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

文档序号：1301582 发布日期：2020-08-07 浏览：24次中文

阅读说明：本技术 含氟醚化合物、含氟醚组合物、涂布液、物品及其制造方法 (Fluorine-containing ether compound, fluorine-containing ether composition, coating liquid, article, and method for producing same ) 是由古川丰星野泰辉松浦启吾宇野诚人安乐英一郎于 2018-12-25 设计创作，主要内容包括：提供：能够形成与以往同样地指纹污迹去除性、耐摩擦性优异、且与以往相比耐光性更优异的表面层的含氟醚化合物。一种含氟醚化合物,其由A1-O-(Rf1O)m-A2表示。其中,A1为全氟烷基等,A2为-Q1[-C(R11)b(R12)3-b]a等,Rf1为氟代亚烷基,m为2～500,Q1为a+1价的有机基团,R11为-Q2-Si(R21)c(R22)d(R23)e、R12为氢原子、卤素原子等,a为1～3的整数,b为2或3,Q2为单键或2价的有机基团,R21为-Q3-Si(R31)3-g(R32)g,R22为烷基,R23为水解性基团或羟基,c、d及e为0～3,c+d+e为3,多个R11中、至少1个R11中的c为2或3,Q3为2价的有机基团,R31为烷基,R32为水解性基团或羟基,g为1～3。(Providing: a fluorine-containing ether compound capable of forming a surface layer having excellent fingerprint stain removability and abrasion resistance as in the conventional case and having more excellent light resistance than in the conventional case. A fluorine-containing ether compound represented by formula A 1 ‑O‑(R f1 O) m ‑A 2 And (4) showing. Wherein A is 1 Is perfluoroalkyl, etc., A 2 is-Q 1 [‑C(R 11 ) b (R 12 ) 3‑b ] a Etc. R f1 Is a fluoroalkylene group, m is 2 to 500, Q 1 Is an organic radical of valency a +1, R 11 is-Q 2 ‑Si(R 21 ) c (R 22 ) d (R 23 ) e 、R 12 Is a hydrogen atom, a halogen atom or the like, a is an integer of 1 to 3, b is 2 or 3, Q 2 Is a single bond or a 2-valent organic radical, R 21 is-Q 3 ‑Si(R 31 ) 3‑g (R 32 ) g ，R 22 Is alkyl, R 23 Is a hydrolyzable group or a hydroxyl group, c, d and e are 0 to 3, c + d + e is 3, R's are more than one 11 Middle, at least 1R 11 C in (1) is 2 or 3, Q 3 Is an organic radical having a valence of 2, R 31 Is alkyl, R 32 Is a hydrolyzable group or a hydroxyl group, and g is 1 to 3.)

1. A fluorine-containing ether compound which is a compound represented by the following formula (1),

A¹-O-(R^f1O)_m-A²(1)

wherein the content of the first and second substances,

A¹comprises the following steps: a perfluoroalkyl group having 1 to 20 carbon atoms, a group represented by the following formula (g1-1), a group represented by the following formula (g1-2), orA group represented by the following formula (g1-3),

A²comprises the following steps: a group represented by the following formula (g1-1), a group represented by the following formula (g1-2), or a group represented by the following formula (g1-3),

R^f1is a fluorinated alkylene group, and is,

m is an integer of 2 to 500,

(R^f1O)_moptionally 2 or more R's having different carbon numbers^f1A group formed by O and a group formed by O,

-Q¹[-C(R¹¹)_b(R¹²)_3-b]_a(g1-1)

-Q¹[-N(R¹¹)₂]_a(g1-2)

-Q¹[-Z(R¹¹)_n]_a(g1-3)

wherein the content of the first and second substances,

Q¹is an organic radical of valency a +1, where, with O (R)^f1O)_mThe terminal oxygen atom of (A) is bonded to the terminal CF₂Or a CHF (CHF) gas,

z is a group having a ring structure of n +1 valence having Q directly bonded thereto¹And a carbon atom or a nitrogen atom of (C) and a direct bond R¹¹A carbon atom or a nitrogen atom of (a),

R¹¹is a group represented by the following formula (g2),

R¹²is a hydrogen atom, a halogen atom, a hydroxyl group or a 1-valent organic group,

a is an integer of 1 to 3,

b is a number of 2 or 3,

n is an integer of 2 or more,

when a is 2 or more, a [ -C (R)¹¹)_b(R¹²)_3-b]Optionally the same or different, a [ -N (R)¹¹)₂]Optionally the same or different, a [ -Z (R)¹¹)_n]Optionally the same or different, and optionally,

plural R¹¹Optionally the same or different, and optionally,

-Q²-Si(R²¹)_c(R²²)_d(R²³)_e(g2)

wherein the content of the first and second substances,

Q²is a single bond or a 2-valent organic group,

R²¹is a group represented by the following formula (g3),

R²²is an alkyl group, and is,

R²³is a hydrolyzable group or a hydroxyl group,

c. d and e are each independently an integer of 0 to 3,

c + d + e is 3,

A¹and A²Plural R in each¹¹In (1) at least¹¹C in (a) is 2 or 3,

when c is 2 or more, c R²¹Optionally the same or different, and optionally,

when d is 2 or more, d R²²Optionally the same or different, and optionally,

when e is 2 or more, e R²³Optionally the same or different, and optionally,

-Q³-Si(R³¹)_3-g(R³²)_g(g3)

wherein the content of the first and second substances,

Q³is an organic group having a valence of 2,

R³¹is an alkyl group, and is,

R³²is a hydrolyzable group or a hydroxyl group,

g is an integer of 1 to 3,

when g is 1, 2R³¹Optionally the same or different, and optionally,

when g is 2 or more, g R³²Optionally the same or different.

2. The fluorine-containing ether compound according to claim 1, wherein a is 1.

3. The fluorine-containing ether compound according to claim 1 or 2, wherein Q is²Is a single bond or C1-C6 alkylene.

4. The fluoroether compound according to any one of claims 1 to 3, wherein Q is³Is an alkylene group having 2 to 6 carbon atoms.

5. The fluoroether compound according to any one of claims 1 to 4, wherein A is¹Is a C1-20 perfluoroalkyl group.

6. A fluoroether composition, comprising: 1 or more of the fluorine-containing ether compound according to any one of claims 1 to 5, and other fluorine-containing ether compounds.

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 characterized by 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. The article according to claim 8, wherein the surface layer is provided on a surface of a member constituting a finger touch surface of the touch panel.

10. A method for producing an article, characterized in that a surface layer is formed on the surface of a substrate by treating the surface of the substrate with a dry coating method using the fluorine-containing ether compound according to any one of claims 1 to 5 or the fluorine-containing ether composition according to claim 6, wherein the surface layer is formed from the fluorine-containing ether compound or the fluorine-containing ether composition.

11. A method for producing an article, comprising applying the coating liquid according to claim 7 to the surface of a substrate by a wet coating method and drying the coating liquid to form a surface layer on the surface of the substrate, wherein the surface layer is formed from the fluorine-containing ether compound or the fluorine-containing ether composition.

