JP2013129695A - Water-repellent film forming composition, substrate with water-repellent film, and article for transportation device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-repellent film-forming composition, capable of forming a water-repellent layer having sufficient water repellency (particularly, dynamic water repellency), abrasion resistance and weather resistance with less environmental loads, a substrate with the water-repellent layer, which has sufficient water repellency (particularly, dynamic water repellency), abrasion resistance and weather resistance with less environmental loads, and an article for transportation device including the substrate with the water-repellent film.SOLUTION: The water-repellent film-forming composition includes: a silane compound (A) having 1-6C perfluoroalkyl group and a group including no perfluoroalkylene group in a linking group and a compound (B) including a silane compound (b1) having 1-6C perfluoroalkyl and a group including no perfluoroalkylene group in a linking group and/or a silane compound (b2) having a perfluoroether group including 1-6C perfluoroalkyl; and/or a partial hydrolysis polycondensate of the compound (A) and the compound (B).

Description

  The present invention relates to a composition for forming a water-repellent film, a substrate with a water-repellent film having a water-repellent film formed using the composition, and an article for transport equipment comprising the substrate with a water-repellent film.

  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.

As a water repellent composition for automobile glass that satisfies this requirement, for example, a composition containing a compound represented by the following formula (I) and a solvent has been proposed (see Patent Document 1).
(Rf ¹ ) _a Si (R) _b (NCO) _4-ab (I).
(Where Rf ¹ is an organic group having a perfluoroalkyl group having 8 to 16 carbon atoms, R is a hydrogen atom or an organic group having 1 to 16 carbon atoms, a is 1 or 2, and b Is 0 or 1.)

However, compounds having a perfluoroalkyl group having 8 or more carbon atoms have been subject to legal regulations and voluntary regulations in recent years due to their high environmental impact. Therefore, a fluorine-containing compound for a water / oil repellent composition having a perfluoroalkyl group having 6 or less carbon atoms is required. However, a water-repellent layer obtained by using a water- and oil-repellent composition containing a fluorine-containing compound having a perfluoroalkyl group having 6 or less carbon atoms, for example, CF ₃ (CF ₂ ) ₅ —CH ₂ CH ₂ —SiCl _3. Has poor crystallinity based on the perfluoroalkyl group (that is, the property of packing between molecules) compared to the conventional water repellent layer formed using a compound having a perfluoroalkyl group having 8 or more carbon atoms. In particular, there are problems that the dynamic water repellency is lowered and the weather resistance and wear resistance are not sufficient.

Japanese Patent No. 2800786

  The present invention provides a water-repellent film-forming composition that can form a water-repellent layer having sufficient water repellency (particularly dynamic water repellency), abrasion resistance and weather resistance and has a low environmental load, and sufficient water repellency ( It is an object of the present invention to provide a substrate with a water-repellent layer and a substrate for transport equipment comprising the substrate with a water-repellent film, particularly having dynamic water repellency), abrasion resistance and weather resistance and low environmental load.

The present invention includes the following compound (A) and the following compound (B) and / or a partially hydrolyzed cocondensate of the following compound (A) and the following compound (B) for forming a water repellent film. A composition is provided.
Compound (A): a fluorine-containing organosilicon compound selected from a compound represented by the following general formula (1) and a partial hydrolysis-condensation product thereof.
R ^F1 —Y ¹ —SiR ¹ _(3-n1) X ¹ _n1 (1)
(However, in Formula (1), R ^F1 is a linear perfluoroalkyl group having carbon number p,
Y ¹ is a polyfluoroalkylene group having a carbon number q, both ends of —CH ₂ —, one or more perfluoroalkylene groups, and no etheric oxygen atom between carbon-carbon atoms,
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 hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms,
X ¹ is a hydrolyzable group;
n1 is an integer of 1 to 3,
When a plurality of R ¹ and X ¹ are present, these may be different from each other or the same. )
Compound (B): A fluorine-containing organosilicon compound selected from the following compound (b1), the following compound (b2), and partial hydrolysis cocondensates thereof.
Compound (b1): a fluorine-containing organosilicon compound selected from a compound represented by the following general formula (2) and a partial hydrolysis condensate thereof.
(R ^F2 -Y ² ) _a -SiR ² _(4-a-n2) X ² _n2 (2)
(However, in Formula (2), R ^<F2> is a C1-C6 perfluoroalkyl group,
Y ² is a divalent organic group not containing a perfluoroalkylene group,
a is 1 or 2,
R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms,
X ² is a hydrolyzable group,
n2 is an integer of 1 to 3, a + n2 is 3 or 4,
When a plurality of R ^F2 —Y ² and X ² are present, these may be different from each other or the same. )
Compound (b2): a fluorine-containing organosilicon compound selected from a compound represented by the following general formula (3) and a partial hydrolysis-condensation product thereof.
R ^F3 —O— (R ^F4 —O) _m —R ^F5 —Y ³ —SiR ³ _(3-n3) X ³ _n3 (3)
(However, in Formula (3), R ^<F3 > is a C1-C6 perfluoroalkyl group,
R ^F4 and R ^F5 are perfluoroalkylene groups having 1 to 3 carbon atoms,
Y ³ is an alkylene group or an alkylene group which may have one selected from an amide bond, a urethane bond and an etheric oxygen atom between the terminal or carbon-carbon atom bonded to R ^F5 ,
m is an integer from 1 to 50;
R ³ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms,
X ³ is a hydrolyzable group,
n3 is an integer of 1 to 3,
When a plurality of R ³ and X ³ are present, these may be different from each other or the same. )

The present invention is a substrate with a water-repellent film having a substrate and a water-repellent film on at least a part of the surface of the substrate, wherein the water-repellent film is composed of one or more layers, and the present invention is formed on the outermost layer. A substrate with a water-repellent film having a water-repellent film formed using the composition for forming a water-repellent film is provided.
The present invention provides an article for transport equipment comprising the substrate with a water-repellent film of the present invention.

  According to the present invention, a water-repellent film-forming composition capable of forming a water-repellent layer having sufficient water repellency (particularly dynamic water repellency), abrasion resistance and weather resistance and having a low environmental load, and sufficient water repellency. It is possible to provide a substrate with a water-repellent layer that has aqueous (particularly dynamic water repellency), abrasion resistance, and weather resistance and has a low environmental load, and an article for a transportation device comprising the substrate with the water-repellent film.

Embodiments of the present invention will be described below. In addition, this invention is limited to the following description and is not interpreted.
The compound represented by Formula (1) in this specification is called compound (1). The same applies to other compounds. In addition, the polyfluoroalkylene group in the present specification refers to a group in which two or more hydrogen atoms of the alkylene group are substituted with fluorine atoms. The perfluoroalkyl group and the perfluoroalkylene group are groups in which all of the hydrogen atoms of the alkyl group and the alkylene group are substituted with fluorine atoms, respectively.

[Composition for water-repellent film formation]
The composition for forming a water-repellent film of the present invention comprises the compound (A) and the compound (B) and / or a partially hydrolyzed cocondensate of the compound (A) and the compound (B). including.
The excellent dynamic water repellency of the water repellent film (water repellent layer in the substrate with the water repellent film of the present invention) formed by using the water repellent film forming composition of the present invention is a molecule of the above compound (B). It depends on the structure. More specifically, the fluorine-containing organic group possessed by the compound (B) contributes to the improvement of the mobility or falling property of water droplets on the coating surface in the water-repellent film. Moreover, the abrasion resistance and weather resistance of the water-repellent film can be enhanced by blending the compound (A) with the water-repellent film-forming composition of the present invention. In addition, both the compound (A) and the compound (B) are fluorine-containing compounds having a perfluoroalkyl group having 6 or less carbon atoms and have a small load on the environment.

Hereinafter, the compound (A) and the compound (B) contained in the composition for forming a water-repellent film of the present invention will be described.
[Compound (A)]
The compound (A) contained in the composition of the present invention is a fluorine-containing organosilicon compound selected from the compound represented by the following general formula (1) and a partial hydrolysis condensate thereof.
R ^F1 —Y ¹ —SiR ¹ _(3-n1) X ¹ _n1 (1)
(However, in Formula (1), R ^F1 is a linear perfluoroalkyl group having carbon number p,
Y ¹ is a polyfluoroalkylene group having a carbon number q, both ends of —CH ₂ —, one or more perfluoroalkylene groups, and no etheric oxygen atom between carbon-carbon atoms,
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 hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms,
X ¹ is a hydrolyzable group;
n1 is an integer of 1 to 3,
When a plurality of R ¹ and X ¹ are present, these may be different from each other or the same. )

Compound (1) includes one polyfluoroalkyl group (R ^F1 —Y ¹ ), 3-n1 hydrocarbon group (R ¹ ), and n1 (where n1 is an integer of 1 to 3) per silicon atom. It is a fluorine-containing hydrolyzable silicon compound in which one hydrolyzable group (X ¹ ) is bonded.
^{R F1} -Y ¹ - R ^F1 is at the base, the carbon number p (. Here, p is an integer from 2 to 6) is a linear perfluoroalkyl group, if p is 2 or more, the water repellent Excellent oil repellency. 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 ¹ is —CH ₂ — at both ends, contains one or more perfluoroalkylene groups, does not contain an etheric oxygen atom between carbon-carbon atoms, and has a carbon number q (where q is 4 or more It is an integer.) Polyfluoroalkylene group. Y ¹ is preferably a linear polyfluoroalkylene group. q represents the number of carbon atoms of Y ¹ and is 4 or more. However, the larger the value of q, the higher the melting point of the compound (1), and the handling may be worsened. Therefore, the preferable upper limit of q is 28, 22 is more preferable, and 16 is particularly preferable.
The R ^F1 —Y ¹ — group has a long chain length composed of R ^F1 having 2 to 6 carbon atoms and a linking group (Y ¹ ) having 4 or more carbon atoms, specifically, the carbon number represented by p + q is 10 or more polyfluoroalkyl groups. When p + q is within this range, the crystallinity due to the R ^F1 —Y ¹ — group is maintained, and the resulting water-repellent layer has dynamic water repellency and excellent weather resistance and wear resistance. p + q is preferably 10-30, more preferably 10-24, and particularly preferably 10-18.

Since the terminal on the R ^F1 side in Y ¹ is —CH ₂ —, a compound having a perfluoroalkyl group having 8 or more carbon atoms is not generated as a decomposition product, so that the compound (1) has little environmental load. .
Terminus of Si side in Y ^1, from the viewpoint of ease of synthesis of the weather resistance and compounds of the resulting water-repellent layer _{(1), -CH 2 CH 2} -, - CH 2 CH 2 CH 2 -, - CH ₂ CH ₂ CH ₂ CH ₂ — may be mentioned, and —CH ₂ CH ₂ — is particularly preferable.

