JP6036132B2 - Substrate with water repellent film and article for transportation equipment - Google Patents

Description

  The present invention relates to a substrate with a water-repellent film comprising a water-repellent film having both water repellency and durability, and an article for transport equipment comprising the substrate with a water-repellent film.

  Conventionally, in various technical fields, it has been strongly required to impart water repellency to the surface of a substrate. There are two types of water repellency: static water repellency (a property that prevents water droplets from sticking) and dynamic water repellency (a property that allows water droplets to easily roll, water slidability). Many. In particular, articles for transportation equipment such as automobile glass are required to be excellent in both static water repellency and dynamic water repellency.

  As a method for imparting water repellency to the surface of a substrate, a water-repellent coating is generally formed on the surface of the substrate, and a coating having excellent water repellency (hereinafter referred to as “water-repellent film”). Technological developments have been made on compositions for forming sucrose.

  In the composition for forming a water repellent film, a dimethyl silicone compound having a hydrolyzable group was used as a composition for forming a water repellent film having excellent dynamic water repellency in addition to static water repellency. Compositions are known. As such a composition, for example, Patent Document 1 discloses a surface treatment containing a linear dimethyl silicone compound having a fluoroalkyl group or an alkyl group at one end and a hydrolyzable group at the other end. Agents are described. The functional layer obtained by the surface treating agent described in Patent Document 1 is a functional layer excellent in both static water repellency and dynamic water repellency. In Patent Document 1, in order to further improve the water repellency durability, A base layer formed using a trifunctional or tetrafunctional hydrolyzable silane compound is provided between the functional layer and the functional layer. By providing such a base layer, durability such as stability over time is improved, but the base layer is not sufficient in terms of moisture resistance.

  On the other hand, there is no problem in terms of moisture resistance, and a water-repellent film using a hydrolyzable silane compound having a fluorine-containing alkyl group that is excellent in static water repellency is known. Compositions for application have been developed. As such a composition, Patent Document 2 describes a composition in which a hydrolyzable silane compound having a fluorinated polyether group and a hydrolyzable silane compound having a fluorinated alkyl group are combined. However, in the water-repellent film using this composition, depending on the application, in terms of the initial dynamic water repellency compared to the water-repellent film using the dimethyl silicone compound having a hydrolyzable group, Compared to a water-repellent film using a hydrolyzable silane compound having an alkyl group, it was not necessarily sufficient in terms of moisture resistance.

JP 2002-97192 A International Publication No. 2011-016458

  The present invention has been made from the above viewpoint, and has a water repellent film substrate having a water repellent film excellent in both static water repellency and dynamic water repellency and excellent in durability such as moisture resistance. Another object of the present invention is to provide an article for transport equipment comprising the substrate with the water-repellent film.

The present invention provides a substrate with a water-repellent film and an article for transport equipment having the following configuration.
[1] 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,
The water repellent film is sequentially from the substrate side.
An underlayer formed by using an underlayer-forming composition containing a component (A) comprising a compound represented by the following formula (1) and / or a partially hydrolyzed condensate thereof, and represented by the following formula (2) A water repellent layer formed using a composition for forming a water repellent layer comprising the component (B) comprising the compound and / or a partially hydrolyzed condensate thereof,
A substrate with a water repellent film.
X ¹ ₃ Si— (CH ₂ ) _m —SiX ¹ ₃ (1)
(However, in the formula (1), X ¹ each independently represents a hydrolyzable group or a hydroxyl group, m is an integer of 1 to 8.)
R ³ — (SiR ² ₂ O) _k —SiR ² ₂ —Y ¹ —Si (R ¹ ) _{3 -n} (X ² ) _n (2)
(In the formula (2), R ³ represents an alkyl group having 10 or less carbon atoms or —Y ¹ —Si (R ¹ ) _3-n (X ² ) _n group, and R ² each independently represents a carbon atom. An alkyl group having a number of 3 or less, Y ¹ is independently an alkylene group having 2 to 4 carbon atoms, R ¹ is independently a monovalent hydrocarbon group, and X ² is independently hydrolyzed. Represents a decomposable group, k is an integer of 10 to 200, and n is an integer of 1 to 3.)

[2] The underlayer-forming composition includes the component (A) and the component (C) composed of a compound represented by the following formula (3) and / or a partial hydrolysis condensate thereof, or The water-repellent film according to [1], comprising a partially hydrolyzed cocondensate of the component (A) and the component (C) (however, the component (A) and / or the component (C) may be included). With base.
Si (X ³ ) ₄ (3)
(However, in formula (3), X ³ each independently represents a halogen atom, an alkoxy group or an isocyanate group.)

[3] The content ratio of the compound-derived component represented by the formula (1) and the compound-derived component represented by the formula (3) in the composition for forming an underlayer is represented by the formula (1). Compound-derived component: The water-repellent film according to [2], wherein the mass ratio represented by the compound-derived component represented by the formula (3) is 0.1: 0.9 to 0.9: 0.1 With base.
[4] The content ratio of the compound-derived component represented by the formula (1) and the compound-derived component represented by the formula (3) in the composition for forming an underlayer is represented by the formula (1). Compound-derived component: The water-repellent film according to [3], which is 0.1: 0.9 to 0.6: 0.4 as a mass ratio represented by the compound-derived component represented by the formula (3) With base.

[5] The substrate with a water-repellent film according to any one of [1] to [4], wherein in the formula (1), X ¹ is an alkoxy group or an isocyanate group, and m is an integer of 1 to 3.
[6] In the formula (2), R ² is 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 10 to 150. The substrate with a water-repellent film according to any one of [1] to [5], which is an integer and n is 3.
[7] The composition for forming the underlayer has a total solid content substantially consisting of only the compound-derived component represented by the formula (1), or the compound-derived component represented by the formula (1) and the formula The substrate with a water-repellent film according to any one of [1] to [6], comprising only the component derived from the compound represented by (3).
[8] The substrate with a water-repellent film according to any one of [1] to [7], wherein the composition for forming a water-repellent layer is composed entirely of the component (B).
[9] The substrate with a water-repellent film according to any one of [1] to [8], wherein the substrate is made of glass.
[10] An article for transport equipment comprising the substrate with a water-repellent film according to any one of [1] to [9].

  According to the present invention, a substrate with a water-repellent film having a water-repellent film that is excellent in both static water repellency and dynamic water repellency and excellent in durability such as moisture resistance, and the substrate with the water-repellent film. It is possible to provide an article for transportation equipment.

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 group represented by the formula (1a) is referred to as group (1a). The same applies to other compounds and groups. The “component derived from compound (1)” in this specification refers to the partial hydrolysis condensate of compound (1) and the compound (1) in the partial hydrolysis cocondensate of compound (1) and other hydrolyzable silane compounds. It is used as a generic term for the derived unit and the unreacted compound (1). Moreover, in this specification, the total solid content means the component which finally becomes a layer constituent component among the components which each composition for layer formation contains, and is volatilization which volatilizes by the heating in layer formation processes, such as an organic solvent. All components other than sex components are shown.

[Substrate with water-repellent film]
The substrate with a water-repellent film according to 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. It has a water-repellent layer formed using the foundation layer formed using the composition for base layer formation containing A) component, and the water-repellent layer formation composition containing (B) component.

Component (A): a compound represented by the following formula (1) and / or a partial hydrolysis condensate thereof.
X ¹ ₃ Si— (CH ₂ ) _m —SiX ¹ ₃ (1)
(However, in the formula (1), X ¹ each independently represents a hydrolyzable group or a hydroxyl group, m is an integer of 1 to 8.)

Component (B): a compound represented by the following formula (2) and / or a partially hydrolyzed condensate thereof.
R ³ — (SiR ² ₂ O) _k —SiR ² ₂ —Y ¹ —Si (R ¹ ) _{3 -n} (X ² ) _n (2)
(In the formula (2), R ³ represents an alkyl group having 10 or less carbon atoms or —Y ¹ —Si (R ¹ ) _3-n (X ² ) _n group, and R ² each independently represents a carbon atom. An alkyl group having a number of 3 or less, Y ¹ is independently an alkylene group having 2 to 4 carbon atoms, R ¹ is independently a monovalent hydrocarbon group, and X ² is independently hydrolyzed. Represents a decomposable group, k is an integer of 10 to 200, and n is an integer of 1 to 3.)

The compound (1) has hydrolyzable silyl groups or silanol groups at both ends with a divalent organic group in between, and the underlayer formed using this has an action of the organic group derived from the compound (1). Thus, it is considered that the water-repellent film can be maintained without being peeled from the substrate even in an environment with high hydrophobicity and high humidity. Compound (2) is a linear silicone compound having a hydrolyzable silyl group at the end, and the water-repellent layer formed using this is both static and dynamic water-repellent. It is excellent.
Hereinafter, the components of the substrate with a water-repellent film of the present invention will be described.

(Substrate)
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.

  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 is formed on at least a part of the surface of the substrate. The region where the water-repellent film on the substrate surface is formed is not particularly limited, and may be formed in a region required according to the application. In the case where the substrate is plate-shaped, it is usually formed on both main surfaces of the substrate or one of the main surfaces.

(Water repellent film)
The water-repellent film included in the substrate with the water-repellent film has a base layer and a water-repellent layer in order from the substrate side. The water repellent film may further have an intermediate layer or the like between the base layer and the water repellent layer, but a water repellent film composed only of the base layer and the water repellent layer is preferred.

