WO2019049753A1

WO2019049753A1 - Fluorine-containing ether compound, composition and article

Info

Publication number: WO2019049753A1
Application number: PCT/JP2018/031999
Authority: WO
Inventors: 星野　泰輝; 誠人宇野; 健二石関; 弘賢山本; 勇佑冨依; 啓吾松浦
Original assignee: Ａｇｃ株式会社
Priority date: 2017-09-05
Filing date: 2018-08-29
Publication date: 2019-03-14
Also published as: CN111051383A; CN111051383B; JP7067562B2; JPWO2019049753A1

Abstract

Provided are: a fluorine-containing ether compound which exhibits excellent solubility in a non-fluorine organic solvent, and which is capable of forming a surface layer that has excellent wear resistance even in cases where a composition obtained by dissolving this fluorine-containing ether compound in a non-fluorine organic solvent is used; a composition; and an article. A fluorine-containing ether compound which is characterized by having: a poly(oxyfluoroalkylene) chain that contains an oxyfluoroalkylene unit represented by formula A1; and two or more groups represented by formula B. In formula A1, X1 represents a fluoroalkylene group which contains one or more hydrogen atoms. In formula B, R represents a monovalent hydrocarbon group; and L represents a hydrolyzable group or a hydroxyl group. (OX1) formula A1 -Si(R)nL3-n formula B

Description

Fluorine-containing ether compounds, compositions and articles

The present invention relates to fluorine-containing ether compounds, compositions and articles.

Since a fluorine-containing compound exhibits high lubricity, water and oil repellency, etc., it is suitably used as a surface treatment agent. When the surface treatment agent imparts water and oil repellency to the surface of the substrate, the dirt on the surface of the substrate can be easily wiped off, and the dirt removability is improved. Among the above-mentioned fluorine-containing compounds, a fluorine-containing ether compound having a poly (oxyperfluoroalkylene) chain in which an ether bond (-O-) is present in the middle of the perfluoroalkylene chain is a compound having excellent flexibility. Excellent dirt removability.

The surface treatment agent containing the above-mentioned fluorine-containing ether compound has a performance (friction resistance) in which water and oil repellency hardly decreases even if it is repeatedly rubbed with a finger (friction resistance) and a performance capable of easily removing fingerprints attached to the surface by wiping (fingerprint stain It is used as a surface treatment agent of the member which comprises the surface touched by the finger of a touch panel, for example for which the removal property is required to be maintained for a long time.
As said fluorine-containing ether compound, the compound which has a poly (oxyperfluoro alkylene) chain | strand and has a hydrolysable silyl group at the terminal is used widely (patent document 1).

JP 2014-218639 A

On the other hand, the fluorine-containing ether compounds described in Patent Document 1 have high solubility in fluorine-based organic solvents, but non-fluorinated organic solvents widely used in industrial processes (especially ketone-based organic solvents, ether-based organic solvents) And so forth (general-purpose solvents), etc.).
From the industrial point of view, a fluorine-containing ether that can be dissolved in a non-fluorinated organic solvent and can form a surface layer excellent in abrasion resistance even when using a composition dissolved in a non-fluorinated organic solvent There is a need for compounds.

In view of the above problems, the present invention forms a surface layer excellent in solubility in a non-fluorinated organic solvent, and also excellent in abrasion resistance when a composition dissolved in a non-fluorinated organic solvent is used. It is an object of the present invention to provide a possible fluorine-containing ether compound, composition and article.

The present invention provides fluorine-containing ether compounds, compositions and articles having the following constitutions [1] to [13].
[1] A fluorine-containing ether compound having a poly (oxyfluoroalkylene) chain containing an oxyfluoroalkylene unit represented by Formula A1 and two or more groups represented by Formula B.
(OX ¹ ) Formula A1
-Si (R) _n L _3-n formula B
However, in the formula
X ¹ is a fluoroalkylene group having one or more hydrogen atoms.
R is a monovalent hydrocarbon group.
L is a hydrolyzable group or a hydroxyl group.
n is an integer of 0 to 2.

[2] The fluorinated ether compound of [1], wherein the carbon number of the oxyfluoroalkylene unit is 2 to 6.
[3] The fluorine-containing ether compound of [1] or [2], wherein at least a part of the oxyfluoroalkylene units contained in the poly (oxyfluoroalkylene) chain is a carbon number of 2 oxyfluoroalkylene units.
[4] The fluorine-containing ether compound according to any one of [1] to [3], wherein the poly (oxyfluoroalkylene) chain further contains an oxyperfluoroalkylene unit represented by Formula A2.
(OX ² ) Formula A2
However, in the formula
X ² is a perfluoroalkylene group.
[5] The fluorinated ether compound of [4], wherein the carbon number of the oxyperfluoroalkylene unit is 1 to 6.
[6] The poly (oxyfluoroalkylene) chain includes a number of oxyfluoroalkylene units represented by the formula A1 and b number of oxyperfluoroalkylene units represented by the formula A2, and a is 2 or more. The fluorine-containing ether compound according to any one of [1] to [5], wherein b is an integer of 0 or more and a + b is 8 or more.

[7] The fluorine-containing ether compound of any one of [1] to [6], which is a compound represented by the following formula 1.
R ¹ -[(OX ¹ ) _a (OX ² ) _b ]-Y-Z (R ² ) _q (R ³ ) _r-q formula 1
However, in the formula
R ¹ is an alkyl group which may have a fluorine atom, or —YZ (R ² ) _q (R ³ ) _rq .
X ¹ is a fluoroalkylene group having one or more hydrogen atoms.
X ² is a perfluoroalkylene group.
Y is a single bond or a divalent linking group.
Z is a carbon atom, a silicon atom or a nitrogen atom.
R ² is a hydrogen atom, a hydroxyl group or an alkyl group.
R ³ is -L ¹ -Si (R) _n L _3-n . L ¹ is an alkylene group which may have —O—.
a is an integer of 2 or more, b is an integer of 0 or more, and a + b is an integer of 8 or more.
When Z is a carbon atom or a silicon atom, r is 3 and q is an integer of 0 to 2. When Z is a nitrogen atom, r is 2 and q is an integer of 0 to 1.

[8] The fluorine-containing ether compound of [7], wherein Z is a carbon atom or a silicon atom, and q is 0 or 1.
[9] A composition comprising the fluorine-containing ether compound of any one of the above [1] to [8] and a liquid medium.
[10] A substrate, and a surface layer formed of the composition according to claim 9 or the fluorine-containing ether compound of any one of [1] to [8] on the substrate. Article to be characterized.
[11] A surface treatment agent containing the fluorine-containing ether compound of any one of the above [1] to [8].

[12] A fluorine-containing ether compound represented by the following formula 3.
^{^{_{^{R 11 - [(OX 1)}}}} a (OX 2) b] -Y-Z (R 2) q (L 2 -CH = CH 2) r-q Formula 3
However, in the formula
R ¹¹ is an alkyl group which may have a fluorine atom, or —Y—Z (R ² ) _q (L ² —CH = CH ₂ ) _r—q .
X ¹ is a fluoroalkylene group having one or more hydrogen atoms.
X ² is a perfluoroalkylene group.
Y is a single bond or a divalent linking group.
Z is a carbon atom, a silicon atom or a nitrogen atom.
R ² is a hydrogen atom, a hydroxyl group or an alkyl group.
a is an integer of 2 or more, b is an integer of 0 or more, and a + b is an integer of 8 or more.
L ² is an alkylene group which may have —O—, a single bond or —O—.
When Z is a carbon atom or a silicon atom, r is 3 and q is an integer of 0 to 2. When Z is a nitrogen atom, r is 2 and q is an integer of 0 to 1.

[13] A process for producing a fluorine-containing ether compound represented by the formula 1, which comprises subjecting the fluorine-containing ether compound represented by the formula ₃ to a hydrosilylation reaction with HSi (R) _n L _3-n .
R ¹ -[(OX ¹ ) _a (OX ² ) _b ]-Y-Z (R ² ) _q (R ³ ) _r-q formula 1
^{^{_{^{R 11 - [(OX 1)}}}} a (OX 2) b] -Y-Z (R 2) q (L 2 -CH = CH 2) r-q Formula 3
However, in the formula
R ¹ is an alkyl group which may have a fluorine atom, or —YZ (R ² ) _q (R ³ ) _rq .
R ¹¹ is an alkyl group which may have a fluorine atom, or —Y—Z (R ² ) _q (L ² —CH = CH ₂ ) _r—q .
X ¹ is a fluoroalkylene group having one or more hydrogen atoms.
X ² is a perfluoroalkylene group.
Y is a single bond or a divalent linking group.
Z is a carbon atom, a silicon atom or a nitrogen atom.
R ² is a hydrogen atom, a hydroxyl group or an alkyl group.
R ³ is -L ¹ -Si (R) _n L _3-n .
L ¹ is an alkylene group which may have —O—.
a is an integer of 2 or more, b is an integer of 0 or more, and a + b is an integer of 8 or more.
L ² is an alkylene group which may have —O—, a single bond or —O—.
When Z is a carbon atom or a silicon atom, r is 3 and q is an integer of 0 to 2. When Z is a nitrogen atom, r is 2 and q is an integer of 0 to 1.

