JP2014156061A - Substrate having base layer and water-repellent film and article transportation device including the substrate having base layer and water-repellent film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate which has a base layer having a water-repellent film having excellent chemical resistance and initial water slipping property while maintaining high durability and a water-repellent film and to provide an article for transportation device including the substrate.SOLUTION: There are provided: a base layer formed using a composition for forming a base layer containing (A) a compound represented by the formula (1) and (B) a compound represented by the formula (2); a substrate having a water-repellent film formed by a composition for forming a water-repellent film containing at least one selected from (C) a silane compound having a polyfluoroalkyl group and its partially-hydrolyzed condensate in at least one part on the base layer; and an article for transportation device including the substrate.

Description

  The present invention relates to a substrate having a base layer and a water-repellent film, and an article for transportation equipment including the substrate having the base layer and the water-repellent film.

  Conventionally, in various technical fields, it has been strongly required to impart water repellency to the surface of a substrate. As a method for imparting water repellency to the surface of a substrate, it is common to form a film having water repellency on the surface of the substrate, and technical development relating to a composition for forming a film having water repellency is performed. Has been made. In particular, when the substrate is a substrate contained in an article for transportation equipment such as automobile glass, it is required to impart durability properties such as salt spray resistance and abrasion resistance to the water-repellent coating. Yes. As a substrate having such properties, Patent Document 1 discloses that an undercoat layer formed using a primer of a bissilane compound and a hydrophobic film containing at least one fluorinated alkylsilane are formed on the undercoat layer. A substrate having a hydrophobic coating obtained by forming is disclosed.

Special table 2009-502470 gazette

  The hydrophobic coating of the base material disclosed in Patent Document 1 is excellent in durability, particularly salt spray resistance, but improved in terms of chemical resistance (for example, alkali resistance) and initial water slidability. It was found by the present inventors' research that there is room for this. The present invention has been made from the above viewpoint, and has a water repellent film excellent in chemical resistance and initial water slidability while maintaining high durability, and a substrate having a base layer and a water repellent film, and An object of the present invention is to provide an article for transport equipment including the substrate.

The present invention has the following configuration.
[1] (A) Formula (1): A ¹ ₃ Si— (CHR ¹ ) _a —SiA ¹ ₃
(Where
A ¹ is each independently a hydrolyzable group or a hydroxyl group,
R ¹ is H or CH ₃
a is an integer of 1 to 9, wherein each (CHR ¹ ) unit may be the same or different), and (B) Formula (2): SiX ¹ ₄
(In the formula, each X ¹ is independently a halogen atom, an alkoxy group or an isocyanato group)
(C) a silane compound having a polyfluoroalkyl group at least partially on the underlayer formed using the underlayer-forming composition containing the compound represented by the formula: A substrate having a water-repellent film formed using a composition for forming a water-repellent film containing at least one selected from the above.

[2] (C) A silane compound having a polyfluoroalkyl group is
(C1) a polyfluoroalkylsilane compound,
(C2) Polyfluoropolyether silane compound, and (c3) Formula (3): R ^f1- (SiR ² ₂ O) _b -SiR ² ₂ -Y ¹ -Si (R ³ ) _c (X ² ) _3-c
(Where
R ^f1 is a linear polyfluoroalkyl group having 1 to 8 carbon atoms,
Y ¹ is an alkylene group having 2 to 4 carbon atoms,
R ² is independently an alkyl group having 1 to 6 carbon atoms, wherein each SiR ² ₂ O unit may be the same or different,
Each R ³ is independently a monovalent hydrocarbon group;
Each X ² is independently a hydrolyzable group;
b is an integer of 5 to 150;
c is an integer of 0 to 2)
The substrate according to [1], which is one or more silane compounds selected from the group consisting of compounds represented by:

[3] (c1) The polyfluoroalkylsilane compound is
Equation ^{(4): R f2 -Q 1} -SiR 4 d A 2 3-d
(Where
R ^f2 is a group: C _e F _{2e + 1} (where e is an integer from 1 to 8);
Q ¹ is a divalent hydrocarbon group having 1 to 6 carbon atoms,
Each R ⁴ is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms;
A ² is each independently a hydroxyl group or a hydrolyzable group,
d is an integer of 0 to 2),
(C2) a polyfluoropolyether silane compound is
Equation ^{(5): Z 1 -R f3} -Z 2
(Where
R ^f3 _{is, -O- (C f F 2f O} ) g - ( where, f is, an integer from 1 to 6, g is 1 or more is an integer, each _-C f _F 2f O-units May be the same or different)
Z ¹ and Z ² are each independently R ^f4 , or a group: —Q ² — {CH ₂ CH (SiR ⁵ _h A ³ _3-h )} _j —H, one of which is a group: -Q ² - a _{^{{CH 2 CH (SiR 5 h}} a 3 3-h)} j -H ( wherein,
R ^f4 is a group: C _k F _{2k + 1} (where k is an integer from 1 to 6);
Q ² is — (CH ₂ ) _m — (where m is an integer of 2 to 12), or one selected from an ester bond, an ether bond, an amide bond, a urethane bond, and a phenylene group. containing more than - _{(CH 2) m} - and is, -CH ₂ - some units or the whole, -CF ₂ - units and / or -CF (CF ₃₎ - may be replaced by units,
R ⁵ is each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and the hydrocarbon group may contain a substituent,
A ³ is each independently a hydroxyl group or a hydrolyzable group,
h is an integer of 0 to 2,
j is an integer of 1 to 20, and the substrate according to [2].
[4] The substrate according to [3], wherein the compound of the formula (4) is a compound having a number average molecular weight of 2600 or more or a partial hydrolysis-condensation product thereof.

[5] In Formula (1), A ¹ is an alkoxy group or an isocyanato group, R ¹ is H, and a is an integer of 1 to 3, [1] to [4] Substrate.
[6] Any of [1] to [5], wherein the mass ratio of the compound of formula (1) to the compound of formula (2) is 0.1: 0.9 to 0.9: 0.1 A substrate as described.
[7] The substrate according to any one of [1] to [6], wherein the substrate includes glass.
[8] An article for transportation equipment comprising the substrate according to any one of [1] to [7].

  According to the present invention, a substrate having a base layer and a water repellent film excellent in chemical resistance and initial water slidability while maintaining high durability and salt spray resistance, and a substrate having a base layer and a water repellent film It is possible to provide articles for transportation equipment including

Hereinafter, embodiments of the present invention will be described. In addition, this invention is limited to the following description and is not interpreted.
In the present specification, a compound or group represented by the formula is also expressed as a compound or group with the number of the formula, for example, a compound represented by the formula (1) is also expressed as a compound (1). In the present specification, the “part derived from the compound (1)” means the compound (1) in the partially hydrolyzed condensate of the compound (1) and the partially hydrolyzed cocondensate of the compound (1) and other hydrolyzable silane compounds. ) And the unreacted compound (1). Further, in the present specification, the total solid content means a component that finally becomes a constituent component of the underlayer or the water-repellent film among the components contained in the underlayer or the water-repellent film-forming composition, such as an organic solvent. All the components other than the volatile components that volatilize by heating or the like in the layer formation process are shown.

[Substrate having base layer and water-repellent film]
A substrate having an underlayer and a water-repellent film according to the present invention comprises an underlayer formed using a substrate and an underlayer-forming composition containing (A) compound (1) and (B) compound (2), and It is formed by using a composition for forming a water repellent film comprising at least one selected from (C) a silane compound having a polyfluoroalkyl group and a partial hydrolysis condensate thereof on at least a part of the underlayer. It has a water repellent film. The base | substrate which has a base layer and a water repellent film of this invention has a base layer and a water repellent layer in an order from the base | substrate side. In the present invention, an intermediate layer may be further provided between the underlayer and the water-repellent film layer, but a substrate having only the underlayer and the water-repellent film is preferable.
Hereinafter, constituent elements of a substrate having an underlayer and a water-repellent film according to the present invention will be described.

