JP2014040373A - Fluorine-containing compound, coating composition, base material having water-repellent layer, and method for producing the material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorine-containing compound from which a water-repellent layer having sufficient water repellency (particularly, dynamic water repellency), wear resistance and weather resistance can be formed and which has a low environmental load and to provide a coating composition, a base material having the water-repellent layer, and a method for producing the base material having the water-repellent layer.SOLUTION: The fluorine-containing compound shown by a formula: R-Y-Si(R)(X)is used. In the formula, Ris a straight-chain perfluoroalkyl group having p carbon atoms; Y is a straight-chain fluoroalkylene group (in which an etheric oxygen atom can be contained optionally) which has a -CH- group at the R-side terminal thereof and q carbon atoms; p is an integer of 2-6; q is another integer of 4 or lager; p+q is a different integer of 10 or larger; Ris a monovalent hydrocarbon group; X is a hydrolyzable group; and n is some other integer of 1-3.

Description

  The present invention relates to a fluorine-containing compound, a coating composition using the fluorine-containing compound, a substrate having a water-repellent layer comprising the coating composition, and a method for producing the same.

  As a method for imparting water repellency to the surface of a substrate, a water / oil repellent composition containing a fluorine-containing compound having a perfluoroalkyl group and a hydrolyzable silyl group and a solvent is applied to the substrate and dried to repel the substrate. Methods for forming an aqueous film are known. Examples of the water / oil repellent composition include a water repellent composition for automobile glass. The water repellent layer formed from the water repellent composition for automobile glass is required to have high dynamic water repellency (property of water droplets to be easily rolled, water drop removability), abrasion resistance and weather resistance.

The following are proposed as a water repellent composition for automobile glass that satisfies this requirement.
(1) A composition comprising a compound represented by the following formula (I) and a solvent (Patent Document 1).
(Rf ¹ ) _a Si (R ¹ ) _b (NCO) _4-ab (I).
However, Rf ¹ is an organic group having a perfluoroalkyl group of 8-16 carbon atoms, ^{R 1} is hydrogen atom or an organic group having 1 to 16 carbon atoms, a is 1 or 2, b Is 0 or 1.

  However, recently, it has been pointed out that a compound having a perfluoroalkyl group having 8 or more carbon atoms has a high environmental load. Therefore, a fluorine-containing compound for a water / oil repellent composition having a perfluoroalkyl group having 6 or less carbon atoms is required. However, the water-repellent layer composed of the water- and oil-repellent composition containing the fluorine-containing compound having a perfluoroalkyl group having 6 or less carbon atoms is compared with the water-repellent layer formed from the conventional water- and oil-repellent composition, Since the crystallinity based on the perfluoroalkyl group (that is, the property of packing between molecules) is inferior, water repellency, particularly dynamic water repellency is lowered.

The following compounds have been proposed as fluorine-containing compounds having a perfluoroalkyl group having 6 or less carbon atoms.
(2) A compound represented by the following formula (II) (Patent Document 2).
_{C n F 2n + 1 (CH} 2 CF 2) a (CF 2 CF 2) b (CH 2 CH 2) c OR ··· (II).
However, R is a hydrogen atom or a (meth) acryloyl group, n is an integer of 1-6, a is an integer of 1-4, b is an integer of 1-3, c Is an integer from 1 to 3.

(3) A compound represented by the following formula (III) (Patent Document 3) and a mold release agent containing the compound (Patent Document 4).
_{C n F 2n + 1 (CH} 2 CF 2) a (CF 2 CF 2) b (CH 2 CH 2) c P (O) (OH) 2 ··· (III).
However, n is an integer of 1-6, a is an integer of 1-4, b is an integer of 1-3, c is an integer of 1-3.

(4) A compound represented by the following formula (IV) (Patent Document 5).
_{CF 3 (CF 2) n CH} 2 (CF 2) m CH = CH 2 ··· (IV).
However, n is an integer of 0-5 and m is an integer of 1-7.

Japanese Patent No. 2800786 International Publication No. 2007/105633 Japanese Patent No. 4509893 Japanese Patent No. 4506894 International Publication No. 2009/151110

However, when a water repellent layer is formed using a water / oil repellent composition containing a compound represented by the formula (II), adhesion to a substrate (particularly glass) is low, and wear resistance and weather resistance are reduced. Inferior to sex.
The compound represented by the formula (III) is used as a mold release agent for a metal substrate, but is not suitable for other substrates (particularly glass).
The water repellent layer comprising the water / oil repellent composition containing the compound represented by formula (IV) also has low adhesion to the substrate (particularly glass) and is inferior in wear resistance and weather resistance.

  The present invention is capable of forming a water-repellent layer having sufficient water repellency (particularly dynamic water repellency), abrasion resistance and weather resistance, and has a low environmental load and a coating composition and sufficient water repellency ( In particular, the present invention provides a substrate with a water-repellent layer having a dynamic water repellency), abrasion resistance and weather resistance, and having a low environmental load, and a method for producing the same.

The present invention is the following [1] to [11].
[1] A fluorine-containing compound represented by the following formula (1).
R _< ^F _> -Y-Si (R _< ¹ _> ) _3-n (X) _n ... (1).
However, ^RF is a linear perfluoroalkyl group having carbon number p,
Y is a linear fluoroalkylene group having a carbon number of q having a terminal of R ^F side of —CH ₂ — or a group in which an etheric oxygen atom is inserted between carbon-carbon bonds of the group,
p is an integer of 2 to 6,
q is an integer of 4 or more,
p + q is an integer of 10 or more,
R ¹ is a monovalent hydrocarbon group,
X is a hydrolyzable group,
n is an integer of 1 to 3.

[2] A fluorine-containing compound represented by the following formula (11) or the following formula (12).
^{_{R F -CH 2 CH 2 - (}} CF 2) r -CH 2 CH 2 -Si (R 1) 3-n (X) n ··· (11).
However, ^RF is a linear perfluoroalkyl group having carbon number p,
p is an integer of 2 to 6,
r is an integer of 1 or more,
p + r + 4 is an integer of 10 or more,
R ¹ is a monovalent hydrocarbon group,
X is a hydrolyzable group,
n is an integer of 1 to 3.

^{_{R F - {(CH 2 CH}} 2) a · (CH 2 CF 2) b · (CF 2 CF 2) c} -CH 2 CH 2 -Si (R 1) 3-n (X) n ··· ( 12).
However, ^RF is a linear perfluoroalkyl group having carbon number p,
p is an integer of 2 to 6,
_{- {(CH 2 CH 2)} a · (CH 2 CF 2) b · (CF 2 CF 2) c} - is of a number - _(CH 2 CH ₂₎ - units, b number of - _(CH 2 CF ₂ ) -unit and c units of-(CF ₂ CF ₂ ) -units, the terminal on the R ^F side is always-(CH ₂ CH ₂ ) -unit or-(CH ₂ CF ₂ )- Other than the unit, the arrangement of the units is not limited.
a is an integer of 0 to 10,
b is an integer of 0 to 20,
c is an integer of 0 to 10,
a + b is an integer of 1 or more, b + c is an integer of 1 or more,
p + 2a + 2b + 2c + 2 is an integer of 10 or more,
R ¹ is a monovalent hydrocarbon group,
X is a hydrolyzable group,
n is an integer of 1 to 3.

[3] A fluorine-containing compound represented by any one of the following formula (12a), the following formula (12b), and the following formula (12c).
^{_{R F - (CH 2 CF 2}} ) b - (CF 2 CF 2) c -CH 2 CH 2 -Si (R 1) 3-n (X) n ··· (12a).
However, ^RF is a linear perfluoroalkyl group having carbon number p,
p is an integer of 2 to 6,
_{- (CH 2 CF 2) b} - (CF 2 CF 2) c - may, b number of - _{(CH 2} CF 2) - units and c pieces of - _{(CF 2 CF} 2) - units have been described order It is a structure that is connected by,
b is an integer of 1 to 20,
c is an integer of 1 to 10,
p + 2b + 2c + 2 is an integer of 10 or more,
R ¹ is a monovalent hydrocarbon group,
X is a hydrolyzable group,
n is an integer of 1 to 3.

^{_{R F - (CH 2 CF 2}} ) b -CH 2 CH 2 -Si (R 1) 3-n (X) n ··· (12b).
However, ^RF is a linear perfluoroalkyl group having carbon number p,
p is an integer of 2 to 6,
b is an integer of 1 to 20,
p + 2b + 2 is an integer of 10 or more,
R ¹ is a monovalent hydrocarbon group,
X is a hydrolyzable group,
n is an integer of 1 to 3.

^{_{R F - {(CH 2 CH}} 2) - (CF 2 CF 2)} d -CH 2 CH 2 -Si (R 1) 3-n (X) n ··· (12c).
However, ^RF is a linear perfluoroalkyl group having carbon number p,
p is an integer of 2 to 6,
d is an integer of 1 to 10,
p + 4d + 2 is an integer of 10 or more,
R ¹ is a monovalent hydrocarbon group,
X is a hydrolyzable group,
n is an integer of 1 to 3.

[4] The fluorine-containing compound according to any one of [1] to [3] and / or a hydrolysis-condensation product formed by dehydration condensation of part or all of the hydrolyzable group of the fluorine-containing compound, a solvent, A coating composition comprising:
[5] The coating composition according to [4], wherein the total amount of the fluorine-containing compound and the hydrolysis condensate is 0.1 to 50% by mass in the total mass of the coating composition.
[6] The coating composition according to [4] or [5], wherein the solvent is an organic solvent.
[7] The coating composition according to any one of [4] to [6], which is a composition for a water / oil repellent.

[8] A substrate with a water-repellent layer, comprising a substrate and a water-repellent layer formed from the coating composition according to any one of [4] to [7] on the surface of the substrate.
[9] The substrate with a water repellent layer according to [8], wherein the substrate is a translucent substrate.
[10] An article for transport equipment on which the substrate with a water-repellent layer according to [9] is mounted.
[11] A method for producing a substrate with a water repellent layer, wherein the coating composition according to any one of [4] to [7] is applied to the surface of the substrate to form a water repellent layer.

The fluorine-containing compound of the present invention can form a water-repellent layer having sufficient water repellency (particularly dynamic water repellency), abrasion resistance and weather resistance, and has little environmental load.
The coating composition of the present invention can form a water-repellent layer having sufficient water repellency (particularly dynamic water repellency), abrasion resistance and weather resistance, and has little environmental load.
The substrate with a water repellent layer of the present invention has sufficient water repellency (particularly dynamic water repellency), abrasion resistance and weather resistance, and has a low environmental load.
According to the method for producing a substrate with a water repellent layer of the present invention, a substrate with a water repellent layer having sufficient water repellency (particularly dynamic water repellency), abrasion resistance and weather resistance, and having a low environmental load. Can be manufactured.