According to the present invention, a fluorine-containing ether compound having excellent solubility in a non-fluorinated organic solvent, and excellent friction resistance even when using a composition dissolved in a non-fluorinated organic solvent, a composition, and Can provide an article.

In the present specification, the compound represented by Formula 1 is referred to as Compound 1. The compounds represented by other formulas are similarly described. The oxyfluoroalkylene unit represented by formula A1 is described as unit A1. The units represented by other formulas are similarly described. The group represented by Formula B is referred to as a group B. The same applies to groups represented by other formulas.
In the present specification, when “the alkylene group may have an A group”, the alkylene group may have an A group between carbon-carbon atoms in the alkylene group, and an alkylene group— It may have an A group at the end, such as an A group.
The meanings of the terms in the present invention are as follows.
The "surface layer" means a layer formed on a substrate. The surface layer may be formed directly on the substrate, or may be formed on the substrate via another layer formed on the surface of the substrate.
The “number average molecular weight” of the fluorine-containing ether compound is calculated by determining the number (average value) of oxyfluoroalkylene units based on the end group by ¹ H-NMR and ¹⁹ F-NMR.

[Fluorine-containing ether compounds]
The fluorine-containing ether compound of the present invention (hereinafter, also referred to as “specific compound”) has a poly (oxyfluoroalkylene) chain containing the unit A1 and two or more groups B.
The specific compound is excellent in solubility in non-fluorinated organic solvents (in particular, ketone organic solvents, ether organic solvents). The reason for this is presumed to be that the affinity to a non-fluorinated organic solvent is improved by using a poly (oxyfluoroalkylene) chain containing a unit A1 having a hydrogen atom. In addition, since a specific compound has a fluorine atom, it is excellent also in the solubility with respect to a fluorine-type organic solvent.
Moreover, the surface layer formed using a specific compound is excellent in abrasion resistance. The reason for this is presumed to be that by having two or more groups B, the reaction point between the specific compound and the base material is increased, and the adhesion between the surface layer and the base material is improved.

The specific compound has a poly (oxyfluoroalkylene) chain containing unit A1.
(OX ¹ ) Formula A1
X ¹ is a fluoroalkylene group having one or more hydrogen atoms.
The carbon number of X ¹ is preferably 1 to 6, more preferably 2 to 6, and particularly preferably 2 to 4.
The hydrogen atom which X ¹ has is 1 or more, 1 or 3 is preferable at the point which is excellent in the balance with the solubility with respect to the non-fluorine type organic solvent of a specific compound, and the abrasion resistance of surface layer, 1 or 3 Particularly preferred is two.

X ¹ has one or more fluorine atoms. The number of fluorine atoms of X ¹ is one or more, and is preferably 1 to 11, in that the balance between the solubility of the specific compound in a non-fluorinated organic solvent and the friction resistance of the surface layer is excellent. One is particularly preferred.
X ¹ is preferably linear from the viewpoint that the abrasion resistance of the surface layer is more excellent.

Specific examples of the unit A1 include (OCF ₂ CHF), (OCHFCF ₂ ), (OCF ₂ CH ₂ ), (OCH ₂ CF ₂ ), (OCF ₂ CF ₂ CHF), (OCHFCF ₂ CF ₂ ), (OCF) ₂ CF ₂ CH ₂ ), (OCH ₂ CF ₂ CF ₂ ), (OCF ₂ CF ₂ CF ₂ CH ₂ ), (OCH ₂ CF ₂ CF ₂ CF ₂ ), (OCF ₂ CF ₂ CF ₂ CF ₂ CH ₂ ) , (OCH ₂ CF ₂ CF ₂ CF ₂ CF ₂ ), (OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ ), and (OCH ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ ).

Assuming that the number of units A1 contained in the poly (oxyfluoroalkylene) chain is a, a is preferably an integer of 2 or more, more preferably an integer of 2 to 200, more preferably an integer of 5 to 150, and 8 to The integer of 100 is more preferable, and the integer of 10 to 50 is particularly preferable.

The poly (oxyfluoroalkylene) chain may contain only one type of unit A1 or may contain two or more types of unit A1.
As two or more types of units A1, for example, two or more types of units A1 having different carbon numbers, two or more types of units A1 having different numbers of hydrogen atoms, presence or absence of side chains even if the number of carbon atoms is the same And two or more units of different types of A.
The bonding order of the two or more units A1 is not limited, and may be arranged randomly, alternately, or in blocks.

The a (OX ¹ ) s of the poly (oxyfluoroalkylene) chain are represented by (OX ¹ ) _a . ^(OX _{1) a,} the number of (OX ¹⁾ is intended to represent that it is a number, it does not represent an arrangement of a number of (OX ^1). Similarly, the number of which will be described later ^(OX _{2) b} also (OX ²⁾ is intended to represent that the number b and is not intended to represent the arrangement of the b-number of (OX ^2).
Therefore, in the poly (oxyfluoroalkylene) chain represented by [(OX ¹ ) _a (OX ² ) _b ] described later, the poly (oxyfluoro alkylene) chain is a (OX ¹ ) and b (OX ¹ ) chains. ²⁾ is intended to represent that it has a, it does not represent that it has a block of a number (OX ¹⁾ of the block and b pieces of (OX ^2). [(OX ¹ ) _a (OX ² ) _b ] may be any arrangement of (OX ¹ ) and (OX ² ) in random, alternating or block, and in any arrangement, a (( It represents that it is a poly (oxy fluoro alkylene) chain which has OX ¹ ) and b pieces (OX ² ).
Below _{_{_{_{[(OC 2 H m1 F (}}}} 4-m1)) a1 (OC 3 H m2 F (6-m2)) a2 (OC 4 H m3 F (8-m3)) a3 (OC 5 H m4 F (10 _{_{_{_{-m4)) a4 (OC 6 H}}}} m5 F (12-m5)) a5], [(OC 2 H m1 F (4-m1)) a1 (OC 3 H m2 F (6-m2)) a2 (OC 4 _{_{_{_{H m3 F (8-m3)}}}} ) a3 (OC 5 H m4 F (10-m4)) a4 (OC 6 H m5 F (12-m5)) a5 (OX 2) b] versa is expressed, such as .

The poly (oxy-fluoroalkylene) chain has ^{_{_{_{(OX 1) a, [(}}}} OC 2 H m1 F (4-m1)) a1 (OC 3 H m2 F (6-m2)) a2 (OC 4 H m3 F _{_{_{_{(8-m3)) a3 (}}}} OC 5 H m4 F (10-m4)) a4 (OC 6 H m5 F (12-m5)) a5] is preferred.
m1 is an integer of 1 to 3, m2 is an integer of 1 to 5, m3 is an integer of 1 to 7, m4 is an integer of 1 to 9, and m5 is an integer of 1 to 11.
Each of a 1, a 2, a 3, a 4 and a 5 is independently an integer of 0 or more, preferably 100 or less.
a1 + a2 + a3 + a4 + a5 is an integer of 2 or more, preferably an integer of 2 to 200, more preferably an integer of 5 to 150, still more preferably an integer of 8 to 100, and particularly preferably an integer of 10 to 50.
Among them, an integer of 1 or more is preferable, and an integer of 2 to 200 is particularly preferable because a1 is more excellent in the solubility of the specific compound in the non-fluorinated organic solvent.
_{_{_{_{Also, C 3 H m2 F (6}}}} -m2), C 4 H m3 F (8-m3), C 5 H m4 F (10-m4) and _{_{_{C 6 H m5 F (12-}}} m5) has a surface layer Linear is preferable from the viewpoint of more excellent friction resistance.