12. A fluorine-containing ether compound which is a compound represented by the following formula (2),

A¹⁰-O-(R^f1O)_m-A²⁰(2)

wherein the content of the first and second substances,

A¹⁰comprises the following steps: a perfluoroalkyl group having 1 to 20 carbon atoms, a group represented by the following formula (g4-1), a group represented by the following formula (g4-2), or a group represented by the following formula (g4-3),

A²⁰comprises the following steps: a group represented by the following formula (g4-1), a group represented by the following formula (g4-2), or a group represented by the following formula (g4-3),

R^f1is a fluorinated alkylene group, and is,

m is an integer of 2 to 500,

(R^f1O)_moptionally 2 or more R's having different carbon numbers^f1A group formed by O and a group formed by O,

-Q¹[-C(R¹¹⁰)_b(R¹²)_3-b]_a(g4-1)

-Q¹[-N(R¹¹⁰)₂]_a(g4-2)

-Q¹[-Z(R¹¹⁰)_n]_a(g4-3)

wherein the content of the first and second substances,

Q¹is an organic radical of valency a +1, where, with O (R)^f1O)_mThe terminal oxygen atom of (A) is bonded to the terminal CF₂Or a CHF (CHF) gas,

z is a group having a ring structure of n +1 valence having Q directly bonded thereto¹And a carbon atom or a nitrogen atom of (C) and a direct bond R¹¹⁰A carbon atom or a nitrogen atom of (a),

R¹¹⁰is a group represented by the following formula (g5),

R¹²is a hydrogen atom, a halogen atom, a hydroxyl group or a 1-valent organic group,

a is an integer of 1 to 3,

b is a number of 2 or 3,

n is an integer of 2 or more,

when a is 2 or more, a [ -C (R)¹¹⁰)_b(R¹²)_3-b]Optionally the same or different, a [ -N (R)¹¹⁰)₂]Optionally the same or different, a [ -Z (R)¹¹⁰)_n]Optionally the same or different, and optionally,

plural R¹¹⁰Optionally the same or different, and optionally,

-Q²-Si(R²¹⁰)_c(R²²)_d(R²³)_e(g5)

wherein the content of the first and second substances,

Q²is a single bond or a 2-valent organic group,

R²¹⁰is a group represented by the following formula (g6),

R²²is an alkyl group, and is,

R²³is a hydrolyzable group or a hydroxyl group,

c. d and e are each independently an integer of 0 to 3,

c + d + e is 3,

A¹⁰and A²⁰Plural R in each¹¹⁰In (1) at least¹¹⁰C in (a) is 2 or 3,

when c is 2 or more, c R²¹⁰Optionally the same or different, and optionally,

when d is 2 or more, d R²²Optionally the same or different, and optionally,

when e is 2 or more, e R²³Optionally the same or different, and optionally,

-Q³⁰-CH＝CH₂(g6)

wherein the content of the first and second substances,

Q³⁰is a single bond or a 2-valent organic group.

13. The fluorine-containing ether compound according to claim 12, wherein A is¹⁰Is a C1-20 perfluoroalkyl group.

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 the same.

Background

The fluorine-containing ether compound having a poly (oxyperfluoroalkylene) chain is suitably used for a surface treatment agent because it can form a surface layer exhibiting high lubricity, water-and oil-repellency, and the like on the surface of a substrate. A surface treatment agent comprising a fluorine-containing ether compound is used for applications requiring maintenance of the following properties for a long period of time: the surface layer is used as a surface treatment agent for a member constituting a finger touch surface of a touch panel, a spectacle lens, a display of a wearable terminal, for example, because the surface layer is repeatedly rubbed with a finger, and has a property of being less likely to reduce water-and oil-repellent properties (rubbing resistance) and a property of being able to easily remove a fingerprint attached to the surface layer by wiping (fingerprint stain removal property).

As a fluorine-containing ether compound capable of forming a surface layer excellent in abrasion resistance and fingerprint stain removability on the surface of a base material, the following has been proposed.

A fluorine-containing ether compound in which 3 hydrolyzable silyl groups are introduced into one end of a poly (oxyperfluoroalkylene) chain via a branched chain based on a carbon atom (patent document 1).

A fluorine-containing ether compound in which 2 hydrolyzable silyl groups are introduced into one end of a poly (oxyperfluoroalkylene) chain via a branch chain based on a nitrogen atom (patent document 2).

Disclosure of Invention

Problems to be solved by the invention

The fluorine-containing ether compounds described in patent documents 1 and 2 are excellent not only in fingerprint stain removal property and abrasion resistance but also in light resistance. Recently, further improvement in light resistance is sometimes required for a surface layer of a member or the like constituting a finger touch surface of a touch panel. Therefore, a fluorine-containing ether compound capable of forming a surface layer having more excellent light resistance while maintaining fingerprint stain removability and rubbing resistance is required.

An object of the present invention is to provide: a fluorine-containing ether compound capable of forming a surface layer having excellent fingerprint stain removability and abrasion resistance as in the conventional case and having more excellent light resistance than in the conventional case; a fluorine-containing ether composition containing a fluorine-containing ether compound and a coating liquid; an article having a surface layer which is excellent in fingerprint stain removability and rubbing resistance as in the conventional art and is more excellent in light resistance than in the conventional art, and a method for producing the same.

It is another object of the present invention to provide a fluorinated ether compound useful as an intermediate of fluorinated ether compounds which can be suitably used for a surface treatment agent.

Means for solving the problems

The present invention provides a fluorinated ether compound having the following configurations [1] to [13], a fluorinated ether composition, a coating liquid, an article, a method for producing an article, and other embodiments of a fluorinated ether compound.

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

A¹-O-(R^f1O)_m-A²(1)

Wherein the content of the first and second substances,

A¹comprises the following steps: a perfluoroalkyl group having 1 to 20 carbon atoms, a group represented by the following formula (g1-1), a group represented by the following formula (g1-2), or a group represented by the following formula (g1-3),

A²comprises the following steps: a group represented by the following formula (g1-1), a group represented by the following formula (g1-2), or a group represented by the following formula (g1-3),

R^f1is a fluorinated alkylene group, and is,

m is an integer of 2 to 500,

(R^f1O)_moptionally 2 or more R's having different carbon numbers^f1O, or a salt thereof.

-Q¹[-C(R¹¹)_b(R¹²)_3-b]_a(g1-1)

-Q¹[-N(R¹¹)₂]_a(g1-2)

-Q¹[-Z(R¹¹)_n]_a(g1-3)

Wherein the content of the first and second substances,

Q¹an organic radical having a +1 valency (wherein, with O (R)^f1O)_mThe terminal oxygen atom of (A) is bonded to the terminal CF₂Or CHF. ),

z is a group having a valence of n +1The n + 1-valent ring structure has a direct bond Q¹And a carbon atom or a nitrogen atom of (C) and a direct bond R¹¹A carbon atom or a nitrogen atom of (a),

R¹¹is a group represented by the following formula (g2),

R¹²is a hydrogen atom, a halogen atom, a hydroxyl group or a 1-valent organic group,

a is an integer of 1 to 3,

b is a number of 2 or 3,

n is an integer of 2 or more,

plural R¹¹Optionally the same or different.