  In the present specification, a compound represented by the formula (1) is referred to as a compound (1). The same applies to compounds represented by other formulas. Further, the perfluoroalkyl group in the present specification refers to a group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms. The fluoroalkylene group refers to a group in which one or more hydrogen atoms of the alkylene group are substituted with fluorine atoms. The perfluoroalkylene group refers to a group in which all hydrogen atoms of the alkylene group are substituted with fluorine atoms.

<Fluorine-containing compounds>
(Compound (1))
The fluorine-containing compound of the present invention is compound (1).
R _< ^F _> -Y-Si (R _< ¹ _> ) _3-n (X) _n ... (1).

R ^F is a linear perfluoroalkyl group having a carbon number p (where p is an integer of 2 to 6). Hereinafter, a straight-chain perfluoroalkyl group of R ^F group. When p is 2 or more, the water and oil repellency is excellent. If p is 6 or less, there is little environmental load by the decomposition product of a fluorine-containing compound. p is preferably 2, 4 or 6 from the viewpoint of availability of raw materials.

Y is a linear fluoroalkylene group having a carbon number q (where q is an integer of 4 or more) whose terminal on the R ^F side is —CH ₂ —, or a carbon-carbon bond of the group It is a group having an etheric oxygen atom inserted between them. In the case of the latter group, the number of etheric oxygen atoms is 1 or more. Y is preferably a linear fluoroalkylene group. q represents the number of carbon atoms of Y. If q is too large, the melting point of the fluorine-containing compound is increased, and the handleability is deteriorated. The upper limit of q is preferably 28, more preferably 22, and particularly preferably 16.
The fluorine-containing compound of the present invention is characterized in that a linking group (Y) having a certain chain length exists between ^RF and Si, more preferably, the molecular chain length is long. is there. P + q which is a number expressing the chain length of the molecule is 10 or more. When p + q is within this range, the crystallinity due to the R ^F —Y— group is maintained, and the resulting water-repellent layer has good dynamic water repellency. p + q is preferably 10-30, more preferably 10-24, and particularly preferably 10-18.

The terminal on the R ^F side in Y is —CH ₂ —. If the terminal on the R ^F side is —CH ₂ —, a compound having an R ^F group having 8 or more carbon atoms is not generated as a decomposition product, so that the environmental load is small.
The end of the Si side in Y is —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ OCH ₂ in terms of weather resistance of the resulting water-repellent layer and ease of synthesis of the fluorine-containing compound. CH ₂ CH ₂ — can be mentioned, and —CH ₂ CH ₂ — is particularly preferable.

R ^F and Y are linear. When R ^F and Y are linear, the R ^F —Y— group is linear, the crystallinity of the fluorine-containing compound is maintained, and the resulting water-repellent layer has good dynamic water repellency.

R ¹ is a monovalent hydrocarbon group (excluding a hydrocarbon group having an R ^F group), and an alkyl group having 1 to 4 carbon atoms is preferable from the viewpoint of availability of raw materials and handleability. When two or more R ¹ exists in a fluorine-containing compound, R ¹ may be the same group or different groups, and the same group is preferable from the viewpoint of availability.

X is a hydrolyzable group. The hydrolyzable group is a group that can form Si—OH by hydrolysis of the Si—X group.
Examples of X include an alkoxy group, an acyloxy group, a ketoxime group, an alkenyloxy group, an amino group, an aminoxy group, an amide group, an isocyanate group, a halogen atom, and the like, and the stability of the fluorine-containing compound and the ease of hydrolysis. From the viewpoint of balance, an alkoxy group, an isocyanate group, and a halogen atom (particularly a chlorine atom) are preferable. As an alkoxy group, a C1-C3 alkoxy group is preferable and a methoxy group or an ethoxy group is more preferable. When a plurality of X are present in the fluorine-containing compound, X may be the same group or different groups, and the same group is preferable from the viewpoint of availability.

  n is an integer of 1 to 3. If n is 1 or more, the adhesiveness of the obtained water-repellent layer and a base material will become favorable. n is preferably 2 or 3, and particularly preferably 3, from the viewpoint of adhesion between the obtained water-repellent layer and the substrate.

  As the compound (1), from the viewpoint of water repellency (particularly dynamic water repellency), abrasion resistance and weather resistance of the obtained water repellent layer, and ease of synthesis of the fluorine-containing compound, The following compound (12) is preferable.

(Compound (11))
^{_{R F -CH 2 CH 2 - (}} CF 2) r -CH 2 CH 2 -Si (R 1) 3-n (X) n ··· (11).
However, R ^F is an R ^F group having carbon number p,
p is an integer of 2 to 6,
r is an integer of 1 or more,
p + r + 4 (p + r + 4 corresponds to p + q in formula (1)) is an integer of 10 or more,
R ¹ is a monovalent hydrocarbon group,
X is a hydrolyzable group,
n is an integer of 1 to 3.

The meanings and preferred embodiments of R ^F , p, p + r + 4, R ¹ , X and n are the same as those of the compound (1). When r is too large, the melting point of the fluorine-containing compound is increased, and the handleability is deteriorated. The preferable upper limit of r is 24, 18 is more preferable, and 12 is particularly preferable. If p + q + 4 is within this range, the crystallinity of the fluorine-containing compound is maintained by the R ^F —CH ₂ CH ₂ — (CF ₂ ) _r —CH ₂ CH ₂ — group, and the dynamic water repellency of the resulting water repellent layer is improved. It becomes good. p + r + 4 is preferably 10-30, more preferably 10-24, and still more preferably 10-18.
Preferable specific examples of compound (11) include the following compounds.
_{CF 3 CF 2 -CH 2 CH 2} - (CF 2) 6 -CH 2 CH 2 -SiCl 3,
_{CF 3 (CF 2) 3 -CH} 2 CH 2 - (CF 2) 6 -CH 2 CH 2 -SiCl 3,
_{CF 3 (CF 2) 5 -CH} 2 CH 2 - (CF 2) 6 -CH 2 CH 2 -SiCl 3,
_{CF 3 (CF 2) 3 -CH} 2 CH 2 - (CF 2) 6 -CH 2 CH 2 -Si (OCH 3) 3,
_{CF 3 (CF 2) 3 -CH} 2 CH 2 - (CF 2) 6 -CH 2 CH 2 -Si (CH 3) (OCH 3) 2,
_{CF 3 (CF 2) 3 -CH} 2 CH 2 - (CF 2) 6 -CH 2 CH 2 -Si (OCH 2 CH 3) 3,
_{CF 3 (CF 2) 3 -CH} 2 CH 2 - (CF 2) 6 -CH 2 CH 2 -Si (NCO) 3,
_{CF 3 (CF 2) 3 -CH} 2 CH 2 - (CF 2) 2 -CH 2 CH 2 -SiCl 3,
_{CF 3 (CF 2) 3 -CH} 2 CH 2 - (CF 2) 4 -CH 2 CH 2 -SiCl 3.

(Compound (12))
^{_{R F - {(CH 2 CH}} 2) a · (CH 2 CF 2) b · (CF 2 CF 2) c} -CH 2 CH 2 -Si (R 1) 3-n (X) n ··· ( 12).
However, R ^F is an R ^F group having carbon number p,
p is an integer of 2 to 6,
_{- {(CH 2 CH 2)} a · (CH 2 CF 2) b · (CF 2 CF 2) c} - is of a number - _(CH 2 CH ₂₎ - units, b number of - _(CH 2 CF ₂ ) -unit and c units of-(CF ₂ CF ₂ ) -units, the terminal on the R ^F side is always-(CH ₂ CH ₂ ) -unit or-(CH ₂ CF ₂ )- Other than the unit, the arrangement of the units is not limited.
a is an integer of 0 to 10,
b is an integer of 0 to 20,
c is an integer of 0 to 10,
a + b is an integer of 1 or more, b + c is an integer of 1 or more,
p + 2a + 2b + 2c + 2 (p + 2a + 2b + 2c + 2 corresponds to p + q in formula (1)) is an integer of 10 or more,
R ¹ is a monovalent hydrocarbon group,
X is a hydrolyzable group,
n is an integer of 1 to 3.

The meanings and preferred embodiments of R ^F , p, p + 2a + 2b + 2c + 2, R ¹ , X and n are the same as those of the compound (1).

If p + 2a + 2b + 2c + 2 in the compound (12) is 10 or more, it is contained by the group R ^F — {(CH ₂ CH ₂ ) _a · (CH ₂ CF ₂ ) _b · (CF ₂ CF ₂ ) _c } —CH ₂ CH ₂ —. The crystallinity of the fluorine compound is maintained, and the resulting water-repellent layer has good dynamic water repellency. When p + 2a + 2b + 2c + 2 becomes too large, the melting point of the fluorine-containing compound becomes high, and the handleability deteriorates. p + 2a + 2b + 2c + 2 is preferably 10-30, more preferably 10-24, and particularly preferably 10-18.
1-13 are preferable, as for a + b + c, 1-10 are more preferable, and 1-7 are especially preferable. a is preferably 0-6, particularly preferably 0-3. b is preferably from 0 to 13, and particularly preferably from 0 to 4. c is preferably from 0 to 12, and particularly preferably from 0 to 6.

  As the compound (12), the compound (12a), the compound (12b), or the compound (12c) is preferable from the viewpoint of easy synthesis of the fluorine-containing compound.

(Compound (12a))
^{_{R F - (CH 2 CF 2}} ) b - (CF 2 CF 2) c -CH 2 CH 2 -Si (R 1) 3-n (X) n ··· (12a).
However, R ^F is an R ^F group having carbon number p,
p is an integer of 2 to 6,
b is an integer of 1 to 20,
c is an integer of 1 to 10,
p + 2b + 2c + 2 (p + 2b + 2c + 2 corresponds to p + q in formula (1)) is an integer of 10 or more,
R ¹ is a monovalent hydrocarbon group,
X is a hydrolyzable group,
n is an integer of 1 to 3.

The meanings and preferred embodiments of R ^F , p, p + 2b + 2c + 2, R ¹ , X and n are the same as those of the compound (12).