Incidentally, a1 one _{_{_{(OC 2 H m1 F (4}}} -m1)), a2 amino _{_{_{(OC 3 H m2 F (6}}} -m2)), a3 amino _{_{_{(OC 4 H m3 F (8}}} -m3)), a4 amino _{_{_{(OC 5 H m4 F (10}}} -m4)), binding order of a5 pieces _{_{_{(OC 6 H m5 F (12}}} -m5)) is not limited.
When a1 is 2 or more, a plurality of (OC ₂ H _m1 F _{(4-m1) 2} ) may be the same or different.
When a2 is 2 or more, a plurality of (OC ₃ H _m2 F _(6-m2) ) may be the same or different.
When a3 is 2 or more, a plurality of (OC ₄ H _m3 F _(8-m3) ) may be the same or different.
When a4 is 2 or more, a plurality of (OC ₅ H _m4 F _(10-m4) ) may be the same or different.
When a5 is 2 or more, a plurality of (OC ₆ H _m5 F _(10-m5) ) may be the same or different.

Among them, at least a part of (OX ¹ ) _a is an OX ¹ having 2 carbon atoms, that is, (OC ₂ H _m1 F _(4-m1) ) in that the solubility of the specific compound in the non-fluorinated organic solvent is more excellent. Is preferred.
The following (1) to (5) are preferable as (OX ¹ ) _a possessed by the poly (oxyfluoroalkylene) chain.
_{_{_{_{(1) [(OC 2 H}}}} m1 F (4-m1)) a1 (OC 3 H m2 F (6-m2)) a2]
_{_{_{_{(2) [(OC 2 H}}}} m1 F (4-m1)) a1 (OC 4 H m3 F (8-m3)) a3]
_{_{_{_{(3) [(OC 2 H}}}} m1 F (4-m1)) a1 (OC 5 H m4 F (10-m4)) a4]
_{_{_{_{(4) [(OC 2 H}}}} m1 F (4-m1)) a1 (OC 6 H m5 F (12-m5)) a5]
(5) [(OC ₂ H _m1 F _(4-m1) ) a ₁ ]
The above (1) corresponds to an aspect in which a3, a4 and a5 are 0, and a1 + a2 is an integer of 2 or more. The above (2) corresponds to an aspect in which a2, a4 and a5 are 0, and a1 + a3 is an integer of 2 or more. The above (3) corresponds to an aspect in which a2, a3 and a5 are 0, and a1 + a4 is an integer of 2 or more. The above (4) corresponds to an embodiment in which a2, a3 and a4 are 0, and a1 + a5 is an integer of 2 or more. The above (5) represents a poly (oxyfluoroalkylene) chain having a total of a1 two or more different (OC ₂ H _m1 F _{(4-m1) 2} ) and a1 being an integer of 2 or more. Also in the above (1) to (4), when a1 is an integer of 2 or more, it may have two or more different (OC ₂ H _m1 F _(4-m1) ).

The poly (oxyfluoroalkylene) chain may further contain an oxyperfluoroalkylene unit in addition to the unit A1.
Specifically, the poly (oxyfluoroalkylene) chain may contain the unit A2.
(OX ² ) Formula A2
X ² is a perfluoroalkylene group.
The carbon number of X ² is preferably 1 to 6.
The group X ² is preferably linear from the viewpoint that the abrasion resistance of the surface layer is more excellent.

The poly (oxyfluoroalkylene) chain may contain only one type of unit A2, or may contain two or more types of unit A2.
Examples of two or more types of units A2 include two or more types of units A2 having different carbon numbers, and two or more types of units A2 having different side chains and having different types of side chains even if the number of carbons is the same. .

Specific examples of the unit A2 include (OCF ₂ ), (OCF ₂ CF ₂ ), (OCF ₂ CF ₂ CF ₂ ), (OCF (CF ₃ ) CF ₂ ), (OCF ₂ CF ₂ CF ₂ CF ₂ ), _{_{_{_{(OCF (CF 3) CF 2}}}} CF 2), (OCF 2 CF 2 CF 2 CF 2 CF 2), include _{_{(OCF 2 CF 2 CF 2 CF}} 2 CF 2 CF 2).

When the number of units A2 contained in the poly (oxyfluoroalkylene) chain is b, b is an integer of 0 or more, preferably an integer of 0 to 200, more preferably an integer of 0 to 50, and 0 to 10 The integer of is more preferable, and the integer of 0 to 2 is particularly preferable.

When the poly (oxyfluoroalkylene) chain contains the unit A1 and the unit A2, the bonding order of the unit A1 and the unit A2 is not limited. For example, the units A1 and A2 may be arranged randomly, alternately, and in blocks.
When the poly (oxyfluoroalkylene) chain contains a units of A1 and b units of A2, a + b is an integer of 8 or more, preferably an integer of 8 to 400, and more preferably an integer of 8 to 200. And an integer of 8 to 120 is more preferable, and an integer of 10 to 52 is particularly preferable.

The specific compound has two or more groups B.
-Si (R) _n L _3-n formula B

The number of groups B possessed by the specific compound is 2 or more, and 2 to 10 are preferable, 2 to 5 are more preferable, and 2 or 3 in that the friction resistance of the surface layer is more excellent. Is particularly preferred.
Two or more groups B may be the same or different. It is preferable that they are the same as each other from the viewpoint of the availability of raw materials and the ease of production of a specific compound.

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

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

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

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

As a specific compound, the compound 1 is preferable at the point which is excellent by the solubility with respect to the non-fluorinated organic solvent of a specific compound, and the abrasion resistance of a surface layer.
R ¹ -[(OX ¹ ) _a (OX ² ) _b ]-Y-Z (R ² ) _q (R ³ ) _r-q formula 1

R ¹ is an alkyl group which may have a fluorine atom, or —YZ (R ² ) _q (R ³ ) _rq . The definitions of Y, Z, R ¹ , R ² , r and q are as described later.
The number of carbon atoms in the alkyl group which may have a fluorine atom is preferably 1 to 20, and more preferably 1 to 10 in that it is excellent in the solubility of the specific compound in the non-fluorinated organic solvent and the abrasion resistance of the surface layer. More preferably, 1 to 6 is particularly preferred.
The alkyl group which may have a fluorine atom may be linear or branched, and is preferably linear from the viewpoint that the abrasion resistance of the surface layer is more excellent.
The alkyl group which may have a fluorine atom may be a group in which all hydrogen atoms in the alkyl group are substituted with a fluorine atom (perfluoroalkyl group).

Specific examples of the alkyl group which may have a fluorine atom include CH _3- , CF _3- , CF ₃ CH _2- , CF ₃ CF _2- , CF ₃ CF ₂ CF _2- , and (CF ₃ ) ₂ CH—, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ —, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ —.

The group represented by [(OX ¹ ) _a (OX ² ) _b ] is a poly (oxyfluoroalkylene) chain.
The definitions of X ¹ , X ² , a and b are as described above. However, a + b in Formula 1 is an integer of 8 or more, preferably an integer of 8 to 400, more preferably an integer of 8 to 200, still more preferably an integer of 8 to 120, and particularly preferably an integer of 10 to 52.
In [(OX ¹ ) _a (OX ² ) _b ], the binding order of (OX ¹ ) and (OX ² ) is not limited. For example, (OX ¹ ) and (OX ² ) may be arranged randomly, alternately, and in blocks.
Further, a plurality of (OX ¹⁾ may be be the same or different. That is, (OX ¹ ) _a may be composed of two or more (OX ¹ ) different in X ¹ . The bonding order of two or more (OX ¹ ) is not limited, and may be arranged randomly, alternately, or in blocks.
Furthermore, when b is 2 or more, a plurality of (OX ² ) may be the same or different. That is, (OX ² ) _b may be composed of two or more (OX ² ) different in X ² . The bonding order of two or more (OX ² ) is not limited, and may be arranged randomly, alternately, and in blocks.

As the group represented by [(OX ¹ ) _a (OX ² ) _b ], [(OC ₂ H _m1 F _(4-m1) ) _a1 (OC ₃ H _m2 F _(6-m2) ) _a2 (OC ₄ _{_{_{_{H m3 F (8-m3)}}}} ) a3 (OC 5 H m4 F (10-m4)) a4 (OC 6 H m5 F (12-m5)) a5 (OX 2) b] is preferred.
The definitions of m1, m2, m3, m4, m5, a1, a2, a3, a4 and a5 are as described above.