<Underlayer>
The underlayer is formed in a predetermined region on the substrate surface using a composition for forming an underlayer containing a component (A) comprising a compound represented by the following formula (1) and / or a partial hydrolysis condensate thereof.
X ¹ ₃ Si— (CH ₂ ) _m —SiX ¹ ₃ (1)
(However, in the formula (1), X ¹ each independently represents a hydrolyzable group or a hydroxyl group, m is an integer of 1 to 8.)

In the formula (1), X ¹ is a hydrolyzable group or a hydroxyl group. The hydrolyzable group is a group that can form Si—OH by hydrolysis of the Si—X ¹ group.
Examples of the hydrolyzable group represented by 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. In view of the balance between the stability of the compound (1) and the ease of hydrolysis, X ¹ is preferably an alkoxy group or an isocyanate group. 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 methoxy group, an ethoxy group, or an isocyanate group. These are appropriately selected and used according to the purpose of manufacture, application and the like. A plurality of X ¹ present in the compound (1) may be the same group or different groups, and the same group is preferable from the viewpoint of availability.

  In the formula (1), m represents the number of carbon atoms of a divalent hydrocarbon group sandwiched between hydrolyzable silyl groups or silanol groups. m is an integer of 1 to 8, and an integer of 1 to 3 is preferable. When the number of carbon atoms of the divalent hydrocarbon group is in the above range, the underlayer has an appropriate hydrophobicity and can improve the moisture resistance of the water-repellent film. Note that when m is 9 or more, the dynamic water repellency deteriorates.

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. In this invention, a compound (1) may be used individually by 1 type, and may use 2 or more types together.

  The component (A) contained in the underlayer forming composition may be a partial hydrolysis condensate of 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. 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. In addition, it is also possible to make water required for a hydrolysis exist in a reaction system by using the aqueous solution of these catalysts.

  The degree of condensation (degree of multimerization) of the partially hydrolyzed condensate must be such that the product is dissolved in the solvent. The component (A) may be the compound (1) or a partial hydrolysis condensate of the compound (1), and a mixture of the compound (1) and the partial hydrolysis condensate, for example, It may be a partially hydrolyzed condensate of compound (1) containing compound (1) of the reaction.

  There are commercially available compounds as the compound represented by the general formula (1) and partial hydrolysis-condensation products thereof, and such commercially available products can be used in the present invention.

  It is preferable that the composition for base layer formation contains (C) component which consists of a compound and / or its partial hydrolysis-condensation product represented by following formula (3) in addition to the said (A) component. In this case, the composition for forming the underlayer may contain the component (A) and the component (C) alone, or may contain these partial hydrolysis cocondensates. When the composition for base layer formation contains the partial hydrolysis cocondensate of (A) component and (C) component, you may contain (A) component and / or (C) component separately from this.

Si (X ³ ) ₄ (3)
(However, in formula (3), X ³ each independently represents a halogen atom, an alkoxy group or an isocyanate group.)

In the above formula (3), X ³ 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 (3). In this invention, a compound (3) may be used individually by 1 type, and may use 2 or more types together. In combination with the compound (1), the compound (3) preferably has a hydrolyzable group that is the same group or atom as the hydrolyzable group of the compound (1). Moreover, the partial hydrolysis-condensation product of a compound (3) can be obtained by the method similar to having demonstrated in manufacture of the partial hydrolysis-condensation product of a compound (1). Moreover, it can obtain similarly about the partial hydrolysis cocondensate of (A) component and (C) component. In addition, there exists a commercial item as a compound shown by General formula (3), or its partial hydrolysis-condensation product, It is possible to use such a commercial item for this invention.

  When the underlayer-forming composition contains both the component (A) and the component (C), it is preferable to use these partial hydrolysis cocondensates, and partial hydrolysis of the compounds (1) and (3). It is more preferable to use a cocondensate. By using a partially hydrolyzed cocondensate, it is considered that the underlayer can be formed as a layer in which units derived from both compounds are uniformly distributed.

  The composition for forming an undercoat layer contains the compound (3) -derived component in addition to the compound (1) -derived component as described above, so that the sliding property of the resulting water-repellent film with respect to minute water droplets is improved. preferable. The content ratio of the compound (1) -derived component and the compound (3) -derived component in the composition for forming an underlayer is 0 as a mass ratio represented by [compound (1) -derived component: compound (3) -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 (3) -derived component in such a mass ratio, the moisture-repellent film in the resulting water-repellent film has improved moisture resistance and sliding properties against minute water droplets. It is possible to improve both.

  In addition, the content ratio of the component (1) -derived component and the compound (3) -derived component in the underlayer-forming composition is determined when a partially hydrolyzed condensate or a partially hydrolyzed cocondensate is used. It can be calculated from the amounts of the compound (1) and the compound (3) used in the above.

  The composition for forming the underlayer is an optional component such as a metal oxide ultrafine particle, a coloring material such as a dye or a pigment, an antifouling material, various resins, etc., as long as the effects of the present invention are not impaired. A functional additive may be included. However, depending on the amount of the functional additive added to the underlayer-forming composition, the performance of the resulting water-repellent film may be deteriorated. Therefore, when the composition for forming the underlayer does not contain the component derived from the compound (3), it is preferable that the total solid component consists essentially of the component derived from the compound (1), and includes the component derived from the compound (3). In the case, it is preferable that the total solid component consists essentially of the compound (1) -derived component and the compound (3) -derived component. In the present specification, that the total solid content is substantially composed of only a certain component means that the content ratio of the component in the total solid content is 90% by mass or more.

  The composition for forming an underlayer usually contains an organic solvent in consideration of economic efficiency, workability, ease of control of the thickness of the obtained underlayer, and the like in addition to the solid content as a layer constituent component. The organic solvent is not particularly limited as long as it dissolves the solid content contained in the underlayer-forming composition. As the organic solvent, alcohols, ethers, ketones, aromatic hydrocarbons, paraffinic hydrocarbons, acetate esters and the like are preferable. 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.

  When the composition for base layer formation contains a partial hydrolysis-condensation product and a partial hydrolysis-condensation product, it may contain the solvent used in order to manufacture these. Moreover, the organic solvent which such a solvent and the composition for base layer formation contain may be the same. The underlayer-forming composition may further contain a component such as a catalyst used in partial hydrolysis condensation or partial hydrolysis cocondensation. When the total solid content of the composition for forming the underlayer is substantially composed only of the component derived from the compound (1), when using the partially hydrolyzed condensate of the compound (1), the composition for forming the underlayer is It is preferable that it is the solution of the partial hydrolysis-condensation product obtained by manufacture of the partial hydrolysis-condensation product of compound (1) itself. Similarly, when the total solid content of the composition for forming the underlayer is substantially composed only of the component derived from the compound (1) and the component derived from the compound (3), partial hydrolysis condensation of the component (A) and the component (C) When using the product, the composition for forming the underlayer is a solution of the partially hydrolyzed cocondensate obtained by the production of the partially hydrolyzed cocondensate of the components (A) and (C). preferable.

  The proportion of the organic solvent in the composition for forming the underlayer is preferably 400 to 100,000 parts by mass with respect to 100 parts by mass of the total mass of the component derived from the compound (1) and the component derived from the compound (3). If the content of the organic solvent is within the above range, there is no risk of processing unevenness occurring in the underlayer, and there is no problem in economic efficiency, workability, ease of controlling the thickness of the processing layer, and the like. The amount of the organic solvent in the underlayer-forming composition is more preferably 900 to 3,500 parts by mass with respect to 100 parts by mass of the total mass of the compound (1) -derived component and the compound (3) -derived component. 1,100 to 2,000 parts by mass is particularly preferable.

  Furthermore, in the composition for forming an underlayer, even if it does not contain a partial hydrolysis condensate or a partial hydrolysis cocondensate, the hydrolysis condensation reaction of component (A), or component (A) and (C In order to promote the hydrolysis co-condensation reaction of the component, it is also preferable to add a catalyst such as the same acid catalyst as used in the partial hydrolysis-condensation reaction 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. As a quantity of a catalyst, 0.01-5 mass parts is preferable with respect to 100 mass parts of total mass of a component (1) origin component and a compound (3) origin component. In the underlayer forming composition, the amount of the catalyst is not included in the solid content.

  The underlayer-forming composition may contain water for the above-mentioned components to undergo a hydrolysis condensation reaction or a hydrolysis cocondensation reaction. 1-50 mass parts is preferable with respect to 100 mass parts of total mass of the component (1) origin component and the compound (3) origin component of water in the composition for base layer formation. In addition, even if the composition for forming the underlayer does not contain water, in the process of forming the following underlayer, the moisture in the atmosphere is used to perform hydrolysis condensation reaction and hydrolysis cocondensation reaction of the contained components. Can do.

  Here, the composition for forming the underlayer is a compound in which the hydrolyzable group of the compound (1) or the compound (3) is a chlorine atom, or a partially hydrolyzed condensate thereof, as the component (A) or the component (C). In the case of containing a partially hydrolyzed cocondensate or the like, since these have high reactivity, it is preferable that the catalyst and water are not substantially contained in consideration of storage stability. “Substantially not contained” means that the content is 0.3% by mass or less with respect to the total amount of the composition for forming an underlayer.

  As a method for forming the underlayer using the underlayer-forming composition, a known method for an organosilane compound-based surface treatment agent can be used. For example, the composition for forming the underlayer is applied to the surface of the substrate by methods such as brush coating, flow coating, spin coating, dip coating, squeegee coating, spray coating, and hand coating, and is necessary in the air or in a nitrogen atmosphere. The base layer can be formed by curing after drying according to the above. 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. The thickness of the underlayer is not particularly limited as long as it is a thickness that can impart moisture resistance, adhesion, and barrier properties such as alkali from the substrate to the water-repellent film. In consideration of economy, a thickness of 50 nm or less is preferable, and the lower limit is the thickness of the monomolecular layer.