-Q²-Si(R²¹)_c(R²²)_d(R²³)_e(g2)

Wherein the content of the first and second substances,

Q²is a single bond or a 2-valent organic group,

R²¹is a group represented by the following formula (g3),

R²²is an alkyl group, and is,

R²³is a hydrolyzable group or a hydroxyl group,

c. d and e are each independently an integer of 0 to 3,

c + d + e is 3,

A¹and A²Plural R in each¹¹In (1) at least¹¹C in (a) is 2 or 3,

when c is 2 or more, c R²¹Optionally the same or different, and optionally,

when d is 2 or more, d R²²Optionally the same or different, and optionally,

when e is 2 or more, e R²³Optionally the same or different.

-Q³-Si(R³¹)_3-g(R³²)_g(g3)

Wherein the content of the first and second substances,

Q³is an organic group having a valence of 2,

R³¹is an alkyl group, and is,

R³²is a hydrolyzable group or a hydroxyl group,

g is an integer of 1 to 3,

when g is 1, 2R³¹Optionally the same or different, and optionally,

when g is 2 or more, g R³²Optionally the same or different.

[2] The fluorine-containing ether compound according to [1], wherein a is 1.

[3]According to [1]Or [2]]The fluorine-containing ether compound, wherein Q is²Is a single bond or C1-C6 alkylene.

[4]According to [1]～[3]The fluorine-containing ether compound according to any one of the above, wherein Q is³Is an alkylene group having 2 to 6 carbon atoms.

[5]According to [1]～[4]The fluorine-containing ether compound according to any one of the above, wherein A is¹Is a C1-20 perfluoroalkyl group.

[6] A fluoroether composition, comprising: 1 or more of the fluorine-containing ether compound according to any one of the above [1] to [5], and another fluorine-containing ether compound.

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

[8] An article comprising a substrate and, superimposed on a surface thereof, a surface layer comprising the fluorine-containing ether compound according to any one of the above [1] to [5] or the fluorine-containing ether composition according to the above [6 ].

[9] The article according to item [8], wherein the surface layer is provided on a surface of a member constituting a finger touch surface of the touch panel.

[10] A method for producing an article, characterized in that a surface layer is formed on the surface of a substrate by treating the surface of the substrate with a dry coating method using the fluorine-containing ether compound according to any one of the above [1] to [5] or the fluorine-containing ether composition according to [6], the surface layer being formed of the fluorine-containing ether compound or the fluorine-containing ether composition.

[11] A method for producing an article, characterized in that the surface layer is formed on the surface of a substrate by applying the coating liquid according to [7] to the surface of the substrate by a wet coating method and drying the coating liquid, wherein the surface layer is formed from the fluorine-containing ether compound or the fluorine-containing ether composition.

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

A¹⁰-O-(R^f1O)_m-A²⁰(2)

Wherein the content of the first and second substances,

A²⁰comprises the following steps: a group represented by the following formula (g4-1), a group represented by the following formula (g4-2), or a group represented by the following formula (g4-3),

R^f1is a fluorinated alkylene group, and is,

m is an integer of 2 to 500,

(R^f1O)_moptionally 2 or more R's having different carbon numbers^f1O, or a salt thereof.

-Q¹[-C(R¹¹⁰)_b(R¹²)_3-b]_a(g4-1)

-Q¹[-N(R¹¹⁰)₂]_a(g4-2)

-Q¹[-Z(R¹¹⁰)_n]_a(g4-3)

Wherein the content of the first and second substances,

Q¹an organic radical having a +1 valency (wherein, with O (R)^f1O)_mThe terminal oxygen atom of (A) is bonded to the terminal CF₂Or CHF. ),

z is a group having a ring structure of n +1 valence having Q directly bonded thereto¹And a carbon atom or a nitrogen atom of (C) and a direct bond R¹¹⁰A carbon atom or a nitrogen atom of (a),

R¹¹⁰is a group represented by the following formula (g5),

R¹²is a hydrogen atom, a halogen atom, a hydroxyl group or a 1-valent organic group,

a is an integer of 1 to 3,

b is a number of 2 or 3,

n is an integer of 2 or more,

plural R¹¹⁰Optionally the same or different.

-Q²-Si(R²¹⁰)_c(R²²)_d(R²³)_e(g5)

Wherein the content of the first and second substances,

Q²is a single bond or a 2-valent organic group,

R²¹⁰is a group represented by the following formula (g6),

R²²is an alkyl group, and is,

R²³is a hydrolyzable group or a hydroxyl group,

c. d and e are each independently an integer of 0 to 3,

c + d + e is 3,

A¹⁰and A²⁰Plural R in each^{110 in}At least 1R¹¹⁰C in (a) is 2 or 3,

when c is 2 or more, c R²¹⁰Optionally the same or different, and optionally,

when d is 2 or more, d R²²Optionally the same or different, and optionally,

when e is 2 or more, e R²³Optionally the same or different.

-Q³⁰-CH＝CH₂(g6)

Wherein the content of the first and second substances,

Q³⁰is a single bond or a 2-valent organic group.

[13]According to [12]]The fluorine-containing ether compound wherein A¹⁰Having 1 to 20 carbon atomsA perfluoroalkyl group.

ADVANTAGEOUS EFFECTS OF INVENTION

The fluorine-containing ether compound of the present invention can form a surface layer having excellent fingerprint stain removability and abrasion resistance as in the conventional case, and having more excellent light resistance than in the conventional case.

The fluorine-containing ether composition of the present invention can form a surface layer having excellent fingerprint stain removability and abrasion resistance as in the conventional case, and having more excellent light resistance than in the conventional case.

The coating liquid of the present invention can form a surface layer having excellent fingerprint stain removability and rubbing resistance as in the conventional art, and having more excellent light resistance than in the conventional art.

The article of the present invention has a surface layer which is excellent in fingerprint stain removability and rubbing resistance as in the conventional article, and is more excellent in light resistance than in the conventional article.

The method for producing an article of the present invention can produce an article having a surface layer which has fingerprint stain removability and excellent rubbing resistance as in the conventional method, and which has more excellent light resistance than in the conventional method.

The other embodiment of the fluorine-containing ether compound of the present invention is useful as an intermediate of a fluorine-containing ether compound suitably used for a surface treatment agent.

Detailed Description

In the present specification, the compound represented by formula (1) will be referred to as compound (1). The compounds represented by the other formulae are also described in the same manner.

In addition, the group represented by formula (g1) is described as group (g 1). Groups represented by other formulae are also described.

The chemical formula of the oxyfluoroalkylene unit is represented by the oxygen atom shown on the right side of the fluoroalkylene group.