Y is a single bond or a divalent linking group.
The bivalent linking group may be, for example, a bivalent hydrocarbon group (a bivalent saturated hydrocarbon group, a bivalent aromatic hydrocarbon group, an alkenylene group, an alkynylene group). The hydrogen group may be linear, branched or cyclic and includes, for example, an alkylene group The carbon number is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. The divalent aromatic hydrocarbon group preferably has 5 to 20 carbon atoms, for example, a phenylene group, etc. Other than that, an alkenylene group having 2 to 20 carbon atoms and an alkynylene group having 2 to 20 carbon atoms , A divalent heterocyclic group, -O-, -S-, -SO _2- , -N (R ⁴ )-, -C (O)-, -Si (R ⁵ ) ₂ And groups in which two or more of these are combined. R ⁴ is a hydrogen atom or an alkyl group (preferably having a carbon number of 1 to 10). R ⁵ is an alkyl group (preferably having a carbon number of 1 to 10) or a phenyl group.
The above examples of a group formed by combining two or more kinds of these, for ^{example, -C (O) N (R} 4) -, - C (O) N (R 4) - alkylene radical -, - O-alkylene group -, And -OC (O)-.

Among them, Y is a single bond, —O—, —C (O) —, —C (O) N (R ⁴ ) —, —C (O) N, in that it is easier to synthesize a specific compound. (R ⁴ ) -alkylene group- and -O-alkylene group- are preferable.

Z is a carbon atom, a nitrogen atom or a silicon atom.

R ² is a hydrogen atom, a hydroxyl group or an alkyl group.
The carbon number of the alkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1.
When q is 2, two R ^{2 s} may be the same or different. From the viewpoint of the availability of raw materials and the ease of production of compound 1, they are preferably the same.

R ³ is -L ¹ -Si (R) _n L _3-n .
The definitions of R, L and n are as described above.
L ¹ is an alkylene group which may have —O—.
When the alkylene group has -O-, it is preferable to have -O- at the end between carbon and carbon atoms or on the Z side.
The carbon number of L ¹ is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

When Z is a carbon atom or a silicon atom, r is 3 and q is an integer of 0 to 2, preferably 0 or 1. When Z is a nitrogen atom, r is 2 and q is an integer of 0 to 1, preferably 0.
When there are a plurality of R ³ in one molecule, the plurality of R ³ may be the same or different. From the viewpoint of the availability of raw materials and the ease of production of compound 1, they are preferably the same.

As the compound 1, the compound 2 is preferable in that it is excellent in the solubility of the specific compound in the non-fluorinated organic solvent and the friction resistance of the surface layer.
R ¹ -[(OC ₂ H _{m 1} F _{(4-m 1)} ) a ₁ (OC ₃ H _{m 2} F _(6-m ₂ ₎ ) a ₂ (OC ₄ H _{m 3} F _{(8-m 3)} ) a ₃ (OC ₅ H _{m 4} F _{( _{_{_{10-m4)) a4 (OC}}}} 6 H m5 F (12-m5)) a5 (OX 2) b] -Y-Z (R 2) q (R 3) r-q formula 2
The definition of each group is as described above.

Specific examples of compound 1 include the following. In the following table, t represents an integer of 1 or more. t is preferably an integer of 50 or less.

The specific compound can be produced by a known production method. For example, it can be produced by hydrosilylation reaction of compound 3 with HSi (R) _n L _3-n .
^{^{_{^{R 11 - [(OX 1)}}}} a (OX 2) b] -Y-Z (R 2) q (L 2 -CH = CH 2) r-q Formula 3
In the formula, X ¹ , X ² , Y, Z, R ² , a, b, q and r are as defined above, and R ¹¹ is an alkyl group which may have a fluorine atom, or Y—Z (R ² ) _q (L ² -CH = CH ₂ ) _r-q , L ² is an alkylene group which may have -O-, a single bond or -O-, L ² -CH = When CH ₂ is hydrosilylated, it becomes L ^{1 of} Compound 1. Compound 3 is, for example, when Y is -C (O) NHCH _2- , R ¹ -[(OX ¹ ) _a (OX ² ) _b ] -C (O) OR is known by a known method using R ¹ -OH as a raw material. ⁵ (wherein R ⁵ is an alkyl group having 1 to 6 carbon atoms) can be obtained by reaction with NH ₂ -CH ₂ -Z (R ² ) _q (L ² -CH = CH ₂ ) _r-q .

〔Composition〕
The composition of the present invention (hereinafter also referred to as "the present composition") contains a specific compound and a liquid medium.

The specific compounds may be used alone or in combination of two or more.
The content of the specific compound is preferably 0.001 to 30% by mass, particularly preferably 0.01 to 20% by mass, with respect to the total mass of the composition.

Examples of the liquid medium include water and organic solvents. Specific examples of the organic solvent include fluorine-based organic solvents and non-fluorine-based organic solvents.
The organic solvents may be used alone or in combination of two or more.

Specific examples of the fluorinated organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines and fluoroalcohols.
The fluorinated alkane is preferably a compound having 4 to 8 carbon atoms. For example, C ₆ F ₁₃ H (AC-2000: product name, manufactured by AGC), C ₆ F ₁₃ C ₂ H ₅ (AC-6000: product name) , AGC), C ₂ F ₅ CHFCHFCF ₃ (Bartrel: product name, manufactured by Dupont).
Specific examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, 1,3-bis (trifluoromethyl) benzene, and 1,4-bis (trifluoromethyl) benzene.
The fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms. For example, CF ₃ CH ₂ OCF ₂ CF ₂ H (AE-3000: product name, manufactured by AGC), C ₄ F ₉ OCH ₃ (Novec-7100: Product name, manufactured by 3M), C ₄ F ₉ OC ₂ H ₅ (Novec-7200: product name, manufactured by 3M), C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ (Novec-7300: product name, 3M company).
Specific examples of fluorinated alkylamines include perfluorotripropylamine and perfluorotributylamine.
Specific examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol and hexafluoroisopropanol.

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

The content of the liquid medium is preferably 70 to 99.999% by mass, particularly preferably 80 to 99.99% by mass, with respect to the total mass of the composition.

The composition of the present invention may contain components other than the specific compound and the liquid medium.
Examples of other components include by-products produced in the process of producing a specific compound, and compounds unavoidable for production of unreacted starting materials and the like.
In addition, additives such as an acid catalyst and a basic catalyst which promote the hydrolysis and condensation reaction of the hydrolyzable silyl group may be mentioned. Specific examples of the acid catalyst include hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid and p-toluenesulfonic acid. Specific 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, more preferably 0 to 5% by mass, and particularly preferably 0 to 1% by mass, with respect to the specific compound.

[Articles]
The article of the present invention has a substrate and a surface layer formed of the specific compound or the present composition on the substrate.
That is, a surface treatment agent containing a specific compound is used for surface treatment of an article.

The surface layer contains a compound obtained through hydrolysis reaction and condensation reaction of a specific compound.
The thickness of the surface layer is preferably 1 to 100 nm, particularly preferably 1 to 50 nm. The thickness of the surface layer is determined using an X-ray diffractometer for thin film analysis (ATX-G: product name, manufactured by RIGAKU Co., Ltd.) to obtain an interference pattern of the reflected X-ray by the X-ray reflectance method. It can be calculated from the vibration period.

The substrate is not particularly limited as long as the substrate is required to be imparted with water and oil repellency. Specific examples of the material of the substrate include metals, resins, glasses, sapphires, ceramics, stones, and composite materials of these. The glass may be chemically strengthened. The substrate may be subjected to a surface treatment with a compound described in paragraphs 0089 to 0095 of WO 2011/016458, SiO ₂ or the like.
As a base material, the base material for touchscreens and a display base material are preferable, and the base material for touchscreens is especially preferable. The touch panel substrate preferably has a light transmitting property. “Having light transmittance” means that the vertical incident visible light transmittance according to JIS R 3106: 1998 (ISO 9050: 1990) is 25% or more. As a material of the base material for touchscreens, glass or transparent resin is preferable.
Moreover, as a base material, the glass or the resin film used for exterior parts (except a display part) in apparatuses, such as a mobile telephone (for example, smart phone), a portable information terminal, a game machine, and a remote control, is also preferable.

The above-mentioned article can be manufactured, for example, by the following method.
-A method of treating the surface of a substrate by a dry coating method using a specific compound or the present composition to obtain the above-mentioned article.
-A method of applying the present composition to the surface of a substrate by a wet coating method and drying it to obtain the above-mentioned article.
In the wet coating method, it is also possible to use a composition containing a hydrolysed compound and a liquid medium by hydrolyzing a specific compound in advance using an acid catalyst, a basic catalyst or the like.