(Water repellent layer)
The water-repellent layer is formed by using a water-repellent layer-forming composition containing a component (B) comprising a compound represented by the following formula (2) and / or a partially hydrolyzed condensate thereof. Formed on the surface.
R ³ — (SiR ² ₂ O) _k —SiR ² ₂ —Y ¹ —Si (R ¹ ) _{3 -n} (X ² ) _n (2)
(In the formula (2), R ³ represents an alkyl group having 10 or less carbon atoms or —Y ¹ —Si (R ¹ ) _3-n (X ² ) _n group, and R ² each independently represents a carbon atom. An alkyl group having a number of 3 or less, Y ¹ is independently an alkylene group having 2 to 4 carbon atoms, R ¹ is independently a monovalent hydrocarbon group, and X ² is independently hydrolyzed. Represents a decomposable group, k is an integer of 10 to 200, and n is an integer of 1 to 3.)

Compound (2) is a linear polyorganosiloxane in which a hydrolyzable silyl group is bonded to one end or both ends via an alkylene group. When R ³ is an alkyl group having 10 or less carbon atoms, the compound (2) is a linear polyorganosiloxane having a hydrolyzable silyl group at one end and hydrolyzable silyl groups at both ends. Compared with the case of having, it is excellent in the point of sliding-down with respect to a fine water droplet. In this case, R ³ is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a linear alkyl group having 1 to 5 carbon atoms.

In formula (2), the repeating unit of SiR ² ₂ O and R ² in —SiR ² ₂ — linked thereto are each independently an alkyl group having 3 or less carbon atoms, and a straight chain having 3 or less carbon atoms. The alkyl group is preferably a methyl group. R ² may be different from each other, but is preferably the same. K which is the repeating number of SiR ² ₂ O is an integer of 10 to 200, preferably 10 to 150, and more preferably 15 to 120. If the number of k is in the above range, it is possible to achieve both static water repellency and dynamic water repellency in the resulting water repellent film. The compound (2) is often used as a mixture in which the number of repeating units of SiR ² ₂ O is different. When the compound (2) is such a mixture, the number of each repeating unit is shown as 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.

X ² in the hydrolyzable silyl group (—Si (R ¹ ) _{3 -n} (X ² ) _n ) possessed by the terminal of the compound (2) represents a hydrolyzable group. When R ³ represents -Y ¹ -Si (R ¹ ) _3-n (X ² ) _n group, the compound (2) becomes a linear polyorganosiloxane having hydrolyzable silyl groups at both ends; This is preferable in terms of excellent moisture resistance and chemical resistance compared to a compound having a hydrolyzable silyl group at one end. In the compound (2), the hydrolyzable silyl groups at both ends may be the same or different.

X ² includes the same groups or atoms as those of X ¹ above. From the viewpoint of the balance between the stability of the compound (2) and the ease of hydrolysis, an alkoxy group, an isocyanate group and a halogen atom are preferred. 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 ² in the compound (2) 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. Compound (2) X ² is 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.

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

Each R ¹ is independently a monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, and an aryl group. R ¹ is preferably a monovalent saturated hydrocarbon group. 1-6 are preferable, as for the carbon atom number of a monovalent saturated hydrocarbon group, 1-3 are more preferable, and 1-2 are especially preferable. R ¹ is preferably an alkyl group having 1 to 6 carbon atoms because synthesis is simple, and an alkyl group having 1 to 3 carbon atoms is more preferable in terms of easy availability and handling of raw materials. An alkyl group having 1 to 2 carbon atoms is particularly preferable. The number of R ^{1 in} the hydrolyzable silyl group possessed by the compound (2) is 3-n. When a plurality of R ¹ are present in the hydrolyzable silyl group, R ¹ may be the same group or different groups, and the same group is preferable from the viewpoint of availability.

In Formula (2), Y ¹ which is a group linking (SiR ² ₂ O) _k —SiR ² ₂ — and a hydrolyzable silyl group independently represents an alkylene group having 2 to 4 carbon atoms. Y ¹ is preferably an alkylene group having 2 or 3 carbon atoms. When Y ¹ is an alkylene group having 2 carbon atoms, in the present specification, it is represented as —C ₂ H ₄ — in the molecular formula of formula (2), which is represented by —CH ₂ CH ₂ — and —CH (CH ₃ ) —. A mixture such as These are mixtures that are difficult to separate in the production process, and even if used as a mixture, the effects of the present invention are not affected. Similarly, when Y ¹ is an alkylene group having 3 carbon atoms, it is represented as —C ₃ H ₆ — in the molecular formula of formula (2), which represents —CH ₂ CH ₂ CH ₂ — and —CH (CH ₃ ) CH. ₂ - mixtures, or _-CH 2 _CH 2 CH ₂ - and _-CH 2 CH (CH ₃₎ - may be a mixture of.

As described above, Y ¹ may be a mixture of a branched alkylene group and a linear alkylene group, but it is most preferable that all of them are linear alkylene groups. The ratio of the branched alkylene group and the linear alkylene group in Y ¹ is preferably 50 to 100, more preferably 75 to 100, as the ratio of the linear alkylene group when the whole is 100.

In the compound (2), R ² in the formula (2) 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 10 A compound in which n is an integer of 150 and n is 3.

Specific examples of the compound (2) include the following compounds. In each compound, k is an integer of 10 to 150.
_{CH 3 (Si (CH 3)} 2 O) k Si (CH 3) 2 C 2 H 4 SiCl 3
_{CH 3 (Si (CH 3)} 2 O) k Si (CH 3) 2 C 2 H 4 Si (OCH 3) 3
_{CH 3 (Si (CH 3)} 2 O) k Si (CH 3) 2 C 2 H 4 Si (OC 2 H 5) 3
_{C 4 H 9 (Si (CH} 3) 2 O) k Si (CH 3) 2 C 2 H 4 SiCl 3
_{C 4 H 9 (Si (CH} 3) 2 O) k Si (CH 3) 2 C 2 H 4 Si (OCH 3) 3
_{C 4 H 9 (Si (CH} 3) 2 O) k Si (CH 3) 2 C 2 H 4 Si (OC 2 H 5) 3
Cl ₃ SiC ₂ H ₄ (Si (CH ₃ ) ₂ O) _k Si (CH ₃ ) ₂ C ₂ H ₄ SiCl ₃
(CH ₃ O) ₃ SiC ₂ H ₄ (Si (CH ₃ ) ₂ O) _k Si (CH ₃ ) ₂ C ₂ H ₄ Si (OCH ₃ ) _{3
(C 2 H 5 O) 3} SiC 2 H 4 (Si (CH 3) 2 O) k Si (CH 3) 2 C 2 H 4 Si (OC 2 H 5) 3
In this invention, a compound (2) may be used individually by 1 type, and may use 2 or more types together.

Compound (2) can be produced by a known method.
For example, in the formula (2), R ³ is an alkyl group having 10 or less carbon atoms, and a hydrolyzable silyl group (—Si (R ¹ ) ₃ via —C ₂ H ₄ — as Y ^{1 at} one end. _-n ^(X _{2) n)} linear polydimethylsiloxane having _{^{(R 3 (Si (CH 3}} ) 2 O) k Si (CH 3) 2 C 2 H 4 Si (R 1) 3-n (X ² ) _n ) can be produced as follows.
In polydimethylsiloxane (R ³ (Si (CH ₃ ) ₂ O) _k Si (CH ₃ ) ₂ H) having R ³ at one end and a hydrogen atom at the other end, in the presence of a hydrosilylation catalyst, CH ₂ = CHSi (R ¹ ) _3-n (X ² ) _n is reacted.
The compound (2) obtained by this reaction is a mixture of a compound in which Y ¹ is —CH ₂ CH ₂ — and a compound in which —CH (CH ₃ ) — is present. In the above reaction, CH ₂ ═CH— is changed to CH ₂ ═CH—CH ₂ —, whereby the compound (2) in which Y ¹ is —C ₃ H ₆ — is obtained.

Formula (2) is linear polydimethyl having a hydrolyzable silyl group (—Si (R ¹ ) _{3 -n} (X ² ) _n ) as —Y ^{1 at} both ends via —C ₂ H ₄ —. In the case of siloxane, polydimethylsiloxane (H (Si (CH ₃ ) ₂ O) _k Si (CH ₃ ) ₂ H) having hydrogen atoms at both ends is added to CH ₂ ═CHSi () in the presence of a hydrosilylation catalyst. _{^{R 1) 3-n (X}} 2) by reacting _{^{n, (X 2) n (}} R 1) 3-n SiC 2 H 4 (Si (CH 3) 2 O) k Si (CH 3) 2 C ₂ H ₄ Si (R ¹ ) _3-n (X ² ) _n is obtained. Also in this case, the compound (2) is a mixture of a compound in which Y ¹ is —CH ₂ CH ₂ — and a compound in which —CH (CH ₃ ) — is used.

Incidentally, as a material used for the hydrosilylation reaction, a polydimethylsiloxane having a vinyl group at the ^terminal, even with ^{_{HSi (R 1) 3-n}} (X 2) n, likewise the compound (2) is obtained.