In the formula (12a), when p + 2b + 2c + 2 is 10 or more, the crystallinity of the fluorine-containing compound is maintained by the R ^F — (CH ₂ CF ₂ ) _b — (CF ₂ CF ₂ ) _c —CH ₂ CH ₂ — group. The resulting water-repellent layer has good dynamic water repellency. When b and c are too large, the melting point of the fluorine-containing compound is increased, and the handleability is deteriorated. 1-12 are preferable and, as for b, 1-6 are especially preferable. c is preferably from 1 to 12, and particularly preferably from 1 to 6. b + c is preferably 2 to 13, more preferably 2 to 10, and particularly preferably 2 to 7. p + 2b + 2c + 2 is preferably 10-30, more preferably 10-24, and particularly preferably 10-18.
Preferable specific examples of the compound (12a) include the following compounds.
_{CF 3 CF 2 -CH 2 CF 2} - (CF 2 CF 2) 2 -CH 2 CH 2 -SiCl 3,
_{CF 3 (CF 2) 3 -CH} 2 CF 2 -CF 2 CF 2 -CH 2 CH 2 -SiCl 3,
_{CF 3 (CF 2) 3 -CH} 2 CF 2 - (CF 2 CF 2) 3 -CH 2 CH 2 -SiCl 3,
_{CF 3 (CF 2) 3 -} (CH 2 CF 2) 3 -CF 2 CF 2 -CH 2 CH 2 -SiCl 3,
_{CF 3 (CF 2) 3 -} (CH 2 CF 2) 3 - (CF 2 CF 2) 3 -CH 2 CH 2 -SiCl 3,
_{CF 3 (CF 2) 5 -CH} 2 CF 2 -CF 2 CF 2 -CH 2 CH 2 -SiCl 3,
_{CF 3 (CF 2) 3 -CH} 2 CF 2 -CF 2 CF 2 -CH 2 CH 2 -Si (OCH 3) 3,
_{CF 3 (CF 2) 3 -CH} 2 CF 2 -CF 2 CF 2 -CH 2 CH 2 -Si (CH 3) (OCH 3) 2,
_{CF 3 (CF 2) 3 -CH} 2 CF 2 -CF 2 CF 2 -CH 2 CH 2 -Si (OCH 2 CH 3) 3,
_{CF 3 (CF 2) 3 -CH} 2 CF 2 -CF 2 CF 2 -CH 2 CH 2 -Si (NCO) 3.

(Compound (12b))
^{_{R F - (CH 2 CF 2}} ) b -CH 2 CH 2 -Si (R 1) 3-n (X) n ··· (12b).
However, R ^F is an R ^F group having carbon number p,
p is an integer of 2 to 6,
b is an integer of 1 to 20,
p + 2b + 2 (p + 2b + 2 corresponds to p + q in Formula (1)) is an integer of 10 or more,
R ¹ is a monovalent hydrocarbon group,
X is a hydrolyzable group,
n is an integer of 1 to 3.

The meanings and preferred embodiments of R ^F , p, p + 2b + 2, R ¹ , X and n are the same as those of the compound (12).

In the formula (12b), when p + 2b + 2 is 10 or more, the crystallinity of the fluorine-containing compound is maintained by the R ^F — (CH ₂ CF ₂ ) _b —CH ₂ CH ₂ — group, and the resulting water-repellent layer is activated. Excellent water repellency. However, when b is too large, the melting point of the fluorine-containing compound is increased, and the handleability is deteriorated. 1-13 are preferable, as for b, 1-10 are more preferable, and 1-7 are especially preferable. p + 2b + 2 is preferably 10 to 30, more preferably 10 to 24, and particularly preferably 10 to 16.
Preferable specific examples of the compound (12b) include the following compounds.
_{CF 3 CF 2 - (CH 2} CF 2) 3 -CH 2 CH 2 -SiCl 3,
_{CF 3 (CF 2) 3 -} (CH 2 CF 2) 3 -CH 2 CH 2 -SiCl 3,
_{CF 3 (CF 2) 5 -} (CH 2 CF 2) 3 -CH 2 CH 2 -SiCl 3,
_{CF 3 (CF 2) 3 -} (CH 2 CF 2) 3 -CH 2 CH 2 -Si (OCH 3) 3,
_{CF 3 (CF 2) 3 -} (CH 2 CF 2) 3 -CH 2 CH 2 -Si (CH 3) (OCH 3) 2,
_{CF 3 (CF 2) 3 -} (CH 2 CF 2) 3 -CH 2 CH 2 -Si (OCH 2 CH 3) 3,
_{CF 3 (CF 2) 3 -} (CH 2 CF 2) 3 -CH 2 CH 2 -Si (NCO) 3,
_{CF 3 (CF 2) 3 -} (CH 2 CF 2) 6 -CH 2 CH 2 -SiCl 3.

(Compound (12c))
^{_{R F - {(CH 2 CH}} 2) - (CF 2 CF 2)} d -CH 2 CH 2 -Si (R 1) 3-n (X) n ··· (12c).
However, R ^F is an R ^F group having carbon number p,
p is an integer of 2 to 6,
d is an integer of 1 to 10,
p + 4d + 2 (p + 4d + 2 corresponds to p + q in formula (1)) is an integer of 10 or more,
R ¹ is a monovalent hydrocarbon group,
X is a hydrolyzable group,
n is an integer of 1 to 3.

The meanings and preferred embodiments of R ^F , p, p + 4d + 2, R ¹ , X and n are the same as those of the compound (12).

In the formula (12c), when p + 4d + 2 is 10 or more, the crystallinity of the fluorine-containing compound is maintained by the R ^F — {CH ₂ CH ₂ CF ₂ CF ₂ } _d —CH ₂ CH ₂ — group, and the obtained repellent property is obtained. The dynamic water repellency of the water layer is improved. When d is too large, the melting point of the fluorine-containing compound is increased, and the handleability is deteriorated. d is preferably 1 to 7, more preferably 1 to 5, and particularly preferably 1 to 4. p + 4d + 2 is preferably 10 to 32, more preferably 10 to 26, and particularly preferably 10 to 20.
Preferable specific examples of compound (12c) include the following compounds.
_{CF 3 CF 2 - {(CH} 2 CH 2) - (CF 2 CF 2)} 3 -CH 2 CH 2 -SiCl 3,
_{CF 3 (CF 2) 3 -} {(CH 2 CH 2) - (CF 2 CF 2)} - CH 2 CH 2 -SiCl 3,
_{CF 3 (CF 2) 3 -} {(CH 2 CH 2) - (CF 2 CF 2)} 3 -CH 2 CH 2 -SiCl 3,
_{CF 3 (CF 2) 5 -} {(CH 2 CH 2) - (CF 2 CF 2)} - CH 2 CH 2 -SiCl 3,
_{CF 3 (CF 2) 3 -} {(CH 2 CH 2) - (CF 2 CF 2)} - CH 2 CH 2 -Si (OCH 3) 3,
_{CF 3 (CF 2) 3 -} {(CH 2 CH 2) - (CF 2 CF 2)} - CH 2 CH 2 -Si (CH 3) (OCH 3) 2,
_{CF 3 (CF 2) 3 -} {(CH 2 CH 2) - (CF 2 CF 2)} - CH 2 CH 2 -Si (OCH 2 CH 3) 3,
_{CF 3 (CF 2) 3 -} {(CH 2 CH 2) - (CF 2 CF 2)} - CH 2 CH 2 -Si (NCO) 3.
Examples of the compounds other than the compounds (12a) to (12c) include the following compounds.
_{CF 3 (CF 2) 3 -} (CH 2 CH 2) - (CF 2 CF 2) - (CH 2 CF 2) -CH 2 CH 2 -SiCl 3,
_{CF 3 (CF 2) 3 -} (CH 2 CF 2) - (CH 2 CH 2) - (CF 2 CF 2) -CH 2 CH 2 -SiCl 3,
_{CF 3 (CF 2) 3 -} (CH 2 CF 2) - (CF 2 CF 2) - (CH 2 CH 2) -CH 2 CH 2 -SiCl 3,
_{CF 3 (CF 2) 3 -} (CH 2 CH 2) 2 - (CF 2 CF 2) - (CH 2 CF 2) -CH 2 CH 2 -SiCl 3,
_{CF 3 (CF 2) 3 -} (CH 2 CH 2) - (CF 2 CF 2) 2 - (CH 2 CF 2) -CH 2 CH 2 -SiCl 3,
_{CF 3 (CF 2) 3 -} (CH 2 CH 2) - (CF 2 CF 2) - (CH 2 CF 2) 2 -CH 2 CH 2 -SiCl 3,
_{CF 3 (CF 2) 3 -} (CH 2 CH 2) 2 - (CF 2 CF 2) 2 - (CH 2 CF 2) 2 -CH 2 CH 2 -SiCl 3,
_{CF 3 (CF 2) 3 -} (CH 2 CH 2) - (CF 2 CF 2) - (CH 2 CF 2) -CH 2 CH 2 -Si (OCH 3) 3,
_{CF 3 (CF 2) 3 -} (CH 2 CH 2) - (CF 2 CF 2) - (CH 2 CF 2) -CH 2 CH 2 -Si (CH 3) (OCH 3) 2,
_{CF 3 (CF 2) 3 -} (CH 2 CH 2) - (CF 2 CF 2) - (CH 2 CF 2) -CH 2 CH 2 -Si (OCH 2 CH 3) 3,
_{CF 3 (CF 2) 3 -} (CH 2 CH 2) - (CF 2 CF 2) - (CH 2 CF 2) -CH 2 CH 2 -Si (NCO) 3.

<Method for producing fluorine-containing compound>
As a manufacturing method of a compound (1), the manufacturing method of the following compound (11) and the manufacturing method of a compound (12) are mentioned.

(Production method of compound (11))
First, compound (4) is obtained by addition reaction of perfluoroalkyl iodide (compound (2)) and α, ω-divinylperfluoroalkane (compound (3)), and then compound (4) is reduced to a reducing agent (for example, In this method, compound (5) is obtained by reduction with tributyltin hydride, tris (trimethylsilyl) silane, etc., and then compound (11) is obtained by hydrosilylation reaction between compound (5) and compound (6). (However, the meanings in the following formula are the same as those in the compound (11)).
R ^F -I (2),
_{CH 2 = CH- (CF 2)} r -CH = CH 2 ··· (3),
R ^F —CH ₂ CHI— (CF ₂ ) _r —CH═CH ₂ (4).
R ^F —CH ₂ CH ₂ — (CF ₂ ) _r —CH═CH ₂ (5).
HSi (R ¹ ) _3-n (X) _n (6),
_{^{R F -CH 2 CH 2 - (}} CF 2) r -CH 2 CH 2 -Si (R 1) 3-n (X) n ··· (11).
The manufacturing method, both ends of the Y is _-CH 2 CH ₂ - is a process for the preparation of a compound when it is (1). A compound in which Y has another structure performs the same reaction using another compound having a different-(CF ₂ ) _r -moiety in formula (3) instead of the compound represented by formula (3). Can be manufactured.

