface layer is excellent.

Wherein, optionally in R ^f1 And A ¹ Or A ² The terminal carbon atom of the linkage is bonded with a fluorine atom. In addition, in R ^f2 And Q ¹ At least one fluorine atom is bonded to the terminal carbon atom of the linkage.

R ^f1 The polyfluoropolyether chain in (1) optionally has substituents. The substituent can impart adhesion to the polyfluoroether chain, or introduce another compound such as a polyfluoropolyether chain from the substituent. The substituent is preferably at the end of the polyfluoropolyether chain. Namely, R ^f1 The structure represented by the following formula (3A) is preferred.

L ¹ -R ^f11a -(OR ^f12 ) _m1 -(CH ₂ ) _s1 -formula (3A)

Wherein the content of the first and second substances,

L ¹ is hydrogen atom, fluorine atom, hydroxyl, -C (O) X, -C (O) OR ¹⁰ 、-C(O)N(R ¹⁰ ) ₂ ，

X is a hydrogen atom or a halogen atom,

R ¹⁰ each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and optionally having a fluorine atom, or a phenyl group optionally having a fluorine atom, wherein R's are present in plural ¹⁰ When a plurality of R is present ¹⁰ Are optionally the same as or different from each other,

R ^f11a a fluoroalkylene group having 1 to 20 carbon atoms,

R ^f12 a fluoroalkylene group having 1 to 6 carbon atoms,

m1 is an integer of 0 to 500, and when m1 is 2 or more, a plurality of R's are present ^f12 Optionally the same or different, and optionally,

s1 is an integer of 0 to 20.

In addition, L is ¹ When it is a hydrogen atom or a fluorine atom, L ¹ -R ^f11a And R of the following formula (3) ^f11 The same applies to the preferred embodiment.

Examples of the halogen atom in X include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As R ¹⁰ Among them, preferred is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms optionally having a fluorine atom.

In addition, s1 is preferably an integer of 1 to 6 from the viewpoint of ease of synthesis of the present compound.

From the viewpoint of fingerprint removability and finger slipperiness, R ^f2 The polyfluoropolyether chain in (4) is preferably a structure represented by the following formula (3).

R ^f11 -(OR ^f12 ) _m1 -formula (3)

Wherein the content of the first and second substances,

R ^f11 is a fluoroalkyl group having 1 to 20 carbon atoms,

R ^f12 a fluoroalkylene group having 1 to 6 carbon atoms,

R ^f11 The fluoroalkyl group constituting the end of the polyfluoropolyether chain has 1 to 20 carbon atoms from the viewpoint of excellent abrasion resistance of the surface layer and excellent fingerprint stain removability.

As R ^f11 The fluoroalkyl group (2) is preferably 60% or more, more preferably 80% or more, and even more preferably substantially 100%, that is, a perfluoroalkyl group, from the viewpoint of further improving the abrasion resistance of the surface layer and the fingerprint stain removability.

R ^f11 The fluoroalkyl group(s) in (b) may be a linear or branched fluoroalkyl group, or may have a ring structure.

The linear or branched fluoroalkyl group may have 1 to 20 carbon atoms, and is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3, from the viewpoint of excellent abrasion resistance of the surface layer and fingerprint stain removal property.

Examples of the fluoroalkyl group having a straight chain or a branched chain 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 ) -and the like.

R ^f11 The fluoroalkyl group having a ring structure (also referred to as fluorocycloalkyl group) of (2) has preferably 3 to 20 carbon atoms, more preferably 4 to 8 carbon atoms, and particularly preferably 4 to 6 carbon atoms. When the amount is within the above range, the surface layer is excellent in abrasion resistance and fingerprint stain removability.

Examples of the fluoroalkyl group having a ring structure include groups of the following formulae. Wherein in the formula,. Indicates a bond.

Wherein a part of the fluorine atoms in the formula are optionally substituted with hydrogen atoms.

R ^f12 The fluoroalkylene group has 1 to 6 carbon atoms from the viewpoint of excellent abrasion resistance of the surface layer and excellent fingerprint stain removability.

As R ^f12 The fluoroalkylene group (b) is preferably a perfluoroalkylene group having a fluorination rate represented by the above formula (1) of 60% or more, more preferably 80% or more, and even more preferably substantially 100%, from the viewpoint of further improving the abrasion resistance of the surface layer and the fingerprint stain removability. When the fluorination rate is not less than the lower limit, the amount of fluorine in the polyfluoropolyether chain increases, and the slidability and fingerprint removability are improved.

R ^f12 The fluoroalkylene group(s) may be linear, branched, or cyclic.

Examples of the fluoroalkylene group having a linear or branched chain include-CF ₂ -、-CF ₂ CF ₂ -、-CF ₂ CF ₂ CF ₂ -、-CF ₂ CF ₂ CF ₂ CF ₂ -、-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ -、-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ -、-CF ₂ CF(CF ₃ ) -and the like.

Examples of the fluoroalkylene group having a ring structure include groups of the following formula. Wherein ×, in the formula, represents a connecting bond.

Wherein a part of fluorine atoms in the formula are optionally substituted with hydrogen atoms.

m1 represents an oxyfluoroalkylene group OR ^f12 The number of repetitions of (a). m1 is an integer of 0 to 500, and is preferably 1 to 500, more preferably 2 to 300, from the viewpoint of further excellent water/oil repellency, abrasion resistance, and fingerprint stain removability.

(OR) of formulae (3) and (3A) ^f12 ) _m1 The structure represented by the following formula (3B) is preferred.

[(OR ¹¹ ) _m11 (OR ¹² ) _m12 (OR ¹³ ) _m13 (OR ¹⁴ ) _m14 (OR ¹⁵ ) _m15 (OR ¹⁶ ) _m16 ]Formula (3B)

Wherein the content of the first and second substances,

R ¹¹ is a fluoroalkylene group having 1 carbon atom,

R ¹² is a fluoroalkylene group having 2 carbon atoms,

R ¹³ is a fluoroalkylene group having 3 carbon atoms,

R ¹⁴ is a fluoroalkylene group having 4 carbon atoms,

R ¹⁵ is a fluoroalkylene group having 5 carbon atoms,

R ¹⁶ is a fluoroalkylene group having 6 carbon atoms,

m11, m12, m13, m14, m15 and m16 each represent an integer of 0 or 1 or more, and m11+ m12+ m13+ m14+ m15+ m16 is an integer of 1 to 500.

In the formula (3B), (OR) ¹¹ )～(OR ¹⁶ ) The bonding order of (2) is arbitrary. M11 to m16 in the formula (3B) each represent (OR) ¹¹ )～(OR ¹⁶ ) The number of (2) does not indicate the arrangement. For example, (OR) ¹⁵ ) _m5 Is represented by (OR) ¹⁵ ) The number of (A) is m5, not representing (OR) ¹⁵ ) _m5 Block configuration structure of (2). Likewise, (OR) ¹¹ )～(OR ¹⁶ ) The order of description of (a) does not indicate the bonding order of the respective units.

R ¹¹ ～R ¹⁶ Specific examples of (3) can be referred to the above-mentioned R ^f12 Specific examples of (3) are as follows.

Among formula (3B), (OR) is preferred from the viewpoint of excellent water-and oil-repellency, abrasion resistance and fingerprint stain removability ^f12 ) _m1 Preferably, the structure is represented by any one of the following formulas (3C) to (3F).

(OR ¹¹ ) _m11 -(OR ¹² ) _m12 (3C)

(OR ¹² ) _m12 -(OR ¹⁴ ) _m14 (3D)

(OR ¹³ ) _m13 (3F)

Wherein the symbols of formulae (3C) to (3F) are the same as those of formula (3A).

In the above formula (3C) and formula (3D), (OR) ¹¹ ) And (OR) ¹² )、(OR ¹² ) And (OR) ¹⁴ ) The bonding order of (2) is arbitrary. In formula (3C), for example (OR) ¹¹ ) And (OR) ¹² ) Can be alternately configured, (OR) ^f1 ) And (OR) ^f2 ) The organic compound may be arranged in blocks, respectively, or may be random. The same applies to formula (3D).

In the formula (3C), m11 is preferably 1 to 30, more preferably 1 to 20. M12 is preferably 1 to 30, more preferably 1 to 20.

In the formula (3D), m12 is preferably 1 to 30, more preferably 1 to 20. M14 is preferably 1 to 30, more preferably 1 to 20.

In the formula (3F), m13 is preferably 1 to 30, more preferably 1 to 20.

In addition, among the polyfluoropolyether chain of the formula (3B), (OR) is preferable from the viewpoint of improving the slidability ¹¹ ) The ratio of (a) to (b) is high. Specifically, the ratio represented by the following formula (2) is preferably 0.2 or more, preferably 0.5 or more, preferably 1.0 or more, and more preferably 2.0 or more.

Mathematical formula (2): m 11/(m 12+ m13+ m14+ m15+ m 16)

R ^f3 Is a 2-valent polyfluoropolyether chain. The present compound has a polyfluoropolyether chain, and thus the fingerprint removability and the finger sliding property of the surface layer are excellent.

As R ^f3 The polyfluoropolyether chain (b) has a fluorination rate represented by the above formula (1) of preferably 60% or more, more preferably 80% or more, and even more preferably substantially 100%, from the viewpoint of further improving the abrasion resistance of the surface layer and the fingerprint stain removability. When the fluorination rate is not less than the lower limit, the amount of fluorine in the polyfluoropolyether chain increases, and the slidability and fingerprint removability are improved.

From the viewpoint of satisfying both of the fingerprint stain removability and the sliding resistance of the surface layer, R ^f3 The molecular weight of (A) is preferably 1000 to 20000, more preferably 2,500 to 15000, and further preferably 3000 to 10000. If R is ^f3 When the molecular weight of (2) is not less than the lower limit, the flexibility of the polyfluoropolyether chain is improved, the fluorine content in the molecule is increased, and the finger slipping property and the fingerprint removability are improved. On the other hand, if R ^f3 When the molecular weight of (2) is not more than the upper limit, the surface layer has excellent abrasion resistance.

Wherein, in R ^f3 And Q ² And Q ³ The terminal carbon atom to which the fluorine atom is bonded.

From the viewpoint of fingerprint removability and finger slipperiness, R ^f3 The structure represented by the following formula (4) is preferred.

-R ^f13 -(OR ^f13 ) _m2 -formula (4)

Wherein the content of the first and second substances,

R ^f13 a fluoroalkylene group having 1 to 6 carbon atoms,

m2 is an integer of 0 to 500, and when m2 is 1 or more, a plurality of R's are present ^f13 OptionalThe same or different.