In any of the above methods, Y ¹ is obtained as a mixture of a branched alkylene group and a linear alkylene group. Case X ² is a chlorine atom, among these synthetic methods, polydimethyl siloxane and _{^{HSi (R 1) 3-n}} (X 2) synthesis method using a _n with a terminal vinyl group, ^{Y 1} is When the linear alkylene group, for example, Y ¹ is C ₂ H ₄ , the ratio of the compound that becomes —CH ₂ CH ₂ — becomes higher, which is more preferable.

  The component (B) contained in the composition for forming a water repellent layer may be a partially hydrolyzed condensate of compound (2). However, the degree of condensation (degree of multimerization) of the partially hydrolyzed condensate needs to be such that the product is dissolved in the solvent. Component (B) 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 composition for forming a water-repellent layer is an arbitrary material such as ultrafine particles of metal oxide, coloring materials such as dyes or pigments, antifouling materials, various resins, etc., as long as the effects of the present invention are not impaired. A functional additive may be included as a component. However, the addition of the functional additive to the water repellent layer-forming composition may cause a decrease in the performance of the resulting water repellent film depending on the amount thereof. Therefore, in the composition for forming a water repellent layer, it is preferable that the total solid component consists essentially of the component (B).

  The composition for forming a water-repellent layer usually contains an organic solvent in consideration of economic efficiency, workability, ease of control of the thickness of the resulting underlayer, etc., in addition to the solid content as a layer constituent component. . The organic solvent is not particularly limited as long as it dissolves the solid content contained in the water repellent layer forming composition. As an organic solvent, the same compound as the composition for base layer formation is mentioned. 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.

  When the composition for water repellent layer formation contains the partial hydrolysis-condensation product, the solvent used in order to manufacture this may be included. Moreover, the organic solvent which such a solvent and the composition for water-repellent layer formation contain may be the same. The composition for forming a water repellent layer may further contain components such as a catalyst used in the partial hydrolysis condensation. When the total solid content of the composition for forming a water repellent layer consists essentially of the component (B), when using the partially hydrolyzed condensate of compound (2), the composition for forming the water repellent layer is: It is preferable that it is the solution of the partial hydrolysis-condensation product itself obtained by manufacture of the partial hydrolysis-condensation product of a compound (2). The proportion of the organic solvent in the water repellent layer forming composition can be the same as the proportion of the organic solvent in the underlayer forming composition.

  Further, in the composition for forming a water repellent layer, even if it does not contain a partial hydrolysis-condensation product, in order to promote the hydrolysis-condensation reaction of the component (B), It is also preferable to blend a catalyst such as the same acid catalyst as that used. Even when the partial hydrolysis-condensation product is contained, when the catalyst used for the production thereof does not remain in the composition, it is preferable to blend the catalyst. As the catalyst, an acid catalyst is preferable. As a quantity of a catalyst, 0.01-10 mass parts is preferable with respect to 100 mass parts of (B) component (component (2) origin component).

  The composition for forming a water repellent layer may contain water for the above-mentioned components to undergo hydrolysis condensation reaction. The water content in the composition for forming a water repellent layer is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the component (B) (component derived from the compound (2)). In addition, even if the composition for water-repellent layer formation does not contain water, in the process of forming the following water-repellent layer, the hydrolysis condensation reaction of the contained components can be performed using moisture in the atmosphere.

  Here, when the composition for forming a water repellent layer contains, as the component (B), a compound (2) in which the hydrolyzable group of the compound (2) is a chlorine atom, a partially hydrolyzed condensate, or the like, Considering storage stability because of high reactivity, it is preferable that the catalyst and water are not substantially contained. “Substantially not contained” means that the content is 0.3% by mass or less based on the total amount of the water repellent layer forming composition.

  As a method for forming the water repellent layer using the water repellent layer forming composition, a known method for an organosilane compound-based surface treatment agent can be used. For example, the water repellent layer forming composition is applied to the surface of the base layer on the substrate by a method such as brush coating, flow coating, spin coating, dip coating, squeegee coating, spray coating, hand coating, etc. In the inside, the water-repellent layer can be formed by drying and curing as necessary. 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. The thickness of the water repellent layer is not particularly limited as long as the water repellent film can provide a performance excellent in both static water repellency and dynamic water repellency. In consideration of economy, a thickness of 50 nm or less is preferable, and the lower limit is the thickness of the monomolecular layer.

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

  The thus obtained water-repellent film of the substrate with a water-repellent film of the present invention is excellent in both static water repellency and dynamic water repellency and also in durability such as moisture 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.

  Since the water-repellent film surface is excellent in both static water repellency and dynamic water repellency, the substrate with a water-repellent film of the present invention or the article for transport equipment comprising the substrate has less adhesion of water droplets to the surface, Adhering water droplets are removed 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, since the water-repellent film is excellent in durability such as moisture resistance, the water-repellent film can be maintained even in long-term use under various use conditions including outdoor use as an article for transport equipment. Can do.

  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, even in an environment where water droplets freeze, the surface of the water-repellent film is difficult to be iced, and even when icing, it has a low adhesive force and is likely to fall naturally. 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 1-5, Examples 7-11, Examples 13-17, Examples 19-23, Examples 25-29, Examples 31-35, Examples 37-41, Examples 43-47, Examples 49-53, Examples 55- 59, Examples 61 to 65, Examples 67 to 71, and Examples 73 to 77 are examples. Examples 6, 12, 18, 24, 30, 36, 42, 48, 54, 60, 66, 72, 78, 79 Is a comparative example.

  As the compound (2) to be blended in the composition for forming a water repellent layer, the following compounds (21) to (30) were synthesized and used according to the following Synthesis Examples 1 to 10. Moreover, the hydrolyzable silane compound (F1) having the following fluorine-containing polyether group to be blended in the water repellent layer forming composition used in the comparative example was synthesized according to Synthesis Example 11.

Compound _{(21); CH 3 (Si} (CH 3) 2 O) 19 Si (CH 3) 2 C 2 H 4 SiCl 3
Compound _{(22); CH 3 (Si} (CH 3) 2 O) 39 Si (CH 3) 2 C 2 H 4 SiCl 3
Compound _{(23); CH 3 (Si} (CH 3) 2 O) 58 Si (CH 3) 2 C 2 H 4 SiCl 3
Compound _{(24); CH 3 (Si} (CH 3) 2 O) 90 Si (CH 3) 2 C 2 H 4 SiCl 3
Compound _{(25); Cl 3 SiC 2} H 4 (Si (CH 3) 2 O) 60 Si (CH 3) 2 C 2 H 4 SiCl 3
Compound _{(26); CH 3 (Si} (CH 3) 2 O) 58 Si (CH 3) 2 C 2 H 4 Si (OCH 3) 3
Compound (27); (CH ₃ O) ₃ SiC ₂ H ₄ (Si (CH ₃ ) ₂ O) ₆₀ Si (CH ₃ ) ₂ C ₂ H ₄ Si (OCH ₃ ) ₃
Compound _{(28); C 4 H 9} (Si (CH 3) 2 O) 60 Si (CH 3) 2 C 2 H 4 SiCl 3
Compound _{(29); CH 3 (Si} (CH 3) 2 O) 60 Si (CH 3) 2 C 2 H 4 SiCl 3
Compound _{(30); CH 3 (Si} (CH 3) 2 O) 120 Si (CH 3) 2 C 2 H 4 SiCl 3
Compound (F1); CF ₃ O (CF ₂ CF ₂ O) _a CF ₂ CONHC ₃ H ₆ Si (OCH ₃ ) ₃
(However, in compound (F1), a is 7-8, and the average value is 7.3.)

[Synthesis Example 1] Synthesis Example of Compound (21) (Production of Hydrogen Polydimethylsiloxane (1-A))
Trimethylsilanol (1.50 g) and THF (3.0 g) were charged into a reactor equipped with a stirrer and a dropping funnel (internal volume 100 mL, glass), and stirred in an ice bath. To this was added dropwise 11.1 mL of a n-butyllithium hexane solution (1.5 mol / L). After stirring for 1 hour, a solution of hexamethylcyclotrisiloxane (23.43 g) dissolved in THF (20 g) was slowly added dropwise. After completion of the dropwise addition, the ice bath was removed and the mixture was stirred for 12 hours. Dimethylchlorosilane (2.40 g) was added dropwise thereto, and the mixture was further stirred for 12 hours.

A 10% by mass aqueous sodium hydrogen carbonate solution was added to the resulting reaction crude liquid to separate it into two layers, and the organic layer was washed with distilled water. This organic layer was dehydrated with magnesium sulfate, and the volatile component was removed under the condition of 50 ° C./10 mmHg to obtain 25.8 g of the compound (1-A) represented by the following formula (1-A). The yield was 99%. The number of repeating units is an average value obtained from ¹ H-NMR, and the same applies to the number of repeating units shown in the following examples.
CH ₃ (Si (CH ₃ ) ₂ O) ₁₉ Si (CH ₃ ) ₂ H (1-A)

The measurement result of ¹ H-NMR (300.4 MHz, standard: C ₆ D ₆ (= 7.00 ppm)) of the obtained compound (1-A) is 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: C 6 D 6) δ (} ppm): 4.88 (1H, m, H-Si), 0.0~0.3 (123H, m, CH 3 -Si).

(Production of Compound (21))
In a reactor equipped with a stirrer and a Dimroth (internal volume 50 mL), compound (1-A) (15.0 g), vinyltrichlorosilane (2.93 g), and Pt catalyst (Pt 1,3-divinyl-1, (2,9% xylene solution of 1,3,3-tetramethyldisiloxane complex) (0.019 g) was added and stirred at room temperature for 24 hours.
Volatile components were removed from the obtained reaction crude liquid under conditions of 50 ° C./10 mmHg, and one end was a mixture of compounds represented by the following formulas (1a) and (1b), respectively, and the ratio of each compound 16.5 g of the compound (21) represented by the following formula (21), which is 55:45 as [the compound of the group (1a): the compound of the group (1b)]. The yield was 100%.