As described above, R ^F1 is preferably linear and Y ¹ is preferably linear. If in addition to R ^F1 Y ¹ is straight-chain, R ^{F1 -Y} 1 ^- group is a linear, increasing more the crystallinity of the compound (1), the dynamic water repellency of the resulting water-repellent layer Ya It can contribute to the improvement of weather resistance and wear resistance.

X ¹ is a hydrolyzable group. The hydrolyzable group is a group that can form Si—OH by hydrolysis of the Si—X ¹ group.
Examples of X ¹ 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, and a halogen atom. The stability of the compound (1) and the ease of hydrolysis can be given. From the standpoint of balance, an alkoxy group, an isocyanate group and a halogen atom are preferable. As the halogen atom, a chlorine atom is preferable. As an alkoxy group, a C1-C4 alkoxy group is preferable and a methoxy group or an ethoxy group is more preferable. X ¹ in the compound (1) is particularly preferably a chlorine atom, a methoxy group, or an ethoxy group. These are appropriately selected and used according to the purpose of manufacture, application and the like. When a plurality of X ¹ are present in compound (1), X ¹ may be the same group or different groups, and the same group is preferable from the viewpoint of availability.

n1 represents the number of hydrolyzable groups (X ¹ ) in the compound (1), and the number is an integer of 1 to 3. If n1 is 1 or more, the adhesiveness of the obtained water-repellent layer and a base material will become favorable. n1 is preferably 2 or 3, and particularly preferably 3, from the viewpoint of adhesion between the obtained water-repellent layer and the substrate.

R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and an alkyl group having 1 to 4 carbon atoms is preferable from the viewpoint of easy availability and handling of raw materials. The number of R ^{1 in} the compound (1) is 3-n1. When the compound (1) R ¹ in the presence plurality may be in R ¹ are different even in the same group group, in terms of it is ease to obtain the same group.
In this invention, a compound (1) may be used individually by 1 type, and may use 2 or more types together.

The compound (1) is represented by the following formula (1-1) from the viewpoint of water repellency (particularly dynamic water repellency), abrasion resistance and weather resistance of the resulting water repellent layer, and ease of synthesis. Are preferred.
R ^F1 —CH ₂ CH ₂ — (CF ₂ ) _r —CH ₂ CH ₂ —SiR ¹ _(3-n1) X ¹ _n1 (1-1)
(However, in formula (1-1), the meanings and preferred embodiments of R ^F1 , R ¹ , X ¹ , and n1 are the same as those in the above formula (1). R is an integer of 1 or more, meaning p + r + 4 The preferred embodiment is the same as p + q in the above formula (1).)

In order to make p + r + 4 the same as p + q in the above formula (1), that is, preferably 10-30, more preferably 10-24, particularly preferably 10-18, the preferred upper limit of r is 24, More preferably, 12 is particularly preferable. When p + q + 4 is within the above range, the crystallinity of the compound (1-1) is maintained by the R ^F1 —CH ₂ CH ₂ — (CF ₂ ) _r —CH ₂ CH ₂ — group, and the resulting water repellent layer has a dynamic structure. Water repellency is improved.

Preferable specific examples of compound (1-1) include compounds represented by any of the following formulas (1-11) to (1-15). However, the meaning and preferred embodiment of X ¹ in each formula are the same as those in the above formula (1).
_{CF 3 (CF 2) 3 -CH} 2 CH 2 - (CF 2) 6 -CH 2 CH 2 -SiX 1 3 ... (1-11),
_{CF 3 CF 2 -CH 2 CH 2} - (CF 2) 6 -CH 2 CH 2 -SiX 1 3 ... (1-12),
_{CF 3 (CF 2) 5 -CH} 2 CH 2 - (CF 2) 6 -CH 2 CH 2 -SiX 1 3 ... (1-13),
_{CF 3 (CF 2) 3 -CH} 2 CH 2 - (CF 2) 2 -CH 2 CH 2 -SiX 1 3 ... (1-14),
_{CF 3 (CF 2) 3 -CH} 2 CH 2 - (CF 2) 4 -CH 2 CH 2 -SiX 1 3 ... (1-15).

Compounds (1-11) to (1-15) can be used alone or in combination of two or more. In the present invention, among these, the compound (1-11) is preferable, and the compound represented by the following formula (1-11a) is particularly preferable.
_{CF 3 (CF 2) 3 -CH} 2 CH 2 - (CF 2) 6 -CH 2 CH 2 -SiCl 3 ... (1-11a).

Examples of the method for producing the compound (1) used in the present invention include the following production methods for the compound (1-1).
First, compound (1c) is obtained by addition reaction of perfluoroalkyl iodide (compound (1a)) with α, ω-divinylperfluoroalkane (compound (1b)), and then compound (1c) is reduced with a reducing agent (for example, , Tributyltin hydride, tris (trimethylsilyl) silane, etc.) to obtain compound (1d), and then compound (1-1) is obtained by hydrosilylation reaction between compound (1d) and compound (1e). Is the method. However, the meanings of R ^F1 , R ¹ , X ¹ , n1, and r in the following formulas are the same as those in the compound (1-1).

R ^F1 -I (1a),
_{CH 2 = CH- (CF 2)} r -CH = CH 2 ... (1b),
_{^{R F1 -CH 2 CHI- (CF 2}} ) r -CH = CH 2 ... (1c).
_{^{R F1 -CH 2 CH 2 - (}} CF 2) r -CH = CH 2 ... (1d).
HSiR ¹ _(3-n1) X ¹ _n1 (1e),
_{^{R F1 -CH 2 CH 2 - (}} CF 2) r -CH 2 CH 2 -SiR 1 (3-n1) X 1 n1 ... (1-1).

The manufacturing method described above, both ends of the Y is _-CH 2 CH ₂ - is a process for the preparation of a compound when it is (1). For compounds in which Y has another structure, the same reaction is performed using another compound having a different-(CF ₂ ) _r -moiety in formula (1b) instead of the compound represented by formula (1b). Can be manufactured.

Further, for example, the compound _(1a), by appropriately reacting the CH 2 = CH ₂ and / or _CH 2 = CF _2, is allowed to react with _CF 2 = CF ₂ and if necessary by represented by the following formula (1f) A compound is synthesized.
^{_{R F1 - {(CH 2 CH}} 2) x · (CH 2 CF 2) y · (CF 2 CF 2) z} -I ... (1f).
(R ^F1 is the same as the above formula (1), x is an integer of 0 to 10, y is an integer of 0 to 20, z is an integer of 0 to 10, x + y is an integer of 1 or more, and y + z is 1 or more. (It is an integer and the number of carbon atoms as the compound (1f) is 8 or more.)
The compound (1f) is subjected to an addition reaction with ethylene, then dehydroiodinated in the presence of a base, and the compound (1e) is subjected to a hydrosilylation reaction, whereby the compound (1f) is classified. A compound represented by the following formula (12) can be produced. In Formula (12), R ^F1 , R ¹ , X ¹ and n1 are the same as in Formula (1) above, and x, y and z are the same as in Compound (1f).
^{_{R F1 - {(CH 2 CH}} 2) x · (CH 2 CF 2) y · (CF 2 CF 2) z} -CH 2 CH 2 -R 1 (3-n1) X 1 n1 ... (12)

  The compound (A) contained in the composition for forming a water repellent film of the present invention may be a partially hydrolyzed condensate of the compound (1). The partially hydrolyzed condensate of a hydrolyzable silicon compound such as the compound (1) is all or one of the hydrolyzable groups possessed by the compound in the presence of a catalyst such as an acid catalyst or an alkali catalyst and water in a solvent. An oligomer (multimer) produced by hydrolysis of a part followed by dehydration condensation. However, the degree of condensation (degree of multimerization) of this partially hydrolyzed condensate needs to be such that the product is dissolved in the solvent. Compound (A) may be compound (1) or a partial hydrolysis condensate of compound (1), and a mixture of compound (1) and its partial hydrolysis condensate, for example, It may be a partially hydrolyzed condensate of compound (1) containing compound (1) of the reaction.

[Compound (B)]
The compound (B) contained in the composition of the present invention is a fluorine-containing organosilicon compound selected from the following compound (b1), the following compound (b2), and partial hydrolysis cocondensates thereof.

The compound (b1) is a fluorine-containing organosilicon compound selected from a compound represented by the following general formula (2) and a partial hydrolysis condensate thereof.
(R ^F2 -Y ² ) _a -SiR ² _(4-a-n2) X ² _n2 (2)
(However, in Formula (2), R ^<F2> is a C1-C6 perfluoroalkyl group,
Y ² is a divalent organic group not containing a perfluoroalkylene group,
a is 1 or 2,
R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms,
X ² is a hydrolyzable group,
n2 is an integer of 1 to 3, a + n2 is 3 or 4,
When a plurality of R ^F2 —Y ² and X ² are present, these may be different from each other or the same. )

Compound (2) includes a (wherein a is 1 or 2) fluorine-containing organic group (R ^F2 —Y ² —) group and 4-a-n2 (where a + n2 is 3 or 4) on a silicon atom. This is a fluorine-containing hydrolyzable silicon compound in which n hydrocarbon groups (R ² ) and n ² (where n ² is an integer of 1 to 3) hydrolyzable groups (X ² ) are bonded.
In group, R ^F2 carbon number of 1 to 6 carbon atoms which may have a ring structure ^- - R ^{F2 -Y} 2 shows a perfluoroalkyl group containing no etheric oxygen atom between carbon atoms. R ^F2 may have a straight chain structure, a branched structure, a cyclic structure, or a structure partially having a branched structure and a cyclic structure as long as the above conditions are satisfied. Good. Among these, as R ^F2 , a linear structure or a branched structure is preferable, and a linear structure is more preferable. R ^F2 preferably has 3 to 6 carbon atoms.

Y ² is a divalent organic group not containing a perfluoroalkylene group. Y number ² carbons, preferably 1 to 15, more preferably 1 to 10, 1 to 6 is particularly preferred. Y ² is preferably — (CH ₂ ) _e (e is an integer from 1 to 6), —CONH (CH ₂ ) _g (g is an integer from 1 to 5) and —CONH (CH ₂ ) a divalent organic group selected from _h NH (CH ₂ ) _5-h (h is an integer of 1 to 4), more preferably — (CH ₂ ) ₂ , —CONH (CH ₂ ) ₃ , —CONH (CH ₂ ) ₂ NH (CH ₂ ) _{3 and the} like.