(Method for producing compound (12))
First, compound (2) is reacted with a compound arbitrarily selected from compounds (7a) to (7c) to obtain compound (8).
R ^F -I (2),
CH ₂ = CH ₂ (7a),
CH ₂ = CF ₂ (7b),
CF ₂ = CF ₂ (7c),
_{^{R F - {(CH 2 CH}} 2) a · (CH 2 CF 2) b · (CF 2 CF 2) c} -I ··· (8).

Examples of the subsequent reaction include the following method A and method B.
[Method A]
Compound (9) is obtained by addition reaction of compound (8) and ethylene (compound (7a)), and then compound (10) is obtained by dehydroiodination of compound (9) in the presence of a base. The compound (12) is obtained by hydrosilylation reaction of the compound (10) and the compound (6).
^{_{R F - {(CH 2 CH}} 2) a · (CH 2 CF 2) b · (CF 2 CF 2) c} -CH 2 CH 2 -I ··· (9).
^{_{R F - {(CH 2 CH}} 2) a · (CH 2 CF 2) b · (CF 2 CF 2) c} -CH = CH 2 ··· (10).
HSi (R ¹ ) _3-n (X) _n (6),
^{_{R F - {(CH 2 CH}} 2) a · (CH 2 CF 2) b · (CF 2 CF 2) c} -CH 2 CH 2 -Si (R 1) 3-n (X) n ··· ( 12).

[Method B]
Compound (14) is obtained by addition reaction of compound (8) and vinylsilane compound (compound (13)), and then compound (14) is reduced to a reducing agent (for example, tributyltin hydride, tris (trimethylsilyl) silane, or the like. To obtain compound (12).
^{_{CH 2 = CH-Si (R}} 1) 3-n (X) n ··· (13),
^{_{R F - {(CH 2 CH}} 2) a · (CH 2 CF 2) b · (CF 2 CF 2) c} -CH 2 CHI-Si (R 1) 3-n (X) n ··· (14 ).
^{_{R F - {(CH 2 CH}} 2) a · (CH 2 CF 2) b · (CF 2 CF 2) c} -CH 2 CH 2 -Si (R 1) 3-n (X) n ··· ( 12).

Either method A or method B may be adopted. However, when the compound (8) contains a —CF ₂ —CH ₂ —CF ₂ — structure, the dehydrofluorination reaction proceeds depending on the type of base and reaction conditions of the dehydroiodination reaction, and the structure May change to —CF═CH—CF ₂ — or —CF ₂ —CH═CF—. Such changes can adversely affect the weather resistance of the product. Therefore, it is preferable to employ Method B for the compound (12) having a —CF ₂ —CH ₂ —CF ₂ — structure.
Even when the compound (8) contains a —CF ₂ —CH ₂ —CH ₂ — structure, the structure can be changed to a —CF═CH—CH ₂ — structure. However, since this change is easy to avoid depending on the type of base and reaction conditions, Method A and Method B can be used.

  As specific examples of the method for producing compound (12), the method for producing compound (12a), the method for producing compound (12b), and the method for producing compound (12c) are shown below.

(Method for producing compound (12a))
First, compound (2b) is added to compound (7b) to obtain compound (8b), then compound (8b) is added to compound (7c) to obtain compound (8a), and then compound (8b) is obtained. Compound (14a) is obtained by addition reaction between (8a) and compound (13), and then compound (14a) is reduced with a reducing agent (for example, tributyltin hydride, tris (trimethylsilyl) silane, etc.) Method for obtaining compound (12a) (wherein the symbols in the formula have the same meaning as in compound (12a)).
R ^F -I (2),
CH ₂ = CF ₂ (7b),
R ^F — (CH ₂ CF ₂ ) _b —I (8b).
CF ₂ = CF ₂ (7c),
_{^{R F - (CH 2 CF 2}} ) b - (CF 2 CF 2) c -I ··· (8a).
_{^{CH 2 = CH-Si (R}} 1) 3-n (X) n ··· (13),
_{^{R F - (CH 2 CF 2}} ) b - (CF 2 CF 2) c -CH 2 CHI-Si (R 1) 3-n (X) n ··· (14a).
_{^{R F - (CH 2 CF 2}} ) b - (CF 2 CF 2) c -CH 2 CH 2 -Si (R 1) 3-n (X) n ··· (12a).

(Method for producing compound (12b))
First, compound (7b) is added to compound (2) to obtain compound (8b), and then compound (8b) and compound (13) are subjected to addition reaction to obtain compound (14b). Method of reducing compound (1 (4b) with a reducing agent (for example, tributyltin hydride, tris (trimethylsilyl) silane, etc.) to obtain compound (12b) (wherein the symbol in the formula represents the meaning in compound (12b)) The same meaning).
R ^F -I (2),
CH ₂ = CF ₂ (7b),
R ^F — (CH ₂ CF ₂ ) _b —I (8b).
_{^{CH 2 = CH-Si (R}} 1) 3-n (X) n ··· (13),
_{^{R F - (CH 2 CF 2}} ) b -CH 2 CHI-Si (R 1) 3-n (X) n ··· (14b).
_{^{R F - (CH 2 CF 2}} ) b -CH 2 CH 2 -Si (R 1) 3-n (X) n ··· (12b).

(Method for producing compound (12c))
First, compound (7a) is added to compound (2) to obtain compound (8c), then compound (8c) is compound (7a) in 1-fold mol, compound (7c) is then in 1-fold mol, Next, the compound (7a) is reacted in a 1-fold mol, and then the compound (7c) is reacted in a 1-fold mol. If necessary, 1 molar times the compound (7a), then the compound (7c) by repeating an operation to 1-fold molar _{reaction, -CH 2 CH 2 CF 2 CF} 2 - d items with Compound (9c) Get. Next, compound (10c) is obtained by dehydroiodination of compound (9c) in the presence of a base, and then compound (12c) is obtained by hydrosilylation reaction between compound (10c) and compound (6). Method (however, the symbols in the formulas have the same meaning as in compound (12c)).
R ^F -I (2),
CH ₂ = CH ₂ (7a),
R ^F —CH ₂ CH ₂ —I (8c).
CF ₂ = CF ₂ (7c),
R ^F — {CH ₂ CH ₂ CF ₂ CF ₂ } _d —CH ₂ CH ₂ —I (9c).
R ^F — {CH ₂ CH ₂ CF ₂ CF ₂ } _d —CH═CH ₂ (10c).
HSi (R ¹ ) _3-n (X) _n (6),
^{_{R F - {(CH 2 CH}} 2) - (CF 2 CF 2)} d -CH 2 CH 2 -Si (R 1) 3-n (X) n ··· (12c).

  The fluorine-containing compound of the present invention obtained by the production method described above may be used after removing impurities by a method such as purification by a known method (distillation or the like), or may be used as it is. Moreover, when it obtains as a mixture of the fluorine-containing compound of this invention, each may be used after isolate | separating, and may be used as it is.

(Use)
The fluorine-containing compound of the present invention can be used as a water / oil repellent, a mold release agent, an antifouling agent, a fingerprint removal performance imparting agent, an easy cleaning imparting agent, etc. It is suitable as a water repellent.

(Function and effect)
In the fluorine-containing compound of the present invention, R ^F has 2 or more carbon atoms, the R ^F —Y— group has 10 or more carbon atoms, and the R ^F —Y— group is linear. The crystallinity of the fluorine-containing compound is maintained by the ^F— Y— group, and the water repellency (particularly dynamic water repellency) of the resulting water repellent layer is improved.
Moreover, since it has a hydrolyzable silyl group, ie, -Si (R ¹ ) _3-n (X) _n group, the water repellent layer obtained has high adhesion to the substrate (particularly glass), and the water repellent obtained The layer has good wear resistance and weather resistance.
Further, since the number of carbon atoms in R ^F is 6 or less and the terminal on the R ^F side in Y is —CH ₂ —, the environmental load due to the decomposition product of the fluorine-containing compound is small.

<Coating composition>
The coating composition of the present invention includes the fluorine-containing compound of the present invention and / or a hydrolysis-condensation product formed by hydrolysis and condensation of a part or all of the hydrolyzable groups of the fluorine-containing compound and a solvent. These fluorine-containing compounds may be used singly or in a case where a hydrolytic condensation reaction is performed, or one kind or two or more kinds may be used. When using 2 or more types, you may use 2 or more types of compounds from which a structure other than a hydrolysable group and / or this group differs.

(Hydrolysis condensate)
As a generation mechanism of the hydrolysis condensate, a part or all of the hydrolyzable silyl group (Si—X group) of the fluorine-containing compound is hydrolyzed to form a silanol group (Si—OH group), and then the silanol It is considered that the groups are formed by dehydration condensation to form oligomers (multimers). The hydrolysis condensation reaction is preferably carried out in a solvent in the presence of a catalyst (an acid catalyst, an alkali catalyst, etc.) and water. The hydrolysis condensate may contain an unreacted fluorine-containing compound. However, if the hydrolysis-condensation product proceeds too much, it becomes difficult to dissolve in the solvent, and therefore a certain degree of condensation is required.

The hydrolysis condensate reaction may be promoted by heating. However, if the reaction proceeds too much, the degree of condensation may increase and a solvent-insoluble product may be produced. As long as an appropriate amount of catalyst is present, it is preferable to react at room temperature.
You may use the solution of the obtained hydrolysis-condensation product as a coating composition of this invention as it is.

  The solvent used for the hydrolysis condensation is preferably a solvent that dissolves the fluorine-containing compound of the present invention and its hydrolysis-condensation product, and an organic solvent is particularly preferred. Organic solvents include alcohols, ethers, ketones, esters, aromatic hydrocarbons, paraffinic hydrocarbons, fluorine-containing organic solvents (hydrofluorocarbons, hydrochlorofluorocarbons, hydrofluoroethers, polyfluoroalcohols, etc.) From the viewpoint of cost, organic solvents other than the fluorine-containing organic solvent are preferable. In particular, heptane and butyl acetate are preferable in terms of cost and handling. An organic solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it.

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 alkali catalyst include sodium hydroxide, potassium hydroxide, ammonia and the like.

Hydrolysis condensate reaction is
A method of dissolving the fluorine-containing compound of the present invention in an organic solvent and adding the catalyst and water separately or an aqueous solution of the catalyst, or
A method of adding a catalyst or an aqueous solution of a catalyst to a solution obtained by dissolving or mixing the fluorine-containing compound of the present invention in an organic solvent containing water;
It is preferable to implement by such as.