_{-Si (CH 3) 2 CH 2} CH 2 SiCl 3 ... (1a)
_{-Si (CH 3) 2 CH (} CH 3) SiCl 3 ... (1b)
_{CH 3 (Si (CH 3)} 2 O) 19 Si (CH 3) 2 C 2 H 4 SiCl 3 ... (21)

The measurement result of ¹ H-NMR (300.4 MHz, standard: C ₆ D ₆ (= 7.00 ppm)) of the obtained compound (21) is shown below.
¹ H-NMR (solvent: C ₆ D ₆ ) δ (ppm): 1.06 (1.1 H, m, SiCH ₂ [CH ₂ ] SiCl ₃ ), 0.97 (1.35 H, d, SiCH ([[ _{CH 3]) SiCl 3),} 0.55 (1.1H, m, Si [CH 2] CH 2 SiCl 3), 0.0~0.3 (123.5H, m, CH 3 -Si and Si [ _{CH] (CH 3) SiCl 3} ).

[Synthesis Example 2] Synthesis Example of Compound (22) (Production of Hydrogen Polydimethylsiloxane (2-A))
Trimethylsilanol (0.75 g) and THF (3.0 g) were charged into a reactor equipped with a stirrer and a dropping funnel (internal volume 100 mL, glass), and stirred in an ice bath. To this, 5.5 mL of a hexane solution (1.5 mol / L) of n-butyllithium was added dropwise. After stirring for 1 hour, a solution of hexamethylcyclotrisiloxane (24.20 g) dissolved in THF (20 g) was slowly added dropwise. After completion of the dropwise addition, the ice bath was removed and the mixture was stirred for 12 hours. Dimethylchlorosilane (1.20 g) was added dropwise thereto, and the mixture was further stirred for 12 hours.

A 10% by mass aqueous sodium hydrogen carbonate solution was added to the resulting reaction crude liquid to separate it into two layers, and the organic layer was washed with distilled water. This organic layer was dehydrated with magnesium sulfate, and the volatile component was removed under the condition of 50 ° C./10 mmHg to obtain 25.0 g of the compound (2-A) represented by the following formula (2-A). The yield was 99%.
_{CH 3 (Si (CH 3)} 2 O) 39 Si (CH 3) 2 H ... (2-A)

The measurement result of ¹ H-NMR (300.4 MHz, standard: C ₆ D ₆ (= 7.00 ppm)) of the obtained compound (2-A) is shown below.
¹ H-NMR _{(solvent: C 6 D 6) δ (} ppm): 4.88 (1H, m, H-Si), 0.0~0.3 (243H, m, CH 3 -Si).

(Production of Compound (22))
In a reactor equipped with a stirrer and a Dimroth (internal volume 50 mL), compound (2-A) (15.0 g), vinyltrichlorosilane (1.64 g), and Pt catalyst (Pt 1,3-divinyl-1, (2 mass% xylene solution of 1,3,3-tetramethyldisiloxane complex) (0.010 g) was added and stirred at room temperature for 24 hours.

Volatile components were removed from the obtained reaction crude liquid under conditions of 50 ° C./10 mmHg, and one end was a mixture of compounds each having group (1a) and group (1b), and the ratio of each compound was [group 16.5 g of the compound (22) represented by the following formula (22), which is 52:48 as the compound (1a): the compound of the group (1b)]. The yield was 100%.
_{CH 3 (Si (CH 3)} 2 O) 39 Si (CH 3) 2 C 2 H 4 SiCl 3 ... (22)

The measurement result of ¹ H-NMR (300.4 MHz, standard: C ₆ D ₆ (= 7.00 ppm)) of the obtained compound (22) is shown below.
¹ H-NMR (solvent: C ₆ D ₆ ) δ (ppm): 1.06 (1.04H, m, SiCH ₂ [CH ₂ ] SiCl ₃ ), 0.98 (1.44H, d, SiCH ([[ _{CH 3]) SiCl 3),} 0.55 (1.04H, m, Si [CH 2] CH 2 SiCl 3), 0.0~0.3 (243.5H, m, CH 3 -Si and Si [ _{CH] (CH 3) SiCl 3} ).

[Synthesis Example 3] Synthesis Example of Compound (23) (Production of Hydrogen Polydimethylsiloxane (3-A))
Trimethylsilanol (1.00 g) and THF (5.0 g) were charged into a reactor equipped with a stirrer and a dropping funnel (internal volume 200 mL, made of glass), and stirred in an ice bath. 7.0 mL of a hexane solution (1.5 mol / L) of n-butyllithium was added dropwise thereto. After stirring for 1 hour, a solution of hexamethylcyclotrisiloxane (49.39 g) dissolved in THF (45 g) was slowly added dropwise. After completion of the dropping, the ice bath was removed and the mixture was stirred for 12 hours. Dimethylchlorosilane (1.15 g) was added dropwise thereto, and the mixture was further stirred for 12 hours.

A 10% by mass aqueous sodium hydrogen carbonate solution was added to the resulting reaction crude liquid to separate it into two layers, and the organic layer was washed with distilled water. This organic layer was dehydrated with magnesium sulfate, and the volatile component was removed under the condition of 50 ° C./10 mmHg to obtain 50.6 g of the compound (3-A) represented by the following formula (3-A). The yield was 99%.
CH ₃ (Si (CH ₃ ) ₂ O) ₅₈ Si (CH ₃ ) ₂ H (3-A)

The measurement result of ¹ H-NMR (300.4 MHz, standard: C ₆ D ₆ (= 7.00 ppm)) of the obtained compound (3-A) is shown below.
¹ H-NMR _{(solvent: C 6 D 6) δ (} ppm): 4.88 (1H, m, H-Si), 0.0~0.3 (357H, m, CH 3 -Si).

(Production of Compound (23))
In a reactor equipped with a stirrer and a Dimroth (internal volume 50 mL), compound (3-A) (20.0 g), vinyltrichlorosilane (1.40 g), and Pt catalyst (Pt 1,3-divinyl-1, (2 mass% xylene solution of 1,3,3-tetramethyldisiloxane complex) (0.021 g) was added and stirred at room temperature for 24 hours.

Volatile components were removed from the obtained reaction crude liquid under conditions of 50 ° C./10 mmHg, and one end was a mixture of compounds each having group (1a) and group (1b), and the ratio of each compound was [group 20.5 g of the compound (23) represented by the following formula (23), which was 60:40 as the compound (1a): the compound of the group (1b)], was obtained. The yield was 99%.
CH ₃ (Si (CH ₃ ) ₂ O) ₅₈ Si (CH ₃ ) ₂ C ₂ H ₄ SiCl ₃ (23)

The measurement result of ¹ H-NMR (300.4 MHz, standard: C ₆ D ₆ (= 7.00 ppm)) of the obtained compound (23) is shown below.
¹ H-NMR (solvent: C ₆ D ₆ ) δ (ppm): 1.05 (1.2 H, m, SiCH ₂ [CH ₂ ] SiCl ₃ ), 0.98 (1.2 H, d, SiCH ([ _{CH 3]) SiCl 3),} 0.55 (1.2H, m, Si [CH 2] CH 2 SiCl 3), 0.0~0.3 (357H, m, CH 3 -Si and Si [CH] (CH ₃ ) SiCl ₃ ).

[Synthesis Example 4] Synthesis Example of Compound (24) (Production of Hydrogen Polydimethylsiloxane (4-A))
Trimethylsilanol (0.75 g) and THF (5.0 g) were charged into a reactor equipped with a stirrer and a dropping funnel (internal volume 200 mL, glass), and stirred in an ice bath. To this, 5.5 mL of a hexane solution (1.5 mol / L) of n-butyllithium was added dropwise. After stirring for 1 hour, a solution of hexamethylcyclotrisiloxane (55.50 g) dissolved in THF (50 g) was slowly added dropwise. After completion of the dropping, the ice bath was removed and the mixture was stirred for 12 hours. Dimethylchlorosilane (0.88 g) was added dropwise thereto, and the mixture was further stirred for 12 hours.

A 10% by mass aqueous sodium hydrogen carbonate solution was added to the resulting reaction crude liquid to separate it into two layers, and the organic layer was washed with distilled water. This organic layer was dehydrated with magnesium sulfate, and the volatile component was removed under the condition of 50 ° C./10 mmHg to obtain 55.8 g of the compound (4-A) represented by the following formula (4-A). The yield was 98%.
CH ₃ (Si (CH ₃ ) ₂ O) ₉₀ Si (CH ₃ ) ₂ H (4-A)

The measurement result of ¹ H-NMR (300.4 MHz, standard: C ₆ D ₆ (= 7.00 ppm)) of the obtained compound (4-A) is shown below.
¹ H-NMR _{(solvent: C 6 D 6) δ (} ppm): 4.88 (1H, m, H-Si), 0.0~0.3 (549H, m, CH 3 -Si).

(Production of Compound (24))
In a reactor equipped with a stirrer and a Dimroth (internal volume 50 mL), compound (4-A) (20.0 g), vinyltrichlorosilane (0.95 g), and Pt catalyst (Pt 1,3-divinyl-1, (2,8% xylene solution of 1,3,3-tetramethyldisiloxane complex) (0.008 g) was added and stirred at room temperature for 48 hours.