Specific examples of the dry coating method include a vacuum evaporation method, a CVD method, and a sputtering method. Among these, the vacuum evaporation method is preferable in terms of suppressing the decomposition of the specific compound and the simplicity of the apparatus. At the time of vacuum deposition, a pellet-like substance in which a specific compound or the present composition is impregnated into a porous metal body such as iron or steel may be used.
Specific examples of the wet coating method include spin coating method, wipe coating method, spray coating method, squeegee coating method, dip coating method, die coating method, ink jet method, flow coating method, roll coating method, casting method, Langmuir-Blodgett And gravure coating.

The article may have a surface layer formed of the other compound or the composition including the other compound on the other side than the surface having the specific compound or the surface layer formed of the present composition. Good.
Other compounds include poly (oxyperfluoroalkylene) chains and other fluorine-containing ether compounds having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom. Other fluorine-containing ether compounds include compound 4.
[A-O-Z ^1- (R ^f O) _r- ] _j Z ² [-SiR _n L _3-n ] _g Formula 4
A is a perfluoroalkyl group or -Q [-SiR _n L _3-n ] _k .
Q is a (k + 1) valent linking group.
k is an integer of 1 to 10.
The definitions of R, L and n are as defined for R, L and n of group B respectively.
Z ¹ is a single bond, an oxyfluoroalkylene group having 1 to 20 carbon atoms in which one or more hydrogen atoms have been substituted by a fluorine atom, or 1 to 20 carbon atoms in which one or more hydrogen atoms have been substituted in a fluorine atom It is a poly (oxyfluoroalkylene) group.
R ^f is a perfluoroalkylene group.
r is an integer of 2 to 200, and Z ² is a (j + g) -valent linking group.
j and g are each independently an integer of 1 or more.

Other fluorine-containing ether compounds may also be commercially available products. For example, KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., Optool (registered trademark) DSX manufactured by Daikin Industries, Ltd., Optool (registered trademark) AES, Optool (registered trademark) UF 503, Optool (registered trademark) UD 509, Afluid (registered trademark) S550 manufactured by AGC, Inc. can be mentioned.

Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these examples. In addition, the compounding quantity of each component shows a mass reference | standard. Of Examples 1 to 9, Examples 1 to 5, 8 and 9 are Examples, and Examples 6 and 7 are Comparative Examples.

〔Evaluation method〕
(Solubility)
The appearance of the diluted solution diluted with acetone so that the concentration of the fluorinated ether compound was 1% by mass was visually observed, and the solubility of the fluorinated ether compound was evaluated based on the following criteria.
○ (good): The state in which the components contained in the diluted solution are separated can not be confirmed, and there is no turbidity of the diluted solution.
X (poor): The components contained in the diluted solution are in a separated state or the diluted solution has turbidity.

(Anti-friction)
The water contact angle was measured for the evaluation samples before and after the friction resistance test. The smaller the decrease in water contact angle after friction, the smaller the decrease in performance due to friction, and the better the friction resistance. 20 degrees or less is preferable and, as for the fall of a water contact angle, 15 degrees or less is more preferable.
<Measurement method of water contact angle>
The contact angle (water contact angle) of about 2 μL of distilled water placed on the surface of the surface layer was measured using a contact angle measurement device (DM-500: product name, manufactured by Kyowa Interface Science Co., Ltd.). It measured in five different places in the surface of a surface layer, and computed the average value. The 2θ method was used to calculate the contact angle.
<Test method of abrasion resistance>
For the surface layer, a cellulose non-woven fabric (Bencott M-3: product name, manufactured by Asahi Kasei Corp.) was used using a reciprocating traverse tester (manufactured by Keienute) in accordance with JIS L 0849: 2013 (ISO 105-X12: 2001). Load: 1 kg, friction length: 4 cm, speed: reciprocated 10,000 times at 30 rpm.

[Example 1]
Compound 1-1 was synthesized by the following procedure.

(Example 1-1)
In a 100 mL recovery flask connected to a reflux condenser, 10.0 g of Compound X1 and 2.61 g of potassium carbonate powder were placed. While stirring the mixture in the naphtha flask at 120 ° C. under a nitrogen atmosphere, 106.9 g of the compound X2 was added dropwise to the eggplant flask while controlling the internal temperature to 130 ° C. or less. After the entire amount had been dropped, the mixture in the naphtha flask was stirred for a further 1 hour while maintaining the temperature at 120 ° C., the heating was stopped and the stirring was continued until the temperature dropped to 25 ° C. An aqueous solution of hydrochloric acid was placed in an eggplant flask to treat excess potassium carbonate, and water and C ₆ F ₁₃ H (Asahiculin (registered trademark) AC-2000, manufactured by AGC) were added to separate the layers. . After washing with water three times, the organic phase was recovered and concentrated by an evaporator to obtain a highly viscous oligomer. Again, the obtained oligomer was diluted with 100 g of CF ₃ CH ₂ OCF ₂ CF ₂ H (Asahiclin® AE-3000, manufactured by AGC), and developed into silica gel column chromatography (developing solvent: AK-225) I took it out. For each fraction, an average value of the unit number n was determined from an integral value of ¹⁹ F-NMR, and 48.0 g of a compound X3 was obtained by combining fractions having an average value of n of 13 to 16.

NMR spectrum of compound X3;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 2.4 (2 H), 4.1 (2 H), 4.5 (2 H), 4.8 (26 H) , 6.7 to 6.9 (14H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -81 (3F), -84 to -85 (28F), -89 to -91 (28F), -114 (2F), -120 (26F), -122 (4F), -123 (2F), -124 (2F), -127 (30F), -145 (14F).
The average value of the unit number n: 14, the number average molecular weight of the compound X3: 4,260.

(Example 1-2)
J. Org. Chem. , 64, 1999, p. The compound X3 obtained in Example 1-1 was oxidized according to the method described in 2564-2566 to obtain a compound X4.

NMR spectrum of compound X4;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 2.4 (2 H), 4.5 (2 H), 4.8 (26 H), 6.7 to 6. 9 (14H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -81 (3F), -84 to -85 (28F), -89 to -91 (28F), -114 (2F), -120 (26F), -122 (2F), -123 (2F), -124 (4F), -127 (30F), -145 (14F).
The average value of the unit number n: 14, the number average molecular weight of the compound X4: 4,270.

(Example 1-3)
In a 100 mL recovery flask, 40.0 g of the compound X4 obtained in Example 1-2 and 10 mL of methanol were placed, and stirred at 25 ° C. for 12 hours. From NMR, it was confirmed that compound X4 was all converted to compound X5. The solvent was distilled off under reduced pressure to obtain 6.40.1 g (yield 100%) of compound X5.

NMR spectrum of compound X5;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 2.4 (2 H), 3.9 (3 H), 4.5 (2 H), 4.8 (26 H) , 6.7 to 6.9 (14H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -81 (3F), -84 to -85 (28F), -89 to -91 (28F), -114 (2F), -118 (2F), -120 (26F), -122 (2F), -123 (2F), -124 (2F), -126 (2F), -127 (28F), -145 (14F) ).
The average value of the unit number n: 14, the number average molecular weight of the compound X5: 4,280.

(Example 1-4)
In a 50 mL eggplant flask, 10.0 g of the compound X5 obtained in Example 1-3 and 0.40 g of the compound X6 were charged, and stirred for 12 hours. From NMR, it was confirmed that compound X5 was all converted to compound 3-1. In addition, methanol, which is a by-product, was produced. The resulting solution was diluted with 9.0 g of AC-2000, and purified by silica gel column chromatography (developing solvent: AC-2000) to obtain 9.2 g (yield 89%) of compound 3-1.

NMR spectrum of compound 3-1;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 2.4 (8 H), 3.4 (2 H), 4.5 (2 H), 4.8 (26 H) 5.2 (6 H), 5.9-6.2 (3 H), 6.7-6.9 (14 H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -81 (3F), -84 to -85 (28F), -89 to -91 (28F), -114 (2F), -120 (28F), -122 (2F), -123 (2F), -124 (2F), -126 (2F), -127 (28F), -145 (14F).
The average number of units n: 14, the number average molecular weight of compound 3-1: 4,420.