The R ^F2 —Y ² — group is a fluorine-containing organic group composed of the above-mentioned R ^F2 having 1 to 6 carbon atoms and Y ² not containing a perfluoroalkylene group. Since Y ² does not have a perfluoroalkylene group, a compound having a perfluoroalkyl group having 8 or more carbon atoms as a decomposition product is not generated, so that the compound (2) has little environmental load. In the compound (2), the number of R ^F2 —Y ² — groups bonded to the silicon atom is represented by a. a is 1 or 2, and when a is 2, the R ^F2- Y ² -groups may be the same or different, and are preferably the same group from the viewpoint of availability. In the present invention, a is preferably 1.

Compound (2) in the hydrolyzable group (X ²⁾ it may be the same, including the hydrolyzable group in the compound (1) (X ^1), the preferred embodiments. Incidentally, the compound (2) X ² in the case where there are a plurality, may be X ² are different even in the same group group, it is preferable in terms of ease availability of the same group.

n2 represents the number of hydrolyzable groups (X ² ) in the compound (2), and the number is an integer of 1 to 3. If n2 is 1 or more, the adhesiveness of the water-repellent layer obtained and a base material will become favorable. n2 is preferably 2 or 3, and particularly preferably 3, from the viewpoint of adhesion between the obtained water-repellent layer and the substrate.

R ² represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. Among these, a hydrocarbon group having 1 to 4 carbon atoms is preferable because the raw materials are easily obtained and handled. A methyl group or an ethyl group is particularly preferable.
In this invention, a compound (2) may be used individually by 1 type, and may use 2 or more types together.

The compound (2) includes the following formulas (2-1) to (2) from the viewpoint of water repellency (particularly dynamic water repellency), abrasion resistance and weather resistance of the resulting water repellent layer, and ease of synthesis. The compound represented by any one of -6) is preferable.
_{F (CF 2) e - (} CH 2) f -SiX 2 3 ... (2-1)
_{F (CF 2) e - (} CH 2) f -SiR 2 X 2 2 ... (2-2)
_{F (CF 2) e -CONH (} CH 2) g -SiX 2 3 ... (2-3)
_{F (CF 2) e -CONH (} CH 2) g -SiR 2 X 2 2 ... (2-4)
_{F (CF 2) e -CONH (} CH 2) h NH (CH 2) 5-h -SiX 2 3 ... (2-5)
_{F (CF 2) e -CONH (} CH 2) h NH (CH 2) 5-h -SiR 2 X 2 2 ... (2-6)
(In the formulas (2-1) to (2-6), e is an integer of 1 to 6, f is an integer of 1 to 6, g is an integer of 1 to 5, and h is 1. Is an integer of ˜4, and X ² is a hydrolyzable group which may be the same or different.

Compounds (2-1) to (2-6) can be used alone or in combination of two or more. In the present invention, among these, the compound (2-1) is preferable, and the compound represented by the following formula (2-11) is particularly preferable.
F (CF ₂ ) ₆ (CH ₂ ) ₂ SiX ² ₃ (2-11)
(However, in Formula (2-11), X ² is a hydrolyzable group which may be the same or different from each other.)
As the compound (2-11), the following compounds in which all three hydrolyzable groups are chlorine atoms are preferred.
_{C 6 F 13 CH 2 CH 2} SiCl 3 ... (2-11a)
The compound (2) used in the present invention can be produced by a general method. Moreover, since there exists a commercial item as a compound (A), it is also possible to use such a commercial item for this invention.

  Here, the compound (b1) may be a partial hydrolysis-condensation product of the compound (2). The partial hydrolysis-condensation product is the same as that described for the partial hydrolysis-condensation of the compound (1) in the compound (A). Compound (b1) may be compound (2) or a partial hydrolysis condensate of compound (2), and a mixture of compound (2) and its partial hydrolysis condensate, for example, It may be a partially hydrolyzed condensate of compound (2) containing compound (2) of the reaction.

The compound (b2) is a fluorine-containing organosilicon compound selected from a compound represented by the following general formula (3) and a partial hydrolysis condensate thereof.
R ^F3 —O— (R ^F4 —O) _m —R ^F5 —Y ³ —SiR ³ _(3-n3) X ³ _n3 (3)
(However, in Formula (3), R ^<F3 > is a C1-C6 perfluoroalkyl group,
R ^F4 and R ^F5 are perfluoroalkylene groups having 1 to 3 carbon atoms,
Y ³ is an alkylene group or an alkylene group which may have one selected from an amide bond, a urethane bond and an etheric oxygen atom between the terminal or carbon-carbon atom bonded to R ^F5 ,
m is an integer from 1 to 50;
R ³ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms,
X ³ is a hydrolyzable group,
n3 is an integer of 1 to 3,
When a plurality of R ³ and X ³ are present, these may be different from each other or the same. )

Compound (3) includes, on a silicon atom, one fluorine-containing organic group composed of a perfluoroether group (R ^F3 —O— (R ^F4 —O) _m —R ^F5 —) and a linking group (—Y ³ —). , A fluorine-containing hydrolyzable silicon compound in which 3-n3 hydrocarbon groups (R ³ ) and n1 (where n1 is an integer of 1 to 3) hydrolyzable groups (X ³ ) are bonded to each other. .
The terminal R ^F3 in the perfluoroether group represents a perfluoroalkyl group that does not contain an etheric oxygen atom between carbon-carbon atoms having 1 to 6 carbon atoms which may have a ring structure. R ^F3 may have a straight chain structure, a branched structure, a cyclic structure, or a structure partially having a branched structure and a cyclic structure as long as the above conditions are satisfied. Good. Among these, as R ^F3 , a linear structure or a branched structure is preferable, and a linear structure is more preferable. R ^F3 preferably has 1 to 3 carbon atoms.

In perfluoroether group, the carbon number of the perfluoro perfluoroalkylene group constituting the repeating unit (oxyalkylene) group (R ^{F4 -O)} (R ^F4) is from 1 to 3, the m indicating the number of repeating units, 1 ~ 50. When m is 2 or more, R ^{F4 of} each repeating unit may be the same or different. Specifically, (R ^F4 —O) _m is (CF ₂ O) _s , (CF ₂ CF ₂ O) _j , (CF ₂ CF ₂ CF ₂ O) _t , (CF (CF ₃ ) CF ₂ O _{) u, (CF 2 CF 2} O) j - (CF 2 O) s, (CF (CF 3) CF 2 O) u - include _(CF 2 _{O) s} or the like. However, when (R ^F4 —O) _m is composed of one kind of perfluoro (oxyalkylene) group, s, j, t and u are each an integer of 1 to 50. (R ^F4 —O) When _m is composed of two or more perfluoro (oxyalkylene) groups, the sum (s + j + t + u) of s, j, t and u is an integer of 1 to 50.

Among these, (R F4 ^-O) _m, often the proportion of oxygen atoms per unit molecular weight, flexibility is improved, in terms of water repellency (particularly dynamic water repellency) is high, (CF ₂ CF ₂ O) _j (j is an integer of 1 to 50) is particularly preferable.
M which shows the repeating number of a perfluoro (oxyalkylene) group becomes like this. Preferably it is an integer of 3-18, More preferably, it is 4-12, More preferably, it is an integer of 5-10. By setting the number of m within this range, it becomes possible to impart sufficient water repellency (particularly dynamic water repellency) to the water repellent film formed from the composition of the present invention.
In addition, the compound (3) is often used as a mixture in which the number of repeating units of the perfluoro (oxyalkylene) group is different. When compound (3) is such a mixture, the number of each repeating unit is shown by an average value. In the case of an average value, the number of repeating units is not necessarily an integer, but a preferable range of numerical values is the same as described above.

In the perfluoroether group, the carbon number of the perfluoroalkylene group (R ^F5 ) located on the linking group (—Y ³ —) side of (R ^F4 —O) _m is 1 to 3. R ^F5 is preferably —CF ₂ —.

In the compound (3), a linking group (—Y ³ —) that binds a perfluoroether group (R ^F3 —O— (R ^F4 —O) _m —R ^F5 —) to a silicon atom is an alkylene group or R It is an alkylene group which may have one kind selected from an amide bond, a urethane bond and an etheric oxygen atom between the terminal or carbon-carbon atom bonded to ^F5 .

Y carbon number of ^3, preferably 1 to 8, more preferably 2 to 5, particularly preferably 2 to 3. Specifically, as Y ³ , CONH (CH ₂ ) _{k 1} , CH ₂ OCONH (CH ₂ ) _{k 1} , (CH ₂ ) _{k 2} O (CH ₂ ) _{k 1} , (CH ₂ ) _k 1 (where k1 is 1 to 4 It is an integer, and k2 is an integer of 0 to 3.). Among _{these, -CONHC 3 H 6 -, -} CONHC 2 H 4 -, - C 2 H 4 - is preferable.
The perfluoroether group (R ^F3 —O— (R ^F4 —O) _m —R ^F5 —) possessed by the compound (3) has 1 to 6 carbon atoms in the terminal perfluoroalkyl group R ^F3 as a decomposition product. Since a compound having a perfluoroalkyl group having 8 or more carbon atoms is not produced, the compound (3) has a low environmental load.

Compound (3) in the hydrolyzable group (X ³⁾ it may be the same, including the hydrolyzable group in the compound (1) (X ^1), the preferred embodiments. Incidentally, the compound (3) X ³ in the case where there are a plurality, may be the X ³ are different even in the same group group, it is preferable in terms of ease availability of the same group.

n3 represents the number of hydrolyzable groups (X ³ ) in the compound (3), and the number is an integer of 1 to 3. If n3 is 1 or more, the adhesiveness of the water-repellent layer obtained and a base material will become favorable. n3 is preferably 2 or 3, and particularly preferably 3, from the viewpoint of the adhesion between the resulting water-repellent layer and the substrate.

R ³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. Among these, a hydrocarbon group having 1 to 4 carbon atoms is preferable because the raw material is easily obtained and handled. A methyl group or an ethyl group is particularly preferable.
In this invention, a compound (3) may be used individually by 1 type, and may use 2 or more types together.