Volatile components were removed from the obtained reaction crude liquid under conditions of 50 ° C./10 mmHg, and one end was a mixture of compounds each having group (1a) and group (1b), and the ratio of each compound was [group 20.3 g of the compound (24) represented by the following formula (24), which was 60:40 as the compound of (1a): the compound of group (1b)], was obtained. The yield was 99%.
CH ₃ (Si (CH ₃ ) ₂ O) ₉₀ Si (CH ₃ ) ₂ C ₂ H ₄ SiCl ₃ (24)

The measurement result of ¹ H-NMR (300.4 MHz, standard: C ₆ D ₆ (= 7.00 ppm)) of the obtained compound (24) is shown below.
¹ H-NMR (solvent: C ₆ D ₆ ) δ (ppm): 1.05 (1.2 H, m, SiCH ₂ [CH ₂ ] SiCl ₃ ), 0.98 (1.2 H, d, SiCH ([ _{CH 3]) SiCl 3),} 0.55 (1.2H, m, Si [CH 2] CH 2 SiCl 3), 0.0~0.3 (550H, m, CH 3 -Si and Si [CH] (CH ₃ ) SiCl ₃ ).

[Synthesis Example 5] Synthesis Example of Compound (25) In a reactor equipped with a stirrer and a Dimroth (internal volume 50 mL), DMS-V21 (trade name, manufactured by Gelest, both end vinyl polydimethylsiloxane, (Si (CH ₃ ) ₂ O) unit repeat number 60) (20.0 g), trichlorosilane (2.02 g), and Pt catalyst (1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of Pt) 2 mass% xylene solution) (0.021 g) was added and stirred at room temperature for 24 hours.

Volatile components were removed from the obtained reaction crude liquid under the conditions of 50 ° C./10 mmHg, and both ends were a mixture of compounds each having either group (1a) or group (1b), and [group (1a ): Group (1b)] was obtained in an amount of 90:10, and 10.1 g of compound (25) represented by the following formula (25) was obtained. The yield was 98%.
Cl ₃ SiC ₂ H ₄ (Si (CH ₃ ) ₂ O) ₆₀ Si (CH ₃ ) ₂ C ₂ H ₄ SiCl ₃ (25)

The measurement result of ¹ H-NMR (300.4 MHz, standard: C ₆ D ₆ (= 7.00 ppm)) of the obtained compound (25) is shown below.
¹ H-NMR (solvent: C ₆ D ₆ ) δ (ppm): 1.05 (3.6 H, m, SiCH ₂ [CH ₂ ] SiCl ₃ ), 0.98 (0.6 H, d, SiCH ([[ _{CH 3]) SiCl 3),} 0.55 (3.6H, m, Si [CH 2] CH 2 SiCl 3), 0.0~0.3 (366H, m, CH 3 -Si and Si [CH] (CH ₃ ) SiCl ₃ ).

Synthesis Example 6 Synthesis Example of Compound (26) In a reactor equipped with a stirrer and a Dimroth (internal volume 50 mL), compound (3-A) (20.0 g), vinyltrimethoxysilane (1.33 g), and Pt catalyst (2 mass% xylene solution of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of Pt) (0.086 g) was added and heated to 60 ° C. in an oil bath. And stirred for 6 hours.

Volatile components were removed from the obtained reaction crude liquid under the conditions of 50 ° C./10 mmHg, and one end was a mixture of compounds represented by the following formulas (6a) and (6b), respectively, Was 20.4 g of the compound (26) represented by the following formula (26), in which [Compound of group (6a): Compound of group (6b)] was 80:20. The yield was 99%.
—Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ (6a)
_{-Si (CH 3) 2 CH (} CH 3) Si (OCH 3) 3 ... (6b)
_{CH 3 (Si (CH 3)} 2 O) 58 Si (CH 3) 2 C 2 H 4 Si (OCH 3) 3 ... (26)

The measurement result of ¹ H-NMR (300.4 MHz, standard: C ₆ D ₆ (= 7.00 ppm)) of the obtained compound (26) is shown below.
¹ H-NMR (solvent: C ₆ D ₆ ) δ (ppm): 3.35 (9H, s, OCH ₃ ), 1.17 (0.6 H, d, SiCH ([CH ₃ ]) Si (OCH _{3 ) 3), 0.63 (3.2H,} m, Si [CH 2 CH 2] Si (OCH 3) 3), 0.0~0.3 (357H, m, CH 3 -Si and Si [CH] (CH ₃ ) Si (OCH ₃ ) ₃ ).

Synthesis Example 7 Synthesis Example of Compound (27) In a reactor equipped with a stirrer and a Dimroth (internal volume 50 mL), DMS-V21 (20.0 g), trimethoxysilane (1.66 g), and Pt catalyst (Pt (2-26% xylene solution of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex) (0.026 g) was added, heated to 80 ° C. in an oil bath, and stirred for 4 hours. did.

Volatile components were removed from the obtained reaction crude liquid under the conditions of 50 ° C./10 mmHg, and both ends were a mixture of compounds each having one of groups (6a) and (6b), [group (6a ): Group (6b)] was obtained in an amount of 80:20, and 10.1 g of compound (27) represented by the following formula (27) was obtained. The yield was 98%.
(CH ₃ O) ₃ SiC ₂ H ₄ (Si (CH ₃ ) ₂ O) ₆₀ Si (CH ₃ ) ₂ C ₂ H ₄ Si (OCH ₃ ) ₃ (27)

The measurement result of ¹ H-NMR (300.4 MHz, standard: C ₆ D ₆ (= 7.00 ppm)) of the obtained compound (27) is shown below.
¹ H-NMR (solvent: C ₆ D ₆ ) δ (ppm): 3.35 (18H, s, OCH ₃ ), 1.16 (1.2 H, d, SiCH ([CH ₃ ]) Si (OCH _{3 ) 3), 0.64 (6.4H,} m, Si [CH 2 CH 2] Si (OCH 3) 3), 0.0~0.3 (366H, m, CH 3 -Si and Si [CH] (CH ₃ ) Si (OCH ₃ ) ₃ ).

[Synthesis Example 8] Synthesis Example of Compound (28) To a reactor equipped with a stirrer and a Dimroth (internal volume 50 mL), MCR-H21 (trade name, manufactured by Gelest, one-end butyl-one-end hydridopolydimethylsiloxane, Si (CH ₃ ) ₂ O) unit repeat number 60) (10.0 g), vinyltrichlorosilane (0.70 g), and Pt catalyst (Pt 1,3-divinyl-1,1,3,3-tetra A 2 mass% xylene solution of a methyldisiloxane complex) (0.010 g) was added, and the mixture was stirred at room temperature for 24 hours.

Volatile components were removed from the obtained reaction crude liquid under conditions of 50 ° C./10 mmHg, and one end was a mixture of compounds each having group (1a) and group (1b), and the ratio of each compound was [group 10.1 g of the compound (28) represented by the following formula (28), which was 52:48 as the compound (1a): the compound of the group (1b)]. The yield was 98%.
_{CH 3 CH 2 CH 2 CH 2} (Si (CH 3) 2 O) 60 Si (CH 3) 2 C 2 H 4 SiCl 3 ... (28)

The measurement result of ¹ H-NMR (300.4 MHz, standard: C ₆ D ₆ (= 7.00 ppm)) of the obtained compound (28) is shown below.
¹ H-NMR (solvent: C ₆ D ₆ ) δ (ppm): 1.25 (4H, m, CH ₃ [CH ₂ CH ₂ ] CH ₂ ), 1.05 (1.04H, m, SiCH ₂ [ _{CH 2] SiCl 3), 0.98} (1.44H, d, SiCH ([CH 3]) SiCl 3), 0.80 (3H, t, [CH 3] CH 2), 0.55 (1. _{04H, m, Si [CH 2} ] CH 2 SiCl 3), 0.48 (2H, q, CH 2 CH 2 [CH 2] Si), 0.0~0.3 (363H, m, CH 3 -Si And Si [CH] (CH ₃ ) SiCl ₃ ).

[Synthesis Example 9] Synthesis Example of Compound (29) (Production of Vinyl Polydimethylsiloxane (1-B))
Trimethylsilanol (0.50 g) was charged into a reactor equipped with a stirrer and a dropping funnel (internal volume: 100 mL, made of glass) and stirred in an ice bath. To this, 3.7 mL of a n-butyllithium hexane solution (1.5 mol / L) was added dropwise. After stirring for 1 hour, a solution of hexamethylcyclotrisiloxane (24.66 g) dissolved in THF (25 g) was slowly added dropwise. After completion of the dropwise addition, the ice bath was removed and the mixture was stirred for 5 hours. Chlorodimethylvinylsilane (1.00 g) was added dropwise thereto, and the mixture was further stirred for 12 hours.

A 10% by mass aqueous sodium hydrogen carbonate solution was added to the resulting reaction crude liquid to separate it into two layers, and the organic layer was washed with distilled water. This organic layer was dehydrated with magnesium sulfate, and volatile components were removed under the condition of 50 ° C./10 mmHg to obtain 25.2 g of the compound (1-B) represented by the following formula (1-B). The yield was 98%.
_{CH 3 (Si (CH 3)} 2 O) 60 Si (CH 3) 2 CH = CH 2 ... (1-B)
The measurement result of ¹ H-NMR (300.4 MHz, standard: C ₆ D ₆ (= 7.00 ppm)) of the obtained compound (1-B) is shown below.
¹ H-NMR (solvent: C ₆ D ₆ ) δ (ppm): 5.6 to 6.1 (3H, m, H—Si), 0.0 to 0.3 (369H, m, CH ₃ —Si) ).