(Example 1-5)
In a 10 mL glass sample bottle, 6.0 g of the compound 3-1 obtained in Example 1-4, platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene solution (platinum Content: 2% by mass of 0.06 g, HSi (OCH ₃ ) ₃ of 1.01 g, aniline of 0.02 g, 1,3-bis (trifluoromethyl) benzene (manufactured by Tokyo Chemical Industry Co., Ltd.) 1. 0 g was added and stirred at 40 ° C. for 8 hours. After completion of the reaction, the solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a 1.0 μm pore diameter to obtain 6.5 g (yield 100%) of compound 1-1.

NMR spectrum of compound 1-1;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.7 (6 H), 1.3 to 1.7 (12 H), 2.4 (2 H), 3. 4 (2 H), 3.6 (27 H), 4.5 (2 H), 4.8 (26 H), 6.7 to 6.9 (14 H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -81 (3F), -84 to -85 (28F), -89 to -91 (28F), -114 (2F), -120 (28F), -122 (2F), -123 (2F), -124 (2F), -126 (2F), -127 (28F), -145 (14F).
The average value of the unit number n: 14, the number average molecular weight of the compound 1-1: 4,780.

[Example 2]
Compound 1-2 was synthesized by the following procedure. The reaction formula is shown together with Example 3 described later.

(Example 2-1)
In a 100 mL eggplant flask, 50.0 g of tetrahydrofuran was placed and cooled to 0 ° C. 15 mL of 0.7 mol / L allylmagnesium bromide was dropped into the eggplant flask, 20.5 g of the compound X5 obtained in Example 1-3 was dropped, and the mixture in the eggplant flask was further stirred for 2 hours. The reaction is terminated by adding 30 mL of a 1 mol / L aqueous hydrochloric acid solution to the mixture, and the lower layer is subjected to silica gel column chromatography (developing solvent: C ₆ F ₁₃ C ₂ H ₅ (manufactured by AGC, ASAHIKLIN (registered trademark) AC-6000). ) To give 16.1 g (yield 78%) of compound 3-2.

NMR spectrum of compound 3-2;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 2.4 to 2.6 (6 H), 4.5 (2 H), 4.8 (26 H), 5. 2-5.3 (4H), 5.9-6.0 (2H), 6.7 to 6.9 (14H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -81 (3F), -84 to -85 (28F), -89 to -91 (28F), -114 (2F), -116 (2F), -120 (26F), -121 (2F), -122 (2F), -123 (2F), -124 (2F), -127 (28F), -145 (14F) ).
The average number of units n: 14, the number average molecular weight of compound 3-2: 4,340.

(Example 2-2)
In the same manner as in Example 1-5 except that Compound 3-1 was changed to 6.0 g of Compound 3-2 obtained in Example 2-1, 6.3 g (yield 100%) of Compound 1-2 was obtained. The

NMR spectrum of compound 1-2;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.7 (4 H), 1.6 to 1.8 (4 H), 1.9 to 2.0 (4 H) ), 2.4 (2H), 3.6 (18H), 4.5 (2H), 4.8 (26H), 6.7 to 6.9 (14H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -81 (3F), -84 to -85 (28F), -89 to -91 (28F), -114 (2F), -116 (2F), -120 (26F), -121 (2F), -122 (2F), -123 (2F), -124 (2F), -127 (28F), -145 (14F) ).
The average number of units n: 14, the number average molecular weight of the compound 1-2: 4,580.

[Example 3]
Compound 1-3 was synthesized by the following procedure. The reaction formula is shown together with Example 2 above.

(Example 3-1)
In a 50 mL recovery flask, 10.0 g of the compound 3-2 obtained in Example 2-1, 1.5 g of allyl bromide, 0.03 g of tetrabutylammonium iodide and 0.7 g of potassium hydroxide are placed. The mixture is stirred at 80 ° C. for 5 hours. The mixture was cooled to 25 ° C., charged with 10 g of AE-3000 and washed twice with water. The obtained crude solution was purified by silica gel column chromatography (developing solvent: AC-6000) to obtain 9.3 g (yield 92%) of compound 3-3.

NMR spectrum of compound 3-3;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 2.4 to 2.7 (8 H), 4.5 (2 H), 4.8 (26 H), 5. 0-5.3 (6 H), 5.8-6.0 (3 H), 6.7-6.9 (14 H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -81 (3F), -84 to -85 (28F), -89 to -91 (28F), -111 (2F), -114 (2F), -120 (26F), -122 (2F), -123 (4F), -124 (2F), -127 (28F), -145 (14F).
Average number of units n: 14, Number average molecular weight of compound 3-3: 4,380.

(Example 3-2)
In the same manner as in Example 1-5 except that Compound 3-1 was changed to 6.0 g of Compound 3-3 obtained in Example 3-1, 6.5 g (yield 100%) of Compound 1-3 was obtained. The

NMR spectrum of compound 1-3;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.6 to 0.8 (6 H), 1.6 to 1.8 (6 H), 1.9 to 2 .0 (4 H), 2.4 (2 H), 3.6 (29 H), 4.5 (2 H), 4.8 (26 H), 6.7 to 6.9 (14 H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -81 (3F), -84 to -85 (28F), -89 to -91 (28F), -111 (2F), -114 (2F), -120 (26F), -122 (2F), -123 (4F), -124 (2F), -127 (28F), -145 (14F).
Average number of units n: 14, Number average molecular weight of compounds 1-3: 4,740.

[Example 4]
Compound 1-4 was synthesized by the following procedure.

(Example 4-1)
In a 50 mL recovery flask, 8.0 g of the compound X3 obtained in Example 1-1, 0.34 g of allyl bromide, 0.08 g of tetrabutylammonium bromide, and 0.60 g of a 48% by mass aqueous potassium hydroxide solution are placed. The mixture was stirred at 80 ° C. for 5 hours. The mixture was cooled to 25 ° C., charged with 10 g of AC-6000 and washed twice with water. The obtained crude solution was purified by silica gel column chromatography (developing solvent: AC-6000) to obtain 7.9 g (yield 98%) of compound X6.

NMR spectrum of compound X6;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 2.4 (2 H), 4.0 (2 H), 4.2 (2 H), 4.5 (2 H) 4.8 (26 H), 5.2-5.4 (2 H), 5.8-6.0 (1 H), 6.7- 6.9 (14 H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -81 (3F), -84 to -85 (28F), -89 to -91 (28F), -114 (2F), -120 (26F), -122 (4F), -123 (2F), -124 (2F), -127 (30F), -145 (14F).
The average value of the unit number n: 14, the number average molecular weight of the compound X6: 4,300.

(Example 4-2)
In a 20 mL closed PTFE container, 7.5 g of the compound X6 obtained in Example 4-1, a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 0.03 g of 2% by mass), 0.35 g of HSiCl ₃ and 3.0 g of 1,3-bis (trifluoromethyl) benzene were added, and the mixture was stirred at 40 ° C. for 8 hours. After completion of the reaction, the solvent and the like were distilled off under reduced pressure to obtain 7.7 g (yield 99%) of compound X7.

NMR spectrum of compound X7;
¹ H-NMR (30.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 1.4 to 1.5 (2 H), 1.9 (2 H), 2.4 (2 H), 3. 6 (2 H), 4.0 (2 H), 4.5 (2 H), 4.8 (26 H), 6.7 to 6.9 (14 H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -81 (3F), -84 to -85 (28F), -89 to -91 (28F), -114 (2F), -120 (26F), -122 (4F), -123 (2F), -124 (2F), -127 (30F), -145 (14F).
The average value of the unit number n: 14, the number average molecular weight of the compound X7: 4,430.

(Example 4-3)
In a 50 mL recovery flask, 7.5 g of the compound X7 obtained in Example 4-2 and 20.0 g of tetrahydrofuran were charged, and cooled to 0 ° C. 12 mL of 0.7 mol / L allylmagnesium bromide was dropped into the eggplant flask, and the mixture in the eggplant flask was further stirred for 2 hours. The mixture was returned to 25 ° C. and stirred for additional 8 hours, and the reaction was quenched by adding 10 mL of 1 mol / L aqueous hydrochloric acid solution. 10 g of AC-6000 was added to the obtained mixture to extract the lower layer, which was purified by silica gel column chromatography (developing solvent: AC-6000) to obtain 6.9 g (yield 92%) of compound 3-4 Obtained.