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

"hydrolyzable silyl group" refers to a group that undergoes a hydrolysis reaction to form a silanol group (Si-OH). The hydrolyzable silyl group is, for example, Si (R) in the formula (g3)³¹)_3-g(R³²)_g。

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

For the "number average molecular weight" of the fluorine-containing ether compound, the compound is obtained by¹H-NMR and¹⁹F-NMR was calculated by obtaining the number (average value) of oxyperfluoroalkylene groups based on the terminal group. The terminal group is, for example, A in the formula (1)¹Or Si (R) in the formula (g3)³¹)_3-g(R³²)_g。

[ fluorine-containing ether Compound ]

The fluorine-containing ether compound of the present invention is the compound (1).

A¹-O-(R^f1O)_m-A²(1)

Wherein A is¹A perfluoroalkyl group having 1 to 20 carbon atoms, a group (g1-1), a group (g1-2) or a group (g1-3), A²Is a group (g1-1), a group (g1-2) or a group (g1-3), R^f1Is a fluoroalkylene group, m is an integer of 2 to 500, (R)^f1O)_mOptionally 2 or more R's having different carbon numbers^f1O, or a salt thereof.

-Q¹[-C(R¹¹)_b(R¹²)_3-b]_a(g1-1)

-Q¹[-N(R¹¹)₂]_a(g1-2)

-Q¹[-Z(R¹¹)_n]_a(g1-3)

Wherein Q is¹An organic radical having a +1 valency (wherein, with O (R)^f1O)_mThe terminal oxygen atom of (A) is bonded to the terminal CF₂Or CHF. ) And Z is a group having a ring structure of n +1 valence having Q directly bonded thereto¹And a carbon atom or a nitrogen atom of (C) and a direct bond R¹¹Carbon atom or nitrogen atom of (2), R¹¹Is a group (g2), R¹²Is a hydrogen atom, a halogen atom, a hydroxyl group or a 1-valent organic group, a is an integer of 1 to 3, b is 2 or 3, n is an integer of 2 or more, and when a is 2 or more, a is [ -C (R)¹¹)_b(R¹²)_3-b]Optionally the same or different, a [ -N (R)¹¹)₂]Optionally the same or different, a [ -Z (R)¹¹)_n]Optionally, the same or different, a plurality of R¹¹Optionally the same or different.

-Q²-Si(R²¹)_c(R²²)_d(R²³)_e(g2)

Wherein Q is²Is a single bond or a 2-valent organic radical, R²¹Is a group (g3), R²²Is alkyl, R²³Is a hydrolyzable group or a hydroxyl group, c, d and e are each independently an integer of 0 to 3, c + d + e is 3, A¹And A²Plural R in each¹¹In (1) at least¹¹Wherein c is 2 or 3, and when c is 2 or more, c R are²¹Optionally the same or different, when d is 2 or more, d R²²Optionally the same or different, e is 2 or more, e R²³Optionally the same or different.

-Q³-Si(R³¹)_3-g(R³²)_g(g3)

Wherein Q is³Is an organic radical having a valence of 2, R³¹Is alkyl, R³²Is a hydrolyzable group or a hydroxyl group, g is an integer of 1 to 3, and when g is 1, 2R³¹Optionally the same or different, g is 2 or more, g R³²Optionally the same or different.

As A¹The perfluoroalkyl group having 1 to 20 carbon atoms is preferable because the surface layer has more excellent lubricity and abrasion resistance. A. the¹The compound (1) is perfluoroalkyl group A¹Having CF at the end₃-, whereby one end of the compound (1) is CF₃And the other terminal is a hydrolyzable silyl group or a silanol group. Using one end being CF₃The compound (1) having a hydrolyzable silyl group or silanol group at the other end can form a surface layer having a low surface energy, and therefore, the compound (1) (A) having a hydrolyzable silyl group or silanol group at both ends¹The compounds (1)) represented by the groups (g1) to (g3) are more excellent in lubricity and friction resistance of the surface layer.

For A¹The number of carbon atoms of the perfluoroalkyl group (b) is preferably 1 to 10, more preferably 1 to 10, from the viewpoint of more excellent lubricity and abrasion resistance of the surface layer formed of the compound (1)1 to 6, particularly preferably 1 to 3.

For R^f1The number of carbon atoms of (b) is preferably 1 to 6, from the viewpoint of further improving the abrasion resistance of the surface layer and the fingerprint stain removability.

As R^f1The linear fluoroalkylene group is preferable in that the surface layer is more excellent in the friction resistance and lubricity.

As R^f1The perfluoroalkylene group is preferable because the surface layer is more excellent in the friction resistance and the lubricity.

For all R^f1The proportion of the perfluoroalkylene group in (b) is preferably 60 mol% or more, more preferably 80 mol% or more, and particularly preferably 100 mol%, from the viewpoint that the friction resistance and lubricity of the surface layer are more excellent.

m is preferably an integer of 2 to 200, more preferably an integer of 5 to 150, and particularly preferably an integer of 10 to 100. When m is equal to or more than the lower limit of the above range, the water-and oil-repellency of the surface layer is more excellent. When m is equal to or less than the upper limit of the above range, the surface layer is more excellent in the friction resistance. That is, when the number average molecular weight of the compound (1) is too large, the number of hydrolyzable silyl groups or silanol groups present per unit molecular weight decreases, and the abrasion resistance of the surface layer decreases.

(R^f1O)_mIn (A), more than 2 kinds of R exist^f1In the case of O, each R^f1The bonding order of O is not limited. For example, the presence of CF₂O and CF₂CF₂In the case of O, CF₂O and CF₂CF₂O may be arranged randomly, alternately, or in blocks.

There are more than 2R^f1O is: there are more than 2 kinds of R with different carbon numbers^f1O; there are 2 or more kinds of R having different hydrogen atoms^f1O; there are more than 2 kinds of R having different positions of hydrogen atom^f1O; and 2 or more kinds of R having different side chains types (number of side chains, number of carbon atoms of side chains, etc.) even if the number of carbon atoms is the same^f1O。

With respect to 2 or more kinds of R^f1Configuration of O, e.g., { (CF)₂O)_m1(CF₂CF₂O)_m2The structures shown represent m1 (CF)₂O) and m2 (CF)₂CF₂O) are randomly configured. In addition, (CF)₂CF₂O-CF₂CF₂CF₂CF₂O)_m5The structure shown represents m5 (CF)₂CF₂O) and m5 (CF)₂CF₂CF₂CF₂O) are alternately arranged.

As (R)^f1O)_mPreferably (R)^f1O)_mHas the following structure.