The amount of the catalyst used for the production of the hydrolysis-condensation product is preferably 0.0001 to 1 part by mass, particularly preferably 0.001 to 0.1 part by mass with respect to 1 part by mass of the fluorine-containing compound. When the amount of the catalyst is within this range, the hydrolysis effect is sufficiently exhibited and the composition is excellent in stability.
The amount of water used for the production of the hydrolysis-condensation product is preferably 0.00001 to 0.1 parts by mass, particularly preferably 0.0001 to 0.01 parts by mass with respect to 1 part by mass of the fluorine-containing compound. When the amount of water is within this range, the hydrolysis effect is sufficiently exhibited, and the composition is excellent in stability.

(solvent)
The coating composition of the present invention preferably contains a solvent from the viewpoints of economy, workability, ease of control of the thickness of the resulting water-repellent layer, and the like. As a solvent, the organic solvent mentioned as a solvent used for manufacture of a hydrolysis-condensation product is preferable.
The organic solvent may be added separately, and when it contains a hydrolysis condensate, it may contain the solvent used for the production of the hydrolysis condensate. The solvent used for the production of the hydrolysis-condensation product may be used.

(Other ingredients)
The coating composition of the present invention may contain a catalyst in order to promote hydrolysis and condensation of the fluorine-containing compound. As the catalyst, an acid catalyst is preferable as the catalyst. By including a catalyst, a water-repellent layer with good water droplet removal and durability can be formed.

  The coating composition of the present invention may contain an additive as an optional component depending on the purpose within a range not impairing the effects of the present invention. Additives include non-fluorinated water repellent materials (one-end reactive polydimethylsiloxane, both-end reactive polydimethylsiloxane, etc.), ultrafine metal oxide particles (silica, alumina, zirconia, titania, etc.), coloring materials (Dyes, pigments, etc.), antifouling materials, curing catalysts, various resins and the like. The additive is preferably selected in consideration of the reactivity or compatibility with essential components.

(Ratio of each component)
0.1-50 mass% is preferable with respect to the total mass of the composition for coating, and, as for the total amount of the fluorine-containing compound and hydrolysis-condensation product of this invention, 0.1-20 mass% is more preferable, 1-15 Mass% is particularly preferred. If the total amount of the fluorine-containing compound and the hydrolysis-condensation product is not less than the lower limit of the above range, the resulting water-repellent layer is less likely to be uneven. If it is below the upper limit of the said range, it is excellent in storage stability.

  As for the quantity of an additive, 0.01-20 mass parts is preferable with respect to 100 mass parts of solid content (component except volatile components, such as an organic solvent) of the composition for coating. Excessive addition of the functional additive to the coating composition may cause a decrease in performance such as water droplet removability of the resulting water-repellent layer.

(Use)
The coating composition of the present invention is used as a composition for a water / oil repellent, a composition for a release agent, a composition for an antifouling agent, a composition for a fingerprint removal performance imparting agent, a composition for an easy cleaning imparting agent, and the like. be able to. Moreover, the transport apparatus which mounted the base material with a water repellent layer of this invention is provided. For example, an automobile or the like on which a substrate with a water repellent layer is mounted as a window glass or the like for an automobile can be provided.

(Function and effect)
Since the coating composition of the present invention described above contains the fluorine-containing compound of the present invention and / or its hydrolysis condensate, sufficient water repellency (particularly dynamic water repellency), abrasion resistance and weather resistance are included. A water-repellent layer having properties can be formed and the environmental load is small.

<Base material with water repellent layer>
The substrate with a water-repellent layer of the present invention has a substrate and a water-repellent layer formed from the coating composition on the surface of the substrate. The water repellent layer is preferably present in the outermost layer. The surface of the substrate and the water repellent layer may be in direct contact or may be in contact with each other through another layer. Other layers will be described later.

(Base material)
The substrate is not particularly limited as long as it is a substrate for which water repellency is required. Examples of the material for the base material include metals, plastics, glass, ceramics, combinations thereof (composite materials, laminated materials, etc.), and the like.

  As a base material, the translucent base material (glass etc.) which lets visible light pass from a transparency point is preferable. Since the water-repellent layer formed using the coating composition of the present invention has high dynamic water repellency, abrasion resistance, and weather resistance, it is a window glass for transportation equipment (trains, automobiles, ships, aircrafts, etc.) Is particularly preferred. Examples of the glass include soda lime glass, borosilicate glass, non-alkali glass, and quartz glass, and soda lime glass is particularly preferable.

The substrate may be a flat plate, or the entire surface or a part thereof may have a curvature.
What is necessary is just to select the thickness of a base material suitably with the use of a base material with a water repellent layer, and it is 1-10 mm normally.

Depending on the purpose, the surface of the substrate may be acid-treated (treated with diluted hydrofluoric acid, sulfuric acid, hydrochloric acid, etc.), alkali-treated (treated with an aqueous sodium hydroxide solution), discharge treatment (plasma irradiation) , Corona irradiation, electron beam irradiation, etc.) may be used.
The base material may be provided with various films formed by vapor deposition film, sputtered film, wet method or the like on its surface. When the base material is soda lime glass, it is preferable in terms of durability to provide a film that prevents elution of sodium ions.

(Water repellent layer)
The water repellent layer is formed so as to cover at least part of the surface of the substrate. The water repellent layer may be formed directly on the surface of the substrate, or may be formed on the surface of another layer formed on the surface of the substrate. In any case, the water repellent layer is formed on the outermost layer of the substrate with a water repellent layer of the present invention.
When the base material is glass manufactured by a float process, it is preferable from the viewpoint of durability to provide a water-repellent layer on the top surface with a small amount of tin on the surface.

  The thickness of the water repellent layer may be any thickness that can achieve both dynamic water repellency (removability of water droplets) and durability (abrasion resistance, weather resistance, etc.), preferably 2 to 30 nm, and preferably 5 to 20 nm. Is particularly preferred. The thickness of the water repellent layer can be appropriately controlled depending on the concentration of the coating composition, application conditions, heating conditions, and the like.

(Other layers)
The other layer is preferably an intermediate layer mainly composed of silica. By providing the intermediate layer, the adhesion between the water-repellent layer and the base material is increased, the denseness of the entire water-repellent layer is increased, and durability (abrasion resistance, weather resistance, etc.) can be improved.

An intermediate | middle layer is a layer specifically formed using the composition for intermediate | middle layer formation containing a silica precursor.
As a silica precursor, the compound chosen from a compound (20), its hydrolysis-condensation product, and perhydropolysilazane is mentioned.
Si (X ¹ ) (X ² ) (X ³ ) (X ⁴ ) (20).
However, X < ¹ > -X < ⁴ > is a halogen atom, an alkoxy group, or an isocyanate group, respectively. X ^{1 to} X ⁴ are each preferably a chlorine atom, an alkoxy group having 1 to 4 carbon atoms or an isocyanate group, and more preferably all of X ^{1 to} X ⁴ are the same.

Specifically, Si (NCO) ₄ , Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) _{4 and the} like are preferably used as the compound (20).
The hydrolyzed condensate of compound (20) can be obtained by the same method as described in the production of the hydrolyzed condensate of the fluorine-containing compound of the present invention.
Commercially available products may be used as the compound (20) and its hydrolysis condensate.
A compound (20) may be used individually by 1 type, and may use 2 or more types together.

Perhydropolysilazane is a linear or cyclic oligomer having a structure represented by —SiH ₂ —NH—SiH ₂ —. The number of silicon atoms per molecule of perhydropolysilazane is preferably 2 to 500.
A commercially available product may be used as perhydropolysilazane.

The composition for forming an intermediate layer may contain a hydrolysis cocondensate of the compound (20) and / or its hydrolysis condensate and the fluorine-containing compound of the present invention and / or its hydrolysis condensate ( If necessary, the compound (20) and / or the fluorine-containing compound of the present invention may further be contained).
The composition for forming an intermediate layer usually contains an organic solvent from the viewpoints of economy, workability, ease of controlling the thickness of the intermediate layer, and the like. As an organic solvent, the organic solvent mentioned as the organic solvent used for the composition for coating is preferable.
The ratio of the silica precursor in the intermediate layer forming composition (100% by mass) can be the same as that in the coating composition.

The thickness of the intermediate layer is not particularly limited, but damage is conspicuous if it is too thick, and is preferably 50 nm or less. The lower limit of the thickness of the intermediate layer is the thickness of the monomolecular layer. The thickness of the intermediate layer can be appropriately controlled depending on the concentration of the intermediate layer forming composition, coating conditions, heating conditions, and the like.
The total thickness of the water repellent layer and other layers (intermediate layer, etc.) is to maintain the function of the water repellent layer, that is, dynamic water repellency (removability of water droplets) and durability (wear resistance, weather resistance, etc.) 2 to 100 nm is preferable and 5 to 20 nm is particularly preferable from the viewpoints of both compatibility and economy.

(Goods for transportation equipment)
The base material with a water-repellent layer of the present invention is suitably used for applications for articles for transportation equipment. Examples of the transportation equipment article include bodies, window glass (front glass, side glass, rear glass), mirrors, bumpers and the like in transportation equipment (trains, automobiles, ships, aircrafts, etc.).

  Since the outermost water-repellent layer has an excellent water droplet removal property, the article for transportation equipment comprising the substrate with a water-repellent layer according to the present invention has little water droplet adhesion to the surface, and the adhered water droplets are repelled promptly. . In addition, due to the interaction with the wind pressure accompanying the operation of the transportation equipment, the attached water droplets move rapidly on the surface and do not accumulate as water droplets. For this reason, the bad influence which a water drop induces can be excluded. Moreover, since the water-repellent layer is also excellent in abrasion resistance and weather resistance, for example, the water droplet removability can be maintained even in long-term use under various use conditions including outdoor use as an article for transport equipment.

  The article for transportation equipment comprising the substrate with a water-repellent layer of the present invention is particularly easy in securing the field of view due to the splashing of water droplets, especially in applications in various fields of view such as various types of window glass. Safety can be improved. Further, it is difficult to freeze even in an environment where water droplets freeze, and even if it freezes, thawing is extremely fast. Furthermore, since there is almost no adhesion of water droplets, the number of cleaning operations can be reduced, and the cleaning operation can be easily performed.

(Manufacturing method of substrate with water repellent layer)
The method for producing a substrate with a water repellent layer of the present invention comprises applying the coating composition of the present invention to the surface of the substrate or the surface of another layer on which the surface of the substrate is formed, and curing it to repel the surface. This is a method of forming an aqueous layer.