R ^f13 Wherein R is a C1-6 fluoroalkylene group ^f12 The same applies to the preferred embodiment.

m2 represents an oxyfluoroalkylene group OR ^f13 The number of repetitions of (a). m2 may be an integer of 0 to 500, and is preferably 1 to 500, more preferably 2 to 300, from the viewpoint of further excellent water/oil repellency, abrasion resistance, and fingerprint stain removability.

(OR) of formula (4) ^f13 ) _m2 The structure represented by the following formula (4A) is preferred.

[(OR ¹¹ ) _m11 (OR ¹² ) _m12 (OR ¹³ ) _m13 (OR ¹⁴ ) _m14 (OR ¹⁵ ) _m15 (OR ¹⁶ ) _m16 ]Formula (4A)

The symbols in formula (4A) are the same as those in formula (3B), and preferably the symbols are the same as those in formula (3B).

T in the formulae (1) and (2) is-Si (R) _3-a (L) _a The reactive silyl groups shown. Wherein R is an alkyl group, L is a hydrolyzable group or a hydroxyl group, 2 or more of L in each T are the same or different, and a is 2 or 3.

The reactive silyl group is a group in which either or both of a hydrolyzable group and a hydroxyl group are bonded to a silicon atom.

The hydrolyzable group is a group that forms a hydroxyl group by a hydrolysis reaction. That is, the hydrolyzable silyl group forms a silanol group (Si — OH) by a hydrolysis reaction. The silanol group further undergoes a dehydration condensation reaction between molecules to form an Si-O-Si bond. The silanol group and the hydroxyl group on the surface of the substrate (substrate-OH) undergo a dehydration condensation reaction to form a chemical bond (substrate-O-Si).

Examples of the hydrolyzable group include an alkoxy group, a halogen atom, an acyl group, and an isocyanate group. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms. The halogen atom is preferably a chlorine atom.

The hydrolyzable group is preferably an alkoxy group or a halogen atom, from the viewpoint of ease of production of the present compound. The hydrolyzable group is preferably an alkoxy group having 1 to 4 carbon atoms from the viewpoint of less outgassing at the time of coating and excellent storage stability of the present compound, and particularly preferably an ethoxy group when long-term storage stability of the present compound is required, and particularly preferably a methoxy group when the reaction time after coating is set to a short time.

Examples of the alkyl group include alkyl groups having 1 to 6 carbon atoms.

Si (-R) in the formula (1) and the formula (2) ¹ ) _3-p1 、Si(-R ¹ ) _3-p2 and-Si (-R) ² ) _3-p3 A structure constituting a part of a linking group for linking the polyfluoropolyether chain and the reactive silyl group.

R ¹ And R ² Each independently being an alkyl group, a hydrolyzable group or a hydroxyl group, a plurality of R's being present ¹ And R ² Optionally identical or different from each other. R ¹ And R ² Examples of the alkyl group and the hydrolyzable group include the same groups as those in the above-mentioned reactive silyl group, and preferred embodiments are also the same.

Among them, preferred are: plural R's present ¹ At least one of them is a hydrolyzable group or a hydroxyl group. Further, it is preferable that: plural of R present ² At least one of them is a hydrolyzable group or a hydroxyl group. In this case, siR is the same as T described above ¹ And SiR ² The water-vapor-phase polymerization causes a dehydration condensation reaction with a hydroxyl group (substrate-OH) on the substrate surface, and the adhesion is further improved.

Q in formula (1) ¹ Is a linking group having a valence of q1+ n1+ r 1. Q ¹ Preferably having at least 1 point of branching (P1) selected from the group consisting of C, N, si, ring structures and q1+ N1+ r1 valent organopolysiloxane residues.

The ring structure is preferably 1 selected from the group consisting of an aliphatic ring having 3 to 8 rings, an aromatic ring having 3 to 8 rings, a heterocyclic ring having 3 to 8 rings, and a condensed ring formed of two or more of these rings, and is particularly preferably a ring structure exemplified by the following formula, from the viewpoint of easy production of the present compound and excellent abrasion resistance, light resistance, and chemical resistance of the surface layer. The ring structure may have a substituent such as a halogen atom, an alkyl group (which may contain an etheric oxygen atom between carbon-carbon atoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group, or an oxy (= O).

Examples of the q1+ n1+ r 1-valent organopolysiloxane residue include the following groups. Wherein R in the formula ⁵ Is a hydrogen atom, an alkyl group, an alkoxy group or a phenyl group. R ⁵ The alkyl group and the alkoxy group of (2) preferably have 1 to 10 carbon atoms, and particularly preferably 1 carbon atom.

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In the present compound (1), si, T or R in the formula (1) ^f2 Optionally bonded directly to the branch point (P1), optionally via a group selected from the group consisting of-C (O) NR ⁶ -、-C(O)O-、-C(O)-、-O-、-NR ⁶ -、-S-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-SO ₂ NR ⁶ -、-Si(R ⁶ ) ₂ -、-OSi(R ⁶ ) ₂ -、-Si(CH ₃ ) ₂ -Ph-Si(CH ₃ ) ₂ -and at least 1 bond (P2) of the group consisting of 2-valent organopolysiloxane residues. Wherein R is ⁶ Is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group, and Ph is a phenylene group. From the viewpoint of easy production of the present compound, R ⁶ The alkyl group (2) has preferably 1 to 3 carbon atoms, particularly preferably 1 to 2 carbon atoms.

Examples of the 2-valent organopolysiloxane residue include groups of the following formula. Wherein R in the formula ⁷ Is a hydrogen atom, an alkyl group, an alkoxy group or a phenyl group. R ⁷ The alkyl group and the alkoxy group of (2) preferably have 1 to 10 carbon atoms, and particularly preferably 1 carbon atom.

The bond (P2) is preferably selected from the group consisting of-C (O) NR from the viewpoint of ease of production of the present compound ⁶ -、-C(O)-、-NR ⁶ At least 1 bond of the group consisting of-and-O-, particularly preferably-C (O) NR ⁶ -or-C (O) -, -O-.

As Q ¹ Examples thereof include a combination of 2 or more of the 2-valent hydrocarbon group and 1 or more of the branch points (P1), and a combination of 2 or more of the hydrocarbon group and 1 or more of the branch points (P1) and 1 or more of the bonds (P2).

Examples of the 2-valent hydrocarbon group include a 2-valent aliphatic hydrocarbon group (alkylene group, cycloalkylene group, etc.) and a 2-valent aromatic hydrocarbon group (phenylene group, etc.). The number of carbon atoms of the 2-valent hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

Among them, Q is preferred from the viewpoint of easy production of the present compound ¹ Preferably, the compound has a structure represented by any one of the following formulae (5-1) to (5-7).

(-A ¹¹ -Q ¹² -)C(-R ^e2 ) _2-d3 (-Q ³² -)(-Q ²² -) _d3 Formula (5-2)

(-A ¹¹ -Q ¹³ -)N(-Q ³³ -)(-Q ²³ -) formula (5-3)

(-A ¹¹ -Q ¹⁴ -)Z(-Q ³⁴ -)(-Q ²⁴ -) _d4 Formula (5-4)

-A ¹¹ -Q ¹² -CH(-Q ³² -)-Si(R ^e3 ) _3-d6 (-Q ²⁵ -) _d6 Formula (5-6)

Wherein, the formula (5-1) > EIn the formula (5-7), A ¹¹ Side and R ^f2 Or R ^f3 Connection, Q ²² 、Q ²³ 、Q ²⁴ Or Q ²⁵ Side to T, Q ³² 、Q ³³ 、Q ³⁴ Or Q ³⁵ By means of Si and R ^f1 The connection is carried out by connecting the two parts,

Q ¹¹ Is a single bond, -C (O) NR ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ -, alkylene; or having-C (O) NR between carbon atoms of an alkylene group having 2 or more carbon atoms ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ -a group of (a) or (b),

Q ¹² is a single bond, alkylene; or a C (O) NR group between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ -a group of (a) or (b),

Q ¹³ is a single bond (wherein, A is-C (O) -), alkylene; having-C (O) NR between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ -a group of (a); or a group having-C (O) -at the N-side terminal of the alkylene group,

Q ²² and Q ³² Each independently is an alkylene group; having-C (O) NR between carbon-carbon atoms of alkylene groups having 2 or more carbon atoms ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ -a group of (a); having-C (O) NR at the end of the alkylene group on the side not bonded to Si ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ -a radical of (a); or having-C (O) NR between carbon atoms of an alkylene group having 2 or more carbon atoms ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ And has-C (O) NR at the end of the side not bonded to Si ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ A group of (A) in which a plurality of Q's are present ²² A plurality of Q's present ²² Optionally the same or different, and optionally,

Q ²³ and Q ³³ Each independently is an alkylene group; or a C (O) NR group between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ -a group of (a) or (b),

Q ²⁵ and Q ³⁵ Each independently is an alkylene group; or at least 2 carbon atomshaving-C (O) NR between carbon-carbon atoms of alkylene groups ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ A group of (A) in which a plurality of Q's are present ²⁵ A plurality of Q's present ²⁵ Optionally the same or different, and optionally,

R ^e2 is a hydrogen atom, a hydroxyl group, an alkyl group or an acyloxy group,

R ^e3 is an alkyl group, and is,

R ⁶ a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group,

d3 is 1 or 2 and is,

d4 is an integer of 1 or more,

d5 is 1 or 2 and is,

d6 is an integer of 1 to 3,

d7 is 1 or 2.

Q is a compound having excellent abrasion resistance, light resistance and chemical resistance in the surface layer, from the viewpoint of easy production of the compound ¹¹ 、Q ¹² 、Q ¹³ 、Q ¹⁴ 、Q ¹⁵ 、Q ²² 、Q ²³ 、Q ²⁴ 、Q ²⁵ 、Q ³² 、Q ³³ 、Q ³⁴ And Q ³⁵ The alkylene group in (1) is preferably a linear alkylene group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Wherein the lower limit of the number of carbon atoms of the alkylene group having a specific bond between carbon-carbon atoms is 2.

The ring structure in Z may be the ring structure in the branch point (P1), and the preferred embodiments are the same. In addition, Q is ¹⁴ 、Q ²⁴ And Q ³⁴ Directly bonded to the ring structure in Z.

From the viewpoint of easy production of the present compound, R ^e1 、R ^e2 And R ^e3 The alkyl group (b) is preferably an alkyl group having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably 1 to 2 carbon atoms.

From the viewpoint of easy production of the present compound, R ^e2 The number of carbon atoms in the alkyl moiety of the acyloxy group(s) is preferably 1 to 6, more preferably 1 to 3, and still more preferably 1 to 2.

From the viewpoint of ease of production of the present compound and excellent abrasion resistance and fingerprint stain removability of the surface layer, d4 is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 or 2.