<Substrate>
The substrate in the substrate having the underlayer and the water-repellent film of the present invention is not particularly limited as long as it is made of a material that is generally required to impart water repellency. Examples of such a substrate include metal, plastic, glass, ceramic, or a combination thereof (composite material, laminated material, etc.). Of these, glass is preferable.

Examples of the glass include soda lime glass, borosilicate glass, alkali-free glass, and quartz glass, and soda lime glass is preferable. When the substrate is soda lime glass, it is preferable from the viewpoint of durability to further provide a film for preventing elution of Na ⁺ ions. When the substrate is glass manufactured by the float process, it is preferable from the viewpoint of durability to provide an underlayer and a water-repellent film on a surface with a small amount of surface tin.

  The shape of the substrate is not particularly limited, and may be a plate shape or a shape having a curvature on the entire surface or part thereof. The thickness of the substrate can be appropriately selected depending on the use of the substrate having a water-repellent film, and is preferably 1 to 10 mm.

  In the base having the base layer and the water repellent film, the base layer and the water repellent film are formed on at least a part of the surface of the base. The region where the base layer and the water-repellent film are formed on the substrate surface is not particularly limited and can be appropriately selected depending on the application. When the substrate is plate-shaped, the base layer and the water repellent film are usually formed on the entire main surface of either or both of the main surfaces of the substrate.

<Underlayer>
The underlayer of the present invention will be described. In this invention, a base layer is formed using the composition for base layer formation containing a compound (1) and a compound (2). The underlayer of the present invention is hydrophobic due to the action of the-(CHR ¹ ) _a -group derived from the compound (1) and can maintain water repellency, and the-(CHR ¹ ) _a -group is Since it is difficult to undergo hydrolysis, chemical resistance and salt spray resistance can be improved. On the other hand, when the compound (1) is used alone, the Si—OH group derived from the compound (1) easily jumps out to the film surface, and the jumped-out Si—OH group interacts with water and interferes with the water. By using the compound (2) in combination, it is possible to suppress the Si—OH group derived from the compound (1) from jumping to the film surface as compared with the case where the compound (1) is used alone, and durability, chemical resistance and The sliding property can be improved while maintaining the salt spray resistance.

<(A) Compound (1)>
The compound (1) will be described. The compound (1) is represented by the above formula (1).

A ¹ in the above formula is a hydrolyzable group or a hydroxyl group. Here, the hydrolyzable group is a group capable of forming Si—OH by hydrolysis of the Si—A ¹ group. For example, an alkoxy group, an acyloxy group, a ketoxime group, an alkenyloxy group, an amino group, an aminoxy Group, amide group, isocyanato group, halogen atom and the like. A ¹ represents an alkoxy group (for example, an alkoxy group having 1 to 4 carbon atoms) or a halogen atom (for example, F, Cl, Br) from the viewpoint of the balance between the stability of the compound (1) and the ease of hydrolysis. And I) and an isocyanato group are preferred, a methoxy group, an ethoxy group, a chlorine atom and an isocyanato group are more preferred, and a methoxy group and an isocyanato group are particularly preferred. When two or more are present, A ¹ may be the same or different, but are preferably the same group from the viewpoint of availability.

  A in the above formula is an integer of 1 to 9, and an integer of 1 to 3 is preferable. When a is in the above range, the underlayer has an appropriate hydrophobicity, and the water repellency and water slidability of the water repellent film can be improved. In addition, if m exceeds 9, there is a problem in that water repellency and water slidability deteriorate.

As the compound (1), specifically, (CH ₃ O) ₃ SiCH ₂ CH ₂ Si (OCH ₃ ) ₃ , (OCN) ₃ SiCH ₂ CH ₂ Si (NCO) ₃ , Cl ₃ SiCH ₂ CH ₂ SiCl ₃ , (CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) _{3 and the} like, preferably (CH ₃ O) ₃ SiCH ₂ CH ₂ Si (OCH ₃ ) ₃ and (OCN) ₃ SiCH ₂ CH ₂ Si (NCO) ₃ .

  Compound (1) may be used alone or in combination of two or more. Compound (1) can be produced by a general production method, and is commercially available.

<(B) Compound (2)>
The compound (2) will be described. The compound (2) is represented by the above formula (2).

X ¹ in the above formula is preferably a chlorine atom, an alkoxy group having 1 to 4 carbon atoms or an isocyanato group, and the four X ¹ are preferably the same. Examples of the compound (2) include Si (NCO) ₄ , Si (OCH ₃ ) ₄ , and Si (OC ₂ H ₅ ) ₄ , and Si (NCO) ₄ and Si (OCH ₃ ) ₄ are preferable.

Compound (2) may be used alone or in combination of two or more. Compound (1) can be produced by a general production method, and is commercially available. Incidentally, ^{A 1} of ^{X 1} and the compound of the compound (2) (1) is preferably the same. However, when both X ¹ of compound (2) and A ^{1 of} (1) are alkoxy groups, there is no problem even if the types of the alkoxy groups are different.

  The content ratio of the compound (1) -derived component and the compound (2) -derived component in the composition for forming an underlayer is 0 as a mass ratio represented by [compound (1) -derived component: compound (2) -derived component]. 0.1: 0.9 to 0.9: 0.1 is preferable, and 0.1: 0.9 to 0.6: 0.4 is more preferable. When the composition for forming the underlayer contains the compound (1) -derived component and the compound (2) -derived component in such a mass ratio, while maintaining durability, chemical resistance and salt spray resistance, It is possible to improve water and initial sliding properties.

  The composition for forming the underlayer can contain a coloring material such as a catalyst, an organic solvent, metal oxide ultrafine particles, a dye or a pigment, and an antifouling material as long as the effects of the present invention are not impaired.

  The composition for forming the underlayer can contain an organic solvent for the purpose of economy, workability, and ease of controlling the thickness of the resulting underlayer. Examples of the organic solvent include alcohols, ethers, ketones, aromatic hydrocarbons, paraffin hydrocarbons, and esters (for example, acetate esters), and alcohols and esters are preferable. The organic solvent may be used alone or in combination of two or more. The proportion of the organic solvent in the composition for forming the underlayer is preferably 400 to 100,000 parts by mass, and preferably 700 to 100 parts by mass with respect to 100 parts by mass of the total mass of the compound (1) -derived component and the compound (2) -derived component. 3,500 parts by mass is more preferred.

  The underlayer forming composition can contain a catalyst such as an acid catalyst and / or an alkali catalyst in order to promote the hydrolysis condensation reaction of the component (A) and / or the component (B). Examples of the acid catalyst include hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, and p-toluenesulfonic acid. Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, and ammonia. The amount of the catalyst is preferably from 0.1 to 10 mol parts, more preferably from 0.2 to 5 mol parts, based on 100 mol parts of the total mol number of the hydrolyzable groups of the compound (1) and the compound (2). .

  The composition for forming the underlayer may contain water for hydrolytic condensation reaction. When contained, the content of water is preferably 1 to 30 mole parts relative to 100 mole parts of the total number of moles of hydrolyzable groups of compound (1) and compound (2).