(Production of Compound (29))
In a reactor equipped with a stirrer and a Dimroth (internal volume 50 mL), compound (1-B) (20.0 g), trichlorosilane (1.17 g), and Pt catalyst (1,3-divinyl-1,1 Pt) , 3,3-tetramethyldisiloxane complex in 2% by mass xylene) (0.015 g) was added and stirred at room temperature for 24 hours.
Volatile components were removed from the obtained reaction crude liquid under conditions of 50 ° C./10 mmHg, and one end was a mixture of compounds each having group (1a) and group (1b), and the ratio of each compound was [group 20.2 g of the compound (29) represented by the following formula (29), which is 94: 6 as the compound of (1a): the compound of group (1b)], was obtained. The yield was 98%.
_{CH 3 (Si (CH 3)} 2 O) 60 Si (CH 3) 2 C 2 H 4 SiCl 3 ... (29)

The measurement result of ¹ H-NMR (300.4 MHz, standard: C ₆ D ₆ (= 7.00 ppm)) of the obtained compound (29) is shown below.
¹ H-NMR (solvent: C ₆ D ₆ ) δ (ppm): 1.05 (1.88H, m, SiCH ₂ [CH ₂ ] SiCl ₃ ), 0.98 (0.18H, d, SiCH ([[ _{CH 3]) SiCl 3),} 0.55 (1.88H, m, Si [CH 2] CH 2 SiCl 3), 0.0~0.3 (369H, m, CH 3 -Si and Si [CH] (CH ₃ ) SiCl ₃ ).

[Synthesis Example 10] Synthesis Example of Compound (30) (Production of Vinyl Polydimethylsiloxane (2-B))
Trimethylsilanol (0.25 g) was charged into a reactor equipped with a stirrer and a dropping funnel (internal volume 100 mL, glass) and stirred in an ice bath. To this, 1.8 mL of a hexane solution (1.5 mol / L) of n-butyllithium was added dropwise. After stirring for 1 hour, a solution of hexamethylcyclotrisiloxane (24.66 g) dissolved in THF (25 g) was slowly added dropwise. After completion of the dropwise addition, the ice bath was removed and the mixture was stirred for 5 hours. Chlorodimethylvinylsilane (0.50 g) was added dropwise thereto, and the mixture was further stirred for 12 hours.
A 10% by mass aqueous sodium hydrogen carbonate solution was added to the resulting reaction crude liquid to separate it into two layers, and the organic layer was washed with distilled water. This organic layer was dehydrated with magnesium sulfate, and the volatile component was removed under the condition of 50 ° C./10 mmHg to obtain 24.8 g of the compound (2-B) represented by the following formula (2-B). The yield was 99%.
_{CH 3 (Si (CH 3)} 2 O) 120 Si (CH 3) 2 CH = CH 2 ... (2-B)

The measurement result of ¹ H-NMR (300.4 MHz, standard: C ₆ D ₆ (= 7.00 ppm)) of the obtained compound (2-B) is shown below.
¹ H-NMR (solvent: C ₆ D ₆ ) δ (ppm): 5.6 to 6.1 (3H, m, H—Si), 0.0 to 0.3 (729H, m, CH ₃ —Si) ).

(Production of Compound (30))
In a reactor equipped with a stirrer and a Dimroth (internal volume 50 mL), compound (2-B) (20.0 g), trichlorosilane (0.60 g), and Pt catalyst (Pt 1,3-divinyl-1,1 , 3,3-tetramethyldisiloxane complex (2 mass% xylene solution) (0.009 g) was added and stirred at room temperature for 24 hours.
Volatile components were removed from the obtained reaction crude liquid under conditions of 50 ° C./10 mmHg, and one end was a mixture of compounds each having group (1a) and group (1b), and the ratio of each compound was [group 20.1 g of the compound (30) represented by the following formula (30) which is 93: 7 as the compound (1a): the compound of the group (1b)] was obtained. The yield was 99%.
_{CH 3 (Si (CH 3)} 2 O) 120 Si (CH 3) 2 C 2 H 4 SiCl 3 ... (30)

The measurement result of ¹ H-NMR (300.4 MHz, standard: C ₆ D ₆ (= 7.00 ppm)) of the obtained compound (30) is shown below.
¹ H-NMR (solvent: C ₆ D ₆ ) δ (ppm): 1.05 (1.86H, m, SiCH ₂ [CH ₂ ] SiCl ₃ ), 0.98 (0.21H, d, SiCH ([[ _{CH 3]) SiCl 3),} 0.55 (1.86H, m, Si [CH 2] CH 2 SiCl 3), 0.0~0.3 (729H, m, CH 3 -Si and Si [CH] (CH ₃ ) SiCl ₃ ).

[Synthesis Example 11] Synthesis Example of Compound (F1) Compound (F1) used in Comparative Example was synthesized by the following method. The abbreviations of the compounds and groups in the synthesis examples were used as follows.
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) _a CH ₂ CH ₂ OH (commercially available polyoxyethylene glycol monomethyl ether, a = 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) a CH 2 CH 2 OC (O) -R F6 (a = 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) _a 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) _a CF ₂ CF ₂ OC (O) —R liquid at room temperature was used. 45.4 g of ^F6 (a = 7 to 8, average value: 7.3) was obtained.

A 300 mL eggplant flask charged with a stirrer chip was sufficiently purged with nitrogen. In an eggplant flask, 40 g of ethanol, 5.6 g of NaF, and R-225 (50 g) were placed. 43.5 g of CF ₃ O (CF ₂ CF ₂ O) _a CF ₂ CF ₂ OC (O) —R ^F6 was dropped into the eggplant flask, and then 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, 26.8 g of a compound (CF ₃ O (CF ₂ CF ₂ O) _a CF ₂ C (O) OCH ₂ CH ₃ (a = 7 to 8, average value: 7.3)) which is liquid at room temperature Got.

100mL round bottom _{flask, CF 3 O (CF 2 CF} 2 O) a 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 (F1) which was liquid at room temperature.

[Preparation of composition for forming water-repellent film]
(Water repellent film forming compositions 1 to 5, water repellent film forming compositions 8 to 10)
In a glass container in which a stirrer and a thermometer were set, the compound (21) obtained above was mixed at a ratio of 10% by mass and butyl acetate (manufactured by Junsei Chemical Co., Ltd.) at 90% by mass. Was stirred for 5 minutes to obtain a composition 1 for forming a water-repellent film. Water repellency was similarly obtained except that the compound (21) was changed to the compound (22), the compound (23), the compound (24), the compound (25), the compound (28), the compound (29), and the compound (30). Film forming composition 2, Water repellent film forming composition 3, Water repellent film forming composition 4, Water repellent film forming composition 5, Water repellent film forming composition 8, Water repellent film forming composition 9 and a composition 10 for forming a water-repellent film were obtained.

(Water repellent film forming compositions 6, 7)
In a glass container in which a stirrer and a thermometer are set, the compound (26) obtained above is mixed at a ratio of 10% by mass and isopropyl alcohol (manufactured by Junsei Chemical Co., Ltd.) at 87% by mass. After stirring for 1 minute, 3% by weight of a 10% by weight aqueous nitric acid solution was added and stirred for 5 minutes at 25 ° C. to obtain a water repellent film-forming composition 6. In addition, content (mass%) of each component is the mass% with respect to the whole quantity of the composition 6 for water-repellent film formation. A water repellent film-forming composition 7 was obtained in the same manner except that the compound (26) was changed to the compound (27).

(Water repellent layer forming composition 11)
The compound (F1) obtained above is used as a hydrolyzable silane compound having a fluorine-containing polyether group, and the water-repellent layer is formed by combining the compound (F1) and a hydrolyzable silane compound having a fluorine-containing alkyl group. Composition 11 was prepared as follows.
In a glass container in which a stirrer and a thermometer are set, 12.4% by mass of isopropyl alcohol (manufactured by Junsei Co., Ltd.), 3.10% by mass of hydrofluoroether (AE3000, manufactured by Asahi Glass Co., Ltd.), C ₆ F ₁₃ C _{2 H 4 Si (OCH 3)} 3 (manufactured by Shin Quest) 0.74 wt%, was placed the compound (F1) 0.32 wt%, and stirred for 30 minutes at 25 ° C.. Subsequently, 0.10 mass% of 10% nitric acid aqueous solution was added, and it stirred at 25 degreeC for 2 hours, and obtained the composition 11 for water-repellent layer formation.

[Preparation of composition for forming underlayer]
(Underlayer forming compositions 1-6)
In a glass container in which a stirrer and a thermometer are set, 8.77 g of isopropyl alcohol (manufactured by Junsei Chemical Co., Ltd.), tetramethoxysilane; Si (OCH ₃ ) ₄ (manufactured by Kanto Chemical Co., Inc., hereinafter “ TMOS ”) and bistrimethoxysilylethane (CH ₃ O) ₃ SiCH ₂ CH ₂ Si (OCH ₃ ) ₃ , manufactured by Kanto Chemical Co., Inc., hereinafter referred to as“ BTME ”. ) Was added at a total of 0.39 g and stirred at 25 ° C. for 3 minutes, and then 0.84 g of a 0.463 wt% aqueous nitric acid solution was added dropwise and stirred at 25 ° C. for 1 hour, thereby forming an underlayer-forming composition 1 6 was obtained.