As Q ¹ In another embodiment of (4), Q having a structure represented by any one of the following formulas (6-1) to (6-7) ¹ 。

(-A ¹¹ -Q ¹² -)C(-R ^e2 ) _2-d3 (-Q ³² -)(-Q ²² -G) _d3 Formula (6-2)

(-A ¹¹ -Q ¹³ -)N(-Q ³³ -)(-Q ²³ -G) formula (6-3)

(-A ¹¹ -Q ¹⁴ -)Z(-Q ³⁴ -)(-Q ²⁴ -G) _d4 Formula (6-4)

(-A ¹¹ -Q ¹⁵ -)Si(-R ^e3 ) _2-d5 (-Q ³⁵ -)(-Q ²⁵ -G) _d5 Formula (6-5)

-A ¹¹ -Q ¹² -CH(-Q ³² -)-Si(R ^e3 ) _3-d6 (-Q ²⁵ -G) _d6 Formula (6-6)

-A ¹¹ -Q ¹² -CH(-Q ²² -G)-Si(R ^e3 ) _2-d7 (-Q ³⁵ -)(-Q ²⁵ -G) _d7 Formula (6-7)

Wherein, in the formulae (6-1) to (6-7), A ¹¹ And R ^f2 Connection, G to T, Q ³² 、Q ³³ 、Q ³⁴ Or Q ³⁵ By means of Si and R ^f1 And (4) connecting.

G is a group represented by the following formula (6-8), and the symbols other than G are the same as those in the formulae (5-1) to (5-7).

-Si(R ⁸ ) _3-k (-Q ⁴¹ -) _k Formula (6-8)

Wherein, in the formula (6-8), si and Q ²² 、Q ²³ 、Q ²⁴ Or Q ²⁵ Or Q ²⁶ Connection, Q ⁴¹ Is connected with T. R is ⁸ Is an alkyl group. Q ⁴¹ Is an alkylene group; having-C (O) NR between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms ⁶ -、-C(O)-、-NR ⁶ -or-O-; or- (OSi (R) ⁹ ) ₂ ) _p -O-, more than 2Q ⁴¹ Optionally the same or different. k is 2 or 3.R ⁸ Is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁹ Is alkyl, phenyl or alkoxy, 2R ⁹ Optionally the same or different. p is an integer of 0 to 5, and when p is 2 or more, 2 or more (OSi (R) ⁹ ) ₂ ) Optionally the same or different.

Q is a compound having excellent abrasion resistance, light resistance and chemical resistance in the surface layer, from the viewpoint of easy production of the compound ⁴¹ The alkylene group (b) has preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms. Wherein the lower limit of the number of carbon atoms of the alkylene group having a specific bond between carbon-carbon atoms is 2.

From the viewpoint of easy production of the present compound, R ⁸ The alkyl group (b) has preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.

From the viewpoint of easy production of the present compound, R ⁹ The alkyl group (b) has preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.

From the viewpoint of excellent storage stability of the present compound, R ⁹ The alkoxy group (b) has preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.

p is preferably 0 or 1.

Q ² Is a Q2+ n2+1 valent linking group, Q ³ Is a q3+ n3+1 valent linking group. Q ² And Q ³ And the aforementioned Q ¹ Likewise, the preferred mode is the same. Wherein in the above-mentioned Q ¹ In the description of (1), the compound (1) is replaced with the compound (2), R ^f2 Is replaced by R ^f3 N1 is replaced by n2 or n3, q1 is replaced by q2 or q3, and r1 is replaced by 1.

Q1 and q2 are each independently an integer of 1 or more, preferably 1 to 6, and more preferably 1 to 3. q3 may be 0 or an integer of 1 or more. q3 is preferably 0 to 6, more preferably 0 to 3. N1, n2 and n3 may be each independently 0 or an integer of 1 or more. n1 to n3 are each independently preferably 0 to 6, more preferably 0 to 3, and still more preferably 1 to 3.

Specific examples of the present compound include the following compounds.

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Wherein m21 to m121 each independently represents a repetition number, OCF in the formula ₂ And OCF ₂ CF ₂ The bonding order of (2) is arbitrary. R ^f Represents a fluoroalkylene or polyfluoropolyether chain. m21 to m121 are each independently an integer of 1 to 500, and m1 is appropriately adjusted within a range of 1 to 500.

< method for producing the present Compound >

As an example of the method for synthesizing the compound (1), a method (a) of reacting the following compound (1A) with the following compound (1B) or the following compound (2B) can be cited.

R ^f2 -Q ¹ (-T) _n1+1 Formula (1A)

R ^f1 -OH formula (1B)

R ^f1 -COOH formula (2B)

The symbols are the same as those in formula (1), and the preferable embodiment is also the same.

In addition, as an example of a method for synthesizing the compound (2), a method (B) of reacting the following compound (2A) with the following compound (1B) or the following compound (2B) can be cited.

(T-) _n2+1 Q ² -R ^f3 -Q ³ (-T) _n3+1 Formula (2A)

R ^f1 -OH formula (1B)

R ^f1 -COOH formula (2B)

The symbols are the same as those in the formula (2), and the preferable embodiment is also the same.

In the above synthesis methods, L of T is reacted with the compound (1B) or the compound (2B). According to this method, R in the compound (1) can be easily produced ^f1 And R ^f2 R in Compound (2) ^f1 And R ^f3 The degree of freedom in molecular design increases for different polyfluoropolyether chains.

When a plurality of L are present in the compound (1A) and the compound (2A), the plurality of L may react with the compound (1B) or the compound (2B) to introduce a plurality of R ^f1 (for example, the following compound (1C) or the following compound (2C)).

{R ^f1 -A ¹ -Si(R ¹ ) ₂ } ₂ -Q ¹ (-T) _n1-1 -R ^f2 Formula (1C)

{R ^f1 -A ¹ -Si(R ¹ ) ₂ } ₂ -Q ² (-T) _n2-1 -R ^f3 -Q ³ (-T) _n3-1 {-Si(R ² ) ₂ -A ² -R ^f1 } ₂ Formula (2C)

The symbols are the same as those in formula (1) or formula (2), and the preferred embodiments are also the same.

However, it was confirmed that: the compound (1) is preferentially produced according to the method (a), and the compound (2) is preferentially produced according to the method (B). The compound (1C) and the compound (2C) present as by-products may also function as a coating agent exhibiting fingerprint removability and finger sliding property, and as described later, may be used as a coating agent in a mixed state with the present compound.

As the compound (1A) and the compound (2A), for example, synthesis can be performed with reference to international publication nos. 2017/038832, 2017/038830, 2018/216630, and the like. Compound (1B) can be synthesized with reference to international publication No. 2017/038832 and the like. Compound (2B) can be synthesized with reference to international publication No. 2017/038832 and the like. Further, commercially available products can be used.

[ composition containing fluorine-containing Compound ]

The composition containing a fluorine-containing compound of the present invention (hereinafter also referred to as the present composition) contains the fluorine-containing compound as the present compound, and contains a fluorine-containing compound other than the present compound and at least any one of the following impurities. Examples of the impurities include compounds which are unavoidable in the production of the present compound and other fluorine-containing compounds. The composition does not contain a liquid medium described later.

Examples of the other fluorine-containing compound include a fluorine-containing compound which is by-produced in the production process of the present compound (hereinafter also referred to as a by-produced fluorine-containing compound), a known fluorine-containing compound which is used for the same purpose as the present compound, and the like. The compounds (1A) and (2A) used as the raw materials in the above synthesis method correspond to known fluorine-containing compounds used for the same purposes as the present compounds.

The other fluorine-containing compound is preferably a compound which has a low risk of reducing the characteristics of the present compound.

From the viewpoint of sufficiently exhibiting the characteristics of the present compound, the content of the other fluorine-containing compound is preferably less than 50% by mass, more preferably less than 30% by mass, and still more preferably less than 10% by mass in the total amount of the present composition.

As the by-product fluorine-containing compound, there may be mentioned a fluorine-containing compound in the case of synthesizing the compound, and the like. Examples thereof include the compound (1C) and the compound (2C) which are by-produced in the above-mentioned synthesis method. Since the compound (1C) and the compound (2C) can also function as a coating agent exhibiting fingerprint removability and finger sliding property, when the present composition contains a by-product fluorine-containing compound, the purification step for removing the by-product fluorine-containing compound or reducing the amount of the by-product fluorine-containing compound can be simplified.

Examples of the known fluorine-containing compound include those described in the following documents.

Perfluoropolyether-modified aminosilane described in Japanese patent application laid-open No. 11-029585,

A silicon-containing organic fluoropolymer described in Japanese patent No. 2874715,

An organosilicon compound described in Japanese patent laid-open publication No. 2000-144097,

Perfluoropolyether-modified aminosilane described in Japanese patent laid-open No. 2000-327772,

Fluorinated siloxane described in JP 2002-506887A,

An organosilicon compound described in JP 2008-534696A,

A fluorinated modified hydrogen-containing polymer described in Japanese patent No. 4138936,

Compounds described in U.S. patent application publication No. 2010/0129672, international publication No. 2014/126064, and Japanese patent application laid-open No. 2014-070163,

Organosilicon compounds described in International publication Nos. 2011/060047 and 2011/059430,

A fluorine-containing organic silane compound described in International publication No. 2012/064649,

Fluorooxyalkylene group-containing polymer described in Japanese patent laid-open No. 2012-72272,

Fluorinated ether compounds described in International publication Nos. 2013/042732, 2013/121984, 2013/121985, 2013/121986, 2014/163004, japanese patent laid-open publication No. 2014-080473, international publication No. 2015/087902, international publication No. 2017/038830, international publication No. 2017/038832, and International publication No. 2017/187775,

Silane compounds containing perfluoro (poly) ether described in Japanese patent laid-open publication No. 2014-218639, international publication Nos. 2017/022437, 2018/079743 and 2018/143433,

Polymer-modified silane containing a fluoropolyether group described in Japanese patent laid-open Nos. 2015-199906, 2016-204656, 2016-210854 and 2016-222859,

A fluorine-containing ether compound described in International publication Nos. 2018/216630, 2019/039226, 2019/039341, 2019/039186, 2019/044479, japanese patent application laid-open Nos. 2019-44158 and 2019/163282.

Further, examples of commercially available fluorine-containing compounds include KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by shin-Etsu chemical industries, afluid (registered trademark) S550 manufactured by AGC, OPTOOL (registered trademark) DSX, OPTOOL (registered trademark) AES, OPTOOL (registered trademark) UF503, OPTOOL (registered trademark) UD509 manufactured by Dajin industries, and the like.

The proportion of the present compound in the present composition is less than 100% by mass, preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more.