  As a method for forming the undercoat layer, a known method for a fluorine-containing organosilane compound-based surface treatment agent can be used. For example, the composition is brushed, flow-coated, spin-coated, or dip-coated on the surface of a substrate. , Squeegee coating, spray coating, hand coating, drying in an air or nitrogen atmosphere as necessary, and curing. The conditions for curing can be appropriately selected, and examples include conditions of a temperature of 20 to 50 ° C. and a humidity of 50 to 95% RH. The time for hardening can be selected suitably, for example, 1 minute-72 hours are mentioned. The thickness of the underlayer is not particularly limited, but is preferably 50 nm or less, and can be, for example, 2 to 20 nm.

<Water repellent film>
The water-repellent film of the present invention will be described. In the present invention, the water repellent film contains at least one selected from (C) a silane compound having a polyfluoroalkyl group and a partially hydrolyzed condensate thereof at least partially on the underlayer of the present invention. It forms using the composition for film formation.

<(C) Silane compound having a polyfluoroalkyl group and its hydrolysis condensate>
The component (C) will be described. The component (C) is a component that imparts a water repellent effect to the water repellent film by the action of the polyfluoroalkyl group. The component (C) preferably has at least one hydrolyzable group in order to improve the adhesion of the water-repellent film. Here, the hydrolyzable group is as exemplified in the compound (1) including preferable ones.

In the component (C), the polyfluoroalkyl group is linear or branched, non-interrupted, or an ester bond (—C (═O) —O—, —O—C (═O) -), Ether bond (-O-), amide bond (-C (= O) NH-, -NH-C (= O)-), urethane bond (-NH-C (= O) -O-,- O—C (═O) —NH—), a phenylene group, and a formula: — (Si (R ² ) ₂ O) _b — (wherein R ² and b are defined by the following formula (3c): An alkyl group interrupted by one or more selected from the group consisting of a divalent organopolysiloxane structure represented by formula (2), wherein two or more hydrogen atoms of the alkyl group are substituted with fluorine atoms Refers to the group. The ratio of fluorine atoms in the polyfluoroalkyl group is (number of fluorine atoms in the polyfluoroalkyl group) / (number of hydrogen atoms in the alkyl group having the same number of carbon atoms corresponding to the polyfluoroalkyl group) × 100 (%) Is preferably 60% or more.

  Although it will not specifically limit if carbon number of a polyfluoroalkyl group is obtained in order to obtain desired water repellency, 1-200 are preferable and 6-100 are more preferable.

A polyfluoroalkyl group is a perfluoroalkyl-alkylene in which the perfluoroalkyl group is directly bonded as a linking group, or an amide bond or an alkylene group via the formula:-(Si (R ² ) ₂ O) _b- A group is preferred. That is, the carbon atom of the alkylene group (—CH ₂ —) is preferably bonded to the silicon atom to which at least one hydrolyzable group is bonded. Here, the alkylene group is preferably a linear or branched alkylene group having 1 to 6 carbon atoms, and more preferably a linear alkylene group having 1 to 6 carbon atoms.

  The perfluoroalkyl group is preferably a linear or branched perfluoroalkyl group having 1 to 100 carbon atoms, which may be interrupted by an ether bond.

Accordingly, as the polyfluoroalkyl group, a perfluoroalkyl-alkylene group, a perfluoroalkyl-alkylene- (Si (R ² ) ₂ O) _b -alkylene group, or a perfluoroalkyl-polyfluoropolyether-amide bond-alkylene group is preferable.

  Examples of such a compound having a polyfluoroalkyl group include (c1) a polyfluoroalkylsilane compound, (c2) a polyfluoropolyethersilane compound, and (c3) a compound represented by formula (3).

<(C1) Polyfluoroalkylsilane Compound>
In the present invention, the polyfluoroalkylsilane compound is a silane compound in which a polyfluoroalkyl group is bonded to a silicon atom, which is linear or branched and is uninterrupted or interrupted by an amide group or an ether group. is there. The compound (c1) does not include a silane compound in which a polyfluoroalkyl group interrupted by two or more ether groups is bonded to a silicon atom. Preferably, it is a compound in which an alkylene group which is non-interrupted or interrupted by an amide group or an ether group is bonded to a silicon atom. As such a polyfluoroalkylsilane compound, a compound represented by the above formula (4) is preferable.

In the formula (4), R ^f2 may be linear or branched. Among these, from the viewpoint of durability, a linear group: CF ₃ (CF ₂ ) _e-1 (where e is as described above) is preferable, and CF ₃ (CF ₂ ) ₃ — is more preferable. _{, CF 3 (CF 2) 4} -, CF 3 (CF 2) 5 -, CF 3 (CF 2) 6 -, CF 3 (CF 2) 7 - , and particularly _CF 3 _{(CF 2) 5} - and CF ₃ (CF ₂ ) ₇ -is preferred.
In Formula (4), Q ¹ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and examples of the hydrocarbon group include a linear or branched alkylene group, an alkylene group having an amide group, Examples include an alkylene group having an ether group. Among these, from the viewpoint of weather resistance, a linear alkylene group having 1 to 6 carbon atoms: — (CH ₂ ) _t — (where t is an integer of 1 to 6) is preferable, and more preferably − (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, and — (CH ₂ ) ₂ — is particularly preferable.

In the formula (4), R ⁴ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and examples of the hydrocarbon group include a linear or branched alkyl group. Among these, from the viewpoint of weather resistance, a linear or branched alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable. When there are a plurality of R ^{4 s} , they may be the same or different, but are preferably the same from the viewpoint of availability.

In Formula (4), A ² is a hydroxyl group or a hydrolyzable group. A ² includes the groups exemplified as A ¹ including preferred ones.

Examples of the compound (4) include the following. In the formula, examples and preferred embodiments of e, t, A ² and R ⁴ are as described above.
Formula _{(4-1): CF 3 (CF} 2) e-1 - (CH 2) t -SiA 2 3
Formula _{(4-2): CF 3 (CF} 2) e-1 - (CH 2) t -SiR 4 A 2 2
As compound (4), compound (4-1) wherein e is 6 or 8 is more preferred.

  Compound (4) may be used alone or in combination of two or more. Compound (4) can be produced by a general production method, and is commercially available.

<(C2) Polyfluoropolyether silane compound>
The polyfluoropolyether silane compound is a compound having a group in which a polyfluoroalkyl group is interrupted by two or more ether bonds. The component (c2) is preferably a compound having a hydroxyl group and / or a hydrolyzable group bonded to silicon at one or both ends. In addition, in the component (c2), a perfluoroether group is bonded to a linear or branched alkylene group via an amide bond or a direct bond as a linking group, and a carbon atom of the alkylene group is bonded to a silicon atom. It is preferable. The component (c2) is preferable in that it has excellent chemical resistance.

  As such a component (c2), a compound represented by the above formula (5) is preferable.

R ^f3 in the above formula (5) is —O— (C _f F _2f O) _g — (where, f is an integer of 1 to 6, g is an integer of 1 or more, and each —C _f F _2f O— units may be the same or different. Here, the —C _f F _2f O— unit may be linear or branched. For example, —CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O—, —CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O—, —CF ₂ CF ₂ CF ₂ CF ₂ O—, —CF ₂ CF ₂ CF ₂ O—, —CF (CF ₃ ) CF ₂ O—, —CF ₂ CF ₂ O -, - _CF 2 O- and the like. g can be appropriately adjusted according to the desired number average molecular weight.

R ^f3 may be a combination of a plurality of units. In this case, each unit may be present in a block or randomly. For _{example, -CF 2 CF 2 CF 2 CF} 2 CF 2 CF 2 O in terms of improving the light resistance _{-, - CF 2 CF 2 CF} 2 CF 2 CF 2 O -, - CF 2 CF 2 CF 2 CF 2 O- preferably contained is, more preferably from the viewpoint of ease of synthesis, which is a unit that combines the _{-CF 2 CF 2 CF 2 CF 2} O- and _-CF 2 _CF 2 O- and _-CF 2 _CF 2 _{O-CF 2} CF ₂ CF ₂ CF ₂ is O-.