The compound (3) includes the following formulas (3-1) to (3) from the viewpoint of water repellency (particularly dynamic water repellency), abrasion resistance and weather resistance of the resulting water repellent layer, and ease of synthesis. -4) is preferred.
_{F (CF 2) i -O- (} CF 2 CF 2 O) j (CF 2) l -CONH (CH 2) k1 SiX 3 3 ... (3-1)
_{F (CF 2) i -O- (} CF 2 CF 2 O) j (CF 2) l -CH 2 OCONH (CH 2) k1 SiX 3 3 ... (3-2)
_{F (CF 2) i -O- (} CF 2 CF 2 O) j (CF 2) l - (CH 2) k2 O (CH 2) k1 SiX 3 3 ... (3-3)
_{F (CF 2) i -O- (} CF 2 CF 2 O) j (CF 2) l - (CH 2) k1 SiX 3 3 ... (3-4)
(In the formulas (3-1) to (3-4), i is an integer of 1 to 6, j is an integer of 1 to 20, l is an integer of 1 to 3, and k1 is 1. an to 4 integer, k2 is an integer of 0 to 3, X ³ is a good hydrolyzable groups be the same or different from one another.)

Preferred specific examples of the compounds (3-1) to (3-4) include compounds represented by any of the following formulas (3-11) to (3-42).
_{CF 3 -O- (CF 2 CF 2} O) j1 -CF 2 -CONHC 3 H 6 SiX 3 3 ... (3-11)
_{CF 3 -O- (CF 2 CF 2} O) j1 -CF 2 -CONHC 2 H 4 SiX 3 3 ... (3-12)
_{CF 3 CF 2 -O- (CF 2} CF 2 O) j1 -CF 2 -CONHC 3 H 6 SiX 3 3 ... (3-13),
_{CF 3 CF 2 CF 2 -O- (} CF 2 CF 2 O) j1 -CF 2 -CONHC 3 H 6 SiX 3 3 ... (3-14),
_{CF 3 -O- (CF 2 CF 2} O) j1 -CF 2 -CH 2 OCONHC 3 H 6 SiX 3 3 ... (3-21),
_{CF 3 -O- (CF 2 CF 2} O) j1 -CF 2 -CH 2 OC 3 H 6 SiX 3 3 ... (3-31),
_{CF 3 -O- (CF 2 CF 2} O) j1 - (CF 2) 2 -OC 3 H 6 SiX 3 3 ... (3-32)
_{CF 3 -O- (CF 2 CF 2} O) j1 -CF 2 -C 3 H 6 SiX 3 3 ... (3-41)
_{CF 3 -O- (CF 2 CF 2} O) j1 -CF 2 -C 2 H 4 SiX 3 3 ... (3-42)
(Wherein (3-11), j1 is an integer of 1 to 9, ^{X 3} is a good hydrolyzable groups be the same or different from one another.)
In the compounds (3-11) to (3-42), the hydrolyzable group (X ³ ) is preferably a methoxy group or an ethoxy group, and preferably three X ³ are the same.

  Compounds (3-1) to (3-4) may be used alone or in combination of two or more. In the present invention, among these, the compound (3-1) is preferable, and the compound (3-11) is more preferable. Furthermore, among the compounds (3-11), a compound represented by the following formula (3-11a) is particularly preferable.

_{CF 3 -O- (CF 2 CF 2} O) j1 -CF 2 -CONHC 3 H 6 Si (OCH 3) 3 ... (3-11a)
(However, j1 = 7-8, an average value: 7.3 is shown.)
The compound (3) used in the present invention can be produced by a known method. For example, the compounds (3-1) to (3-4) can be specifically produced by the method described in WO2009-008380.

  Here, the compound (b2) may be a partial hydrolysis-condensation product of the compound (3). The partial hydrolysis-condensation product is the same as that described for the partial hydrolysis-condensation of the compound (1) in the compound (A). The compound (b2) may be the compound (3) or a partially hydrolyzed condensate of the compound (3), and a mixture of the compound (3) and the partially hydrolyzed condensate, for example, It may be a partial hydrolysis-condensation product of the compound (3) including the reaction compound (3).

  The compound (B) contained in the composition of the present invention is a fluorine-containing organosilicon compound selected from the above compound (b1), the above compound (b2), and a partial hydrolysis cocondensate thereof. Specifically, compound (B) includes compound (2), partial hydrolysis condensate of compound (2), compound (3), partial hydrolysis condensate of compound (3), and compound (2) and compound. One or more selected from the partially hydrolyzed cocondensates of (3) are used.

The composition for forming a water-repellent film of the present invention comprises the compound (A) and the compound (B) and / or a partially hydrolyzed cocondensate of the compound (A) and the compound (B). including. Hereinafter, as necessary, the portion of the compound (A) and the compound (B) and / or the compound (A) and the compound (B) contained in the composition for forming a water-repellent film of the present invention. The hydrolysis cocondensate is referred to as “fluorine-containing hydrolyzable silane compound component”.
The compound (A) and the compound (B) may contain the above-described compound as they are in the water-repellent film forming composition of the present invention, or the compound (A) and the compound (B). It may be contained as a partially hydrolyzed cocondensate. In addition, since the compound which produces | generates the compound which has a C8 or more perfluoroalkyl group as a decomposition product is not contained in a compound (A) and a compound (B) as above-mentioned, the water-repellent film of this invention The environmental impact of the forming composition is low.

  The partially hydrolyzed cocondensate of the compound (A) and the compound (B) is a hydrolyzable property of these compounds in the presence of a catalyst such as an acid catalyst or an alkali catalyst in a solvent, as described above. An oligomer (multimer) formed by hydrolysis of all or part of a group followed by dehydration condensation. Here, since it is obtained by hydrolytic condensation of the compound (A) and the compound (B), it is called a partially hydrolyzed “co” condensate. The degree of condensation (degree of multimerization) of this partially hydrolyzed cocondensate must be such that the product is soluble in the solvent.

  The partially hydrolyzed cocondensate of the compound (A) and the compound (B) dissolves a predetermined amount of the compound (A) and the compound (B) in a solvent, and in the presence of a catalyst such as an acid catalyst or an alkali catalyst and water. And stirring for a predetermined time. As the acid catalyst, hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, p-toluenesulfonic acid and the like can be used. As the alkali catalyst, sodium hydroxide, potassium hydroxide, ammonia or the like can be used. By using an aqueous solution of these catalysts, water necessary for hydrolysis can be present in the reaction system. Although the reaction can be promoted by heating in the presence of a catalyst and water, if the reaction proceeds too much, the degree of condensation will increase too much, and a solvent-insoluble product may be produced. As long as an appropriate amount of catalyst is present, the reaction is preferably performed at room temperature. The obtained solution of the partially hydrolyzed cocondensate can be used as it is as the composition for forming a water-repellent film of the present invention.

  By using the partially hydrolyzed cocondensate, a water repellent film with higher performance can be formed. For example, in the case of a water-repellent film formed from the compound (A) and the compound (B), the water-repellent film is composed of a hydrolysis cocondensate of both compounds, so that the units derived from both compounds are uniformly distributed. It is considered preferable. Since the hydrolysis cocondensate of both compounds is formed in a relatively short time, in the film formed directly from the compound (A) and the compound (B), the distribution of the units derived from both compounds is uniform. May decrease. It is considered that this uniformity is improved by preparing in advance a partially hydrolyzed cocondensate containing units derived from both compounds.

  The composition ratio of the active ingredient in the composition for forming a water-repellent film of the present invention can be determined from the amounts of the compound (A) and the compound (B) to be used. When a composition contains a compound (A) and a compound (B), a composition ratio can be determined by the ratio of both the compounds used in order to manufacture a composition. However, when the composition for forming a water-repellent film of the present invention contains the partially hydrolyzed cocondensate, it is difficult to measure the proportion of units in the partially hydrolyzed cocondensate. In this case, in this invention, the composition ratio of an active ingredient shall be determined with the raw material composition before manufacturing a partial hydrolysis cocondensate. That is, the composition ratio of the active ingredient is determined from the amounts of the compound (A) and the compound (B) used as raw materials for the partially hydrolyzed cocondensate.

  The content ratio of the compound (A) in the composition for forming a water-repellent film of the present invention is represented by [compound (A)] / [compound (A) + compound (B)] × 100. Ratio of compound (A) to total molar amount with (B) (however, in the case where the composition contains a partially hydrolyzed cocondensate, for the hydrolyzed cocondensed product, the compound before the hydrolyzed cocondensation reaction) (A ratio calculated using the total molar amount of (A) and compound (B)) is 10 to 95 mol%, and the resulting water-repellent layer has water repellency (particularly dynamic water repellency). From the point which can fully provide abrasion resistance and weather resistance, it is more preferable that it is 20-95 mol%, and it is especially preferable that it is 40-95 mol%. The content ratio of the compound (A) is preferably 40 mol% or more from the viewpoint that chemical resistance can be further imparted to the resulting water-repellent layer.

  In this case, the content ratio of the compound (B) in the composition of the present invention is 5 to 90 mol% as the ratio of the compound (B) to the total molar amount of the compound (A) and the compound (B). Is more preferable, it is more preferable that it is 5-80 mol%, and it is especially preferable that it is 5-60 mass%. As mentioned above, in the case of a partially hydrolyzed cocondensate, the mol% here means a composition ratio calculated by the molar amount of the compound (A) and the compound (B) before the reaction.

  The composition for forming a water-repellent film of the present invention comprises the compound (A) and the compound (B), comprises the compound (A), the compound (B) and a partial hydrolysis cocondensate thereof, or comprises the compound (A) and the compound (B) may be composed of only essential components consisting of a partially hydrolyzed cocondensate, but considering economics, workability, ease of controlling the thickness of the resulting water-repellent film, etc. Usually, it contains an organic solvent. The organic solvent is not particularly limited as long as it dissolves essential components. As the organic solvent, alcohols, ethers, ketones, aromatic hydrocarbons, paraffin hydrocarbons, acetate esters and the like are preferable, and organic solvents containing fluorine atoms (for example, fluoroalcohols, fluorohydrocarbons) are particularly preferable. Is preferred. The organic solvent is not limited to one kind, and two or more kinds of solvents having different polarities and evaporation rates may be mixed and used.

  Further, when the composition for forming a water-repellent film of the present invention contains a partially hydrolyzed condensate or a partially hydrolyzed cocondensate, it may contain a solvent used for producing these, and the solvent and the water-repellent film. The organic solvent of the composition for forming a water film may be the same. Furthermore, the composition for forming a water-repellent film may contain components such as a catalyst used in partial hydrolysis condensation. In particular, the composition for forming a water-repellent film containing the partially hydrolyzed cocondensate is preferably a solution of the partially hydrolyzed cocondensate obtained by the production of the partially hydrolyzed cocondensate.

  The proportion of the organic solvent in the composition for forming a water-repellent film of the present invention is preferably 100,000 parts by mass or less, particularly 10,000 parts per 100 parts by mass of the total mass of the fluorine-containing hydrolyzable silane compound component. The mass part or less is preferable. If an amount exceeding 100,000 parts by mass is used, processing unevenness may occur in the resulting water-repellent layer.