{(CF₂O)_m1(CF₂CF₂O)_m2}、

(CF₂CF₂O)_m3、

(CF₂CF₂CF₂O)_m4、

(CF₂CF₂O-CF₂CF₂CF₂CF₂O)_m5、

(CF₂CF₂CF₂CF₂CF₂O)_m6(CF₂O)_m7、

(CF₂CF₂CF₂CF₂CF₂O)_m6(CF₂CF₂O)_m7、

(CF₂CF₂CF₂CF₂CF₂CF₂O)_m6(CF₂O)_m7、

(CF₂CF₂CF₂CF₂CF₂CF₂O)_m6(CF₂CF₂O)_m7、

(CF₂CF₂CF₂CF₂CF₂O-CF₂O)_m8、

(CF₂CF₂CF₂CF₂CF₂O-CF₂CF₂O)_m8、

(CF₂CF₂CF₂CF₂CF₂CF₂O-CF₂O)_m8、

(CF₂CF₂CF₂CF₂CF₂CF₂O-CF₂CF₂O)_m8、

(CF₂O-CF₂CF₂CF₂CF₂CF₂O)_m8、

(CF₂O-CF₂CF₂CF₂CF₂CF₂CF₂O)_m8、

(CF₂CF₂O-CF₂CF₂CF₂CF₂CF₂O)_m8、

(CF₂CF₂O-CF₂CF₂CF₂CF₂CF₂CF₂O)_m8。

Wherein m1 is an integer of 1 or more, m2 is an integer of 1 or more, m1+ m2 is an integer of 2 to 500, m3 and m4 are each an integer of 2 to 500, m5 is an integer of 1 to 250, m6 and m7 are each an integer of 1 or more, m6+ m7 is an integer of 2 to 500, and m8 is an integer of 1 to 250.

As (R)^f1O)_mThe following structure is preferred in view of easy production of the compound (1).

{(CF₂O)_m1(CF₂CF₂O)_m2}、

(CF₂CF₂CF₂O)_m4、

(CF₂CF₂O)₂{(CF₂O)_m1(CF₂CF₂O)_m2-2}、

(CF₂CF₂O-CF₂CF₂CF₂CF₂O)_m5-1CF₂CF₂O、

(CF₂CF₂CF₂CF₂CF₂O-CF₂O)_m8、

(CF₂CF₂CF₂CF₂CF₂CF₂O-CF₂O)_m8、

(CF₂CF₂O-CF₂CF₂CF₂CF₂CF₂O)_m8-1CF₂CF₂O、

(CF₂CF₂O-CF₂CF₂CF₂CF₂CF₂CF₂O)_m8-1CF₂CF₂O。

Among them, m2, m5 and m8 are selected so that m2-2, m5-1 and m8-1 are integers of 1 or more.

The amount of a is preferably 1 to 2, and particularly preferably 1, from the viewpoint of easy production of the compound (1) and the viewpoint of uniform application of the compound (1) to the surface of the substrate and excellent physical properties of the surface layer.

Q¹May have a chemical formula selected from the group consisting of-C (O) NR-, -C (O) O-, -C (O) -, -O-, -NR-, -S-, -NHC (O) O-, -NHC (O) NR-, -SO₂NR-and-Si (R)₂A linkage (hereinafter, referred to as "linkage B") in the group consisting of (wherein R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group). The bond B is preferably selected from the group consisting of-C (O) NR-, -C (O) -and-Si (R) in view of more excellent light resistance and chemical resistance of the surface layer₂-a bond of the group.

As Q¹The organic group in (3) is preferably a fluorinated hydrocarbon group, a combination of a fluorinated hydrocarbon group and the bond B and a hydrocarbon group, and particularly preferably a fluorinated hydrocarbon group, from the viewpoint of further improving the light resistance and chemical resistance of the surface layer. Q¹The carbon number of (b) is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

When a is 1, as Q¹From the viewpoint of ease of production of the compound (1) and further excellent light resistance and chemical resistance of the surface layer, the group (g11), the group (g12), the group (g13) or the group (g14) is preferable.

-R^f2-Q¹¹-(g11)

-R^f2-C(O)NR-Q¹¹- (g12)

-R^f2-C(O)CH₂C(O)-Q¹¹- (g13)

-R^f2-C(O)-Q¹¹- (g14)

Wherein R is^f2Is a fluoroalkylene group (wherein, at least 1 fluorine atom is bonded to Q)¹¹Terminal carbon atom on side and O (R)^f1O)_mThe carbon atoms at the lateral ends are bonded. ) Q, Q¹¹Is a single bond or alkylene, R is hydrogen atom, C1-C6 alkyl or phenyl. R^f2Side and O (R)^f1O)_mThe terminal oxygen atom of (2) is bonded.

For R^f2The number of carbon atoms of (b) is preferably 1 to 8, more preferably 1 to 6, and particularly preferably 1 to 5, from the viewpoint of further improving the abrasion resistance and fingerprint stain removal property of the surface layer.

As R^f2The linear fluoroalkylene group is preferable in that the surface layer is more excellent in the friction resistance and lubricity.

As R^f2The perfluoroalkylene group is preferable because the surface layer is more excellent in the friction resistance and the lubricity.

R^f2The structure of (2) depends on the starting materials and the synthesis method used in the production of the compound (1).

Q¹¹The number of carbon atoms of the alkylene group(s) is preferably 1 to 6.

R¹²May have a bond B.

As R¹²The organic group in (3) is preferably a hydrocarbon group, a fluorinated hydrocarbon group, or a combination of a hydrocarbon group and the bond B, and particularly preferably a hydrocarbon group, from the viewpoint of further improving the light resistance and chemical resistance of the surface layer. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof, and particularly preferably an alkyl group. R¹²The carbon number of (b) is preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 to 3.

The ring structure in Z is preferably a ring structure selected from the group consisting of an aliphatic ring having 3 to 8 membered rings, an aromatic ring having 3 to 8 membered rings, a heterocyclic ring having 3 to 8 membered rings, and a condensed ring formed of 2 or more of these rings, and particularly preferably a ring structure exemplified by the following formula, from the viewpoint of easy production of the compound (1) and from the viewpoint of more excellent abrasion resistance, light resistance, and chemical resistance of the surface layer.

The ring structure in Z may have a substituent such as a halogen atom, an alkyl group (optionally containing an etheric oxygen atom between carbon-carbon atoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group, or an oxy group (═ O). In addition, Q is¹、R¹¹Is directly bonded to the ring structure in Z, and therefore is not, for example, an alkylene group bonded to the ring structure, and Q¹、R¹¹To the alkylene group.

N is preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 to 3, from the viewpoint of facilitating production of the compound (1) and from the viewpoint of further improving the abrasion resistance, light resistance and chemical resistance of the surface layer. When n is 2 or more, the compound (1) is firmly bonded to the surface of the base material, and the surface layer is more excellent in abrasion resistance, light resistance and chemical resistance. When n is 6 or less, the raw material can be easily obtained, and the compound (1) can be easily produced. In addition, since the terminal volume of the compound (1) on the hydrolyzable silyl group side does not increase, the density of the compound (1) on the surface of the substrate becomes relatively high. As a result, the surface layer is more excellent in abrasion resistance, light resistance and chemical resistance.

Q²May have a bond B.

As Q²The organic group in (3) is preferably a hydrocarbon group, a fluorinated hydrocarbon group, a combination of a hydrocarbon group and the bond B, or a combination of a fluorinated hydrocarbon group and the bond B and a hydrocarbon group, and particularly preferably a hydrocarbon group, from the viewpoint of further excellent light resistance and chemical resistance of the surface layer. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof, and particularly preferably an alkylene group. For Q²The number of carbon atoms of (b) is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4, from the viewpoint of further excellent light resistance and chemical resistance of the surface layer.