Specifically, R ^f3 represents —O— (CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) _{g 1} — (CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) _{g 2} — (CF ₂ CF ₂ CF _{2 CF 2 O) g3 - (} CF 2 CF 2 CF 2 O) g4 - (CF (CF 3) CF 2 O) g5 - (CF 2 CF 2 O) g6 - (CF 2 O) g7 - ( wherein, g1, g2, g3, g4, g5, g6 and g7 are each independently an integer of 0 or more, but the total of g1, g2, g3, g4, g5, g6 and g7 is 1 or more, The repeating unit may be present in a block or may be present at random. Preferably, the group is —O— (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O). _g8 (where, g8 is an integer of 1 or more) is It is below.

Z ¹ and Z ² in the above formula are each independently R ^f4 or a group: —Q ² — {CH ₂ CH (SiR ⁵ _h A ³ _3-h )} _j —H. the ^group: -Q ₂ - is a _{^{{CH 2 CH (SiR 5 h}} a 3 3-h)} j -H. Preferably, Z ¹ is R ^f4 and Z ² is a group: —Q ² — {CH ₂ CH (SiR ⁵ _h A ³ _3-h )} _j —H, but both are groups: —Q ² — it may be a _{^{{CH 2 CH (SiR 5 h}} a 3 3-h)} j -H.

R ^f4 is a group: C _k F _{2k + 1} (where k is an integer of 1 to 6), and may be linear or branched. Among these, from the viewpoint of ease of synthesis, linear _{groups: CF 3 (CF 2) k} -1 ( where, k is the same as described above), more preferably _CF 3 -, _CF 3 ( CF ₂ ) —, with CF ₃ CF ₂ — being particularly preferred.

^Group: - in _{^{{CH 2 CH (SiR 5 h}} A 3 3-h)} j -H, Q 2 _{is, - -Q 2 (CH 2)} s- ( where, s is 0 to 12 of an integer Or — (CH ₂ ) _m — containing at least one selected from an ester bond, an ether bond, an amide bond and a phenylene group, and a part or all of the —CH ₂ — units are — It may be replaced by CF ₂ -units and / or -CFCF ₃ -units. Q ² preferably contains —C (═O) NH—CH ₂ — or —O—CH ₂ —, and more preferably —CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ —C (= O) NH—CH ₂ — or —CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CH ₂ —O—CH ₂ —.

R ⁵ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and the hydrocarbon group may contain a substituent. Examples of the hydrocarbon group include a linear or branched alkyl group. Among these, from the viewpoint of availability, a linear or branched alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable. Examples of the substituent include a halogen atom (for example, a chlorine atom). When there are a plurality of R ^{5 s} , they may be the same or different, but are preferably the same from the viewpoint of availability.

A ³ is a hydroxyl group or a hydrolyzable group, and examples of hydrolyzable groups in A ¹ and preferred embodiments are applied as the hydrolyzable group. When there are a plurality of A ^{3 s} , they may be the same or different, but are preferably the same from the viewpoint of availability.

  h is an integer of 0 to 2, and is preferably 0 or 1 and more preferably 0 from the viewpoint of adhesion and durability.

  J in the above formula is an integer of 1-20, preferably an integer of 1-5, for example 1.

  The compound (5) preferably has a number average molecular weight of 2600 or more, more preferably 2800 to 100,000, and even more preferably 2800 to 10,000 from the viewpoint of improving chemical resistance and salt spray resistance. Here, the number average molecular weight is a value calculated from the molecular structure specified by NMR analysis.

Examples of the compound (5) include the following.
Formula (5 ′): R ^{f4 ′} —O— (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _g8 —Q ^{2 ′} —CH ₂ CH ₂ SiA ^{3 ′} ₃
(Where
R ^{f4 ′} is CF ₃ or CF ₃ CF ₂ —,
Q ^{2 ′} is —CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ —C (═O) NH—CH ₂ — or —CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CH ₂ —O—CH _2. −
Each A ^{3 ′} is independently an alkoxy group (eg, an alkoxy group having 1 to 4 carbon atoms, preferably a methoxy group or an ethoxy group), a halogen atom (eg, a chlorine atom), or an isocyanato group;
g8 is an integer of 1 or more).

Compound (5) can be synthesized, for example, as follows. As a raw material, a compound having CF ₂ ═CF—O— and a carboxy group or a group that can be converted to a carboxy group is prepared at both ends of the perfluoroalkylene group, and this is prepared in the presence of an alcohol or a fluorine-containing alcohol. Polymerize to form a compound containing perfluorinated oxyalkylene units as repeating units. This is then fluorinated, then reacted with a lower alcohol and, optionally, an ethylenically unsaturated bond is formed at one end, followed by reaction with a hydrolyzable group-containing silane compound having a reactive group. Can be obtained.

In addition to the above, commercially available products such as OPTOOL DSX, OPTOOL AES (manufactured by Daikin Industries), and Dow Corning 2634 coating (manufactured by Dow Corning Toray) can also be used as the compound (5). Moreover, the fluorooxyalkylene group containing polymer composition as described in Unexamined-Japanese-Patent No. 2011-116947 can also be used. In this case, the composition is supplied as a mixture with a compound in which both Z ¹ and Z ² are R ^f4 in formula (5).

<(C3) Compound (3)>
The compound (3) will be described. The compound (3) is represented by the above formula (3), and the compound (3) has a polyfluoroalkyl group at one end and a hydrolyzable silyl group at the other end via an alkylene group. Bonded, linear organopolysiloxane. Compound (3) is preferable in that it has excellent initial water slidability.

R ^f1 in formula (3) is preferably a group: CF ₃ (CF ₂ ) _(7-t1) — (CH ₂ ) _t1 — (wherein t1 is 2 to 4), and CF ₃ (CF _{2 ) 5 - (CH 2) 2} - and more preferably.

R ² in Formula (3) is a linear or branched alkyl group having 1 to 6 carbon atoms. A linear alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group is more preferable. Each SiR ² ₂ O unit may be different, but is preferably the same.

B in Formula (3) is an integer of 5-150, and an integer of 5-120 is preferable. When b is in the above range, both excellent water repellency and water slidability can be achieved. When the compound (c3) is a mixture in which the number of repeating units of SiR ² ₂ O is different, the number of each repeating unit is represented by an average value and is not necessarily represented by an integer. It is the same.

Examples of X ² in Formula (3) include the groups exemplified in X ¹ including preferred ones.

  C in Formula (3) is an integer of 0-2, and 1 or 0 is preferable from the point of adhesiveness, and 0 is more preferable.

R ³ in Formula (3) is each independently a monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include a linear or branched alkyl group. Among these, from the viewpoint of weather resistance, a linear or branched alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable. When there are a plurality of R ^{3 s} , they may be the same or different, but are preferably the same from the viewpoint of availability.

Y ¹ in Formula (3) is an alkylene group having 2 to 4 carbon atoms, and may be linear or branched. Among these, an alkylene group having 2 carbon atoms (C ₂ H ₄ ) and 3 carbon atoms (C ₃ H ₆ ) is preferable. In this specification, “C ₂ H ₄ ” represents —CH ₂ CH ₂ — and a mixture of —CH ₂ CH ₂ — and —CH (CH ₃ ) —, and “C ₃ H ₆ ” represents —CH 2 ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ — and —CH (CH ₃ ) CH ₂ —, and —CH ₂ CH ₂ CH ₂ — and —CH ₂ CH (CH ₃ ) — Indicates a mixture.