  The amount of the organic solvent used in the composition for forming a water-repellent film is 3,500 parts by mass or less with respect to 100 parts by mass of the total mass of the fluorine-containing hydrolyzable silane compound component contained in the composition. Is preferable, and it is more preferably 2,000 parts by mass or less. Thus, in the composition for forming a water-repellent film, by reducing the amount of the organic solvent relative to the solid content, the film thickness of the water-repellent layer formed using this can be easily increased. It becomes possible to contribute to the improvement of alkali resistance, salt water resistance and the like of the water film. The lower limit of the amount of the organic solvent used in the composition for forming a water-repellent film is not particularly limited, but as described above, in consideration of economy, workability, ease of controlling the thickness of the treatment layer, and the like, It is preferable to set the amount of about 500 parts by mass as the lower limit with respect to 100 parts by mass of the total mass of the fluorine-containing hydrolyzable silane compound component contained in the composition.

  The composition for forming a water-repellent film of the present invention may contain a functional additive as an optional component depending on the purpose within a range not impairing the effects of the present invention. The functional additive is preferably selected in consideration of reactivity or compatibility with essential components, and non-fluorinated water repellent materials such as one-end reactive polydimethylsiloxane and both-end reactive polydimethylsiloxane. Preferred examples include ultrafine particles of metal oxides such as silica, alumina, zirconia, and titania, coloring materials such as dyes or pigments, antifouling materials, curing catalysts, and various resins. The addition amount of the functional additive is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total mass of the fluorine-containing hydrolyzable silane compound component contained in the composition for forming a water repellent film. Excessive addition of a functional additive to the composition for forming a water-repellent film may lead to a decrease in performance such as water droplet removability of the resulting water-repellent film.

  Furthermore, in the composition for forming a water-repellent film of the present invention, even if it does not contain a partially hydrolyzed condensate or a partially hydrolyzed cocondensate, the hydrolysis co-reaction between the compound (A) and the compound (B). In order to promote the condensation reaction, it is also preferable to add a catalyst such as the same acid catalyst used in the same reaction as described above. Even when a partially hydrolyzed condensate or a partially hydrolyzed cocondensate is included, when the catalyst used for the production thereof does not remain in the composition, it is preferable to add a catalyst. As the catalyst, an acid catalyst is preferable. The presence of the catalyst makes it possible to form a water-repellent film having good wear resistance and weather resistance. As a quantity of a catalyst, 0.01-5 mass parts is preferable with respect to 100 mass parts of total mass of a fluorine-containing hydrolysable silane compound component.

  The composition for forming a water-repellent film of the present invention may contain water for hydrolysis cocondensation reaction of the fluorine-containing hydrolyzable silane compound component. The water content in the composition for forming a water repellent film is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the total mass of the fluorine-containing hydrolyzable silane compound component. Even if the water repellent film-forming composition does not contain water, hydrofluoric decomposable silane compound components are hydrolyzed and condensed using moisture in the atmosphere in the process of forming the following water repellent layer. be able to.

  As a method for forming a water-repellent layer using the composition for forming a water-repellent film of the present invention, it is possible to use a known method for a fluorine-containing organosilane compound-based surface treatment agent. For example, the composition is applied to the surface of the substrate by a method such as brush coating, flow coating, spin coating, dip coating, squeegee coating, spray coating, or hand coating, and in air or nitrogen atmosphere, as necessary. A water-repellent layer can be formed by curing after drying. The curing conditions are appropriately controlled depending on the type and concentration of the composition to be used. Preferred conditions include a temperature of 20 to 50 ° C. and a humidity of 50 to 90% RH. The time for curing depends on the type, concentration, curing conditions and the like of the composition to be used, but is generally preferably 1 to 72 hours. Depending on the treatment method, an excessive component may be generated and the appearance quality may be impaired. The thickness of the water repellent layer formed from the composition for forming a water repellent film of the present invention is not particularly limited. However, in consideration of economy, the thickness is preferably 50 nm or less, and the lower limit is the thickness of the monomolecular layer. is there.

[Substrate with water-repellent film]
The substrate with a water repellent film of the present invention is a substrate with a water repellent film having a substrate and a water repellent film on at least a part of the surface of the substrate, and the water repellent film is composed of one or more layers, and The outermost layer has a water-repellent layer formed by using the water-repellent film forming composition of the present invention.

  The substrate used for the substrate with a water-repellent film of the present invention is not particularly limited as long as it is a substrate made of a material that is generally required to impart water repellency. Metal, plastic, glass, ceramic, or a combination thereof (composite material, A substrate made of a laminated material or the like is preferably used. A transparent substrate such as glass or plastic is preferred, and glass is particularly preferred. Examples of the glass include ordinary soda lime glass, borosilicate glass, non-alkali glass, and quartz glass. Among these, soda lime glass is particularly preferable. Examples of the plastic include acrylic resins such as polymethyl methacrylate, aromatic polycarbonate resins such as polyphenylene carbonate, and aromatic polyester resins such as polyethylene terephthalate (PET). Among these, polyethylene terephthalate (PET) ) Is preferred.

  The shape of the substrate may be a flat plate, or the entire surface or a part thereof may have a curvature. The thickness of the substrate can be appropriately selected depending on the use of the substrate with a water-repellent film, but is generally preferably 1 to 10 mm.

  The substrate used in the present invention may have an acid treatment (treatment with diluted hydrofluoric acid, sulfuric acid, hydrochloric acid, etc.), alkali treatment (treatment with an aqueous sodium hydroxide solution) or discharge depending on the purpose. Those subjected to treatment (plasma irradiation, corona irradiation, electron beam irradiation, etc.) or the like may be used. Further, the substrate may have a surface provided with various films formed by vapor deposition film, sputtered film, wet method or the like. When the substrate is soda lime glass, it is preferable in terms of durability to provide a film that prevents elution of Na ions. In the case where the substrate is glass manufactured by a float process, it is preferable in terms of durability to provide a water-repellent film on the top surface with a small amount of surface tin.

  In the substrate with a water-repellent film of the present invention, the water-repellent film formed on at least a part of the surface of the substrate is composed of one or more layers, and the composition for forming a water-repellent film of the present invention is used for the outermost layer. A layer made of a water-repellent film (water-repellent layer).

  The water-repellent film in the present invention may be composed of only the water-repellent layer, and may have a layer other than the water-repellent layer in addition to the water-repellent layer depending on the purpose. In addition, the water repellent layer of the substrate with a water repellent film of the present invention is formed on the outermost layer of the water repellent film. The water repellent layer that the water repellent film has as the outermost layer can be formed on the substrate as the outermost layer of the water repellent film by the above-described method using the water repellent film forming composition of the present invention. It is. That is, in the substrate with a water-repellent film of the present invention, the method for producing a substrate with a water-repellent film when the water-repellent film is composed only of a water-repellent layer is the formation of the water-repellent film of the present invention on the substrate surface. The method which has the process of forming a water repellent layer by apply | coating and hardening the composition for water is mentioned.

  Further, as a method for producing a substrate with a water-repellent film of the present invention when the water-repellent film has a layer other than the water-repellent layer, after forming all the layers other than the water-repellent layer on the substrate surface, Examples of the method include a step of forming a water-repellent layer by applying the water-repellent film-forming composition onto the surface of the layer that forms the lower layer of the layer (outermost layer) in the same manner as described above. That is, it is a method having a step of forming a water-repellent layer by applying and curing a water-repellent film-forming composition on the surface of a layer that is formed in advance on the surface of the substrate and that is the lowermost layer of the water-repellent film. .

  The thickness of the water-repellent layer in the substrate with a water-repellent film of the present invention is particularly so long as sufficient water repellency (particularly dynamic water repellency) and durability such as wear resistance and weather resistance are compatible. Not limited. The thickness of the water repellent layer is preferably 1 to 30 nm and more preferably 1 to 20 nm when the water repellent film is composed of only the water repellent layer. Moreover, when the said water repellent film has layers other than a water repellent layer, for example, the following intermediate | middle layers, etc., 1-30 nm is preferable and, as for the thickness of a water repellent layer, 1-20 nm is more preferable. The thickness of the water repellent layer can be appropriately controlled depending on the concentration of the water repellent film forming composition used, coating conditions, heating conditions, and the like.

  In the substrate with a water-repellent film of the present invention, the water-repellent film preferably further includes an intermediate layer mainly composed of silica between the substrate and the water-repellent layer as a layer other than the water-repellent layer. . By providing this intermediate layer, the adhesion between the water-repellent film and the substrate is increased, the denseness of the entire water-repellent film is increased, and durability such as wear resistance and weather resistance can be improved. Become.

Specifically, the intermediate layer mainly composed of silica of the water repellent film includes a compound (C) selected from a compound represented by the following general formula (4), a partially hydrolyzed condensate thereof, and perhydropolysilazane. It can form using the composition for intermediate | middle layer formation containing.
Si (X ⁴ ) ₄ (4)

In the above formula (4), X ⁴ represents a halogen atom, an alkoxy group or an isocyanate group, and may be the same or different. Among these, X ⁴ is a chlorine atom, is preferably an alkoxy group or an isocyanate group having 1 to 4 carbon atoms, preferably further four X ⁴ are identical.

Specifically, Si (NCO) ₄ , Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) _{4 and the} like are preferably used as the compound represented by the general formula (4). Moreover, these partial hydrolysis-condensation products can be obtained by the same method as described in the production of the partial hydrolysis-condensation products of compounds (1) to (3). Moreover, there exists a commercial item as a compound shown by General formula (4), and its partial hydrolysis-condensation product, It is possible to use such a commercial item for this invention.

Perhydropolysilazane is a linear or cyclic oligomer having a structure represented by —SiH ₂ —NH—SiH ₂ —, and the number of silicon atoms per molecule is preferably 2 to 500. There are commercially available perhydropolysilazanes, and such commercially available products can be used in the present invention.
Moreover, 1 type of a compound (C) may be used independently for the said composition for intermediate | middle layer formation, and 2 or more types may be used together.

  The intermediate layer forming composition may consist only of the compound (C) and / or a partially hydrolyzed condensate thereof. However, the economy, workability, ease of controlling the thickness of the treatment layer, etc. are improved. In consideration, it usually contains an organic solvent.

  As an organic solvent, the organic solvent described in the composition for water-repellent film formation can be used preferably. The amount of the organic solvent used in the intermediate layer forming composition can be the same as in the case of the water repellent film forming composition. That is, the amount of the organic solvent used in the intermediate layer forming composition is preferably 100,000 parts by mass or less, particularly 10,000 parts by mass or less, with respect to 100 parts by mass of the solid content contained in the composition. Is preferred. If an amount exceeding 100,000 parts by mass is used, processing unevenness may occur in the resulting water-repellent film.