When the present composition contains another fluorine-containing compound, the proportion of the other fluorine-containing compound in the present composition to the total amount of the present compound and the other fluorine-containing compound is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less.

The total ratio of the present compound to other fluorine-containing compounds in the present composition is preferably 80% by mass or more, and more preferably 85% by mass or more.

When the content of the present compound and the other fluorine-containing compound is within the above range, the surface layer is excellent in water/oil repellency, abrasion resistance, fingerprint stain removal property, finger sliding property, and appearance.

[ coating solution ]

The coating liquid of the present invention (hereinafter also referred to as the present coating liquid) contains the present compound or the present composition, and contains a liquid medium. The coating liquid may be a solution or a dispersion as long as it is a liquid.

The coating liquid may contain the present compound or the present composition, and may contain impurities such as by-products generated in the production process of the present compound.

The concentration of the present compound or the present composition in the present coating liquid is preferably 0.001 to 40% by mass, preferably 0.01 to 20% by mass, and more preferably 0.1 to 10% by mass.

As the liquid medium, an organic solvent is preferable. The organic solvent may be a fluorine-containing organic solvent, a non-fluorine-containing organic solvent, or both.

Examples of the fluorine-containing 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. Examples of the commercially available product include C ₆ F ₁₃ H (ASAHIKLIN (registered trademark) AC-2000)、C ₆ F ₁₃ C ₂ H ₅ (ASAHIKLIN (registered trademark) AC-6000, manufactured by AGC Co., ltd.), C ₂ F ₅ CHFCHFCF ₃ (Vertrel (registered trademark) XF, manufactured by Chemours).

Examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis (trifluoromethyl) benzene.

The fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms. Examples of commercially available products include CF ₃ CH ₂ OCF ₂ CF ₂ H (ASAHIKLIN (registered trademark) AE-3000, manufactured by AGC Co., ltd.), C ₄ F ₉ OCH ₃ (Novec (registered trademark) 7100, manufactured by 3M Co., ltd.), C ₄ F ₉ OC ₂ H ₅ (Novec (registered trademark) 7200, manufactured by 3M Co., ltd.), C ₂ F ₅ CF(OCH ₃ )C ₃ F ₇ (Novec (registered trademark) 7300, manufactured by 3M Co.).

Examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.

Examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol and the like.

The non-fluorine-containing organic solvent is preferably a compound formed only from hydrogen atoms and carbon atoms and a compound formed only from hydrogen atoms, carbon atoms and oxygen atoms, and examples thereof include hydrocarbon-based organic solvents, alcohol-based organic solvents, ketone-based organic solvents, ether-based organic solvents and ester-based organic solvents.

The coating liquid preferably contains 75 to 99.999% by mass of the liquid medium, preferably 85 to 99.99% by mass, and particularly preferably 90 to 99.9% by mass.

The coating liquid may contain other components than the compound or the composition and the liquid medium, within a range not impairing the effects of the present invention.

Examples of the other component include known additives such as an acid catalyst and a basic catalyst which promote hydrolysis and condensation reactions of the hydrolyzable silyl group.

The content of other components in the present coating liquid is preferably 10% by mass or less, more preferably 1% by mass or less.

The total amount of the present compound and other components or the total amount of the present composition and other components (hereinafter also referred to as solid content concentration) in the present coating liquid is preferably 0.001 to 40% by mass, preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, and still more preferably 0.01 to 1% by mass. The solid content concentration of the coating liquid was calculated from the mass of the coating liquid before heating and the mass of the coating liquid after heating for 4 hours in a convection dryer at 120 ℃.

[ article ]

Fig. 1 is a schematic cross-sectional view showing an example of an article of the present invention. The first article of the invention is an article 20 having in sequence a base substrate 12, a base layer 14 and a surface layer 22,

the base layer contains an oxide containing silicon, and the surface layer contains a condensate of the present compound.

The material and shape of the base material in the first article may be appropriately selected depending on the use of the article. Examples of the material of the substrate include glass, resin, sapphire, metal, ceramic, stone, and a composite material thereof. The glass may be chemically strengthened. In particular, substrates required to be water-and oil-repellent include substrates for touch panels, substrates for displays, substrates constituting housings of electronic devices, and the like. The substrate for touch panels and the substrate for displays have light-transmitting properties. "having light transmittance" means: according to JIS R3106:1998 The perpendicular incidence type visible light transmittance of (ISO 9050. As a material of the substrate for a touch panel, glass or a transparent resin is preferable.

The base material may be subjected to surface treatment such as corona discharge treatment, plasma graft polymerization treatment, or the like on the surface provided with the base layer. The surface-treated surface further has excellent adhesion between the base layer and the base layer, and as a result, the wear resistance of the surface layer is further improved. As the surface treatment, corona discharge treatment or plasma treatment is preferable in terms of further excellent abrasion resistance of the surface layer.

The underlayer is a layer containing an oxide containing at least silicon, and may further contain another element. The underlayer contains silicon oxide, and the partial structure (2) of the present compound undergoes dehydration condensation to form an Si — O — Si bond with the underlayer, thereby forming a surface layer having excellent abrasion durability.

The content of silicon oxide in the underlayer may be 65 mass% or more, preferably 80 mass% or more, more preferably 85 mass% or more, and further preferably 90 mass% or more. When the content of the silicon oxide is not less than the lower limit of the above range, a sufficient Si-O-Si bond is formed in the underlayer, and the mechanical properties of the underlayer are sufficiently secured. The content of silicon oxide is a total residual amount obtained by subtracting the total content of other elements (in the case of oxide, the amount in terms of oxide) from the mass of the underlying layer.

From the viewpoint of durability of the surface layer, the oxide in the underlayer preferably further contains 1 or more elements selected from the group consisting of alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium, molybdenum, and tungsten. By containing these elements, the bonding between the underlayer and the present compound is enhanced, and the wear resistance is improved.

When the underlayer contains 1 or more selected from iron, nickel and chromium, the total content thereof is preferably 10 to 1100 mass ppm, more preferably 50 to 1100 mass ppm, further preferably 50 to 500 mass ppm, and particularly preferably 50 to 250 mass ppm, in terms of the ratio to the silicon oxide.

When the base layer contains 1 or more species selected from aluminum and zirconium, the total content thereof is preferably 10 to 2500 mass ppm, more preferably 15 to 2000 mass ppm, and still more preferably 20 to 1000 mass ppm.

When the base layer contains an alkali metal element, the total content thereof is preferably 0.05 to 15% by mass, more preferably 0.1 to 13% by mass, and still more preferably 1.0 to 10% by mass. The alkali metal elements include lithium, sodium, potassium, rubidium, and cesium.

When the base layer contains platinum group elements, the total content thereof is preferably 0.02 mass ppm or more and 800 mass ppm or less, more preferably 0.04 mass ppm or more and 600 mass ppm or less, and still more preferably 0.7 mass ppm or more and 200 mass ppm or less. The platinum group element includes platinum, rhodium, ruthenium, palladium, osmium, and iridium.

When the underlying layer contains 1 or more selected from boron and phosphorus, the ratio of the total molar concentration of boron and phosphorus to the molar concentration of silicon is preferably 0.003 to 9, more preferably 0.003 to 2, and even more preferably 0.003 to 0.5, in terms of the wear resistance of the surface layer.

When the underlayer contains an alkaline earth metal element, the ratio of the total molar concentration of the alkaline earth metal element to the molar concentration of silicon is preferably 0.005 to 5, more preferably 0.005 to 2, and still more preferably 0.007 to 2, in terms of the wear resistance of the surface layer. The alkaline earth metal elements include lithium, sodium, potassium, rubidium, and cesium.

The base layer is preferably a silicon oxide layer containing an alkali metal atom, in order to improve the adhesiveness of the present compound and to improve the water/oil repellency and abrasion resistance of an article. Wherein in the silicon oxide layer, the average value of the concentration of alkali metal atoms in a region having a depth of 0.1 to 0.3nm from the surface in contact with the surface layer is preferably 2.0X 10 ¹⁹ atoms/cm ³ As described above. On the other hand, the average value of the concentration of the alkali metal atoms is preferably 4.0 × 10 in order to sufficiently secure the mechanical properties of the silicon oxide layer ²² atoms/cm ³ The following.

The thickness of the base layer is preferably from 1 to 200nm, particularly preferably from 2 to 20nm. If the thickness of the base layer is not less than the lower limit of the above range, the effect of improving the adhesiveness by the base layer can be easily obtained sufficiently. If the thickness of the base layer is equal to or less than the upper limit of the above range, the wear resistance of the base layer itself becomes high. Examples of the method for measuring the thickness of the base layer include a method based on observation of a cross section of the base layer by an electron microscope (SEM, TEM, or the like); methods using an optical interference film thickness meter, spectroscopic ellipsometer, height difference meter, and the like.

Examples of the method for forming the base layer include a method of depositing a deposition material having a desired composition of the base layer on the surface of the substrate by vapor deposition.

As an example of the vapor deposition method, a vacuum vapor deposition method can be given. The vacuum deposition method is a method in which a deposition material is evaporated in a vacuum chamber and attached to the surface of a substrate.

The temperature during vapor deposition (for example, the temperature of a boat in which a vapor deposition material is placed when a vacuum vapor deposition apparatus is used) is preferably 100 to 3000 ℃, and particularly preferably 500 to 3000 ℃.

The pressure at the time of vapor deposition (for example, the absolute pressure in a tank in which a vapor deposition material is provided when a vacuum vapor deposition apparatus is used) is preferably 1Pa or less, and particularly preferably 0.1Pa or less.

When the base layer is formed using a vapor deposition material, 1 type of vapor deposition material may be used, or 2 or more types of vapor deposition materials containing different elements may be used.

Examples of the evaporation method of the deposition material include a resistance heating method in which the deposition material is melted and evaporated on a resistance heating boat made of a high melting point metal; an electron gun method in which an electron beam is irradiated to a deposition material to directly heat the deposition material to melt and evaporate the surface of the deposition material. As a method for evaporating the vapor deposition material, an electron gun method is preferable because a high melting point substance can be evaporated because it can be locally heated, and because a portion not irradiated with an electron beam is low in temperature, there is no concern about a reaction with a container and contamination of impurities. As a vapor deposition material used in the electron gun method, a molten granular material or a sintered body is preferable in terms of being less likely to scatter even if a gas flow is generated.

The surface layer on the base layer contains a condensate of the above-described present compound. The condensate of the present compound comprises: the hydrolyzable silyl group in the present compound forms a silanol group (Si-OH) by hydrolysis, the silanol group forms an Si-O-Si bond by intermolecular condensation, and the silanol group in the present compound forms an Si-O-Si bond by condensation with a silanol group or an Si-OM group (wherein M is an alkali metal element) on the surface of the underlayer. In addition, the surface layer may contain a condensate of a fluorine-containing compound other than the present compound. That is, the surface layer contains the fluorine-containing compound having the reactive silyl group in a state in which a part or all of the reactive silyl groups of the fluorine-containing compound are subjected to a condensation reaction.