As the compound (3), R ² in the formula (3) is preferably a methyl group, R ³ is a linear alkyl group having 5 or less carbon atoms, X ² is a chlorine atom, and k is 5 A compound having an integer of ˜150 and c = 0.

As the compound (3), the following compound (3-1) may be mentioned. In the formula, examples and preferred embodiments of t1, R ² , b, Y ¹ and X ² are as described above.
Formula (3-1): CF ₃ (CF ₂ ) _(7-t1) — (CH ₂ ) _t1 — (SiR ² ₂ O) _b —SiR ² ₂ —Y ¹ —SiX ² ₃

As the compound (3), the following compounds are more preferable. In the formula, examples and preferred embodiments of b are as described above.
_{C 6 F 13 C 2 H 4} (Si (CH 3) 2 O) b Si (CH 3) 2 C 2 H 4 SiCl 3
_{C 6 F 13 C 2 H 4} (Si (CH 3) 2 O) b Si (CH 3) 2 C 2 H 4 Si (OCH 3) 3
_{C 6 F 13 C 2 H 4} (Si (CH 3) 2 O) b Si (CH 3) 2 C 2 H 4 Si (OC 2 H 5) 3

Compound (3) can be produced by a known method, for example, the method described in JP-A No. 2001-81445. For example, in the formula (3), R ^f2 —C ₂ H ₄ — is present at the terminal, and the hydrolyzable silyl group (Si (R ³ ) is bonded to the other terminal via —C ₂ H ₄ — as Y ^1. Linear polydimethylsiloxane (R ^f1 (Si (CH ₃ ) ₂ O) _k Si (CH ₃ ) ₂ C ₂ H ₄ Si (R ³ ) _c (X ² ) having _c (X ² ) _3-c ) ) _3-c) is a polydimethylsiloxane having a hydrogen atom at both terminals _{(H (Si (CH 3)} 2 O) b Si (CH 3) 2 H), the presence of a hydrosilylation _catalyst, CH 2 = CH It can be produced by a method in which —R ^f2 and CH ₂ ═CH—Si (R ¹ ) _{3 -n} (X ² ) _n are reacted. In the compound (3) obtained by this reaction, Y ¹ is a mixture of —CH ₂ CH ₂ — and —CH (CH ₃ ) —. In the above reaction, CH ₂ ═CH— is changed to CH ₂ ═CH—CH ₂ —, whereby Y ¹ is —CH ₂ CH ₂ CH ₂ —, —CH (CH ₃ ) CH ₂ —, and — CH ₂ CH (CH ₃₎ - is a mixture compound of (3) is obtained.

  Component (C) may be a silane compound having a polyfluoroalkyl group, a partially hydrolyzed condensate of a silane compound having a polyfluoroalkyl group, or a mixture thereof. The mixture may be a partially hydrolyzed condensate of a silane compound having a polyfluoroalkyl group including a silane compound having an unreacted polyfluoroalkyl group.

  Here, the partially hydrolyzed complex of a silane compound having a polyfluoroalkyl group is all or all 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 partial hydrolysis and subsequent dehydration condensation. The degree of condensation (degree of multimerization) of the partially hydrolyzed cocondensate can be adjusted as appropriate.

  The composition for forming a water-repellent film of the present invention is based on 100 parts by mass in total of the component (A) and the component (B) from the viewpoint of efficiently imparting chemical resistance and salt spray resistance to the water-repellent film. It is preferable that it is 10-500 mass parts of (C) component, and it is more preferable that it is 100-300 mass parts.

  The composition for forming a water-repellent layer can contain a coloring material such as a catalyst, an organic solvent, metal oxide ultrafine particles, a dye or a pigment, and an antifouling material as long as the effects of the present invention are not impaired.

  The composition for forming a water-repellent film of the present invention can contain an organic solvent from the viewpoints of workability and ease of controlling the thickness of the water-repellent film. The organic solvent is not particularly limited as long as it dissolves essential components, and alcohols, ethers, ketones, aromatic hydrocarbons, paraffin hydrocarbons, esters (for example, acetate esters), etc. Among them, an organic solvent containing a fluorine atom (for example, fluoroalcohol, fluorohydrocarbon (perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, dichloropentafluoropropane, etc.)) is preferable. The organic solvent may be used alone or in combination of two or more. The composition of this invention may contain the organic solvent used in order to manufacture the partial hydrolysis cocondensation compound of (C) component.

  The proportion of the organic solvent is such that the total mass of the (A) component and the (B) component, or the hydrolysis cocondensate of the (A) component and the (B) component is 100 parts by mass, and the uniformity of the resulting water-repellent film From the point, 9900 mass parts or less are preferable, More preferably, it is 3500 mass parts or less, For example, it can be set as 700-3500 mass parts.

  The composition of this invention can contain a functional additive in the range which does not impair the effect of this invention. Examples of the functional additive include fine particles of metal oxides such as silica, alumina, zirconia, and titania, dyes, pigments, antifouling materials, curing catalysts, and various resins. The additive of the functional additive is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the solid content of the composition (component excluding volatile components such as organic solvents). Yes, for example, 1 to 10 parts by mass.

  Examples of a method for forming a water-repellent film using the water-repellent film-forming composition include a method for forming an underlayer. In addition, you may perform hardening of the composition for base layer formation simultaneously with hardening of the composition for water-repellent film formation. Specifically, after the base layer forming composition is applied to a predetermined region of the substrate surface and dried as necessary, the water repellent film forming composition is applied to the surface and dried as necessary. The base layer and the water repellent film may be cured at the same time by performing a curing process in the same manner as described above.

  The substrate having the base layer and the water-repellent film of the present invention thus obtained is excellent in water repellency, durability and salt spray resistance, as well as in water slidability and chemical resistance.

[Transportation Equipment Items]
The base | substrate which has the base layer and water-repellent film of this invention is used as articles | goods for transport equipment containing this. Examples of transportation equipment include trains, automobiles, ships, and aircraft. Examples of articles used for this include a body, a window glass (for example, a windshield, a side glass, and a rear glass), a mirror, and a bumper. In the present invention, as the article for transport equipment, the article for transport equipment is preferably a window glass for transport equipment, and more preferably an automobile window glass.

  The substrate having an underlayer and a water-repellent film of the present invention or an article for a transport device including the substrate, the surface of the water-repellent film is excellent in both water repellency and water slidability. Adhering water droplets are removed immediately. In addition, due to the interaction with the wind pressure accompanying the operation of the transportation equipment, the attached water droplets move rapidly on the surface and do not accumulate as water droplets. This eliminates the adverse effects induced by moisture. Further, since the water-repellent film of the present invention is excellent in durability such as freckle abrasion resistance, for example, it maintains water repellency and water slidability even when articles for transport equipment are used outdoors for a long period of time. can do.

  The substrate having an undercoat layer and a water-repellent film of the present invention or an article for transport equipment including the substrate can be very easily secured by scattering of water droplets, particularly in applications in transparent field parts such as various window glasses. Safety can be improved in the operation of vehicles and the like. Further, even in an environment where water droplets freeze, it is difficult for the surface of the water-repellent film to be icing, and even if icing, the adhesive force is small, so that it naturally falls easily. 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.