Application methods include brush coating, flow coating, spin coating, dip coating, squeegee coating, spray coating, hand coating, roll coating method, casting method, dip coating method (dipping method), spin coating method, water casting method, Examples thereof include a die coating method, a Langmuir projet method, and a vacuum deposition method. Squeegee application is preferred because there is no factor that impairs the material utilization efficiency, such as material scattering, and the material is not wasted.
Examples of the curing method include a method of curing in air or nitrogen gas after preliminary drying as necessary. By pre-drying, the solvent of the coating composition can be easily removed.

The curing conditions are appropriately controlled depending on the type and concentration of the coating composition. Preferable curing conditions include temperature: 20 to 50 ° C. and humidity: 50 to 90% RH.
The curing time depends on the type, concentration, curing conditions, etc. of the coating composition, but is generally preferably 1 to 72 hours.

After curing, an excess component may be generated on the surface of the water-repellent layer and the appearance quality may be impaired.However, the excess component may be removed by wiping the surface of the water-repellent layer with a solvent, Remove and adjust the appearance.
In order to further adhere the cured water-repellent layer to the substrate, heat treatment may be performed. The heating temperature is usually 50 to 300 ° C. The heating time is usually 1 to 120 minutes.

(Function and effect)
The substrate with a water-repellent layer of the present invention described above has a water-repellent layer formed using the coating composition of the present invention, and therefore has sufficient water repellency (particularly dynamic water repellency) and resistance to water. Abrasion and weather resistance.
In the method for producing a substrate with a water repellent layer of the present invention, the coating composition of the present invention is applied to the surface of the substrate or the surface of another layer on which the surface of the substrate is formed. Therefore, a substrate with a water repellent layer having sufficient water repellency (particularly dynamic water repellency), abrasion resistance and weather resistance and having a low environmental load can be produced.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
Examples 1 to 10 and 14 to 18 are examples, examples 11 and 19 are comparative examples, examples 12 and 20 are reference examples, and example 13 is a preparation example.

<Fluorine-containing compounds>
[Example 1]
30.0 g of compound (2-1) and 92.1 g of compound (3-1) were added to a closed pressure-resistant reactor (100 mL, manufactured by SUS) and stirred. The reactor was then placed in a 200 ° C. oil bath and stirred for 20 hours. The raw material was removed from the obtained reaction crude liquid by simple distillation to obtain 50.0 g of a mixture containing the compound (4-1). The purity by GC (gas chromatography) was 40%, and the yield was 33%.
CF ₃ (CF ₂ ) ₃ -I (2-1),
_{CH 2 = CH- (CF 2)} 6 -CH = CH 2 ··· (3-1),
_{CF 3 (CF 2) 3 -CH} 2 CHI- (CF 2) 6 -CH = CH 2 ··· (4-1).

In a reactor equipped with a stirrer and a dropping funnel (internal volume 100 mL, made of glass), 50.0 g of the mixture containing the compound (4-1) was added and stirred, and the internal temperature of the reactor was adjusted in an oil bath. Heated to 80 ° C. Next, 16.6 g of tributyltin hydride was added dropwise so that the internal temperature of the reactor became 80 to 85 ° C., and the mixture was further stirred for 2 hours. The obtained reaction crude liquid was subjected to simple distillation (boiling point / 5 hPa to 100 ° C./5 hPa), and further, distillate, 0.5 g of activated carbon, and 20 mL of tridecafluorohexylethane (Asahi Glass Co., Ltd., AC-6000) Were mixed and the solid was filtered off. Next, 10.2 g of compound (5-1) (colorless transparent liquid) was obtained by distilling off the solvent of the filtrate. The yield was 62%.
_{CF 3 (CF 2) 3 -CH} 2 CH 2 - (CF 2) 6 -CH = CH 2 ··· (5-1).

The measurement results of ¹ H-NMR (300.4 MHz, standard: TMS) and ¹⁹ F-NMR (282.7 MHz, standard: CFCl ₃ ) of the compound (5-1) are shown below. Each measured value means a measured value derived from the group shown in parentheses following the measured value. If there is a part surrounded by [] in this group, the measured value is surrounded by []. It means the measured value derived from the part. Hereinafter, the NMR measurement results shown in the examples are all the same.
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 2.41 (4H, m, —CF ₂ CH ₂ —), 5.81 (1H, m, —CF ₂ CH═), 5.99 ( _{2H, m, = CH 2)} .
¹⁹ F-NMR (solvent: CDCl ₃ ) δ (ppm): −81.5 (3F, CF ₃ —), −114.3 (2F, —CF ₂ CH═), −115.2 to −115.5 _{(4F, -CH 2 CF 2 -} ), - 122.1~-124.8 (10F, -CF 2 [CF 2] CF 2 -, - 126.5 (2F, CF 3 [CF 2] -).

In a reactor equipped with a stirrer and a Dimroth (internal volume 50 mL), 10.0 g of compound (5-1), 7.09 g of compound (6-1), platinum catalyst (platinum-1,3-divinyl-1) , 1,3,3-tetramethyldisiloxane complex) in a 2% by weight xylene solution and 20 g of 1,3-bis (trifluoromethyl) benzene were added and stirred. The reactor was then placed in a 60 ° C. oil bath and stirred for 12 hours. The reaction crude liquid was subjected to simple distillation (boiling point to 110 ° C./5 hPa) to obtain 10.9 g of compound (11-1) (white solid, melting point: 58 ° C. (DSC)). The yield was 88%.
HSiCl ₃ (6-1),
_{CF 3 (CF 2) 3 -CH} 2 CH 2 - (CF 2) 6 -CH 2 CH 2 -SiCl 3 ··· (11-1).

The measurement results of ¹ H-NMR and ¹⁹ F-NMR of the compound (11-1) are shown below.
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.66 (2H, m, —CH ₂ Si—), 2.2 to 2.5 (6H, m, —CF ₂ CH ₂ —).
¹⁹ F-NMR (solvent: CDCl ₃ ) δ (ppm): −81.6 (3F, CF ₃ —), −115.3 to −116.1 (6F, —CF ₂ CH ₂ —), −122. _{3~-124.9 (10F, -CF 2} [CF 2] CF 2 -, - 126.6 (2F, CF 3 [CF 2] -).

[Example 2]
40.0 g of the compound (2-2) and 95.3 g of the compound (3-1) were added to a closed pressure-resistant reactor (100 mL, manufactured by SUS) and stirred. The reactor was then placed in a 200 ° C. oil bath and stirred for 20 hours. The raw material was removed from the resulting reaction crude liquid by simple distillation to obtain 90.1 g of a mixture containing the compound (4-2). The purity by GC (gas chromatography) was 25%, and the yield was 31%.
CF ₃ (CF ₂ ) ₅ -I (2-2),
_{CH 2 = CH- (CF 2)} 6 -CH = CH 2 ··· (3-1),
_{CF 3 (CF 2) 5 -CH} 2 CHI- (CF 2) 6 -CH = CH 2 ··· (4-2).

A reactor equipped with a stirrer and a dropping funnel (internal volume: 100 mL, made of glass) was charged with 90.1 g of the mixture containing the compound (4-2) and stirred, and the internal temperature of the reactor was adjusted in an oil bath. Heated to 80 ° C. Next, 16.4 g of tributyltin hydride was added dropwise so that the internal temperature of the reactor became 80 to 85 ° C., and the mixture was further stirred for 2 hours. The obtained reaction crude liquid was subjected to simple distillation (boiling point / 3 hPa to 104 ° C./3 hPa), and the distillate was mixed with 0.5 g of activated carbon and 30 mL of AC-6000, and the solid was separated by filtration. Subsequently, the solvent of the filtrate was distilled off to obtain 14.2 g of the compound (5-2) (colorless transparent liquid). The yield was 62%.
_{CF 3 (CF 2) 5 -CH} 2 CH 2 - (CF 2) 6 -CH = CH 2 ··· (5-2).

The measurement results of ¹ H-NMR and ¹⁹ F-NMR of the compound (5-2) are shown below.
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 2.41 (4H, m, —CF ₂ CH ₂ —), 5.81 (1H, m, —CF ₂ CH═), 5.98 ( _{2H, m, = CH 2)} .
¹⁹ F-NMR (solvent: CDCl ₃ ) δ (ppm): -81.3 (3F, CF _3- ), -114.4 (2F, -CF ₂ CH =), -115.2 (4F, -CH _{2 CF 2 -), - 122.0~} -124.2 (14F, -CF 2 [CF 2] CF 2 -, - 126.6 (2F, CF 3 [CF 2] -).

In a reactor equipped with a stirrer and a Dimroth (internal volume 50 mL), 9.12 g of compound (5-2), 2.75 g of compound (6-1), platinum catalyst (platinum-1,3-divinyl-1) , 1,3,3-tetramethyldisiloxane complex) in a 2% by mass xylene solution and 27 g of 1,3-bis (trifluoromethyl) benzene were added and stirred. The reactor was then placed in a 60 ° C. oil bath and stirred for 12 hours. The reaction crude liquid was subjected to simple distillation (boiling point / 3 hPa to 118 ° C./3 hPa) to obtain 7.10 g of compound (11-2) (white solid, melting point: 78 ° C. (DSC)). The yield was 63%.
HSiCl ₃ (6-1),
_{CF 3 (CF 2) 5 -CH} 2 CH 2 - (CF 2) 6 -CH 2 CH 2 -SiCl 3 ··· (11-2).

The measurement results of ¹ H-NMR and ¹⁹ F-NMR of the compound (11-2) are shown below.
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.67 (2H, m, —CH ₂ Si—), 2.2 to 2.5 (6H, m, —CF ₂ CH ₂ —).
¹⁹ F-NMR (solvent: CDCl ₃ ) δ (ppm): −81.3 (3F, CF ₃ —), −115.2 to −116.1 (6F, —CF ₂ CH ₂ —), −122. _{3~-123.9 (14F, -CF 2} [CF 2] CF 2 -, - 126.6 (2F, CF 3 [CF 2] -).