  The amount of the organic solvent used in the composition for forming an intermediate layer is preferably 3,500 parts by mass or less, and 2,000 parts by mass with respect to 100 parts by mass of the total mass of solids contained in the composition. It is more preferable that the amount is not more than parts. Thus, in the composition for forming an intermediate layer, by reducing the amount of the organic solvent relative to the solid content contained, the film thickness of the intermediate layer formed using this can be easily increased, and the water repellent film It is possible to contribute to the improvement of alkali resistance, salt water resistance and the like. The lower limit of the amount of the organic solvent used in the intermediate layer forming composition is not particularly limited, but as described above, considering the economy, workability, ease of controlling the thickness of the treatment layer, etc., the composition Preferably, the lower limit is about 500 parts by mass with respect to 100 parts by mass of the total mass of solids contained in the product.

  Moreover, the composition for intermediate | middle layer formation may also contain a functional additive according to the objective in the range which does not impair the effect of this invention. As the functional additive, those described in the composition for forming a water-repellent film are preferably mentioned. Furthermore, the composition for forming an intermediate layer may contain components such as an acid catalyst and water as necessary, similarly to the composition for forming a water-repellent film. Further, the method for forming the intermediate layer using the intermediate layer forming composition is preferably the same method as the water repellent film forming method described in the water repellent film forming composition of the present invention.

  The thickness of the intermediate layer formed from the composition for forming an intermediate layer is not particularly limited, but if it is too thick, damage is likely to be conspicuous. The lower limit is the thickness of the monomolecular layer. The thickness of the intermediate layer can be appropriately controlled by the concentration of the intermediate layer forming composition, coating conditions, heating conditions, and the like. The total thickness of the water-repellent film is to maintain the function of the water-repellent film in the present invention, that is, to have sufficient water repellency (particularly dynamic water repellency) and durability such as wear resistance and weather resistance. Considering economy, 1 to 100 nm is preferable, and 1 to 20 nm is more preferable.

In the substrate with a water-repellent film of the present invention, the method for producing a substrate with a water-repellent film in the case where the water-repellent film further includes an intermediate layer mainly composed of silica between the substrate and the water-repellent layer. The intermediate layer forming composition is applied to the substrate surface and cured to form an intermediate layer mainly composed of silica, and the water repellent film forming composition of the present invention is formed on the surface of the intermediate layer. And a step of forming a water repellent layer by applying and curing.
The intermediate layer forming composition is applied to the substrate surface and held for a certain period of time to form a coating film. After the water repellent film forming composition is applied to the surface and the coating film is formed, under appropriate conditions. By performing the curing process, it is possible to simultaneously perform the curing process for forming the intermediate layer and the curing process for forming the water repellent layer.

  The water repellent film of the substrate with a water repellent film of the present invention thus obtained has both sufficient water repellency (particularly dynamic water repellency) and durability such as wear resistance and weather resistance.

[Transportation Equipment Items]
The substrate with a water-repellent film of the present invention is suitably used for use as an article for transport equipment comprising the same. Preferred examples of the article for transportation equipment include bodies in trains, automobiles, ships, aircrafts, window glass (front glass, side glass, rear glass), mirrors, bumpers, and the like.

  The substrate with a water-repellent film of the present invention or an article for transport equipment comprising this substrate has excellent water repellency (particularly dynamic water repellency) on the surface of the water-repellent film. Adhered water droplets are repelled immediately. In addition, due to the interaction with the wind pressure associated with the operation of the transport 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 induces can be excluded. In addition, the water-repellent film is excellent in wear resistance and weather resistance. For example, this water-repellent film (especially dynamic repellency) is used even in long-term use under various usage conditions including outdoor use as an article for transport equipment. Water repellency) can be maintained.

  The substrate with a water-repellent film of the present invention or an article for transport equipment comprising this substrate is very easy to secure a field of view by scattering of water droplets, particularly in applications in a transparent field portion such as various window glasses. Safety can be improved in operation. 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.

  Examples of the present invention are shown below, but the present invention is not limited to these examples. Examples 1 to 9 and 12 to 20 are examples, and examples 10, 11, 21, and 22 are comparative examples. Example 23 is a reference example.

The following compounds were used as components to be blended in the water repellent film forming composition.
(Fluorine-containing organosilicon compound)
Compound (1) as the compound _{(1-11a): C 4 F 9} CH 2 CH 2 C 6 F 12 CH 2 CH 2 SiCl 3 ( less prepared in Preparation Example 1.)
Compound (2-11a) as compound (2): C ₆ F ₁₃ CH ₂ CH ₂ SiCl ₃ (manufactured by Synquest)
Compound (3-11a) as compound (3): CF ₃ O (CF ₂ CF ₂ O) _j1 CF ₂ CONHC ₃ H ₆ Si (OCH ₃ ) ₃ (produced in Synthesis Example 2 below, provided that compound (3- 11a), j1 = 7 to 8, average value: 7.3.)
Compound (C): Si (NCO) ₄ (SI-400, trade name, manufactured by Matsumoto Fine Chemical Co., Ltd.)

(solvent)
AE3000: Asahiklin AE3000 (trade name, manufactured by Asahi Glass Co., Ltd., CF ₃ CH ₂ OCF ₂ CHF ₂ )
AC2000: Asahi Clin AC2000 (trade name, manufactured by Asahi Glass Co., Ltd., CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CHF ₂ )

[Synthesis Example 1: Synthesis of Compound (1-11a)]
30.0 g of compound (1a-1) and 92.1 g of compound (1b-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 (1c-1). The purity by GC (gas chromatography) was 40%, and the yield was 33%.
CF ₃ (CF ₂ ) ₃ -I (1a-1),
_{CH 2 = CH- (CF 2)} 6 -CH = CH 2 ... (1b-1),
_{CF 3 (CF 2) 3 -CH} 2 CHI- (CF 2) 6 -CH = CH 2 ... (1c-1).

A reactor equipped with a stirrer and a dropping funnel (internal volume: 100 mL, made of glass) was charged with 50.0 g of the mixture containing the compound (1c-1) 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. Subsequently, the solvent of the filtrate was distilled off to obtain 10.2 g of compound (1d-1) (colorless transparent liquid). The yield was 62%.
_{CF 3 (CF 2) 3 -CH} 2 CH 2 - (CF 2) 6 -CH = CH 2 ... (1d-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 (1d-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 (1e-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 (1-11a) (white solid, melting point: 58 ° C. (DSC)). The yield was 88%.
HSiCl ₃ (1e-1),
_{CF 3 (CF 2) 3 -CH} 2 CH 2 - (CF 2) 6 -CH 2 CH 2 -SiCl 3 ... (1-11a).

The measurement results of ¹ H-NMR and ¹⁹ F-NMR of the compound (1-11a) 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] -).

[Synthesis Example 2: Compound (3-11a)]
The abbreviations of the compounds used in the synthesis examples indicate the following compounds.
R-225: Dichloropentafluoropropane R ^F6 : —CF (CF ₃ ) OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₃
R-113: CCl ₂ FCClF ₂

In the flask, 25 g of CH ₃ O (CH ₂ CH ₂ O) _j1 CH ₂ CH ₂ OH (commercially available polyoxyethylene glycol monomethyl ether, j1 = 7-8, average value: 7.3), R-225 20 g, 1.2 g of NaF, and 1.6 g of pyridine were added and stirred vigorously while keeping the internal temperature at 10 ° C. or lower, and nitrogen was bubbled. Into the flask, 46.6 g of FC (O) —R ^F6 was added dropwise over 3.0 hours while keeping the internal temperature at 5 ° C. or lower. After completion of the dropwise addition, the mixture was stirred at 50 ° C. for 12 hours and then stirred at room temperature for 24 hours to recover the crude liquid. After the crude liquid was filtered under reduced pressure, the recovered liquid was dried with a vacuum dryer (50 ° C., 5.0 torr) for 12 hours to obtain a crude liquid.

The crude liquid was dissolved in 100 mL of R-225 and washed with 1000 mL of saturated aqueous sodium bicarbonate three times to recover the organic phase. After adding 1.0 g of magnesium sulfate to the organic phase and stirring for 12 hours, the magnesium sulfate is removed by filtration under pressure, and R-225 is distilled off from the recovered liquid with an evaporator. _{CH 3 O (CH 2 CH 2} O) j1 CH 2 CH 2 OC (O) -R F6 (j1 = 7~8, average: 7.3)) to give the 56.1g of.

  In a 3000 mL Hastelloy autoclave, 1560 g of R-113 was placed and stirred, and kept at 25 ° C. At the autoclave gas outlet, a cooler maintained at 20 ° C., a NaF pellet packed bed, and a cooler maintained at −20 ° C. were installed in series. Moreover, the liquid return line for returning the liquid aggregated from the cooler hold | maintained at -20 degreeC to an autoclave was installed. After nitrogen gas was blown into the autoclave for 1.0 hour, fluorine gas diluted to 10% with nitrogen gas (hereinafter referred to as 10% fluorine gas) was blown for 1 hour at a flow rate of 24.8 L / hour.

Next, while blowing 10% fluorine gas into the autoclave at the same flow rate, 27.5 g of CH ₃ O (CH ₂ CH ₂ O) _j1 CH ₂ CH ₂ OC (O) —R ^F6 was changed to 1350 g of R-113. The dissolved solution was poured over 30 hours. Next, 12 mL of R-113 was injected while blowing 10% fluorine gas into the autoclave at the same flow rate. At this time, the internal temperature was changed to 40 ° C. Subsequently, 6 mL of an R-113 solution in which 1% by mass of benzene was dissolved was injected. Further, after blowing fluorine gas for 1.0 hour, nitrogen gas was blown for 1.0 hour. After completion of the reaction, the solvent was distilled off by vacuum drying (60 ° C., 6.0 hours), and the compound (CF ₃ O (CF ₂ CF ₂ O) _j1 CF ₂ CF ₂ OC (O) -R liquid at room temperature was removed. 45.4 g of ^F6 (j1 = 7-8, average value: 7.3) was obtained.