The thickness of the surface layer is preferably 1 to 100nm, particularly preferably 1 to 50nm. If the thickness of the surface layer is not less than the lower limit of the above range, the effect of the surface layer can be sufficiently obtained. If the thickness of the surface layer is not more than the upper limit of the above range, the utilization efficiency is high.

The thickness of the surface layer was measured by an X-ray diffractometer for thin film analysis. The thickness of the surface layer can be calculated as follows: an interference pattern reflecting X-rays is obtained by an X-ray reflectance method using an X-ray diffractometer for thin film analysis, and the oscillation period of the interference pattern can be calculated.

The second article of the present invention is based on an article 20 having a substrate 12 and a surface layer 22,

the substrate contains an oxide containing silicon,

the surface layer contains a condensate of the present compound.

The base material of the second article has the composition of the base layer in the first article, and therefore, even if the surface layer is directly formed on the base material, the abrasion durability of the surface layer is excellent.

The material of the base material in the second article may have the composition of the base layer, and may be, for example, a glass base material. The material of the base material is the same as that of the base layer, and therefore, the description thereof will be omitted. Since the surface layer has the same structure as the first article, the description thereof will be omitted.

[ method for producing article ]

The method for manufacturing an article of the present invention is a method comprising: the surface layer is formed by a dry coating method or a wet coating method using the fluorine-containing compound, the composition containing the fluorine-containing compound, or the coating liquid.

The present compounds and the present compositions can be used directly in dry coating processes. The compound and the composition are suitable for forming a surface layer having excellent adhesion by a dry coating method. Examples of the dry coating method include vacuum deposition, CVD, sputtering, and the like. The vacuum deposition method can be suitably used from the viewpoint of suppressing the decomposition of the present compound and the viewpoint of the simplicity of the apparatus.

For the vacuum deposition, a granular material in which the compound is supported on a porous metal body made of a metal material such as iron or steel can be used. The granular substance loaded with the present compound can be produced as follows: the metal porous body is impregnated with a solution of the present compound, dried, and the liquid medium is removed. The coating liquid can be used as a solution of the compound.

The coating liquid can be suitably used for a wet coating method. Examples of the wet coating method include spin coating, wire coating, spray coating, blade coating, dip coating, die coating, ink jet coating, flow coating, roll coating, casting, langmuir-Blodgett method, and gravure coating.

In order to improve the abrasion resistance of the surface layer, an operation for promoting the reaction of the present compound with the base material may be performed as necessary. Examples of such operations include heating, humidification, and light irradiation. For example, the substrate having the surface layer formed thereon is heated in an atmosphere containing moisture, and the hydrolysis reaction of the hydrolyzable group, the reaction of the hydroxyl group or the like on the substrate surface with the silanol group, the formation of a siloxane bond by the condensation reaction of the silanol group, or the like can be promoted.

After the surface treatment, the compound not chemically bonded to the compound in the surface layer, that is, other compound or the base material can be removed as necessary. Specific examples of the method include: a method of allowing a solvent to flow on a surface layer, a method of wiping off with a cloth impregnated with a solvent, and the like.

Examples

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Examples 1 to 10 and 12 are examples, and examples 11 and 13 are comparative examples. In addition, CCl is defined below ₂ FCClF ₂ Denoted as R-113, CClF ₂ CF ₂ CCl ₂ CF ₂ CF ₃ Denoted as R-419, denotes CF ₃ CH ₂ OCF ₂ CF ₂ H noteAE-3000, C ₆ F ₁₃ H is denoted as AC-2000, CF ₃ CF ₂ CHCl ₂ Denoted as AK-225, C ₄ F ₉ OC ₂ H ₅ Designated HFE-7200.

[ example 1] Synthesis of Compound I

(Synthesis examples 1-1)

The following compound (1 a) was synthesized according to the method described in example 3-4 of International publication No. 2017/038832.

Formula (1 a)

Wherein x1 averages 13.

(Synthesis examples 1-2)

The following compound (1 b) was synthesized according to the method described in examples 1 to 5 of International publication No. 2017/038832.

Formula (1 b)

Wherein y1 averages 21 and z1 averages 20.

(Synthesis examples 1 to 3)

At N ₂ In a 50mL flask, HFE-720020.0g, the compound (1 a) 5.0g and the compound (1 b) in an amount equivalent to the molar amount were added under an atmosphere, and the mixture was heated and stirred at 60 ℃ to obtain the compound (I) below. Confirmed by Si-NMR: si of the compound (1 a) forms a bond with OH of the compound (1 b). In addition, the product was confirmed by F-NMR.

Formula (1)

Wherein x1 averages 13, y1 averages 21, and z1 averages 20.

[ example 2] Synthesis of Compound II

(Synthesis example 2-1)

The following compound (2 b) was synthesized according to the method described in example 7 of international publication No. 2013/121984.

Formula (2 b)

Where x2 averages 13.

(Synthesis examples 2-2)

At N ₂ To a 50mL flask were added HFE-720010.0g, the compound (1 a) 2.0g and the compound (2 b) in an amount equivalent to the molar amount thereof under an atmosphere, and the mixture was heated and stirred at 60 ℃ to obtain the compound (II). Confirmed by Si-NMR: si of the compound (1 a) forms a bond with OH of the compound (2 b). In addition, the product was confirmed by F-NMR.

Formula (II)

Where x2 averages 13 and y2 averages 13.

[ example 3] Synthesis of Compound III

(Synthesis example 3-1)

FLUOROL INK (registered trademark) D4000 (the following compound (3 b)) manufactured by Solvay Solexis was prepared.

In N ₂ In a 50mL flask, HFE-720010.0g, the compound (1 a) 1.0g and the compound (3 b) in an amount equivalent to the molar amount were added under an atmosphere, and the mixture was heated and stirred at 60 ℃ to obtain the compound (III). Confirmed by Si-NMR: si of the compound (1 a) forms a bond with OH of the compound (3 b). In addition, the product was confirmed by F-NMR.

Formula (3 b)

Wherein y3 averages 21 and z3 averages 20.

Formula (III)

Wherein x3 averages 13, y3 averages 21, and z3 averages 20.

[ example 4] Synthesis of Compound IV

(Synthesis example 4-1)

The following compound (4 a) was synthesized according to the method described in example 11-3 of International publication No. 2017/038830.

Formula (4 a)

Where x4 averages 13.

(Synthesis examples 4-2)

The following compound (4 b) was synthesized according to the method described in example 1-1 of International publication No. 2017/038832.

Formula (4 b)

Wherein y4 has an average value of 21 and z4 has an average value of 20.

(Synthesis examples 4 to 3)

In N ₂ In a 50mL flask, HFE-720010.0g, the compound (4 a) 2.0g and the compound (4 b) in an amount equivalent to the molar amount were added under an atmosphere, and the mixture was heated and stirred at 60 ℃ to obtain the compound (IV). Confirmed by Si-NMR: si of the compound (4 a) forms a bond with OH of the compound (4 b). In addition, the product was confirmed by F-NMR.

Formula (IV)

Wherein x4 averages 13, y4 averages 21, and z4 averages 20.

[ example 5] Synthesis of Compound V

(Synthesis example 5-1)

The following compound (5 a) was synthesized according to the method described in examples 5 to 8 of International publication No. 2018/216630.

Formula (5 a)

Where x5 averages 9.

(Synthesis examples 5-2)

In N ₂ In a 50mL flask, HFE-720010.0g, the compound (5 a) 1.0g and the compound (1 b) in an amount equivalent to the molar amount were added under an atmosphere, and the mixture was heated and stirred at 60 ℃ to obtain the compound (V). The product was confirmed by NMR. Confirmed by Si-NMR: si of the compound (5 a) forms a bond with OH of the compound (1 b). In addition, the product was confirmed by F-NMR.

Formula (V)

Wherein x5 averages 9, y5 averages 21, and z5 averages 20.

[ example 6] Synthesis of Compound VI

(Synthesis example 6-1)

The following compound (6-1) was synthesized according to the method of example 1 of International publication No. 2013/121984. Wherein, in the silica gel chromatography, a fraction with x6 of the following formula (6-1) having an average value of 5 was separated.

Formula (6-1)

Where x6 averages 5.

(Synthesis examples 6-2)

A100 cc pressure resistant reactor was charged with 9.0g of Compound (6-1), 50g of ASAHIKLIN AK-225 (product name, manufactured by AGC Co., ltd.), and 7.5g of a 2.0M ammonia-methanol solution, and the mixture was stirred at room temperature for 6 hours. Thereafter, the solvent was distilled off to obtain the following compound (6-2).

Formula (6-2)

(Synthesis examples 6 to 3)

9.0g of Compound (6-2), AK-22575g, and 30g of diethyl ether were added to a 300cc eggplant type flask, and stirred while cooling on ice. Thereafter, 0.31g of lithium aluminum hydride was slowly added thereto, and the mixture was stirred at room temperature. Thereafter, 0.3cc of a saturated aqueous solution of sodium sulfate was added and the precipitated solid was removed by Celite filtration. The obtained filtrate was concentrated and purified by silica gel column chromatography to obtain the following compound (6-3).

Formula (6-3)

(Synthesis examples 6-4)

HO (C = O) C (CH) was added to a 50cc eggplant type flask ₂ CH＝CH ₂ ) ₃ 0.2g, 10mL of methylene chloride and 0.2mL of oxalyl chloride were stirred under ice-cooling, and then 0.02g of DMF (N, N-dimethylformamide) was added thereto. Then, the mixture was stirred at room temperature and then concentrated to obtain Cl (C = O) C (CH) ₂ CH＝CH ₂ ) ₃ 0.18g。

In a 50cc eggplant-shaped flask, 1.8g of compound (6-3) and 0.35mL of triethylamine were added, and the above-mentioned Cl (C = O) C (CH) was added ₂ CH＝CH ₂ ) ₃ And 2mL of 1, 3-bistrifluoromethylbenzene. The mixture was stirred for 1 hour to distill off the solvent. The obtained crude product was purified by silica gel column chromatography to obtain the following compound (6-4).