[Composition for forming underlayer]
Underlayer forming compositions 1 to 15 were prepared as follows.
(Underlayer forming compositions 1 to 9)
In a glass container in which a stirrer and a thermometer are set, to 8.77 g of isopropanol (manufactured by Junsei Chemical Co., Ltd.), tetramethoxysilane (TMOS) (manufactured by Kanto Chemical Co., Inc.) and bistrimethoxysilylethane (BTME) in the ratio shown in Table ) (Manufactured by Kanto Chemical Co., Inc.) was added in a total of 0.39 g, and the mixture was stirred at 25 ° C. for 3 minutes. Then, 0.84 g of a 0.463 wt% nitric acid aqueous solution was dropped, and the mixture was stirred for 1 hour. As a result, liquid compositions 1 to 9 were obtained.
(Underlayer forming composition 10-15)
In a glass container with a stirrer and thermometer set, 9.50 g of butyl acetate (manufactured by Junsei Chemical Co., Ltd.), tetraisocyanatosilane (SI400 (trade name, manufactured by Matsumoto Fine Chemical Co., Ltd.)) and bistril in the ratios shown in Table 2 A total of 0.5 g of isocyanatosilylethane (hereinafter also referred to as “BTIE”; manufactured by Matsumoto Fine Chemical Co., Ltd.) was added and stirred at 25 ° C. for 5 minutes to obtain liquid compositions 10 to 15 as a composition for forming an underlayer. .

[Composition for water-repellent film formation]
Each component mix | blended with the composition for water-repellent film formation of this invention is as follows.
<Compound (C)>
Compound (c1-1): CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (Cl ₃ ) ₃ (manufactured by Synquest)
Compound (c1-2): CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (Cl ₃ ) ₃ (manufactured by Synquest)
Compound (c2): CF ₃ CF ₂ OCF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ CF ₂ OCF ₂ CF ₂ O) _n CF ₂ CF ₂ CF ₂ C (═O) NHCH ₂ CH ₂ CH ₂ Si (OMe) ₃ (n≈13)

Compound (c2) was produced as follows (Step 1).
Into a 300 mL three-necked round bottom flask, 14.1 g of sodium borohydride powder was introduced, and 350 g of AK-225 (product name, manufactured by Asahi Glass Co., Ltd., HCFC225) was added. The mixture was stirred while cooling in an ice bath, and a solution containing 100 g of Compound (6), 15.8 g of methanol, and 22 g of AK-225 was slowly added from the dropping funnel under a nitrogen atmosphere so that the internal temperature did not exceed 10 ° C. It was dripped. After the whole amount was dropped, a solution in which 10 g of methanol and 10 g of AK-225 were mixed was further dropped. Thereafter, the ice bath was removed, and stirring was continued while slowly raising the temperature to room temperature. After stirring at room temperature for 12 hours, the mixture was cooled again in an ice bath, and an aqueous hydrochloric acid solution was added dropwise until the liquid became acidic. After completion of the reaction, the organic phase was recovered by washing once with water and once with saturated saline. After the collected organic phase was dried with magnesium sulfate, the solid content was filtered through a filter and concentrated with an evaporator. The collected concentrated liquid was distilled under reduced pressure to obtain 80.6 g (yield 88%) of the compound (7).
CF ₂ = CFO—CF ₂ CF ₂ CF ₂ COOCH ₃ (6),
_{CF 2 = CFO-CF 2 CF} 2 CF 2 CH 2 OH ··· (7).

NMR spectrum of compound (7);
¹ H-NMR (300.4 MHz, solvent: deuterated chloroform, standard: TMS) δ (ppm): 2.2 (1H), 4.1 (2H).
¹⁹ F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl ₃ ) δ (ppm): −85.6 (2F), −114.0 (1F), −122.2 (1F), −123 .3 (2F), -127.4 (2F), -135.2 (1F).

(Process 2)
Into a 500 mL eggplant flask connected with a reflux condenser, 300 g of the compound (7) obtained in Step 1 and 13.5 g of trifluoroethanol (hereinafter also referred to as TFEO) were introduced, and 9.34 g of potassium carbonate powder was added. added. After stirring at 65 ° C. for 1 hour under a nitrogen atmosphere, the temperature was raised to 100 ° C. over 7 hours, and further stirred for 3 hours. It was confirmed by NMR that the vinyl ether group of compound (7) had completely disappeared. A hydrochloric acid aqueous solution was added to treat excess potassium carbonate, and water and AK-225 were added to carry out a liquid separation treatment. After washing with water three times, the organic phase was recovered and concentrated with an evaporator to obtain 279 g of a highly viscous oligomer. Again, it was diluted with 110 g of AK-225, developed on silica gel column chromatography (developing solvent: AK-225), and fractionated. For each fraction, the average value of the number of units (n + 1) was determined from the integrated value of ¹⁹ F-NMR. In the following formula (8), 47 g of the compound (8-i) obtained by combining the fractions in which the average value of (n + 1) is 7 to 10 and the compound (8-) in which the fraction of which the average value of (n + 1) is 13 to 16 are combined. 19 g of ii) was obtained.
_{CF 3 CH 2 -O- (CF 2} CFHO-CF 2 CF 2 CF 2 CH 2 O) n + 1 -H ··· (8).

NMR spectrum of compound (8-i);
¹ H-NMR (300.4 MHz, solvent: heavy acetone, standard: TMS) δ (ppm): 4.1 (2H), 4.8 (16H), 6.7 to 6.9 (8H).
¹⁹ F-NMR (282.7 MHz, solvent: heavy acetone, standard: CFCl ₃ ) δ (ppm): −74.2 (3F), −84.3 to −85.1 (16F), −89.4 to -90.5 (16F), -120.2 (14F), -122.0 (2F), -126.6 (14F), -127.0 (2F), -145.1 (8F).
Average number of units (n + 1): 8.

NMR spectrum of compound (8-ii);
¹ H-NMR (300.4 MHz, solvent: heavy acetone, standard: TMS) δ (ppm): 4.1 (2H), 4.8 (28H), 6.7 to 6.9 (14H).
¹⁹ F-NMR (282.7 MHz, solvent: heavy acetone, standard: CFCl ₃ ) δ (ppm): −74.2 (3F), −84.3 to −85.1 (28F), −89.4 to -90.5 (28F), -120.2 (26F), -122.0 (2F), -126.6 (26F), -127.0 (2F), -145.1 (14F).
Average number of units (n + 1): 14.

(Process 3)
Into a 200 mL eggplant flask connected to a reflux condenser, 114.72 g of the compound (8-ii) obtained in Step 2, 8.1 g of sodium fluoride powder and 101.72 g of AK-225 were introduced, and CF ₃ CF ₂ CF ₂ OCF _(CF 3) were added 95.18g of COF. The mixture was stirred at 50 ° C. for 12 hours under a nitrogen atmosphere, and then stirred overnight at room temperature. After removing the sodium fluoride powder with a pressure filter, excess CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COF and AK-225 were distilled off under reduced pressure. High-polar impurities were removed by silica gel chromatography (developing solvent: AK-225), and 94.57 g of compound (9-ii) in which the average value of the number of units (n + 1) was 14 in the following formula (9) ( Yield 77%) was obtained.
_{CF 3 CH 2 -O- (CF 2} CFHO-CF 2 CF 2 CF 2 CH 2 O) n + 1 -C (= O) CF (CF 3) OCF 2 CF 2 CF 3 ··· (9).

NMR spectrum of compound (9-ii);
¹ H-NMR (300.4 MHz, solvent: deuterated chloroform, standard: TMS) δ (ppm): 4.4 (28H), 4.9 (2H), 6.0-6.2 (14H).
¹⁹ F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl ₃ ) δ (ppm): −75.2 (3F), −80.0 (1F), −81.9 (3F), −82 .7 (3F), -84.7 to -85.0 (28F), -86.0 (1F), -90.5 to -93.0 (28F), -121.1 (2F), -121 .5 (26F), -128.0 (28F), -130.3 (2F), -132.5 (1F), -145.3 (14F).
Average number of units (n + 1): 14.