NMR spectrum of compound 3-4;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.7 (2 H), 1.6 (6 H), 1.8 (2 H), 2.4 (2 H) , 3.6 (2H), 4.0 (2H), 4.5 (2H), 4.8 (26H), 4.9 (6H), 5.7 to 5.9 (3H), 6.7 ~ 6.9 (14H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -81 (3F), -84 to -85 (28F), -89 to -91 (28F), -114 (2F), -120 (26F), -122 (4F), -123 (2F), -124 (2F), -127 (30F), -145 (14F).
The average number of units n: 14, the number average molecular weight of the compound 3-4: 4,450.

(Example 4-4)
In the same manner as in Example 1-5 except that Compound 3-1 was changed to 6.0 g of Compound 3-4 obtained in Example 4-3, 6.5 g (yield 100%) of Compound 1-4 was obtained. The

NMR spectrum of compound 1-4;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.6 to 0.8 (14 H), 1.5 to 1.7 (8 H), 2.4 (2 H) ), 3.6 (29 H), 4.0 (2 H), 4.5 (2 H), 4.8 (26 H), 6.7 to 6.9 (14 H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -81 (3F), -84 to -85 (28F), -89 to -91 (28F), -114 (2F), -120 (26F), -122 (4F), -123 (2F), -124 (2F), -127 (30F), -145 (14F).
The average value of the unit number n: 14, the number average molecular weight of the compound 1-4: 4,810.

[Example 5]
Compounds 1-5 were synthesized by the following procedure.
A compound 1-5 was obtained in the same manner as in Example 1 except that the compound X1 was changed to methanol.
CH ₃ (OCF ₂ CHFOCF ₂ CF ₂ CF ₂ CH ₂ ) _n-1 OCF ₂ CHFOCF ₂ CF ₂ CF ₂ C (O) NHCH ₂ C {CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ } ₃ Formula 1- 5

NMR spectrum of compound 1-5;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.7 (6 H), 1.3 to 1.7 (12 H), 3.4 (2 H), 3. 6 (27 H), 3.7 (3 H), 4.8 (26 H), 6.7 to 6.9 (14 H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -84 to -85 (28F), -89 to -91 (28F), -120 (28F), -126 (2F), -127 (26F), -145 (14F).
Average value of the unit number n: 14, the number average molecular weight of the compound 1-5: 4,450.

[Example 6]
As the compound X8, a commercially available product (manufactured by Wako Chemical Co., Ltd.) was used.
CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ Formula X 8

[Example 7]
As the compound X9, the compound (D) described in Example 1 of JP-A-2014-218639 was used.
CF ₃ CF ₂ CF ₂ (OCF ₂ CF ₂ CF ₂ ) ₂₀ OCF ₂ CF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ Si {CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ } ₃ Formula X 9
[Example 8]
Compounds 1-6 were synthesized by the following procedure.

(Example 8-1)
In a 200 mL three-necked flask, 18.17 g of tetraethylene glycol (TEG), 8 g of N, N-dimethylformamide (DMF), and 3.61 g of potassium carbonate were added, and stirred at 60 ° C. for 1.5 hours under a nitrogen atmosphere. . Thereafter, 8.49 g of compound X10 was slowly added dropwise over 15 minutes, and the mixture was stirred at 60 ° C. for 18 hours as it was. 1N hydrochloric acid was added until it became acidic and stirred, then AK-225 (manufactured by AGC) was added, and then two layers were separated. The organic layer was concentrated and then purified by silica gel column chromatography to obtain 11.1 g (yield 61%) of compound X11.
¹ H-NMR: 6 to 5.8 (2 H), 4.2 (4 H), 3.6 to 3.8 (28 H).
¹⁹ F-NMR: -84 (2F), -86 (2F), -90 (4F), -129 (2F), -144 (2F).
(Example 8-2)
10 g of Compound X11, 20 mL of DMF, and 7.5 g of potassium carbonate were added to a 200 mL eggplant flask, and the mixture was stirred at 60 ° C. for 1 hour under a nitrogen atmosphere. Thereafter, 5 g of allyl bromide was slowly added and stirred for 18 hours. 1N hydrochloric acid was added until it became acidic and stirred, then a 1: 1 solution of ethyl acetate: hexane was added and then two layers were separated. The organic layer was concentrated and then purified by silica gel column chromatography to obtain 10.1 g (yield 91%) of compound 3-6.
¹ H-NMR: 6.2 to 5.8 (4 H), 5.2 to 5.0 (4 H), 4.2 to 4.0 (4 H), 3.6 to 3.8 (32 H)
¹⁹ F-NMR: -84 (2F), -86 (2F), -90 (4F), -129 (2F), -144 (2F)
(Example 8-3)
In a 50 mL eggplant flask, 2.1 g of compound 3-6, 0.0047 g of aniline, 2.1 g of AC-6000 (manufactured by AGC), 0.0096 g of Pt / divinyltetramethyldisiloxane complex, trimethoxysilane 0.93 g was added and stirred overnight at room temperature. After concentration, 2.6 g of compound 1-6 was obtained.
¹ H-NMR: 6 to 5.8 (2 H), 4.0 to 3.4 (54 H), 1.6 to 1.3 (4 H), 0.5 to 0.8 (4 H)
¹⁹ F-NMR: -84 (2F), -86 (2F), -90 (4F), -129 (2F), -144 (2F)
[Example 9]
Compound 1-7 was synthesized by the following procedure.

(Example 9-1)
Compound X12 was synthesized with reference to Example 1-1 of WO2013 / 121984.
In a 200 mL three-necked flask, 10 g of Compound X12, 112 g of ethylene glycol, and 5.0 g of potassium carbonate were added, and the mixture was stirred at 40 ° C. under a nitrogen atmosphere. The reaction solution was added with 1 N hydrochloric acid until it became acidic and stirred, then AE-3000 (manufactured by AGC) was added, and then two layers were separated. The organic layer was concentrated and then purified by silica gel column chromatography to obtain 3.3 g (yield 55%) of compound X13.
¹ H-NMR: 6.5 ( ¹ H), 4.1 (2 H), 3.9 (2 H), 3.8 (2 H).
¹⁹ F-NMR: -84 (2F), -86 (2F), -120 (2F), -126 (2F), -144 (1F).
(Example 9-2)
100 g of Compound X12, 10 g of Compound X13, and 9.2 g of potassium carbonate were added to a 200 mL eggplant flask connected to a reflux condenser, and the mixture was stirred at 60 ° C. under a nitrogen atmosphere. Thereafter, 1 N hydrochloric acid was added until it became acidic and stirred, then AE-3000 (manufactured by AGC) was added, and then two layers were separated. After concentration of the organic layer, 70 g (yield 64%) of compound X14 was obtained.
¹ H-NMR: 6.5 ( ¹⁰ H), 4.1 (20 H), 3.9 (4 H).
¹⁹ F-NMR: -84 (20F), -86 (20F), -120 (20F), -126 (20F), -144 (10F).
The number average molecular weight of the compound X14 is 3500.
(Example 9-3)
In a 200 mL recovery flask, 20 g of Compound X14, 50 mL of DMF, and 15 g of potassium carbonate were added, and the mixture was stirred at 60 ° C. for 1 hour under a nitrogen atmosphere. Thereafter, 10 g of allyl bromide was slowly added and stirred. The reaction solution was added with 1 N hydrochloric acid until it became acidic and stirred, then AE-3000 (manufactured by AGC) was added, and then two layers were separated. The organic layer was concentrated to give 18 g (yield 90%) of compound 3-7.
¹ H-NMR: 6.5 ( ¹⁰ H), 6.1-5.8 (2 H), 5.2-5.0 (4 H), 4.2 (4 H), 4.1 (20 H), 3. 9 (4H).
¹⁹ F-NMR: -84 (20F), -86 (20F), -120 (20F), -126 (20F), -144 (10F).
The number average molecular weight of compound 3-7 is 3600. (Example 9-4)
In a 50 mL eggplant flask, 2.1 g of compound 3-7, 0.0047 g of aniline, 2.1 g of AC-6000 (manufactured by AGC), 0.0096 g of Pt / divinyltetramethyldisiloxane complex, trimethoxysilane 0.93 g was added and stirred overnight at room temperature. After concentration, 2.6 g of compound 1-7 was obtained.
¹ H-NMR: 6.5 ( ¹⁰ H), 4.2 (4 H), 4.1 (20 H), 3.8 (4 H), 1.6 to 1.3 (4 H), 0.5 to 0. 8 (4H).
¹⁹ F-NMR: -84 (2F), -86 (2F), -90 (4F), -129 (2F), -144 (2F).
The number average molecular weight of compound 1-7 is 3800.