As Q²The abrasion resistance, light resistance and chemical resistance of the surface layer are improved from the viewpoint of easy production of the compound (1)In view of excellent characteristics, a single bond or an alkylene group having 1 to 6 carbon atoms is preferable, and a single bond or an alkylene group having 1 to 4 carbon atoms is particularly preferable.

R²²The number of carbon atoms of the alkyl group(s) is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2. R²²When the number of carbon atoms in the alkyl group (b) is in this range, the compound (1) can be easily produced.

R²³The hydrolyzable group of (2) is a group which becomes a hydroxyl group by a hydrolysis reaction. I.e., Si-R²³And converted into silanol groups (Si — OH) by hydrolysis reaction. The silanol groups further react between molecules to form Si-O-Si bonds. 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).

As R²³Examples thereof 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 4 carbon atoms. The halogen atom is preferably a chlorine atom.

As R²³The alkoxy group and the halogen atom are preferable because the compound (1) can be easily produced. As R²³From the viewpoint of less outgassing during coating and excellent storage stability of the compound (1), alkoxy groups having 1 to 4 carbon atoms are preferred, ethoxy groups are particularly preferred when long-term storage stability of the compound (1) is required, and methoxy groups are particularly preferred when the reaction time after coating is short.

Q³May have a bond B.

As Q³The organic group in (3) is preferably a hydrocarbon group and a combination of a hydrocarbon group and the bond B, and particularly preferably a hydrocarbon group, from the viewpoint of further excellent light resistance and chemical resistance of the surface layer. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof, and particularly preferably an alkylene group. For Q³The number of carbon atoms of (b) is preferably 1 to 10, more preferably 2 to 6, and particularly preferably 2 to 4, from the viewpoint of further excellent light resistance and chemical resistance of the surface layer.

As Q³From the viewpoint of easy production of the compound (1) and the viewpoint of more excellent abrasion resistance, light resistance and chemical resistance of the surface layerThe alkylene group has preferably 2 to 6 carbon atoms, and particularly preferably 2 to 4 carbon atoms.

In particular, a is 1, Q²Is a single bond or C1-6 alkylene, Q³In the case of an alkylene group having 2 to 6 carbon atoms, it is considered that the compound (1) more effectively suppresses oxidative decomposition at a C — C bond branched from a carbon atom and improves the strength of an Si — C bond branched from a silicon atom, and the surface layer is more excellent in rubbing resistance and light resistance.

Si(R³¹)_3-g(R³²)_gIs a hydrolyzable silyl group.

The compound (1) has a plurality of hydrolyzable silyl groups at least at one terminal. Since the compound (1) having a plurality of hydrolyzable silyl groups at the end is strongly chemically bonded to the base material, the surface layer has excellent abrasion resistance.

Further, the compound (1) preferably has a hydrolyzable silyl group at only one end. The compound (1) having a hydrolyzable silyl group only at one end is less likely to aggregate, and therefore the surface layer has excellent appearance. Further, the surface layer is also excellent in lubricity and friction resistance.

As R³¹Examples thereof include²²The same applies to the same groups, and also to the preferred embodiments.

As R³²Examples thereof include²³The same applies to the same groups, and also to the preferred embodiments.

g is preferably 2 or 3, particularly preferably 3. By making a plurality of R exist in 1 hydrolyzable silyl group³²Thereby, the adhesion to the base material becomes stronger.

As Si (R)³¹)_3-g(R³²)_gPreferably Si (OCH)₃)₃、SiCH₃(OCH₃)₂、Si(OCH₂CH₃)₃、SiCl₃、Si(OCOCH₃)₃And Si (NCO)₃. Si (OCH) is particularly preferable from the viewpoint of ease of handling in industrial production₃)₃。

Plural Si (R) s in Compound (1)³¹)_3-g(R³²)_gOptionally the same or different. The same group is preferable in terms of ease of production of the compound (1).

Examples of the compound (1) include compounds of the following formula. The compound of the following formula is preferable because it is easy to industrially produce and handle, and the surface layer has excellent water/oil repellency, abrasion resistance, fingerprint stain removal property, lubricity, chemical resistance, light resistance, and chemical resistance, and particularly excellent light resistance.

Wherein G is a polyfluoropolyether chain, i.e. A-O- (R)^f1O)_m-R^f2- (wherein A is a C1-20 perfluoroalkyl group). Preferred embodiments of G are combinations of the above preferred embodiments A¹、(R^f1O)_mAnd R^f2And (5) forming the product.

(Process for producing Compound (1))

Compound (1) can be prepared, for example, by reacting compound (2) with HSi (R)³¹)_3-g(R³²)_gA hydrosilylation reaction is performed.

A¹⁰-O-(R^f1O)_m-A²⁰(2)

Wherein A is¹⁰Is perfluoroalkyl group with 1-20 carbon atoms, group (g4-1), group (g4-2) or group (g4-3), A²⁰Is a group (g4-1), a group (g4-2) or a group (g 4-3).

-Q¹[-C(R¹¹⁰)_b(R¹²)_3-b]_a(g4-1)

-Q¹[-N(R¹¹⁰)₂]_a(g4-2)

-Q¹[-Z(R¹¹⁰)_n]_a(g4-3)

Wherein R is¹¹⁰Is a group (g5) where a is 2 or more, a is [ -C (R)¹¹⁰)_b(R¹²)_3-b]Optionally the same or different, a [ -N (R)¹¹⁰)₂]Optionally the same or different, a [ -Z (R)¹¹⁰)_n]Optionally, the same or different, a plurality of R¹¹⁰Optionally the same or different.

-Q²-Si(R²¹⁰)_c(R²²)_d(R²³)_e(g5)

Wherein R is²¹⁰Is a group (g6), A¹⁰And A²⁰Plural R in each¹¹⁰In (1) at least¹¹⁰Wherein c is 2 or 3, and when c is 2 or more, c R are²¹⁰Optionally the same or different.

-Q³⁰-CH＝CH₂(g6)

Wherein Q is³⁰Is a single bond or a 2-valent organic group.

(R^f1O)_m、Q¹、Z、R¹²、a、b、n、Q²、R²²、R²³C, d and e with (R) described for the compound (1)^f1O)_m、Q¹、Z、R¹²、a、b、n、Q²、R²²、R²³C, d and e are the sameThe same applies to the preferred embodiments.

As A¹⁰The perfluoroalkyl group having 1 to 20 carbon atoms is preferable because the surface layer has more excellent lubricity and abrasion resistance.

For A¹⁰The number of carbon atoms of the perfluoroalkyl group (b) is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 3, from the viewpoint of more excellent lubricity and abrasion resistance of the surface layer.

Q³⁰May have a bond B.