[Example 3]
700 g of compound (2-1) and 4.38 g of di (t-butyl) peroxide are charged into a pressure-resistant reactor (1 L, manufactured by SUS), and the internal temperature of the reactor becomes 115 ° C. in an oil bath. Heated. Subsequently, the compound (7b) was continuously introduced so that the internal pressure of the reactor became 0.7 MPa, and when the introduction amount reached 260 g, the introduction of the compound (7b) was stopped. Thereafter, the reaction was stopped when the internal pressure of the reactor reached 0 MPa. By distillation of the reaction crude liquid, 398.0 g of compound (8b-1) (colorless transparent liquid, boiling point: 54 ° C./66 hPa), 268.9 g of compound (8b-2) (colorless transparent liquid, boiling point: 92 ° C / 66 hPa), and 87.1 g of compound (8b-3) (colorless transparent liquid, boiling point: 114 ° C / 40 hPa).
CF ₃ (CF ₂ ) ₃ -I (2-1),
CH ₂ = CF ₂ (7b),
CF ₃ (CF ₂ ) ₃ —CH ₂ CF ₂ —I (8b-1),
CF ₃ (CF ₂ ) ₃ — (CH ₂ CF ₂ ) ₂ —I (8b-2),
_{CF 3 (CF 2) 3 -} (CH 2 CF 2) 3 -I ··· (8b-3).

150 g of compound (8b-1) and 0.38 g of di (n-propyl) peroxydicarbonate were charged into a pressure-resistant reactor (200 mL, manufactured by SUS), and the internal temperature of the reactor was 55 ° C. in an oil bath. It was heated to become. Subsequently, the compound (7c) was continuously introduced so that the internal pressure of the reactor became 0.7 MPa, and when the introduction amount reached 51 g, the introduction of the compound (7c) was stopped. Thereafter, the reaction was stopped when the internal pressure of the reactor reached 0.0 MPa. By distillation of the reaction crude liquid, 54.1 g of compound (8a-1) (colorless transparent liquid, boiling point: 55 ° C./40 hPa), and 41.3 g of compound (8a-2) (colorless transparent liquid, boiling point: 81 ° C./16 hPa).
CF ₂ = CF ₂ (7c),
_{CF 3 (CF 2) 3 -CH} 2 CF 2 -CF 2 CF 2 -I ··· (8a-1),
_{CF 3 (CF 2) 3 -CH} 2 CF 2 - (CF 2 CF 2) 2 -I ··· (8a-2).

In a reactor (50 mL, glass) equipped with a stirrer and a Dimroth, 15.0 g of the compound (8a-1), 5.0 g of the compound (13-1), N, N′-azobisisobutyronitrile 0.24 g and 15 g of AC-6000 were charged, and the reactor was heated so that the internal temperature of the reactor became 70 ° C. After stirring for 5 hours, 19.1 g of the mixture containing the compound (14a-1) was obtained by distilling off the unreacted compound (13-1) and AC-6000. The purity by GC (gas chromatography) was 49%, and the yield was 48%.
CH ₂ = CHSiCl ₃ (13-1),
_{CF 3 (CF 2) 3 -CH} 2 CF 2 -CF 2 CF 2 -CH 2 CHI-SiCl 3 ··· (14a-1).

The Dim funnel of the reactor containing the above reaction crude liquid was changed to a dropping funnel, and heated in an oil bath so that the internal temperature of the reactor became 80 ° C. Next, 8.98 g of tributyltin hydride was added dropwise so that the internal temperature of the reactor became 80 to 85 ° C., and the mixture was further stirred for 2 hours. The obtained reaction crude liquid was subjected to simple distillation (boiling point / 5 hPa to 70 ° C./5 hPa) to obtain 6.5 g of compound (12a-1) (colorless transparent liquid). The yield was 83%.
_{CF 3 (CF 2) 3 -CH} 2 CF 2 -CF 2 CF 2 -CH 2 CH 2 -SiCl 3 ··· (12a-1).

The measurement results of ¹ H-NMR and ¹⁹ F-NMR of the compound (12a-1) are shown below.
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.67 (2H, m, —CH ₂ Si—), 2.34 (2H, m, —CF ₂ [CH ₂ ] CH ₂ —), _{2.92 (2H, qui, -CF 2} CH 2 CF 2 -).
¹⁹ F-NMR (solvent: CDCl ₃ ) δ (ppm): −81.5 (3F, CF ₃ —), −112.2 to −115.2 (6F, —CF ₂ CH ₂ —), −124. _{6~-125.8 (4F, -CF 2} [CF 2] CF 2 -, - 126.3 (2F, CF 3 [CF 2] -).

[Example 4]
In a reactor (50 mL, glass) equipped with a stirrer and a Dimroth, 14.0 g of the compound (8a-2) obtained in Example 3 above, 3.57 g of the compound (13-2), N, N′— 0.18 g of azobisisobutyronitrile and AC-6000 were added, and the reactor was heated so that the internal temperature of the reactor became 70 ° C. After stirring for 12 hours, 16.6 g of a mixture containing the compound (14a-2) was obtained by distilling off the unreacted compound (13-2) and AC-6000. The purity by GC was 95%, and the yield was 95%.
_{CH 2 = CHSi (OCH 3)} 3 ··· (13-2).
_{CF 3 (CF 2) 3 -CH} 2 CF 2 - (CF 2 CF 2) 2 -CH 2 CHI-Si (OCH 3) 3 ··· (14a-2).

The Dim funnel of the reactor containing the above reaction crude liquid was changed to a dropping funnel, and heated in an oil bath so that the internal temperature of the reactor became 80 ° C. Next, 6.69 g of tributyltin hydride was added dropwise so that the internal temperature of the reactor became 80 to 85 ° C., and the mixture was further stirred for 2 hours. The obtained reaction crude liquid was subjected to simple distillation (boiling point / 5 hPa to 93 ° C./5 hPa) to obtain 13.3 g of the compound (12a-2) (colorless transparent liquid). The yield was 96%.
_{CF 3 (CF 2) 3 -CH} 2 CF 2 - (CF 2 CF 2) 2 -CH 2 CH 2 -Si (OCH 3) 3 ··· (12a-2).

The measurement results of ¹ H-NMR and ¹⁹ F-NMR of the compound (12a-2) are shown below.
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 0.85 (2H, m, —CH ₂ Si—), 2.14 (2H, m, —CF ₂ [CH ₂ ] CH ₂ —), _{2.91 (2H, qui, -CF 2} CH 2 CF 2 -), 3.59 (9H, s, -OCH 3).
¹⁹ F-NMR (solvent: CDCl ₃ ) δ (ppm): −81.5 (3F, CF ₃ —), −112.6 (4F, —CF ₂ CH ₂ CF ₂ —), −117.1 (2F) _{, -CF 2 CH 2 CH 2 -} ), - 121.9~-124.5 (8F, -CF 2 [CF 2] CF 2 -, - 126.3 (2F, CF 3 [CF 2] -).

[Example 5]
In a reactor equipped with a stirrer and a Dimroth (50 mL, made of glass), 20.0 g of the compound (8b-3) obtained in Example 3 above, 9.00 g of the compound (13-2), N, N′— 0.18 g of azobisisobutyronitrile and 20 g of AC-6000 were charged, and the reactor was heated so that the internal temperature of the reactor became 70 ° C. After stirring for 12 hours, 26.1 g of a mixture containing the compound (14b-1) was obtained by distilling off the unreacted raw material and AC-6000. The purity by GC was 80%, and the yield was 82%.
_{CF 3 (CF 2) 3 -} (CH 2 CF 2) 3 -CH 2 CHI-Si (OCH 3) 3 ··· (14b-1).

The Dim funnel of the reactor containing the above reaction crude liquid was changed to a dropping funnel, and heated in an oil bath so that the internal temperature of the reactor became 80 ° C. Next, 11.4 g of tributyltin hydride was added dropwise so that the internal temperature of the reactor became 80 to 85 ° C., and the mixture was further stirred for 2 hours. The obtained reaction crude liquid was subjected to simple distillation (boiling point / 5 hPa to 96 ° C./5 hPa) to obtain 13.9 g of compound (12b-1) (colorless transparent liquid). The yield was 64%.
_{CF 3 (CF 2) 3 -} (CH 2 CF 2) 3 -CH 2 CH 2 -Si (OCH 3) 3 ··· (12b-1).

The measurement results of ¹ H-NMR and ¹⁹ F-NMR of the compound (12b-1) are shown below.
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 0.79 (2H, m, —CH ₂ Si—), 1.98 (2H, m, —CF ₂ [CH ₂ ] CH ₂ —), _{2.5-3.0 (6H, m, -CF 2} CH 2 CF 2 -), 3.58 (9H, s, -OCH 3).
¹⁹ F-NMR (solvent: CDCl ₃ ) δ (ppm): −81.5 (3F, CF ₃ —), −88.5 to −97.6 (6F, —CH ₂ CF ₂ CH ₂ —), — _{113.2 (2F, -CF 2 [CF} 2] CH 2 -), - 124.9 (2F, CF 3 CF 2 [CF 2] -), - 126.3 (2F, CF 3 [CF 2] - ).

<Coating composition>
[Example 6]
In a glass container in which a stirrer is set, 2.22 g of heptane (manufactured by Junsei Kagaku), 2.22 g of butyl acetate (manufactured by Junsei Kagaku), and 0.57 g of compound (11-1) are placed at 25 ° C. Was stirred for 30 minutes to obtain a coating composition (J-1).

[Example 7]
In a glass container in which a stirrer is set, 3.48 g of heptane, 0.87 g of butyl acetate, and 0.65 g of compound (11-2) are added and stirred at 25 ° C. for 30 minutes. J-2) was obtained.

[Example 8]
In a glass container in which a stirrer is set, 0.91 g of heptane, 0.91 g of butyl acetate, and 0.18 g of compound (12a-1) are added, and stirred at 25 ° C. for 30 minutes. J-3) was obtained.

[Example 9]
In a glass container in which a stirrer is set, 4.33 g of isopropanol, 0.13 g of a 1.0 mass% nitric acid aqueous solution and 0.54 g of the compound (12a-2) are added, and stirred at 25 ° C. for 3 hours. A coating composition (J-4) was obtained.

[Example 10]
In a glass container in which a stirrer is set, 4.37 g of isopropanol, 0.13 g of 1.0 mass% nitric acid aqueous solution and 0.50 g of compound (12b-1) are added, and the mixture is stirred at 25 ° C. for 3 hours. A coating composition (J-5) was obtained.

[Example 11]
In a glass container in which a stirrer is set, 2.31 g of heptane, 2.31 g of butyl acetate and 0.39 g of compound (21) (manufactured by Gerest) are stirred at 25 ° C. for 30 minutes for coating. A composition (J-6) was obtained.
_{CF 3 (CF 2) 5 -CH} 2 CH 2 -SiCl 3 ··· (21).