Formula (6-4)

(Synthesis examples 6-5)

To a 50cc eggplant type flask purged with nitrogen, 0.6g of the compound (6-4), 0.003g of a xylene solution of platinum/1, 3-divinyl-1, 3-tetramethyldisiloxane complex (platinum content: 3 mass%), 0.0009g of aniline, and 1.0g of AC-6000 (product name, manufactured by AGC Co., ltd.) were added, 0.11g of trimethoxysilane was added, and the mixture was stirred at 40 ℃. Thereafter, an equivalent amount of a xylene solution of platinum/1, 3-divinyl-1, 3-tetramethyldisiloxane complex (platinum content: 3 mass%), aniline, and AC-6000 were further added thereto, and the mixture was stirred for 7 hours, followed by evaporation of the solvent to obtain the following compound (6 a).

Formula (6 a)

(Synthesis examples 6 to 6)

In N ₂ In a 50mL flask, HFE-720010.0g, the compound (6 a) 0.5g and the compound (1 b) in an amount equivalent to the molar amount were added under an atmosphere, and the mixture was heated and stirred at 60 ℃ to obtain the compound (VI). Confirmed by Si-NMR: si of the compound (6 a) forms a bond with OH of the compound (1 b). In addition, the product was confirmed by F-NMR.

Formula (VI)

Wherein x6 averages 5, y6 averages 21, and z6 averages 20.

[ example 7] Synthesis of Compound VII

(Synthesis example 7-1)

Into a 50ml eggplant type flask, 3.0g of the following compound (7-1) and HO-CH were charged ₂ C(CH ₂ CH＝CH ₂ ) ₃ 0.55g, naF 0.14g, and AC-20003.0g, and stirred at 30 ℃ for 5 hours. The obtained crude product was purified by silica gel chromatography to obtain the following compound (7-2).

Formula (7-1)

Where x7 averages 13.

Formula (7-2)

Synthesis example 7-2

1.0g of the compound (7-2), 0.003g of a xylene solution (platinum content: 3 mass%) of platinum/1, 3-divinyl-1, 3-tetramethyldisiloxane complex, 0.0009g of aniline, and 0.11g of trimethoxysilane were added to a 50cc eggplant type flask purged with nitrogen (AC-60001.0 g), and the mixture was stirred at 40 ℃. Thereafter, an equivalent amount of a xylene solution of platinum/1, 3-divinyl-1, 3-tetramethyldisiloxane complex (platinum content: 3 mass%), aniline, and AC-6000 were further added thereto, and the mixture was stirred, followed by evaporation of the solvent to obtain compound (7 a).

Formula (7 a)

(Synthesis examples 7 to 3)

In N ₂ To a 50mL flask were added HFE-720010.0g, the compound (7 a) 1.5g and the compound (1 b) in an amount equivalent to the molar amount thereof under an atmosphere, and the mixture was heated and stirred at 60 ℃ to obtain the compound (VII). Confirmed by Si-NMR: si of the compound (7 a) forms a bond with OH of the compound (1 b). In addition, the product was confirmed by F-NMR.

Formula (VII)

Wherein x7 averages 13, y7 averages 21, and z7 averages 20.

[ example 8] Synthesis of Compound VIII

(Synthesis example 8-1)

Compound (8-1) was synthesized by the same synthesis method as described in synthesis examples 1 to 4 of japanese patent No. 6024816.

CH ₃ OCOCF ₂ -(OCF ₂ ) _x8 -(OCF ₂ CF ₂ ) _y8 -OCF ₂ CO ₂ CH ₃ Formula (8-1)

Where x8 averages 26 and y8 averages 22.

(Synthesis examples 8-2)

Compound (8-2) was synthesized by the method described in International publication Nos. 2018/216630 (examples 13-1) to 13-2).

CF ₃ CF ₂ CF ₂ -O-CHF-CF ₂ OCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ OTs formula (8-2)

(Ots represents-O-SO) ₂ -Ph-CH ₃ Ph represents a phenylene group. )

(Synthesis examples 8 to 3)

Into a 300mL three-necked flask were charged 4g of the compound (8-2), 30g of the compound (8-1), and 160g of 1, 3-bis (trifluoromethyl) benzene, and 12g of cesium carbonate was added. Stirring was carried out at 70 ℃ under a nitrogen atmosphere. After filtering the solid, washing with water and recovering the organic phase. After concentration under reduced pressure, the mixture was purified by means of silica gel column chromatography to obtain 12g of compound (8-3).

CF ₃ CF ₂ CF ₂ -O-CHF-CF ₂ OCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ O-CH ₂ -CF ₂ -{(OCF ₂ ) _x8 (OCF ₂ CF ₂ ) _y8 }-OCF ₂ -CH ₂ -OH formula (8-3)

(Synthesis examples 8 to 4)

In a 100mL eggplant type flask, 12g of the compound (8-3) and 2.3g of sodium fluoride powder were put, and CF was added ₃ CF ₂ CF ₂ OCF(CF ₃ ) C (O) F11 g. Stirring was carried out under a nitrogen atmosphere. By filteringAfter removing the sodium fluoride powder, the excess CF was distilled off under reduced pressure ₃ CF ₂ CF ₂ OCF(CF ₃ ) C (O) F to obtain 12g of the compound (8-4).

CF ₃ CF ₂ CF ₂ -O-CHF-CF ₂ OCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ O-CH ₂ -CF ₂ -{(OCF ₂ ) _x8 (OCF ₂ CF ₂ ) _y8 }-OCF ₂ -CH ₂ -OC(O)CF(CF ₃ )OCF ₂ CF ₂ CF ₃ Formula (8-4)

(Synthesis examples 8-5)

A cooler maintained at 20 ℃, a NaF pellet packed layer, and a cooler maintained at 0 ℃ were disposed in series at the gas outlet of a 1L nickel autoclave. A liquid-returning line was provided for returning the liquid collected by the cooler maintained at 0 ℃ to the autoclave.

CFE-419 (750 g) was charged into the autoclave, and the mixture was stirred while maintaining the temperature at 25 ℃. After blowing nitrogen gas into the autoclave at 25 ℃ for 1 hour, 20% fluorine gas was blown into the autoclave at 25 ℃ for 1 hour at a flow rate of 2.0L/hour. While blowing 20% fluorine gas at the same flow rate, a solution obtained by dissolving 6.0g of the compound (8-4) in CFE-419 54g was injected into the autoclave over 1 hour. While blowing 20% fluorine gas at the same flow rate, the internal pressure of the autoclave was increased to 0.15MPa (gauge pressure). While heating 4mL of a benzene solution containing 0.05g/mL of benzene in CFE-419 from 25 ℃ to 40 ℃, the solution was injected into the autoclave, and the benzene solution injection port of the autoclave was closed. After stirring, 4mL of the benzene solution was again injected while maintaining the temperature at 40 ℃ and the injection port was closed. The same operation is repeated. The total amount of benzene injected was 0.17g. 20% fluorine gas was blown in at the same flow rate while stirring was continued. The pressure in the autoclave was set to atmospheric pressure, and nitrogen gas was blown in. The contents of the autoclave were concentrated by using a rotary evaporator to obtain 6.1g of compound (8-5).

CF ₃ CF ₂ CF ₂ -O-CF ₂ -CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O-CF ₂ -CF ₂ -{(OCF ₂ ) _x8 (OCF ₂ CF ₂ ) _y8 }-OCF ₂ -CF ₂ -OC(O)CF(CF ₃ )OCF ₂ CF ₂ CF ₃ Formula (8-5)

(Synthesis examples 8 to 6)

6.1g of compound (8-5) and 10g of AK-225 were placed in a round-bottomed PFA flask. While the mixture was stirred with cooling in an ice bath, 10g of methanol was slowly dropped from the dropping funnel under a nitrogen atmosphere. Stirred for 12 hours. The reaction mixture was concentrated by using a rotary evaporator to obtain 5.5g of compound (8-6).

CF ₃ CF ₂ CF ₂ -O-CF ₂ -CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O-CF ₂ -CF ₂ -{(OCF ₂ ) _x8 (OCF ₂ CF ₂ ) _y8 }-OCF ₂ -C(O)OCH ₃ Formula (8-6)

(Synthesis examples 8 to 7)

2.4g of sodium borohydride powder was put into a 300cc three-necked round-bottomed flask, and AC-2000 15g was added. While the mixture was stirred with cooling in an ice bath, a solution prepared by mixing 30g of the compound (8-6), 4g of methanol and AC-2000 60g was slowly dropped from a dropping funnel under a nitrogen atmosphere so that the internal temperature did not exceed 10 ℃. After the entire amount was added dropwise, 4g of methanol was further added dropwise. Thereafter, stirring was carried out at 10 ℃. The mixture was cooled again in an ice bath, and an aqueous hydrochloric acid solution was added dropwise.

After the reaction is finished, the organic phase is recovered by sequentially washing with a hydrochloric acid solution and water. The recovered organic phase was concentrated and distilled off under reduced pressure to obtain compound (8-7).

CF ₃ CF ₂ CF ₂ -O-CF ₂ -CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O-CF ₂ -CF ₂ -{(OCF ₂ ) _x8 (OCF ₂ CF ₂ ) _y8 }-OCF ₂ -CH ₂ -OH formula (8-7)

(Synthesis examples 8 to 8)

HO (C = O) C (CH) was added to a 200cc eggplant type flask ₂ CH＝CH ₂ ) ₃ 0.67g, dichloromethane 33mL, and oxalyl chloride 0.67mL were stirred under ice-cooling, and thereafter, 0.0393g of DMF (N, N-dimethylformamide) was added. Thereafter, the mixture was stirred at room temperature and then concentrated to obtain Cl (C = O) C (CH) ₂ CH＝CH ₂ ) ₃ 0.6g。

In a 50cc eggplant type flask, 7g of the compound (8-7), 0.4g of triethylamine, 0.2g of N, N-dimethyl-4-aminopyridine, and Cl (C = O) C (CH) were added ₂ CH＝CH ₂ ) ₃ 0.6g, stirred at 30 ℃. The obtained reaction solution was purified by silica gel chromatography to obtain compound (8-8).

CF ₃ CF ₂ CF ₂ -O-CF ₂ -CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O-CF ₂ -CF ₂ -{(OCF ₂ ) _x8 (OCF ₂ CF ₂ ) _y8 }-OCF ₂ -CH ₂ -O(C＝O)C(CH ₂ CH＝CH ₂ ) ₃ Formula (8-8)

(Synthesis examples 8 to 9)

1.0g of the compound (8-8), 0.003g of a xylene solution of platinum/1, 3-divinyl-1, 3-tetramethyldisiloxane complex (platinum content: 3 mass%), 0.0009g of aniline, and 0.11g of trimethoxysilane were added to a 50cc eggplant-shaped flask purged with nitrogen (AC-60001.0 g), and the mixture was stirred at 40 ℃ for 4 hours. Thereafter, 0.003g of a xylene solution of platinum/1, 3-divinyl-1, 3-tetramethyldisiloxane complex (platinum content: 3 mass%), aniline and AC-6000 were further added thereto, and after stirring, the solvent was distilled off to obtain 1.1g of the compound (8 a).