A 300 mL eggplant flask charged with a stirrer chip was thoroughly purged with nitrogen. In an eggplant flask, 40 g of ethanol, 5.6 g of NaF, and R-225 (50 g) were placed. After dropping 43.5 g of CF ₃ O (CF ₂ CF ₂ O) _j1 CF ₂ CF ₂ OC (O) —R ^{F6 into} the eggplant flask, the mixture was vigorously stirred while bubbling at room temperature. The eggplant flask outlet was sealed with nitrogen. After 8 hours, a vacuum pump was installed in the cooling pipe to keep the inside of the system under reduced pressure, and excess ethanol and CH ₃ CH ₂ OC (O) —R ^F6 produced by exchange were distilled off. After 24 hours, the compounds are liquid at room temperature _{(CF 3 O (CF 2 CF} 2 O) j1 CF 2 C (O) OCH 2 CH 3 (j1 = 7~8, average: 7.3)) 26.8 g of Got.

100mL round bottom _{flask, CF 3 O (CF 2 CF} 2 O) j1 CF 2 C (O) OCH 2 CH 3 of _{33.1g, NH 2 CH 2 CH 2} CH 2 Si (OCH 3) 3 of 3 0.7 g was added and stirred at room temperature for 2 hours. After completion of the reaction, unreacted NH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ and by-produced ethanol were distilled off under reduced pressure to obtain 32.3 g of the compound (3-11a) which was liquid at room temperature.

[Example 1]
A mixture containing 40% by mass of the compound (1-11a) obtained in Synthesis Example 1 and 60% by mass of AE3000 was used as a compound (A) solution. 6.49 g of AE3000, 1.87 g of AC2000, 1.62 g of the compound (A) solution, 0.023 g of the compound (2-11a) as the compound (B) were added and stirred for 5 minutes to form a water-repellent film. The liquid composition 1 was obtained as a composition.

[Example 2]
6.55 g of AE3000, 1.87 g of AC2000, 1.53 g of the compound (A) solution prepared in the same manner as in Example 1, and 0.046 g of compound (2-11a) as compound (B) were added and stirred for 5 minutes. Thus, a liquid composition 2 was obtained as a composition for forming a water-repellent film.

[Example 3]
6.79 g of AE3000, 1.88 g of AC2000, 1.19 g of the compound (A) solution prepared in the same manner as in Example 1, and 0.14 g of compound (2-11a) as compound (B) were added and stirred for 5 minutes. And the liquid composition 3 was obtained as a composition for water-repellent film formation.

[Example 4]
7.03 g of AE3000, 1.89 g of AC2000, 0.85 g of the compound (A) solution prepared in the same manner as in Example 1 above, and 0.23 g of compound (2-11a) as compound (B) were added and stirred for 5 minutes. And the liquid composition 4 was obtained as a composition for water-repellent film formation.

[Example 5]
7.27 g of AE3000, 1.89 g of AC2000, 0.51 g of the compound (A) solution prepared in the same manner as in Example 1, and 0.32 g of compound (2-11a) as compound (B) were added and stirred for 5 minutes. And the liquid composition 5 was obtained as a composition for water-repellent film formation.

[Example 6]
7.51 g of AE3000, 1.90 g of AC2000, 0.17 g of the compound (A) solution prepared in the same manner as in Example 1 above, and 0.42 g of compound (2-11a) as compound (B) were added and stirred for 5 minutes. And the liquid composition 6 was obtained as a composition for water-repellent film formation.

[Example 7]
7.42 g of AE3000, 0.94 g of AC2000, 1.53 g of the compound (A) solution prepared in the same manner as in Example 1, and the compound (3-11a) obtained in Synthesis Example 2 as Compound (B) 0.11 g was added and stirred for 5 minutes to obtain a liquid composition 7 as a composition for forming a water-repellent film.

[Example 8]
7.39 g of AE3000, 1.03 g of AC2000, 1.36 g of the compound (A) solution prepared in the same manner as in Example 1, and Compound (3-11a) obtained in Synthesis Example 2 as Compound (B) 0.22 g was added and stirred for 5 minutes to obtain a liquid composition 8 as a composition for forming a water-repellent film.

[Example 9]
7.35 g of AE3000, 1.12 g of AC2000, 1.19 g of the compound (A) solution prepared in the same manner as in Example 1, and Compound (3-11a) obtained in Synthesis Example 2 as Compound (B) 0.33 g was added and stirred for 5 minutes to obtain a liquid composition 9 as a water-repellent film forming composition.

[Example 10]
6.43 g of AE3000, 1.86 g of AC2000 and 1.70 g of the compound (A) solution prepared in the same manner as in Example 1 above were added and stirred for 5 minutes to give the liquid composition 10 as a composition for forming a water-repellent film. Obtained.

[Example 11]
7.63 g of AE3000, 1.91 g of AC2000 and 0.46 g of compound (2-11a) as compound (B) were added and stirred for 5 minutes to obtain liquid composition 11 as a composition for forming a water-repellent film. .
The content and total content (% by mass) of each compound in the liquid compositions 1 to 11 as the water repellent film-forming composition obtained in Examples 1 to 11 above, and the compounds (A) and (B) Table 1 shows the mole percentage (mol%) of each compound relative to the total molar amount.

[Preparation of liquid composition for intermediate layer formation]
9.50 g of butyl acetate (manufactured by Junsei Chemical Co., Ltd.) and 0.5 g of SI-400 were stirred for 5 minutes to obtain a liquid composition for forming an intermediate layer.

[Examples 12 to 21]
As a substrate, a clean soda lime glass substrate (water contact angle 5 °, 300 mm × 300 mm × thickness 3 mm), which is polished and cleaned with cerium oxide, is used, and the intermediate layer is formed on the surface of the glass substrate. 0.5 g of the liquid composition was applied by a squeegee coating method and dried for 1 minute. Thereafter, 0.5 g of any one of the liquid compositions 1 to 9 and 11 obtained in Examples 1 to 9 and 11 was applied by a squeegee coating method, and the thermostatic and humidity chamber was set to 50 ° C. and 60% RH. A water-repellent layer was formed by holding for 48 hours to obtain substrates 1 to 10 with a water-repellent film having a water-repellent film composed of an intermediate layer / water-repellent layer.

[Example 22]
In the same manner as in Examples 12 to 21, the intermediate layer-forming liquid composition was applied to the substrate and dried, and then C ₈ F ₁₇ CH ₂ CH ₂ SiCl ₃ (manufactured by Shinquest Co.) was added at 8% by mass. 0.5 g of butyl acetate / heptane = 1/1 solution (liquid composition 12 for forming a water-repellent film) is applied by a squeegee coating method and treated in the same manner as in Examples 12 to 21 to form a water-repellent layer. Thus, a substrate 11 with a water repellent film having a water repellent film composed of an intermediate layer / water repellent layer was obtained. C ₈ F ₁₇ CH ₂ CH ₂ SiCl ₃ is a fluorine-containing organosilicon compound conventionally used for forming a water-repellent film. The obtained water-repellent layer is known to be excellent in water repellency including dynamic water repellency, abrasion resistance and weather resistance, but produces a compound having a C8 or more perfluoroalkyl group as a decomposition product. Therefore, C ₈ F ₁₇ CH ₂ CH ₂ SiCl ₃ is a compound with a high environmental load.

[Evaluation]
Evaluation of the bases 1 to 11 with water-repellent films obtained in Examples 12 to 22 was performed as follows.
<Water repellency>
The water repellency was evaluated by the values of water contact angle (CA) and water fall angle (SA) measured by the following methods. First, initial values were measured before each of the following tests. Static water repellency is evaluated by water contact angle (CA), and dynamic water repellency is evaluated by water falling angle (SA). If these are combined to make the water repellency and one of them is not good, it is judged that the water repellency is not good overall. If the initial water contact angle (CA) is 105 ° or more and the water falling angle (SA) is 15 ° or less, it can be said that the water repellency sufficiently withstands actual use.

(Water contact angle (CA))
The contact angle of a water droplet having a diameter of 1 mm placed on the surface of the water-repellent film-coated substrate 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 film, and the average value was calculated.
(Water drop angle (SA))
After dropping 50 μL of water droplets onto the surface of the water-repellent film substrate held horizontally, the substrate is gradually tilted, and the angle between the water-repellent film-coated substrate and the horizontal plane when the water droplet starts to fall (the falling angle) ) Was measured using SA-11 (manufactured by Kyowa Interface Science Co., Ltd.). Measurement was performed at five different locations on the surface of the water-repellent film, and the average value was calculated. The smaller the falling angle, the better the dynamic water repellency.

<Abrasion resistance>
After the cloth abrasion resistance test was performed on the surface of the water-repellent film of the substrate with the water-repellent film under the following test conditions, the water contact angle and the water falling angle were measured by the above methods.
(Cloth wear resistance test)
(1) Nell cloth abrasion test A cloth abrasion resistance test was conducted under the following test conditions using the following tester in accordance with JIS L0849.
Testing machine: Reciprocating traverse testing machine (manufactured by KT Corporation)
Test conditions: Cotton cloth (according to JIS L0803), load 1.2 kg, wear frequency 3000 reciprocations (2) Kanakin cloth abrasion test A cloth abrasion resistance test is performed under the following test conditions using the following tester in accordance with JIS L0849. It was.
Testing machine: Reciprocating traverse testing machine (manufactured by KT Corporation)
Test conditions: Canakin cloth, load 1.0 kg, wear frequency 2000 reciprocations [water repellent abrasion resistance evaluation standard]
With regard to the flannel cloth abrasion test and the kanakin cloth abrasion test, if the water contact angle (CA) after the test is 80 ° or more and the water falling angle (SA) is 22 ° or less, the water repellency is sufficient for practical use. It can be said that it has sex.

<Weather resistance>
(Outdoor exposure test)
An outdoor exposure test was conducted in accordance with JIS Z2381. That is, the substrate with a water-repellent film was placed outdoors so that the surface of the water-repellent film faced south at an angle of 30 degrees with respect to the horizontal, and 150 days after the start of the test, It was measured. In addition, about the base | substrate with a water-repellent film obtained in Examples 18-20, it was evaluation 100 days after a test start.
(SWOM test)
A SWOM test was conducted according to JIS D0205. That is, after irradiating the water-repellent film surface of the substrate with the water-repellent film with ultraviolet rays (255 ± 10 W / cm ² ) for 2500 hours, the water contact angle and the water falling angle were measured by the above methods. In addition, about the base | substrate with a water-repellent film obtained in Examples 18-20, it was evaluation after 1200 hours irradiation from a test start.

(Water-repellent weather resistance evaluation criteria)
For the SWOM test and outdoor exposure test, if the water contact angle (CA) after the test is 80 ° or more and the water falling angle (SA) is 22 ° or less, the water repellent durability is sufficient for actual use. I can say that.