(Process 4)
An autoclave (made of nickel, internal volume 3 L) was prepared, and a cooler maintained at 0 ° C., a NaF pellet packed layer, and a cooler maintained at 10 ° C. were installed in series at the gas outlet of the autoclave. Moreover, the liquid return line which returns the liquid aggregated from the cooler hold | maintained at -10 degreeC to an autoclave was installed.
2,350 g of R-113 was added to the autoclave and stirred while maintaining at 25 ° C. After nitrogen gas was blown into the autoclave at 25 ° C. for 1 hour, 20% fluorine gas was blown in at 25 ° C. and a flow rate of 4.2 L / hour for 1 hour. Next, while blowing 20% fluorine gas at the same flow rate, a solution prepared by dissolving 213 g of the compound (9-ii) obtained in Step 3 in 732 g of R-113 was injected into the autoclave over 29 hours.
Subsequently, the internal pressure of the autoclave was increased to 0.15 MPa (gauge pressure) while blowing 20% fluorine gas at the same flow rate. 4 mL of a benzene solution containing 0.009 g / mL benzene in R-113 was injected into the autoclave while heating from 25 ° C. to 40 ° C., and the benzene solution inlet of the autoclave was closed. After stirring for 20 minutes, 5 mL of the benzene solution was again injected while maintaining 40 ° C., and the injection port was closed. The same operation was further repeated 7 times. The total amount of benzene injected was 0.4 g.
Further, stirring was continued for 1 hour while blowing 20% fluorine gas at the same flow rate. Subsequently, the pressure in the autoclave was set to atmospheric pressure, and nitrogen gas was blown for 1 hour. The content of the autoclave was concentrated with an evaporator to obtain 250.1 g (yield 99%) of the compound (10-ii) having an average number of units (n) of 13 in the following formula (10).
_{CF 3 CF 2 -O- (CF 2} CF 2 OCF 2 CF 2 CF 2 CF 2 O) n -CF 2 CF 2 OCF 2 CF 2 CF 2 CF 2 O-C (= O) CF (CF 3) OCF ₂ CF ₂ CF ₃ (10).

NMR spectrum of compound (10-ii);
¹⁹ F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl ₃ ) δ (ppm): −80.3 (1F), −82.0 to −82.5 (6F), −84.2 ( 54F), -86.9-88.0 (6F), -89.4 (58F), -126.6 (56F), -130.4 (2F), -132.4 (1F).
Average number of units (n): 13.

(Process 5)
In a 500 mL PFA round bottom eggplant flask, 110 g of the compound (10-ii) obtained in Step 4 and 220 g of AK-225 were placed. The mixture was stirred while being cooled in an ice bath, and 3.5 g of methanol was slowly dropped from the dropping funnel under a nitrogen atmosphere. The mixture was stirred for 12 hours while bubbling with nitrogen. The reaction mixture was concentrated with an evaporator to obtain 103 g (yield: 100%) of the precursor (11-ii) having an average number of units (n) of 13 in the following formula (11).
_{CF 3 CF 2 -O- (CF 2} CF 2 OCF 2 CF 2 CF 2 CF 2 O) n -CF 2 CF 2 OCF 2 CF 2 CF 2 C (= O) OCH 3 ··· (11).

NMR spectrum of precursor (11-ii);
¹ H-NMR (300.4 MHz, solvent: deuterated chloroform, standard: TMS) δ (ppm): 3.9 (3H).
¹⁹ F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl ₃ ) δ (ppm): −84.0 (54F), −88.2 (3F), −89.2 (58F), −119 .8 (2F), -126.5 (54F).
Average number of units (n): 13.

(Step 6)
In a 300 mL eggplant flask, 100.5 g of the precursor (11-ii) obtained in Step 5 and 4.38 g of H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ were added and stirred for 12 hours. From NMR, it was confirmed that 98% of the precursor (11-ii) was converted to the compound (12-ii). Further, all of H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ had reacted, and methanol as a by-product was produced. In this way, a composition containing 97% of the compound (12-ii) having an average value of the number of units (n) of 13 in the following formula (12) was obtained. This composition was used as compound (c2). The number average molecular weight of the compound (12-ii) was 4,900.
CF ₃ CF ₂ —O— (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _n —CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ C (═O) NHCH ₂ CH ₂ CH ₂ —Si ( OCH ₃ ) ₃ (12).

NMR spectrum of compound (12-ii);
¹ H-NMR (300.4 MHz, solvent: deuterated chloroform, standard: TMS) δ (ppm): 0.6 (2H), 1.6 (2H), 2.8 (1H), 3.3 (2H) 3.5 (9H).
¹⁹ F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl ₃ ) δ (ppm): -84.1 (54F), -87.9 (3F), -89.3 (58F), -120 .8 (2F), -126.6 (52F), -127.2 (2F).
Average number of units (n): 13.

Compound _{(c3): CF 3 (CF} 2) 5 CH 2 CH 2 (Si (CH 3) 2 O) 9 Si (CH 3) 2 C 2 H 4 SiCl 3
Compound (c3) was prepared by a method according to Japanese Patent Application Laid-Open No. 2001-81445, using CF ₃ (CF ₂ ) ₅ —CH═CH ₂ , CH ₂ ═CH—SiCl ₃ , and H— (Si (CH ₃ ) ₂ O. ) Prepared using ₉ Si (CH ₃ ) ₂ —H.

[Preparation of water repellent film-forming composition]
(Water repellent film-forming composition 1)
Compound (c1-1) 10% by mass and butyl acetate (manufactured by Junsei Chemical Co., Ltd.) 90% by mass were mixed and stirred for 5 minutes to obtain a liquid composition (water repellent film-forming composition 1).
(Water repellent film-forming composition 2)
Compound (c1-2) 10% by mass and butyl acetate (manufactured by Junsei Chemical Co., Ltd.) 90% by mass were mixed and stirred for 5 minutes to obtain a liquid composition (water repellent film-forming composition 2).
(Water repellent film-forming composition 3)
Compound (c3) 10% by mass and butyl acetate (manufactured by Junsei Chemical Co., Ltd.) 90% by mass were mixed and stirred for 5 minutes to obtain a liquid composition (water repellent film-forming composition 3).
Water repellent film forming composition 4)
5.8 parts by mass of compound (c1-2), 1.28 parts by mass of compound (c2), 18.6 parts by mass of butyl acetate (manufactured by Junsei Kagaku), hydrofluoroether (AE3000, manufactured by Asahi Glass Co., Ltd., CF ₃ CH ₂ OCF ₂ CHF ₂ ) was mixed at a ratio of 74.4 parts by mass and stirred for 5 minutes to obtain a liquid composition (composition 4 for forming a water repellent film).

[Formation of underlayer and water repellent film]
As a substrate, a clean soda lime glass substrate (water contact angle 5 °, 300 mm × 300 mm × thickness 3 mm), which was polished and cleaned with cerium oxide, was used, and Table 3 and Table 4 were formed on the surface of the glass substrate. As shown in Fig. 5, 0.5 g of any of the underlayer-forming compositions 1 to 15 was applied by a squeegee coating method and dried for 1 minute to form an underlayer. Thereafter, as shown in Tables 3 and 4, 0.5 g of any one of the water-repellent film-forming compositions 1 to 4 was applied to the surface of the formed base layer by a squeegee coating method at 50 ° C. and 60%. A water-repellent film was formed by holding for 48 hours in a thermo-hygrostat set to RH to obtain a substrate having a base layer and a water-repellent film. When an excessive composition for forming a water-repellent film was present, it was wiped with a paper waste soaked with isopropyl alcohol.