Formula (8 a)

Where x8 averages 26 and y8 averages 22.

(Synthesis examples 8 to 10)

In N ₂ To a 50mL flask, HFE-720010.0g, 1.0g of the aforementioned compound (8 a), and Mole were added under an atmosphereThe same number of the above-mentioned compounds (1 b) were heated at 60 ℃ and stirred to obtain the following compound (VIII). Confirmed by Si-NMR: si of the compound (8 a) forms a bond with OH of the compound (1 b). In addition, the product was confirmed by F-NMR.

Formula (VIII)

Where x8 averages 26, y8 averages 22, z8 averages 21, and w8 averages 20.

[ example 9] Synthesis of Compound IX

(Synthesis example 9-1)

The following compound (9-1) was obtained according to the method described in example 7 of International publication No. 2013/121984.

CF ₃ -O-(CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _x9 (CF ₂ CF ₂ O)-CF ₂ CF ₂ CF ₂ -CH ₂ OH (8230); formula (9-1)

Where x9 averages 14.

Synthesis example 9-2

The above-mentioned compound (9-1) (6.8g, 1.5mmol), 2, 6-lutidine (0.76g, 7.1mmol) and AE-3000 (28.0 g) were added thereto, and the mixture was stirred at 0 ℃. Trifluoromethanesulfonic anhydride (0.99g, 3.5 mol) was added thereto, and the mixture was stirred at room temperature. After washing with water, the solvent was distilled off, and flash column chromatography was performed using silica gel to obtain 6.8g of the following compound (9-2).

CF ₃ -O-(CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _x9 (CF ₂ CF ₂ O)-CF ₂ CF ₂ CF ₂ -CH ₂ OTf 823080, formula (9-2)

Wherein OTf is trifluoromethanesulfonic group: -O-S (= O) ₂ (-CF ₃ )。

(Synthesis examples 9-3)

Diethyldiallyl malonate (60.0g, 250mmol), lithium chloride (23.7g, 559mmol), water (6.5g, 360mmol) and dimethyl sulfoxide (263 g) were added thereto, and the mixture was stirred at 160 ℃. After cooling to room temperature, water was added, and extraction was performed with ethyl acetate. Hexane was added to the organic layer, which was washed with saturated brine and dried over sodium sulfate. After filtration, the solvent was distilled off, whereby 39.5g of the following compound (9-3) was obtained.

(Synthesis examples 9 to 4)

After addition of THF (260 mL), diisopropylamine (29.8mL, 294mmol), the solution was cooled to-78 ℃. A n-butyllithium hexane solution (2.76M, 96.6mL, 294mmol) was added, and the temperature was raised to 0 ℃. After stirring, it was cooled to-78 ℃ to prepare a solution of Lithium Diisopropylamide (LDA) in THF. The above-mentioned compound (9-3) (39.5g, 235mmol) was added to a THF solution, and after stirring, allyl bromide (24.1mL, 278mmol) was added thereto. The temperature was raised to 0 ℃ and 1M hydrochloric acid (100 mL) was added to the mixture, followed by evaporation of THF under reduced pressure. After extraction with dichloromethane, sodium sulfate was added. After filtration, the solvent was distilled off, and flash column chromatography was performed using silica gel, whereby 45.0g of compound (9-4) was obtained.

(Synthesis examples 9 to 5)

The above-mentioned compound (9-4) (45.0 g, 216mmol) was dissolved in THF (620 mL) and cooled to 0 ℃. A THF solution of lithium aluminum hydride (104mL, 260mmol) was added and stirred. Water and a 15% aqueous solution of sodium hydroxide were added, and the mixture was stirred at room temperature and then diluted with dichloromethane. After filtration, the solvent was distilled off, and flash column chromatography was performed using silica gel, whereby 31.3g of the following compound (9-5) was obtained.

(Synthesis examples 9 to 6)

Acetonitrile (380 mL), the aforementioned compound (9-5) (31.3g, 188mmol), triphenylphosphine (64.3g, 2450 mmol) and carbon tetrachloride (33.9g, 221mmol) were added thereto, and the mixture was stirred at 90 ℃. After concentration, ethyl acetate/hexane was added and stirring was performed. After filtration and concentration, 28.2g of the following compound (9-6) was obtained by distillation (70 ℃ C., 3 hPa).

(Synthesis examples 9 to 7)

THF (35 mL) and iodine (0.180g, 0.71mmol) were added to magnesium (2.36g, 97.2mmol), and the mixture was stirred at room temperature. A solution of the aforementioned compound (9-6) (14.0 g,75.9 mmol) in THF (35 mL) was added, and the mixture was refluxed for 2 hours to prepare a solution (0.80M) of the following compound (9-7).

(Synthesis examples 9 to 8)

1-bromo-4-chlorobutane (2.9g, 16.8mmol), 1-phenyl-1-propyne (0.20g, 1.7mmol), and CuCl were added ₂ (0.05g, 0.36mmol) and stirring was carried out at 0 ℃. The aforementioned compound (9-7) (0.80M, 24.0mL,19.3 mmol) was added and stirred. 1M hydrochloric acid was added, extraction was performed with methylene chloride, and sodium sulfate was added. After filtration and concentration, 3.45g of the following compound (9-8) was obtained by distillation (120 ℃ C., 3 hPa).

(Synthesis examples 9 to 9)

THF (2.6 mL) and iodine (14.0 mg, 0.055mmol) were added to magnesium (0.17g, 6.9 mmol), and the mixture was stirred at room temperature. A solution of the aforementioned compound (9-8) (1.41g, 5.9 mmol) in THF (2.6 mL) was added and heated under reflux for 2 hours, thereby preparing a solution (0.74M) of the following compound (9-9).

(Synthesis examples 9 to 10)

Adding CuCl ₂ (9.9mg, 0.074mmol), 1-phenyl-1-propyne (0.019g, 0.16mmol), 1, 3-bis (trifluoromethyl) benzene (23 mL), and the above-mentioned compound (9-2) (1.5g, 0.32mmol), followed by addition of the above-mentioned compound (9-9) (4.5mL, 1.0M, 3.3mmol). After stirring at room temperature, the mixture was washed with 1M hydrochloric acid and dried over sodium sulfate. After filtration, the solvent was distilled off, and AC-6000 was added. After washing with DMF and MeOH, flash column chromatography was performed using silica gel to obtain 0.25g of the following compound (9-10).

Formula (9-10)

(Synthesis examples 9 to 11)

To this mixture were added AC2000 (1.5 g), a xylene solution of the above-mentioned compound (9-10) (0.25g, 0.048mmol), platinum/1, 3-divinyl-1, 3-tetramethyldisiloxane complex (platinum content: 2%,8.9 mg), aniline (1.3 mg), and trimethoxysilane (26.9mg, 0.221mmol), and the mixture was stirred at 40 ℃ and then the solvent was distilled off under reduced pressure to obtain 0.25g of a fluorinated ether compound (9 a) shown below. The Mw/Mn of compound (9 a) determined by the GPC method was 1.06.

Formula (9 a)

Synthesis examples 9 to 12

In a 100mL PFA eggplant type flask, 0.93g of 20% KBr aqueous solution, 0.2g of 2, 6-tetramethylpiperidine-1-oxide (TEMPO) and 25g of acetonitrile were added to 25g of the following compound (9-12) to obtain a mixture. The resulting mixture was stirred, and a mixture of 18g of a 25 mass% aqueous sodium hypochlorite solution and 2.5g of sodium hydrogencarbonate was slowly added thereto and heated at 40 ℃ for about 48 hours to obtain a reaction mixture. After the resulting reaction mixture was cooled, 30g of a 10% aqueous solution of sulfuric acid and 30g of AC-200030g were added to acidify the reaction mixture. The organic phase was recovered by washing 3 times with water and saturated brine, mixing with 10.0g of silica gel, and filtering through a filter to recover the organic phase. The recovered organic phase was concentrated by a rotary evaporator to obtain the following compound (9 b).

CF ₃ -O-(CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) _y9 CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ -CH ₂ OH type (9-12)

Where y9 averages 13.

Formula (9 b)

(Synthesis examples 9 to 13)

In N ₂ In a 50mL flask, HFE-720010.0g, the compound (9 a) 1.0g and the compound (9 b) in an amount equivalent to the molar amount were added under an atmosphere, and the mixture was heated and stirred at 60 ℃ to obtain the compound (IX) described below. Confirmed by Si-NMR: si of the compound (9 a) forms a bond with OH of the compound (9 b). In addition, the product was confirmed by F-NMR.

Formula (IX)

Where x9 averages 14 and y9 averages 13.

[ example 10] Synthesis of Compound X

(Synthesis example 10-1)

In N ₂ In a 50mL flask, HFE-720010.0g, the compound (9 a) 2.0g and the compound (1 b) in an amount equivalent to the molar amount were added under an atmosphere, and the mixture was heated and stirred at 60 ℃ to obtain the compound (X). The product was confirmed by NMR.

Formula (X)

Wherein x10 averages 14, y10 averages 21, and z10 averages 20.

[ example 11] Synthesis of Compound XI

(Synthesis example 11-1)

The following compound (XI) was obtained in accordance with example 6 of International publication No. 2013/121084.

Formula (XI)

Where x11 averages 13.

[ example 12] Synthesis of Compound XII

(Synthesis example 12-1)

The following compound (12 a) was obtained in synthesis examples 1 and 2 of international publication No. 2019/151445.

Formula (12 a)

Where x12 averages 22.

(Synthesis example 12-2)

In N ₂ In a 50mL flask, HFE-720010.0g, the compound (12 a) 1.0g and the compound (1 b) in an amount equivalent to the molar amount were added under an atmosphere, and the mixture was heated and stirred at 60 ℃ to obtain the compound (XII). Confirmed by Si-NMR: si of the compound (12 a) forms a bond with OH of the compound (1 b). In addition, the product was confirmed by F-NMR.

Formula (XII)

Where x12 averages 22, y12 averages 21, and z12 averages 20.

[ production and evaluation of articles ]

The surface of the substrate was treated with each of the compounds obtained in examples 1 to 12 and a mixture XIII of the compound (1 a) and the compound (1 b) (described as example 13), to obtain an article having a surface layer.

For each example, a surface layer was formed by performing surface treatment using a dry coating method and a wet coating method, respectively, which are described below (also referred to as a process a up to now).

Further, the surface layer was wiped with BEMCOT wetted with isopropyl alcohol in a state where a sufficient load was applied to the article after the process a of each example, thereby preparing it (also referred to as process B).

As the substrate, chemically strengthened glass is used. The obtained article was evaluated by the following method. The results are shown in Table 1.