As Q³⁰The organic group in (3) is preferably a hydrocarbon group and a combination of a hydrocarbon group and the bond B, and particularly preferably a hydrocarbon group, from the viewpoint of further excellent light resistance and chemical resistance of the surface layer. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof, and particularly preferably an alkylene group. For Q³⁰The number of carbon atoms of (b) is preferably 1 to 8, more preferably 2 to 4, and particularly preferably 1 to 2, from the viewpoint of further excellent light resistance and chemical resistance of the surface layer.

As Q³⁰In view of the ease of production of the compound (2) and the more excellent abrasion resistance, light resistance and chemical resistance of the surface layer, a single bond and an alkylene group having 1 to 4 carbon atoms are preferable, and a single bond and an alkylene group having 1 to 2 carbon atoms are particularly preferable.

Q³⁰-CH＝CH₂Q in the group (g3) after hydrosilylation³。

(Process for producing Compound (2))

(i) The compound (2) can be produced, for example, as follows.

Reacting the compound (4) with a Grignard reagent (CH)₂＝CH-Q³⁰MgBr) to give compound (2 a).

A-O-(R^f1O)_m-Q¹-C[-Q²-Si(R²³)_c(R²²)_d]_b(R¹²)_3-b(4)

A-O-(R^f1O)_m-Q¹-C[-Q²-Si(-Q³⁰-CH＝CH₂)_c(R²²)_d]_b(R¹²)_3-b(2a)

Wherein A is a C1-20 perfluoroalkyl group.

(R^f1O)_m、Q¹、R¹²、b、Q²、R²²、R²³C, d and Q³⁰With (R) described in the compounds (1) and (2)^f1O)_m、Q¹、R¹²、b、Q²、R²²、R²³C, d and Q³⁰Similarly, the same applies to the preferred embodiments.

The compound (4) can be prepared, for example, by the methods disclosed in patent document 1 (b-3) and Japanese patent laid-open publication No. 2015-199906 (b-2, R)¹²Hydroxyl group), and the method described in japanese patent application laid-open No. 2016-.

(ii) The compound (2) can be produced, for example, as follows.

Reacting the compound (6) with CH₂＝CH-Si(R²³)_cR²² _dThe reaction gives the compound (7).

A-O-(R^f1O)_m-R^f2-I (6)

A-O-(R^f1O)_m-R^f2-CH₂-CHI-Si(R²³)_c(R²²)_d(7)

Reacting the compound (7) with a Grignard reagent (CH)₂＝CH-Q³⁰MgBr) to give compound (2 b).

A-O-(R^f1O)_m-R^f2-CH₂-CH(-Q³⁰-CH＝CH₂)[-Si(-Q³⁰-CH＝CH₂)_c(R²²)_d](2b)

Wherein A is a C1-20 perfluoroalkyl group.

(R^f1O)_m、R^f2、R²²C, d and Q³⁰With (R) described in the compounds (1) and (2)^f1O)_m、R^f2、R²²C, d and Q³⁰Similarly, the same applies to the preferred embodiments.

The compound (6) can be produced, for example, by the methods described in international publication No. 2009/008380, international publication No. 2013/121984, and international publication No. 2013/121986.

(iii) The compound (2) can be produced, for example, as follows.

Reacting the compound (8) with a Grignard reagent (CH)₂＝CH-Q³⁰MgBr) to give compound (2 c).

A-O-(R^f1O)_m-Q¹-N[-Q²-Si(R²³)_c(R²²)_d]₂(8)

A-O-(R^f1O)_m-Q¹-N[-Q²-Si(-Q³⁰-CH＝CH₂)_c(R²²)_d]₂(2c)

Wherein A is a C1-20 perfluoroalkyl group.

(R^f1O)_m、Q¹、Q²、R²²、R²³C, d and Q³⁰With (R) described in the compounds (1) and (2)^f1O)_m、Q¹、Q²、R²²、R²³C, d and Q³⁰Similarly, the same applies to the preferred embodiments.

Compound (8) can be produced, for example, by the method described in patent document 2.

The compound (1) described above can form a surface layer excellent in fingerprint stain removability, rubbing resistance and light resistance for the following reasons.

The compound (1) has (R)^f1O)_mTherefore, the content of fluorine atoms is large. Therefore, the compound (1) can form a surface layer excellent in abrasion resistance and fingerprint stain removability.

For the compound (1), R bonded to a carbon atom or a nitrogen atom¹¹Is 2 or more and a plurality of R¹¹(i.e., multiple-Q)²-Si(R²¹)_c(R²²)_d(R²³)_e) Middle, at least 1R¹¹C in (b) is 2 or 3, whereby a multi-stage branch chain is introduced at the end by means of a 2-stage branch chain containing a branch chain based on a carbon atom or a nitrogen atom and a branch chain based on a silicon atom at the subsequent stageA hydrolyzable silyl group. Therefore, a surface layer having excellent fingerprint stain removability and abrasion resistance as in the conventional art and having more excellent light resistance than in the conventional art can be formed.

Here, for example, in the case where the compound (1) has the group (g1-1), it can be said that the group (g1-1) is represented by-C (R)¹¹)_b(R¹²)_3-bThe compound (1) has a branch chain based on a carbon atom. In addition, can be said to pass through wherein R¹¹Of (5) to (Q)²-Si(R²¹)_c(R²²)_d(R²³)_eThe compound (1) has a branch based on a silicon atom at the latter stage. The same applies to the case where the compound (1) has the group (g1-2) or the group (g1-3) and the case where it has a plurality of at least 1 group selected from the groups (g1-1) to (g 1-3).

The following reasons are considered as the reason why a surface layer having excellent fingerprint stain removability and abrasion resistance as well as excellent light resistance as compared with the conventional one can be formed by a branched chain based on a carbon atom or a nitrogen atom and a branched chain based on a silicon atom at the subsequent stage.

Since the C — C bond branched from a carbon atom is strong, a surface layer having excellent abrasion resistance can be formed by the fluorine-containing ether compound having a C — C bond branched from a carbon atom. However, when a fluorine-containing ether compound having a C — C bond branched from a carbon atom is exposed to sunlight in the air for a long time, oxidative decomposition gradually occurs, and for example, in a portion of a methine structure, a hydrogen atom is abstracted by a radical to undergo complicated decomposition. Even if the branched portion based on the carbon atom is a quaternary carbon, the carbon radical cut in the C — C bond is stable, and decomposition proceeds with this as a starting point. Branching based on nitrogen atoms is also the same as branching based on carbon atoms.

It is considered that not only oxidative decomposition of Si — C bonds (Si — C bonds branched from silicon atoms) which are considered to be more resistant to oxidation than C — C bonds branched from carbon atoms can be suppressed by introducing a branch chain based on a silicon atom to the rear stage of a branch chain based on a carbon atom or a nitrogen atom in one molecule, but also oxidative decomposition of C — C bonds branched from carbon atoms can be suppressed by the interaction of Si — C bonds branched from silicon atoms and C — C bonds branched from carbon atoms. Meanwhile, it is considered that the strength of the Si-C bond branched from the silicon atom can be maintained in a good state by the interaction between the Si-C bond branched from the silicon atom and the C-C bond branched from the carbon atom.