[Preparation of evaluation sample]
The surface treatment of the substrate was performed by the following wet coating method using the compound obtained in each example, to obtain an evaluation sample in which a surface layer was formed on the surface of the substrate (chemically strengthened glass). However, since the compound X9 had insufficient solubility, an evaluation sample was not prepared.
The evaluation test described above was performed using the obtained evaluation sample, and the results are shown in Table 6.

The compound obtained according to each example and acetone were mixed to obtain a composition for wet coating having a concentration of the compound of 0.05% by mass.
The substrate was dipped in each composition and left for 30 minutes, and then the substrate was pulled up (dip coating method). The coated film was dried at 200 ° C. for 30 minutes and washed with AK-225 to obtain an evaluation sample (article) having a surface layer on the surface of the substrate.

As shown in Table 6, it was confirmed that the specific compound is excellent in the solubility in the non-fluorinated organic solvent, and is also excellent in the abrasion resistance of the surface layer formed using this (Examples 1 to 5, 8, 9) .

The fluorine-containing ether compound of the present invention can be used in various applications where it is required to impart water and oil repellency. For example, a coat of a display input device such as a touch panel, a surface protection coat of a transparent glass or transparent plastic member, an antifouling coat for a kitchen, a water repellent moistureproof coat or an antifouling coat such as an electronic device, a heat exchanger, or a battery It can be used as an antifouling coat for toiletries, a coat on a member that needs to be liquid repellent while conducting, a water repellent / waterproof / sliding water coat of a heat exchanger, a surface low friction coat such as a vibrating screen or the inside of a cylinder. As a more specific example of use, a front face protection plate of a display, an anti-reflection plate, a polarizing plate, an anti-glare plate, or those subjected to anti-reflection film treatment on their surface, a mobile phone (for example, a smartphone), a portable information terminal , Touch panels of devices such as game consoles, remote controls, etc. Coats of various devices having display / input devices that perform operations on the screen with human fingers or palm such as touch panels (for example, for glass or film used for display Coats and coats for glass or film used on exterior parts other than display parts), coats of decorative building materials around water such as toilets, baths, washrooms and kitchens, waterproof coatings for wiring boards, water repellency of heat exchangers Waterproof / slippery coat, water repellent coat of solar cell, waterproof / water repellent coat of printed wiring board, electricity Waterproof and water repellent coating for equipment casings and electronic parts, Coating for improving insulation of power transmission line, Waterproof and water repellent coating for various filters, Waterproof coating for radio wave absorbing material and sound absorbing material, Bath, kitchen equipment, protection for toiletries Examples thereof include dirt coats, low friction coats such as vibrating sieves and the inside of cylinders, machine parts, vacuum equipment parts, bearing parts, automobile parts, surface protection coats such as tools, and the like.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2017-170085 filed on Sep. 05, 2017 are incorporated herein by reference and incorporated as disclosure of the specification of the present invention. It is.

Claims

A fluorine-containing ether compound having a poly (oxyfluoroalkylene) chain containing an oxyfluoroalkylene unit represented by the formula A1 and two or more groups represented by the formula B.
(OX 1 ) Formula A1
-Si (R) n L 3-n formula B
However, in the formula
X 1 is a fluoroalkylene group having one or more hydrogen atoms.
R is a monovalent hydrocarbon group.
L is a hydrolyzable group or a hydroxyl group.
n is an integer of 0 to 2.
The fluorine-containing ether compound according to claim 1, wherein the oxyfluoroalkylene unit has 2 to 6 carbon atoms.
The fluorine-containing ether compound according to claim 1 or 2, wherein at least a part of the oxyfluoroalkylene units contained in a poly (oxyfluoroalkylene) chain is a carbon number of 2 oxyfluoroalkylene units.
The fluorine-containing ether compound according to any one of claims 1 to 3, wherein the poly (oxyfluoroalkylene) chain further contains an oxyperfluoroalkylene unit represented by Formula A2.
(OX 2 ) Formula A2
However, in the formula
X 2 is a perfluoroalkylene group.
5. The fluorine-containing ether compound according to claim 4, wherein the oxyperfluoroalkylene unit has 1 to 6 carbon atoms.
The poly (oxyfluoroalkylene) chain includes a number of oxyfluoroalkylene units represented by the formula A1 and b number of oxyperfluoroalkylene units represented by the formula A2, and a is an integer of 2 or more The fluorine-containing ether compound according to any one of claims 1 to 5, wherein b is an integer of 0 or more and a + b is 8 or more.
The fluorine-containing ether compound according to any one of claims 1 to 6, which is a compound represented by the following formula 1.
R 1 -[(OX 1 ) a (OX 2 ) b ]-Y-Z (R 2 ) q (R 3 ) r-q formula 1
However, in the formula
R 1 is an alkyl group which may have a fluorine atom, or —YZ (R 2 ) q (R 3 ) rq .
X 1 is a fluoroalkylene group having one or more hydrogen atoms.
X 2 is a perfluoroalkylene group.
Y is a single bond or a divalent linking group.
Z is a carbon atom, a silicon atom or a nitrogen atom.
R 2 is a hydrogen atom, a hydroxyl group or an alkyl group.
R 3 is -L 1 -Si (R) n L 3-n . L 1 is an alkylene group which may have —O—.
a is an integer of 2 or more, b is an integer of 0 or more, and a + b is an integer of 8 or more.
When Z is a carbon atom or a silicon atom, r is 3 and q is an integer of 0 to 2. When Z is a nitrogen atom, r is 2 and q is an integer of 0 to 1.
The fluorine-containing ether compound according to claim 7, wherein Z is a carbon atom or a silicon atom, and q is 0 or 1.
A composition comprising the fluorine-containing ether compound according to any one of claims 1 to 8 and a liquid medium.
A substrate, and a surface layer formed of the fluorine-containing ether compound according to any one of claims 1 to 8 or the composition according to claim 9 on the substrate. Article to be.
A surface treatment agent comprising the fluorine-containing ether compound according to any one of claims 1 to 8.
The fluorine-containing ether compound represented by following formula 3
R 11 - [(OX 1) a (OX 2) b] -Y-Z (R 2) q (L 2 -CH = CH 2) r-q Formula 3
However, in the formula
R 11 is an alkyl group which may have a fluorine atom, or —Y—Z (R 2 ) q (L 2 —CH = CH 2 ) r—q .
X 1 is a fluoroalkylene group having one or more hydrogen atoms.
X 2 is a perfluoroalkylene group.
Y is a single bond or a divalent linking group.
Z is a carbon atom, a silicon atom or a nitrogen atom.
R 2 is a hydrogen atom, a hydroxyl group or an alkyl group.
a is an integer of 2 or more, b is an integer of 0 or more, and a + b is an integer of 8 or more.
L 2 is an alkylene group which may have —O—, a single bond or —O—.
When Z is a carbon atom or a silicon atom, r is 3 and q is an integer of 0 to 2. When Z is a nitrogen atom, r is 2 and q is an integer of 0 to 1.
A process for producing a fluorine-containing ether compound represented by the formula 1, which comprises a hydrosilylation reaction of the fluorine-containing ether compound represented by the formula 3 with HSi (R) n L 3-n .
R 1 -[(OX 1 ) a (OX 2 ) b ]-Y-Z (R 2 ) q (R 3 ) r-q formula 1
R 11 - [(OX 1) a (OX 2) b] -Y-Z (R 2) q (L 2 -CH = CH 2) r-q Formula 3
However, in the formula
R 1 is an alkyl group which may have a fluorine atom, or —YZ (R 2 ) q (R 3 ) rq .
R 11 is an alkyl group which may have a fluorine atom, or —Y—Z (R 2 ) q (L 2 —CH = CH 2 ) r—q .
X 1 is a fluoroalkylene group having one or more hydrogen atoms.
X 2 is a perfluoroalkylene group.
Y is a single bond or a divalent linking group.
Z is a carbon atom, a silicon atom or a nitrogen atom.
R 2 is a hydrogen atom, a hydroxyl group or an alkyl group.
R 3 is -L 1 -Si (R) n L 3-n .
L 1 is an alkylene group which may have —O—.
a is an integer of 2 or more, b is an integer of 0 or more, and a + b is an integer of 8 or more.
L 2 is an alkylene group which may have —O—, a single bond or —O—.
When Z is a carbon atom or a silicon atom, r is 3 and q is an integer of 0 to 2. When Z is a nitrogen atom, r is 2 and q is an integer of 0 to 1.