(Dry coating method)

The dry coating was performed using a vacuum deposition apparatus (VTR-350M manufactured by ULVAC corporation) (vacuum deposition method). 0.5g of each compound or mixture obtained in examples 1 to 13 was charged into a molybdenum boat in a vacuum deposition apparatus, and the interior of the vacuum deposition apparatus was evacuated to 1X 10- ³ Pa or less. The boat in which the compound was placed was heated at a temperature rising rate of 10 ℃/min or less, and when the deposition rate based on the crystal oscillation film thickness exceeded 1 nm/sec, the shutter was opened to start film formation on the substrate surface. When the film thickness reached about 50nm, the shutter was closed, and the film formation on the substrate surface was completed. The base material on which the compound had been deposited was heat-treated at 200 ℃ for 30 minutes and washed with isopropyl alcohol, whereby an article having a surface layer on the surface of the base material was obtained.

(Wet coating method)

Each of the compounds or mixtures obtained in examples 1 to 13 was mixed with C as a liquid medium ₄ F ₉ OC ₂ H ₅ (Novec (registered trademark) 7200, manufactured by 3M.) to prepare a coating solution having a solid content of 0.05%. After the substrate was immersed in the coating liquid and left to stand for 30 minutes, the substrate was pulled up (dip coating method). The coating film was dried at 200 ℃ for 30 minutesThe article having a surface layer on the surface of the base material was obtained by washing with isopropyl alcohol.

(evaluation method)

< finger slipping Property >

Using a load fluctuation type frictional wear test system (HHS 2000, manufactured by new eastern science corporation), in the contact area: 3cm × 3cm, load: the coefficient of kinetic friction of the surface layer against an artificial skin (PBZ 13001, manufactured by PhototeCNOFINE corporation) was measured under a condition of 0.98N. The smaller the coefficient of dynamic friction, the more excellent the finger sliding property. The evaluation criteria are as follows.

Excellent: the coefficient of dynamic friction is less than 0.15.

O (good): the coefficient of dynamic friction is 0.15 or more and less than 0.20.

And (b): the coefficient of dynamic friction is 0.20 or more and less than 0.25.

X (not): the coefficient of dynamic friction is 0.25 or more.

< fingerprint removability >

After an artificial fingerprint solution (a liquid containing oleic acid and squalene) was attached to the flat surface of the silicone rubber plug, excess oil was wiped off with a nonwoven fabric (BEMCOT (registered trademark) M-3, manufactured by asahi chemicals), thereby preparing a fingerprint mark. Placing the fingerprint print on a surface layer, under a load: press for 10 seconds at 9.8N. The haze of the portion to which the fingerprint was attached was measured by a haze meter, and used as an initial value. For a portion to which a fingerprint is attached, a reciprocating type threading machine (manufactured by KNT corporation) equipped with a face tissue was used, and under a load: wiping was performed at 4.9N. The haze value was measured every time wiping was repeated, and the number of times of wiping when the haze became 10% or less from the initial value was measured. The smaller the number of wiping times, the easier the removal of fingerprint stains becomes, and the fingerprint stain wiping properties are excellent. The evaluation criteria are as follows.

Excellent: the number of wiping was 3 times or less.

O (good): the number of wiping times is 4 to 6.

Δ (optional): the number of wiping times is 6 to 8.

X (not): the number of wiping was 9 or more.

[ Table 1]

TABLE 1

It has been clarified that: having R as in the case of the compounds I to X ^f1 -A ¹ -Si(R ¹ ) ₂ The surface layer obtained from the present compound having the structure is excellent in finger slipperiness and fingerprint removability. As is clear from comparison with the results of example 13 in which compound (1 a) and compound (1 b) as starting materials of compound I were mixed: the present compound is remarkably excellent in finger sliding property and fingerprint removability with respect to a mixture of raw materials.

Industrial applicability

Examples of articles having a surface layer comprising the compound include optical articles, touch panels, antireflection films, antireflection glasses, and SiO as part of members used as the following products ₂ Treated glass, tempered glass, sapphire glass, quartz substrate, mold metal, and the like are useful.

Preparing a product: a car navigation system, a mobile phone, a digital camera, a digital video camera, a Personal Digital Assistant (PDA), a portable audio player, a car audio system, a game device, a spectacle lens, a lens filter, a sunglass, a medical device (gastroscope or the like), a copier, a Personal Computer (PC), a liquid crystal display, an organic EL display, a plasma display, a touch panel display, a protective film, an antireflection film, antireflection glass, a nanoimprinted template, a mold, or the like.

This application claims priority based on Japanese application No. 2020-137440, filed on 8/17/2020 and the entire disclosure thereof is hereby incorporated by reference.

Description of the reference numerals

10: base material with base layer, 12: base material, 14: a base layer,

20: article, 22: surface layer

Claims

1. A fluorine-containing ether compound represented by the following formula (1) or the following formula (2),

Wherein the content of the first and second substances,

R ^f3 is a 2-valent polyfluoropolyether chain,

A ¹ and A ² Each independently-O-or C (= O) -O-, a plurality of A's being present ¹ And A ² Each independently of the other optionally being the same or different,

Q ¹ a linking group having a valence of q1+ n1+ r1,

Q ² is a q2+ n2+1 valent linking group,

Q ³ a q3+ n3+1 valent linking group,

r is an alkyl group, and R is an alkyl group,

a is 2 or 3, and a is,

q1 is an integer of 1 or more,

when q1 is 1, p1 is 1 or 2,

n1 is an integer of 0 or more, r1 is an integer of 1 or more,

q2 is an integer of 1 or more,

when q2 is 1, p2 is 1 or 2,

n2 is an integer of 0 or more,

q3 is an integer of 0 or more,

n3 is an integer of 0 or more, and q3+ n3 is an integer of 1 or more.

2. The fluoroether compound according to claim 1, wherein R is ^f1 Represented by the following formula (3A),

L ¹ -R ^f11a -(OR ^f12 ) _m1 -(CH ₂ ) _s1 -formula (3A)

X is a hydrogen atom or a halogen atom,

R ¹⁰ each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and optionally having a fluorine atom, or a phenyl group having an optionally having a fluorine atom, wherein R's are present in plural ¹⁰ When a plurality of R is present ¹⁰ Are optionally the same as or different from each other,

R ^f11a a fluoroalkylene group having 1 to 20 carbon atoms,

R ^f12 a fluoroalkylene group having 1 to 6 carbon atoms,

s1 is an integer of 0 to 20.

3. The fluorine-containing ether compound according to claim 1 or 2, wherein R is ^f2 Represented by the following formula (3),

R ^f11 -(OR ^f12 ) _m1 -formula (3)

R ^f11 is a fluoroalkyl group having 1 to 20 carbon atoms,

R ^f12 a fluoroalkylene group having 1 to 6 carbon atoms,

4. The fluorine-containing ether compound according to any one of claims 1 to 3, wherein R is ^f3 Represented by the following formula (4),

-R ^f13 -(OR ^f13 ) _m2 -formula (4)

m2 is an integer of 0 to 500.

5. The fluorine-containing ether compound according to any one of claims 1 to 4, wherein Q is ¹ 、Q ² And Q ³ Each independently represented by any one of the following formulae (5-1) to (5-7),

(-A ¹¹ -Q ¹² -)C(-R ^e2 ) _2-d3 (-Q ³² -)(-Q ²² -) _d3 formula (5-2)

(-A ¹¹ -Q ¹³ -)N(-Q ³³ -)(-Q ²³ -) formula (5-3)

(-A ¹¹ -Q ¹⁴ -)Z(-Q ³⁴ -)(-Q ²⁴ -) _d4 Formula (5-4)

-A ¹¹ -Q ¹² -CH(-Q ³² -)-Si(R ^e3 ) _3-d6 (-Q ²⁵ -) _d6 Formula (5-6)

Q ¹² is a single bond, alkylene; or has-C (O) NR between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ -a group of (a) or (b),

Q ¹³ is a single bond, alkylene; having-C (O) NR between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ -a group of (a); or a group having-C (O) -at the N-side terminal of the alkylene groupWherein Q is ¹³ When it is a single bond, A is-C (O) -,

Q ²² and Q ³² Each independently is an alkylene group; having-C (O) NR between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ -a group of (a); having-C (O) NR at the end of the alkylene group on the side not bonded to Si ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ -a group of (a); or having-C (O) NR between carbon atoms of an alkylene group having 2 or more carbon atoms ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ And has-C (O) NR at the end of the side not bonded to Si ⁶ -、-C(O)-、-OC(O)O-、-NHC(O)O-、-NHC(O)NR ⁶ -、-O-、-SO ₂ NR ⁶ -or-NR ⁶ SO ₂ A group of (A) in which a plurality of Q's are present ²² A plurality of Q's present ²² Optionally the same or different, in the presence of a surfactant,

at Q ²⁴ Or Q ³⁴ The atoms of Z bonded being carbon atomsWhen is, Q ²⁴ And Q ³⁴ Each independently is Q ²² Or Q ³² At Q ²⁴ Or Q ³⁴ When the atom in Z bonded thereto is a nitrogen atom, Q ²⁴ And Q ³⁴ Each independently is Q ²³ Or Q ³³ There are a plurality of Q ²⁴ A plurality of Q's present ²⁴ Optionally the same or different, in the presence of a surfactant,

z is a group having a d4+2 valent ring structure having a valence of Q ¹⁴ 、Q ²⁴ And Q ³⁴ A directly bonded carbon atom or a nitrogen atom,

R ^e1 is a hydrogen atom or an alkyl group, a plurality of R being present ¹ When a plurality of R is present ¹ Optionally the same or different, in the presence of a surfactant,

R ^e2 is a hydrogen atom, a hydroxyl group, an alkyl group or an acyloxy group,

R ^e3 is an alkyl group, and is,

d3 is 1 or 2 and is,

d4 is an integer of 1 or more,

d5 is 1 or 2 and is,

d6 is an integer of 1 to 3,

d7 is 1 or 2.

6. A fluorine-containing ether composition comprising the fluorine-containing ether compound according to any one of claims 1 to 5 and another fluorine-containing ether compound.

7. A coating liquid comprising the fluorine-containing ether compound according to any one of claims 1 to 5 or the fluorine-containing ether composition according to claim 6, and a liquid medium.

8. An article having a surface layer formed of the fluorine-containing ether compound according to any one of claims 1 to 5 or the fluorine-containing ether composition according to claim 6 on the surface of a substrate.

9. A method for producing an article, wherein a surface layer is formed by a dry coating method or a wet coating method using the fluorine-containing ether compound according to any one of claims 1 to 5, the fluorine-containing ether composition according to claim 6, or the coating liquid according to claim 7.