[Evaluation]
Evaluation of the substrates having the underlayer and the water-repellent film of Examples 1 to 19 and Comparative Examples 1 to 10 was performed as follows.
<Water repellency>
The water repellency was evaluated by a water contact angle (CA) measured by the following method. First, initial values were measured before each of the following tests. In addition, if the initial water contact angle (CA) is 100 ° or more, 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 substrate having the base layer and the water repellent film was measured using DM-701 (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.

<Sliding water>
The water slidability was evaluated by the water falling angle (SA) measured by the following method. In addition, initial values were measured before each of the following tests. In addition, if the initial water falling angle (SA) is 15 ° or less, it can be said that the water sliding property sufficiently withstands actual use.
(Water drop angle (SA))
Substrate having a base layer and a water repellent film when a water droplet of 50 μl is dropped on the surface of the base having a base layer and a water repellent film held horizontally and then the substrate is gradually tilted and the water droplet starts to fall. And the horizontal plane (fall angle) were 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 water slidability.

<Chemical resistance>
(Alkali resistance test)
A substrate having an underlayer and 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.
[Chemical resistance evaluation criteria]
About the said alkali resistance test, if the water contact angle (CA) after a test is 70 degrees or more, it can be said that it has chemical resistance sufficient for actual use.
<Salt water spray resistance>
(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 having the base layer and the 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.
[Salt water resistance evaluation criteria]
About the said salt spray test, if the water contact angle (CA) after a test is 70 degrees or more, it can be said that it has salt spray resistance sufficient for actual use.

<Abrasion resistance>
On the surface of the water-repellent film of the substrate having the base layer and the water-repellent film, the Nel cloth abrasion resistance test was performed under the following test conditions, and then the water contact angle (CA) and the water falling angle (SA) were determined by the above methods. It was measured.
(Nel cloth abrasion resistance test)
In accordance with JIS L0849, a flannel cloth abrasion resistance test was performed using the following test machine under the following test conditions.
Testing machine: Reciprocating traverse testing machine (manufactured by KT Corporation)
Test conditions: cotton cloth (conforming to JIS L0803), load 1.2 kg, wear frequency 3000 times [nel wear resistance evaluation criteria]
Regarding the flannel cloth abrasion resistance test, if the water contact angle (CA) after the test is 80 ° or more and the water falling angle (SA) is 30 ° or less, it can be said that the wear resistance is sufficient for actual use.

  The results are summarized in Tables 3 and 4.

  As shown in Tables 3 and 4, it can be seen that the substrates of the examples are excellent in salt spray resistance, alkali resistance, and water slidability, and maintain good durability. In particular, the water slidability is a characteristic necessary for removing water droplets from the glass, and the excellent water slidability of the substrate of the examples is good for removing raindrops when used for automobile window glass, building window glass, etc. It is very effective for ensuring high visibility. In addition, since it has excellent salt spray resistance and alkali resistance, an excellent water droplet removal effect can be maintained for a long time. In particular, the examples using the compound (c3) as a composition for forming a water repellent film are excellent in terms of initial water slidability and excellent in terms of maintaining water repellency after a salt spray resistance test. I understand. Moreover, it turns out that the Example using a compound (c2) is excellent at the point of the water-repellent maintenance after an alkali resistance test and a salt spray resistance test. Furthermore, it turns out that the Example using a compound (c1-1) is excellent at the point of the maintenance of water repellency after an alkali resistance test. On the other hand, in Comparative Examples 1-10, although it is a base | substrate which has a base layer formed using the composition for base layer formation containing only any one of a compound (1) and a compound (2), salt spray resistance Alkaline resistance or water slidability was not sufficient.

Claims (8)

(A) Formula (1): A ¹ ₃ Si— (CHR ¹ ) _a —SiA ¹ ₃
(Where
A ¹ is each independently a hydrolyzable group or a hydroxyl group,
R ¹ is H or CH ₃
a is an integer of 1 to 9, wherein each (CHR ¹ ) unit may be the same or different), and (B) Formula (2): SiX ¹ ₄
(In the formula, each X ¹ is independently a halogen atom, an alkoxy group or an isocyanato group)
(C) a silane compound having a polyfluoroalkyl group at least partially on the underlayer formed using the underlayer-forming composition containing the compound represented by the formula: A substrate having a water-repellent film formed using a composition for forming a water-repellent film containing at least one selected from the above. (C) A silane compound having a polyfluoroalkyl group is
(C1) a polyfluoroalkylsilane compound,
(C2) Polyfluoropolyether silane compound, and (c3) Formula (3): R ^f1- (SiR ² ₂ O) _b -SiR ² ₂ -Y ¹ -Si (R ³ ) _c (X ² ) _3-c
(Where
R ^f1 is a linear polyfluoroalkyl group having 1 to 8 carbon atoms,
Y ¹ is an alkylene group having 2 to 4 carbon atoms,
R ² is independently an alkyl group having 1 to 6 carbon atoms, wherein each SiR ² ₂ O unit may be the same or different,
Each R ³ is independently a monovalent hydrocarbon group;
Each X ² is independently a hydrolyzable group;
b is an integer of 5 to 150;
c is an integer of 0 to 2)
The substrate according to claim 1, which is one or more silane compounds selected from the group consisting of compounds represented by: (C1) the polyfluoroalkylsilane compound is
Equation ^{(4): R f2 -Q 1} -SiR 4 d A 2 3-d
(Where
R ^f2 is a group: C _e F _{2e + 1} (where e is an integer from 1 to 8);
Q ¹ is a divalent hydrocarbon group having 1 to 6 carbon atoms,
Each R ⁴ is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms;
A ² is each independently a hydroxyl group or a hydrolyzable group,
d is an integer of 0 to 2),
(C2) a polyfluoropolyether silane compound is
Equation ^{(5): Z 1 -R f3} -Z 2
(Where
R ^f3 _{is, -O- (C f F 2f O} ) g - ( where, f is, an integer from 1 to 6, g is 1 or more is an integer, each _-C f _F 2f O-units May be the same or different)
Z ¹ and Z ² are each independently R ^f4 , or a group: —Q ² — {CH ₂ CH (SiR ⁵ _h A ³ _3-h )} _j —H, one of which is a group: -Q ² - a _{^{{CH 2 CH (SiR 5 h}} a 3 3-h)} j -H ( wherein,
R ^f4 is a group: C _k F _{2k + 1} (where k is an integer from 1 to 6);
Q ² is — (CH ₂ ) _m — (where m is an integer of 2 to 12), or one selected from an ester bond, an ether bond, an amide bond, a urethane bond, and a phenylene group. containing more than - _{(CH 2) m} - and is, -CH ₂ - some units or the whole, -CF ₂ - units and / or -CF (CF ₃₎ - may be replaced by units,
R ⁵ is each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and the hydrocarbon group may contain a substituent,
A ³ is each independently a hydroxyl group or a hydrolyzable group,
h is an integer of 0 to 2,
The substrate according to claim 2, wherein j is an integer of 1 to 20.   4. The substrate according to claim 3, wherein the compound of the formula (4) is a compound having a number average molecular weight of 2600 or more or a partial hydrolysis condensate thereof. The substrate according to any one of claims 1 to 4, wherein in formula (1), A ¹ is an alkoxy group or an isocyanato group, R ¹ is H, and a is an integer of 1 to 3.   The substrate according to any one of claims 1 to 5, wherein the mass ratio of the compound of formula (1) and the compound of formula (2) is 0.1: 0.9 to 0.9: 0.1. .   The substrate according to claim 1, wherein the substrate comprises glass.   The article for transportation equipment containing the base according to any one of claims 1 to 7.