<Chemical resistance>
(Alkali resistance test)
The substrate with a water-repellent film was immersed in a 0.1 N NaOH aqueous solution (pH: 13) for 3 hours, then washed with water and air-dried, and the water contact angle was measured by the above method.
(Salt spray test (SST))
A salt spray test was conducted in accordance with JIS H8502. That is, the surface of the water-repellent film of the substrate with a water-repellent film was exposed to a salt water atmosphere in a salt spray tester (manufactured by Suga Test Instruments Co., Ltd.) for 300 hours, and then the water contact angle was measured by the above method.
[Water-repellent chemical resistance evaluation criteria]
Regarding the alkali resistance test and the salt spray test, if the water contact angle (CA) after the test is 80 ° or more, it can be said that the water-repellent chemical resistance is sufficient for actual use.
The above evaluation results are shown in Table 2.

From the results shown in Table 2, the water-repellent film-coated substrates 1 to 9 of Examples obtained in Examples 12 to 20 are all excellent in water repellency even after the initial and wear resistance tests and after the weather resistance test. Recognize. Furthermore, about the water-repellent film-coated substrates 1 to 4 and 7 to 9 of Examples 12 to 15 and Examples 18 to 20, the liquid compositions 1 to 4 and 7 to 7 for forming the water-repellent film used were used. Since the content ratio of the compound (A) in 9 is 40 mol% or more of the total molar amount of the compound (A) and the compound (B), the chemical resistance is also excellent.
On the other hand, the substrate 10 with a water-repellent film of Comparative Example obtained in Example 21 has sufficient initial water repellency, particularly dynamic water repellency, but has insufficient wear resistance, weather resistance, and chemical resistance. I understand.
The substrate 11 with a water-repellent film of Reference Example obtained in Example 22 is excellent in water repellency after Examples 12 to 20 and the initial water repellency and abrasion resistance test, and after the weather resistance test. It turns out that sex is not enough.
If the composition for forming a water-repellent film of the present invention is used, it is possible to impart a water repellency (particularly dynamic water repellency) equivalent to that of a conventional composition for forming a water-repellent film to a substrate. Although the wear resistance and weather resistance are sufficient, it can be said that the load on the environment is low.

  The water repellent layer formed on the substrate using the water repellent film forming composition of the present invention has sufficient water repellency (particularly dynamic water repellency), abrasion resistance and weather resistance, and has a low environmental load. . The substrate with a water-repellent film of the present invention has the water-repellent layer as the outermost layer of the water-repellent film, and is a body, window glass (front glass, side glass, rear glass) in transportation equipment such as trains, automobiles, ships and aircraft. ), Suitable for use as articles such as mirrors and bumpers

Claims (14)

The composition for water-repellent film formation containing the following compound (A) and the following compound (B) and / or containing the partial hydrolysis cocondensate of the following compound (A) and the following compound (B).
Compound (A): a fluorine-containing organosilicon compound selected from a compound represented by the following general formula (1) and a partial hydrolysis-condensation product thereof.
R ^F1 —Y ¹ —SiR ¹ _(3-n1) X ¹ _n1 (1)
(However, in Formula (1), R ^F1 is a linear perfluoroalkyl group having carbon number p,
Y ¹ is a polyfluoroalkylene group having a carbon number q, both ends of —CH ₂ —, one or more perfluoroalkylene groups, and no etheric oxygen atom between carbon-carbon atoms,
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 hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms,
X ¹ is a hydrolyzable group;
n1 is an integer of 1 to 3,
When a plurality of R ¹ and X ¹ are present, these may be different from each other or the same. )
Compound (B): A fluorine-containing organosilicon compound selected from the following compound (b1), the following compound (b2), and partial hydrolysis cocondensates thereof.
Compound (b1): a fluorine-containing organosilicon compound selected from a compound represented by the following general formula (2) and a partial hydrolysis condensate thereof.
(R ^F2 -Y ² ) _a -SiR ² _(4-a-n2) X ² _n2 (2)
(However, in Formula (2), R ^<F2> is a C1-C6 perfluoroalkyl group,
Y ² is a divalent organic group not containing a perfluoroalkylene group,
a is 1 or 2,
R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms,
X ² is a hydrolyzable group,
n2 is an integer of 1 to 3, a + n2 is 3 or 4,
When a plurality of R ^F2 —Y ² and X ² are present, these may be different from each other or the same. )
Compound (b2): a fluorine-containing organosilicon compound selected from a compound represented by the following general formula (3) and a partial hydrolysis-condensation product thereof.
R ^F3 —O— (R ^F4 —O) _m —R ^F5 —Y ³ —SiR ³ _(3-n3) X ³ _n3 (3)
(However, in Formula (3), R ^<F3 > is a C1-C6 perfluoroalkyl group,
R ^F4 and R ^F5 are perfluoroalkylene groups having 1 to 3 carbon atoms,
Y ³ is an alkylene group or an alkylene group which may have one selected from an amide bond, a urethane bond and an etheric oxygen atom between the terminal or carbon-carbon atom bonded to R ^F5 ,
m is an integer from 1 to 50;
R ³ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms,
X ³ is a hydrolyzable group,
n3 is an integer of 1 to 3,
When a plurality of R ³ and X ³ are present, these may be different from each other or the same. )   Ratio of compound (A) to total molar amount of compound (A) and compound (B) represented by [compound (A)] / [compound (A) + compound (B)] × 100 in the composition ( However, when the composition contains a partially hydrolyzed cocondensate, for the hydrolyzed cocondensate product, the total molar amount of the compound (A) and the compound (B) before the hydrolyzed cocondensation reaction is used. The composition for water-repellent film formation according to claim 1, wherein the calculated ratio is 10 to 95 mol%.   The composition for water-repellent film formation according to claim 1 or 2, wherein the ratio of the compound (A) to the total molar amount of the compound (A) and the compound (B) in the composition is 40 to 95 mol%. . The composition for water-repellent film formation according to any one of claims 1 to 3, wherein the compound represented by the general formula (1) is a compound represented by the following formula (1-1).
R ^F1 —CH ₂ CH ₂ — (CF ₂ ) _r —CH ₂ CH ₂ —SiR ¹ _(3-n1) X ¹ _n1 (1-1)
(In the formula (1-1), R ^F1 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, and p + r + 4 is 10) And R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, X ¹ is a hydrolyzable group, n1 is an integer of 1 to 3, and R ¹ And when there are a plurality of X ^{1 s} , these may be different or the same.) The compound represented by the general formula (2) is selected from compounds represented by any one of the following formulas (2-1) to (2-6). A composition for forming a water film.
_{F (CF 2) e - (} CH 2) f -SiX 2 3 ... (2-1)
_{F (CF 2) e - (} CH 2) f -SiR 2 X 2 2 ... (2-2)
_{F (CF 2) e -CONH (} CH 2) g -SiX 2 3 ... (2-3)
_{F (CF 2) e -CONH (} CH 2) g -SiR 2 X 2 2 ... (2-4)
_{F (CF 2) e -CONH (} CH 2) h NH (CH 2) 5-h -SiX 2 3 ... (2-5)
_{F (CF 2) e -CONH (} CH 2) h NH (CH 2) 5-h -SiR 2 X 2 2 ... (2-6)
(In the formulas (2-1) to (2-6), e is an integer of 1 to 6, f is an integer of 1 to 6, g is an integer of 1 to 5, and h is 1. -4 is an integer, and X ² is a hydrolyzable group which may be the same or different from each other. The compound represented by the general formula (3) is selected from the compounds represented by any one of the following formulas (3-1) to (3-4). A composition for forming a water film.
_{F (CF 2) i -O- (} CF 2 CF 2 O) j (CF 2) l -CONH (CH 2) k1 SiX 3 3 ... (3-1)
_{F (CF 2) i -O- (} CF 2 CF 2 O) j (CF 2) l -CH 2 OCONH (CH 2) k1 SiX 3 3 ... (3-2)
_{F (CF 2) i -O- (} CF 2 CF 2 O) j (CF 2) l - (CH 2) k2 O (CH 2) k1 SiX 3 3 ... (3-3)
_{F (CF 2) i -O- (} CF 2 CF 2 O) j (CF 2) l - (CH 2) k1 SiX 3 3 ... (3-4)
(In the formulas (3-1) to (3-4), i is an integer of 1 to 6, j is an integer of 1 to 20, l is an integer of 1 to 3, and k1 is 1. an to 4 integer, k2 is an integer of 0 to 3, X ³ is a good hydrolyzable groups be the same or different from one another.) The composition for water-repellent film formation according to any one of claims 1 to 6, wherein the compound represented by the general formula (1) is a compound represented by the following formula (1-11).
CF ₃ (CF ₂ ) ₃ —CH ₂ CH ₂ — (CF ₂ ) ₆ —CH ₂ CH ₂ —SiX ¹ ₃ (1-11)
(However, in Formula (1-11), X ¹ is a hydrolyzable group which may be the same or different from each other.) The composition for water-repellent film formation according to any one of claims 1 to 7, wherein the compound represented by the general formula (2) is a compound represented by the following formula (2-11).
F (CF ₂ ) ₆ (CH ₂ ) ₂ SiX ² ₃ (2-11)
(However, in Formula (2-11), X ² is a hydrolyzable group which may be the same or different from each other.) The composition for water-repellent film formation according to any one of claims 1 to 8, wherein the compound represented by the general formula (3) is a compound represented by the following formula (3-11).
_{CF 3 -O- (CF 2 CF 2} O) j1 -CF 2 -CONHC 3 H 6 SiX 3 3 ... (3-11)
(Wherein (3-11), j1 is an integer of 1 to 9, ^{X 3} is a good hydrolyzable groups be the same or different from one another.)   A substrate with a water-repellent film having a substrate and a water-repellent film on at least a part of the surface of the substrate, wherein the water-repellent film is composed of one or more layers, and the outermost layer has any one of claims 1 to 9 A substrate with a water-repellent film comprising a water-repellent film formed using the composition for forming a water-repellent film according to claim 1. The substrate with water-repellent film according to claim 10, wherein the substrate with water-repellent film further includes an intermediate layer mainly composed of silica between the substrate and the water-repellent film. Using the intermediate layer-forming composition, wherein the intermediate layer contains a compound represented by the following general formula (4), a partially hydrolyzed condensate thereof, and a compound (C) that is at least one selected from bellhydropolysilazane. The substrate with a water-repellent film according to claim 11, which is a formed layer.
Si (X ⁴ ) ₄ (4)
(However, in formula (4), X ⁴ each independently represents a halogen atom, an alkoxy group or an isocyanate group.)   The substrate with a water-repellent film according to claim 10, wherein the substrate is glass.   An article for transportation equipment comprising the substrate with a water-repellent film according to any one of claims 10 to 13.