[Example 12]
In a glass container in which a stirrer is set, 3.63 g of heptane, 0.91 g of butyl acetate, and 0.47 g of compound (22) (manufactured by Gerest) are stirred for 30 minutes at 25 ° C. A composition (J-7) was obtained.
_{CF 3 (CF 2) 7 -CH} 2 CH 2 -SiCl 3 ··· (22).

<Composition for intermediate layer formation>
[Example 13]
In a glass container in which a stirrer and a thermometer are set, 9.70 g of butyl acetate (manufactured by Junsei Kagaku) and 0.30 g of compound (20-1) (manufactured by Matsumoto Pharmaceutical Co., Ltd., SI-400) are placed. The mixture was stirred at 25 ° C. for 30 minutes to obtain an intermediate layer forming composition.
Si (NCO) ₄ (20-1).

<Base material with water repellent layer>
Evaluation of the substrate with a water repellent layer was performed as follows.

(Water droplet removal)
The water drop removability was evaluated by the values of water contact angle (CA) and water drop angle (SA) measured by the following method. First, the initial values of the water contact angle and the water falling angle were measured before the following tests (abrasion resistance, alkali resistance, weather resistance), and the water contact angle and the water falling angle were also measured after each test.
If the water contact angle is 90 ° or more and the water falling angle is 20 ° or less, it can be said that the water droplet removal property can withstand practical use.

(Water contact angle)
The contact angle of a water droplet having a diameter of 1 mm placed on the surface of the water-repellent layer of the substrate with the water-repellent layer was measured using CA-X150 (manufactured by Kyowa Interface Science Co., Ltd.). Measurement was performed at five different locations on the surface of the water repellent layer, and the average value was calculated.

(Water falling angle)
After dropping 50 μL of water droplets onto the surface of the water-repellent layer of the substrate with the water-repellent layer held horizontally, the substrate is gradually tilted, and the substrate with the water-repellent layer and the horizontal surface when the water droplet starts to fall The angle (fall angle) was measured using SA-11 (manufactured by Kyowa Interface Science Co., Ltd.).

(Abrasion resistance)
In accordance with JIS L 0849, a cloth abrasion resistance test was performed under the following test conditions using the following tester, and the water contact angle and the water falling angle were measured by the above methods.
Testing machine: Reciprocating traverse testing machine (manufactured by KT Corporation),
Test conditions: cotton cloth (according to JIS L 0803), load 1 kg, wear frequency 3,000 reciprocations.

(Alkali resistance)
The substrate with a water repellent layer was immersed in an aqueous sodium hydroxide solution having a pH of 11 for 2 hours. After the substrate was washed with water and dried, the water contact angle and the water falling angle were measured by the above methods.

(Weatherability)
[Outdoor exposure test]
An outdoor exposure test was conducted in accordance with JIS Z 2381. That is, a base material with a water-repellent layer was placed outdoors so that the surface of the water-repellent layer faces south at an angle of 30 ° with respect to the horizontal, and the water contact angle was measured by the above method three months after the start of the test. did.
[SWOM test]
The SWOM test was conducted according to JIS D 0205. That is, the surface of the water-repellent layer of the substrate with the water-repellent layer was irradiated with ultraviolet rays for 1,500 hours, and then the water contact angle was measured by the above method.

(Evaluation of durability of water droplet removal)
Regarding the above four tests (abrasion resistance, alkali resistance, weather resistance), the case where all the water contact angles after the test are 90 ° or more is passed “Good (good)”, and the other cases are rejected “×” (Bad).

[Example 14]
As a substrate, a clean soda lime glass plate (water contact angle: 5 °, 300 mm × 300 mm × thickness 3 mm) was prepared by polishing and cleaning the surface with cerium oxide.
On the surface of the glass plate, 2 g of the intermediate layer-forming composition was applied by a squeegee coating method and held at 25 ° C. for 1 minute to form an intermediate layer.
Next, 2 g of the coating composition (J-1) was applied to the surface of the intermediate layer by a squeegee coating method, and kept in a constant temperature and humidity chamber set at 50 ° C. and 60% RH for 48 hours for water repellency. A layer was formed to obtain a substrate with a water-repellent layer. The evaluation results are shown in Table 1.

[Examples 15 to 20]
A substrate with a water repellent layer was obtained in the same manner as in Example 14 except that the coating composition (J-1) was changed to the coating compositions (J-2) to (J-7). The evaluation results are shown in Table 1.

In the table, “−” in the evaluation results means that measurement is impossible due to a low water contact angle.
From the results of Table 1, for the substrates with water-repellent layers of Examples 14 to 18 having water-repellent layers formed using the coating compositions of the present invention obtained in Examples 6 to 10, both are initial and It can be seen that the water drop removal property is excellent even after each test. On the other hand, for the substrate with a water-repellent layer of Example 19 having a water-repellent layer formed using the coating composition of Comparative Example obtained in Example 11, there is no problem with the initial water droplet removability, It can be seen that there is a problem with water drop removal after the abrasion resistance test. Moreover, about the base material with a water-repellent layer of Example 20 which has a water-repellent layer formed using the coating composition of the reference example obtained in Example 12, it was the performance equivalent to Examples 14-18. In other words, if the coating composition containing the fluorine-containing compound of the present invention is used, it is possible to impart excellent water droplet removal properties to the substrate, and furthermore, the load on the environment while having sufficient durability. Is low.

  The fluorine-containing compound of the present invention is useful as a material for forming a water-repellent layer having sufficient water repellency (particularly dynamic water repellency), abrasion resistance and weather resistance, and having a low environmental load. The substrate having the water-repellent layer of the invention is useful as an article (window glass or the like) for transport equipment (train, automobile, ship, aircraft, etc.).

Claims (11)

A fluorine-containing compound represented by the following formula (1).
R _< ^F _> -Y-Si (R _< ¹ _> ) _3-n (X) _n ... (1).
However, ^RF is a linear perfluoroalkyl group having carbon number p,
Y is a linear fluoroalkylene group having a carbon number of q having a terminal of R ^F side of —CH ₂ — or a group in which an etheric oxygen atom is inserted between carbon-carbon bonds of the group,
p is an integer of 2 to 6,
q is an integer of 4 or more,
p + q is an integer of 10 or more,
R ¹ is a monovalent hydrocarbon group,
X is a hydrolyzable group,
n is an integer of 1 to 3. A fluorine-containing compound represented by the following formula (11) or the following formula (12).
^{_{R F -CH 2 CH 2 - (}} CF 2) r -CH 2 CH 2 -Si (R 1) 3-n (X) n ··· (11).
However, ^RF is a linear perfluoroalkyl group having carbon number p,
p is an integer of 2 to 6,
r is an integer of 1 or more,
p + r + 4 is an integer of 10 or more,
R ¹ is a monovalent hydrocarbon group,
X is a hydrolyzable group,
n is an integer of 1 to 3.
^{_{R F - {(CH 2 CH}} 2) a · (CH 2 CF 2) b · (CF 2 CF 2) c} -CH 2 CH 2 -Si (R 1) 3-n (X) n ··· ( 12).
However, ^RF is a linear perfluoroalkyl group having carbon number p,
p is an integer of 2 to 6,
_{- {(CH 2 CH 2)} a · (CH 2 CF 2) b · (CF 2 CF 2) c} - is of a number - _(CH 2 CH ₂₎ - units, b number of - _(CH 2 CF ₂ ) -unit and c units of-(CF ₂ CF ₂ ) -units, the terminal on the R ^F side is always-(CH ₂ CH ₂ ) -unit or-(CH ₂ CF ₂ )- Other than the unit, the arrangement of the units is not limited.
a is an integer of 0 to 10,
b is an integer of 0 to 20,
c is an integer of 0 to 10,
a + b is an integer of 1 or more, b + c is an integer of 1 or more,
p + 2a + 2b + 2c + 2 is an integer of 10 or more,
R ¹ is a monovalent hydrocarbon group,
X is a hydrolyzable group,
n is an integer of 1 to 3. A fluorine-containing compound represented by any one of the following formula (12a), the following formula (12b), and the following formula (12c).
^{_{R F - (CH 2 CF 2}} ) b - (CF 2 CF 2) c -CH 2 CH 2 -Si (R 1) 3-n (X) n ··· (12a).
However, ^RF is a linear perfluoroalkyl group having carbon number p,
p is an integer of 2 to 6,
_{- (CH 2 CF 2) b} - (CF 2 CF 2) c - may, b number of - _{(CH 2} CF 2) - units and c pieces of - _{(CF 2 CF} 2) - units have been described order It is a structure that is connected by,
b is an integer of 1 to 20,
c is an integer of 1 to 10,
p + 2b + 2c + 2 is an integer of 10 or more,
R ¹ is a monovalent hydrocarbon group,
X is a hydrolyzable group,
n is an integer of 1 to 3.
^{_{R F - (CH 2 CF 2}} ) b -CH 2 CH 2 -Si (R 1) 3-n (X) n ··· (12b).
However, ^RF is a linear perfluoroalkyl group having carbon number p,
p is an integer of 2 to 6,
b is an integer of 1 to 20,
p + 2b + 2 is an integer of 10 or more,
R ¹ is a monovalent hydrocarbon group,
X is a hydrolyzable group,
n is an integer of 1 to 3.
^{_{R F - {(CH 2 CH}} 2) - (CF 2 CF 2)} d -CH 2 CH 2 -Si (R 1) 3-n (X) n ··· (12c).
However, ^RF is a linear perfluoroalkyl group having carbon number p,
p is an integer of 2 to 6,
d is an integer of 1 to 10,
p + 4d + 2 is an integer of 10 or more,
R ¹ is a monovalent hydrocarbon group,
X is a hydrolyzable group,
n is an integer of 1 to 3. The hydrofluoric compound according to any one of claims 1 to 3 and / or a hydrolytic condensate produced by dehydration condensation of a part or all of the hydrolyzable groups of the fluorochemical compound,
A coating composition comprising a solvent.   The coating composition according to claim 4, wherein the total amount of the fluorine-containing compound and the hydrolysis condensate is 0.1 to 50% by mass in the total mass of the coating composition.   The coating composition according to claim 4 or 5, wherein the solvent is an organic solvent.   The coating composition according to any one of claims 4 to 6, which is a water / oil repellent composition.   The base material with a water repellent layer which has a base material and the water repellent layer formed from the composition for coating as described in any one of Claims 4-7 on the surface of this base material.   The base material with a water repellent layer according to claim 8, wherein the base material is a translucent base material.   An article for transportation equipment on which the substrate with a water repellent layer according to claim 9 is mounted.   The manufacturing method of the base material with a water repellent layer which apply | coats the coating composition as described in any one of Claims 4-7 on the surface of a base material, and forms a water repellent layer.