Therefore, by introducing 2 kinds of branched structures which are chemically and physically strong but have different characteristics into one molecule, it is possible to form a surface layer which is excellent in fingerprint stain removal performance and rubbing resistance as in the conventional art and which is more excellent in light resistance than in the conventional art. Therefore, the surface layer formed of the compound (1) of the present invention can also withstand a severe evaluation method in which a rubbing resistance test is performed after a light resistance test.

[ fluorinated Ether composition ]

The fluorine-containing ether composition of the present invention (hereinafter, also referred to as "the present composition") comprises: 1 or more compounds (1), and other fluorine-containing ether compounds.

Examples of the other fluorine-containing ether compound include a fluorine-containing ether compound (hereinafter, also referred to as a "by-product fluorine-containing ether compound") which is by-produced in the production process of the compound (1), a known fluorine-containing ether compound used for the same purpose as the compound (1), and the like.

As the other fluorine-containing ether compound, a compound which is less likely to reduce the characteristics of the compound (1) is preferable.

Examples of the by-product fluorine-containing ether compound include unreacted compound (2), compound (4), compound (6), compound (7) and the like, and a fluorine-containing ether compound obtained by isomerizing a part of allyl groups to internal olefins in hydrosilylation in the production of compound (1).

The known fluorinated ether compound includes commercially available fluorinated ether compounds and the like. When the present composition contains a known fluorine-containing ether compound, a new effect such as the characteristic of the compound (1) may be exerted.

The content of the compound (1) in the present composition is preferably 60% by mass or more and less than 100% by mass, more preferably 70% by mass or more and less than 100% by mass, and particularly preferably 80% by mass or more and less than 100% by mass, based on the total amount of the compound (1) and the other fluorine-containing ether compound.

The total content of the compound (1) and the other fluorine-containing ether compound in the present composition is preferably 80 to 100% by mass, particularly preferably 85 to 100% by mass, based on the present composition.

When the content of the compound (1) and the content of the other fluorine-containing ether compound are within the above ranges, the initial water-and oil-repellency, abrasion resistance, fingerprint stain removal property, light resistance and chemical resistance of the surface layer are more excellent.

The composition may contain components other than the compound (1) and other fluorine-containing ether compounds within a range not impairing the effects of the present invention.

Examples of the other components include compound (1), by-products generated in the production process of known fluorine-containing ether compounds (except for by-product fluorine-containing ether compounds), and compounds which are unavoidable in production of unreacted raw materials.

Further, additives such as an acid catalyst and a basic catalyst which promote hydrolysis and condensation reactions of the hydrolyzable silyl group may be mentioned. Examples of the acid catalyst include hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, and the like. Examples of the basic catalyst include sodium hydroxide, potassium hydroxide, and ammonia.

The content of the other components is preferably 0 to 10% by mass, and particularly preferably 0 to 1% by mass, based on the present composition.

[ coating solution ]

The coating liquid of the present invention (hereinafter, also referred to as "the present coating liquid") contains the compound (1) or the present composition and contains a liquid medium. The coating liquid may be a solution or a dispersion.

As the liquid medium, an organic solvent is preferable. The organic solvent may be a fluorine-containing organic solvent or a non-fluorine-containing organic solvent, and may further contain two solvents.

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

The fluorinated alkane is preferably a C4-8 compound. As a commercial productExamples thereof include C₆F₁₃H (ASAHIK L IN (registered trademark) AC-2000, manufactured by AGC K.K.) C₆F₁₃C₂H₅(ASAHIK L IN (registered trademark) AC-6000, manufactured by AGC K.K.) C₂F₅CHFCHFCF₃(Vertrel (registered trademark) XF, manufactured by The Chemours Company, Ltd.).

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. As a commercially available product, CF may be mentioned₃CH₂OCF₂CF₂H (ASAHIK L IN (registered trademark) AE-3000, manufactured by AGC K.K.) C₄F₉OCH₃(Novec (registered trademark) 7100, manufactured by 3M Co.) C₄F₉OC₂H₅(Novec (registered trademark) 7200, manufactured by 3M Co.) C₂F₅CF(OCH₃)C₃F₇(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-fluorinated organic solvent is preferably a compound formed of only hydrogen atoms and carbon atoms, or a compound formed of only hydrogen atoms, carbon atoms, and oxygen atoms, and examples thereof include hydrocarbons, alcohols, ketones, ethers, and esters.

The liquid medium may be a mixed medium obtained by mixing 2 or more kinds of the liquid media.

The content of the compound (1) or the present composition is preferably 0.001 to 10% by mass, particularly preferably 0.01 to 1% by mass, based on the present coating liquid.

The content of the liquid medium is preferably 90 to 99.999% by mass, and particularly preferably 99 to 99.99% by mass, based on the present coating liquid.

[ article ]

The article of the present invention (hereinafter also referred to as "the present article") has a surface layer made of the compound (1) or the present composition on the surface of a substrate.

The surface layer contains the compound (1) in a state in which a part or all of the hydrolyzable silyl groups of the compound (1) undergo hydrolysis reaction and a dehydration condensation reaction.

The thickness of the surface layer is preferably 1 to 100nm, particularly preferably 1 to 50 nm. When the thickness of the surface layer is 1nm or more, the effect of the surface treatment can be easily obtained sufficiently. When the thickness of the surface layer is 100nm or less, the utilization efficiency is high. The thickness of the surface layer can be calculated from the vibration period of the interference pattern obtained by an X-ray reflectance method using an X-ray diffractometer for thin film analysis (ATX-G, manufactured by RIGAKU corporation).

Examples of the substrate include substrates to which water-and oil-repellency is required to be imparted. Examples of the material of the substrate include metal, resin, glass, sapphire, ceramic, stone, and a composite material thereof. The glass may be chemically strengthened. SiO can also be formed on the surface of the substrate₂A base film such as a film.

As the substrate, a substrate for a touch panel, a substrate for a display, and a spectacle lens are preferable, and a substrate for a touch panel is particularly preferable. As a material of the substrate for a touch panel, glass or a transparent resin is preferable.

[ method for producing article ]

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

A method of forming a surface layer formed of the compound (1) or the present composition on the surface of the substrate by treating the surface of the substrate by a dry coating method using the compound (1) or the present composition.

A method of applying the coating liquid to the surface of a substrate by a wet coating method and drying the coating liquid to form a surface layer made of the compound (1) or the present composition on the surface of the substrate.

Examples of the dry coating method include vacuum deposition, CVD, sputtering, and the like. As the dry coating method, a vacuum deposition method is preferable in terms of suppressing decomposition of the compound (1) and convenience of the apparatus. In the case of vacuum deposition, a granular material obtained by impregnating a porous metal body such as iron or steel with the compound (1) or the present composition can be used. A granular material obtained by impregnating a porous metal such as iron or steel with the coating liquid and drying the liquid medium to impregnate the compound (1) or the present composition may also be used.

Examples of the wet coating method include spin coating, wipe coating, spray coating, blade coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, L angmuir-Blodgett method, and gravure coating.

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

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