(Underlayer forming compositions 7 to 12)
In a glass container in which a stirrer and a thermometer are set, tetraisocyanate silane; Si (NCO) ₄ (SI-400 (trade name, Matsumoto) at a ratio shown in Table 1 to 9.50 g of butyl acetate (manufactured by Junsei Chemical Co., Ltd.) Fine Chemical Co., Ltd.)) and bistriisocyanate silylethane ((OCN) ₃ SiCH ₂ CH ₂ Si (NCO) ₃ , Matsumoto Fine Chemical Co., Ltd., hereinafter referred to as “BTIE”) were added in total and added at 25 ° C. for 5 minutes. By stirring, compositions 7 to 12 for forming an underlayer were obtained.

(Underlayer forming composition 13)
In a glass container in which a stirrer and a thermometer are set, 9.70 g of butyl acetate (manufactured by Junsei Chemical Co., Ltd.), tetraisocyanate silane; Si (NCO) ₄ (SI-400 (trade name, manufactured by Matsumoto Fine Chemical Co., Ltd.) 0 30 g was added and stirred at 25 ° C. for 30 minutes to obtain an underlayer-forming composition 13.

[Manufacture of substrate with water repellent film]
(Example 1 to Example 60)
As the substrate, a clean soda lime glass substrate (water contact angle 5 degrees, 300 mm × 300 mm × thickness 3 mm), which was polished and cleaned with cerium oxide, was used. As shown in Fig. 2, 0.5 g of any of the liquid compositions 1 to 6 for forming the underlayer obtained above (only the numbers are shown in the column of the underlayer in Tables 2 and 3) was applied by the squeegee coating method. And dried at 25 ° C. for 1 minute to form a base layer (uncured). Subsequently, on the surface of the formed underlayer (uncured), as shown in Tables 2 and 3, the water-repellent layer-forming compositions 1 to 10 obtained above (in Tables 2 and 3, in the column of the water-repellent layer) 0.5 g of any one of them is applied by a squeegee coating method, and kept in a constant temperature and humidity chamber set at 50 ° C. and 60% RH for 48 hours to form a water repellent layer and at the same time, a base layer After curing, the surface of the water repellent layer was wiped with a paper waste impregnated with 2-propanol, thereby having a water repellent film comprising a base layer / water repellent layer in order from the substrate side. A substrate with a water-repellent film was obtained.

(Example 61 to Example 78)
As the substrate, a clean soda lime glass substrate (water contact angle 5 degrees, 300 mm × 300 mm × thickness 3 mm), which was polished and cleaned with cerium oxide, was used, and the surface of the glass substrate was as shown in Table 3. 0.5 g of any of the underlayer-forming liquid compositions 7 to 12 obtained above (in Table 3, only the numbers are shown in the underlayer column) is applied by squeegee coating, and 1 at 25 ° C. Dried for a minute to form a base layer (uncured). Then, on the surface of the formed underlayer (uncured), as shown in Table 3, the water-repellent layer-forming compositions 1 to 3 obtained above (in Table 3, only the numbers are shown in the column of the water-repellent layer). ) Was applied by a squeegee coating method and kept in a constant temperature and humidity chamber set at 50 ° C. and 60% RH for 48 hours to form a water repellent layer and at the same time, the underlayer was cured. Thereafter, the surface of the water-repellent layer was wiped with a paper cloth soaked with 2-propanol, so that the water-repellent film of Examples 61 to 78 having the water-repellent film composed of the base layer / water-repellent layer in order from the substrate side was attached. A substrate was obtained.

(Example 79)
As the substrate, a clean soda lime glass substrate (water contact angle 5 degrees, 300 mm × 300 mm × thickness 3 mm), which was polished and cleaned with cerium oxide, was obtained on the surface of the glass substrate as described above. 2 g of the underlayer-forming liquid composition 13 was applied by a squeegee coating method and held at 25 ° C. for 1 minute to form an underlayer (uncured). Next, 2 g of the water repellent layer-forming composition 11 obtained above was applied to the surface of the formed underlayer (uncured) by the squeegee coating method, and a constant temperature and humidity chamber set to 50 ° C. and 60% RH. For 48 hours to form a water-repellent layer and at the same time cure the base layer, and then wipe the surface of the water-repellent layer with a paper cloth soaked with 2-propanol in order from the base side / A substrate with a water repellent film of Example 79 having a water repellent film comprising a water repellent layer was obtained.

[Evaluation]
Evaluation of the substrate with a water-repellent film obtained in Examples 1 to 79 was performed as follows. In addition, before each measurement, the dirt on the film surface was removed with a paper waste containing ethanol.
<Initial water repellency>
The water repellency was evaluated by the water contact angle (CA) measured by the following method for static water repellency, and the water falling angle (SA) measured by the following method for dynamic water repellency (water slidability). First, the initial value was measured before the following moisture resistance test. In addition, if the initial water contact angle (CA) is 100 degrees or more and the water falling angle (SA) is 8 degrees 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 substrate 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.

(Water drop angle (SA))
After dropping 50 μL of water droplets on 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 sliding angle, the better the dynamic water repellency (slidability).

<Moisture resistance test>
The substrate with water repellent film obtained in Examples 1 to 79 was subjected to a moisture resistance test in which the substrate was exposed for 500 hours in an environment of 50 ° C. and 95% RH, and then the water contact angle (CA), water The sliding angle (SA) was measured. In addition, if the water contact angle (CA) after a moisture resistance test is 90 degrees or more and the water falling angle (SA) is 10 degrees or less, it can be said that it has sufficient water repellency and water slidability moisture resistance for actual use. .
The results of the initial water repellency measured above and the water repellency after the moisture resistance test are shown in Table 2 (Example 1 to Example 42) and Table 3 (Example 43 to Example 79).

<Outdoor exposure test>
The substrate with water-repellent film obtained in Examples 1 to 79 was subjected to an outdoor exposure test according to 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 after three months had passed since the start of the test, The water falling angle was measured. In addition, if the water contact angle (CA) after an outdoor exposure test is 90 degrees or more and the water falling angle (SA) is 10 degrees or less, it can be said that it has sufficient water repellency and water slidability and moisture resistance for actual use. . The results are shown in Table 2 (Examples 1 to 42) and Table 3 (Examples 43 to 79).

<Slidability of small water drops>
The sliding property of small water droplets on the surface of the water-repellent film of the substrate with the water-repellent film obtained in Examples 1 to 79 was evaluated by the following method. The sliding property of small water droplets is a physical property that is preferably possessed particularly in applications for articles for transportation equipment.
(Small water slidability 1)
As shown in Table 2 (Example), a 6 μL water droplet is placed on the water repellent film of the substrate with a water repellent film inclined at 70 degrees from the horizontal, and the sliding speed is calculated by measuring the time required to move 50 mm and the sliding speed is calculated. 1 to Example 42) and Table 3 (Examples 43 to 79). Note that the evaluation “x” in Example 79 indicates that no movement occurred. In the evaluation of small water droplet sliding property 1, it can be said that if a small water droplet slides, the sliding property is excellent. Furthermore, if the sliding speed is 1 mm / second or more, it can be said that the sliding characteristics of small water droplets are very excellent.

(Small water slidability 2)
Evaluation of small water drop sliding property 2 by visually checking whether or not the water droplet slides 50 mm or more in 5 minutes when a water droplet of 2 μL is placed on the water repellent film of the substrate with the water repellent film inclined at 70 degrees from the horizontal. It was. In the evaluation of small water droplet sliding property 2, Table 2 (Example 1 to Example 42) and Table 3 (Example 43 to Example) are shown as “O” when the water droplet slides 50 mm or more and “X” when the water droplet does not slide 50 mm or more. 79). If the evaluation of small water drop sliding property 2 is “◯”, it can be said that the small water droplet sliding property is very excellent.

As can be seen from Table 2 and Table 3, the compound (2) -derived component (component (B)) is contained on the foundation layer formed using the composition for forming the foundation layer not containing the compound (1) -derived component. Comparative Examples (Examples 6, 12, 18, 24, 30, 36, 42, 48, 54, 60, 66, 72, 78) having a water repellent layer formed using the water repellent layer forming composition While the substrate with a water film is excellent in initial water repellency, the substrate with the water repellent film in the examples is excellent in initial water repellency and can sufficiently maintain the water repellency after the moisture resistance test. Recognize.
Further, in Example 79 using the composition for forming a water repellent layer in which a hydrolyzable silane compound having a fluorine-containing polyether group and a hydrolyzable silane compound having a fluorine-containing alkyl group were combined, although excellent in moisture resistance, It cannot be said that dynamic water repellency is sufficient at the initial stage.

  The substrate with a water-repellent film of the present invention is excellent in both static water repellency and dynamic water repellency, and is excellent in durability such as moisture resistance, and is used for transportation of trains, automobiles, ships, airplanes, etc. It is suitably used for applications such as body, window glass (front glass, side glass, rear glass), mirror, bumper, etc. in equipment.

Claims (10)

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;
The water repellent film is sequentially from the substrate side.
An underlayer formed by using an underlayer-forming composition containing a component (A) comprising a compound represented by the following formula (1) and / or a partially hydrolyzed condensate thereof, and represented by the following formula (2) A water repellent layer formed using a composition for forming a water repellent layer comprising the component (B) comprising the compound and / or a partially hydrolyzed condensate thereof,
A substrate with a water repellent film.
X ¹ ₃ Si— (CH ₂ ) _m —SiX ¹ ₃ (1)
(However, in the formula (1), X ¹ each independently represents a hydrolyzable group or a hydroxyl group, m is an integer of 1 to 8.)
R ³ — (SiR ² ₂ O) _k —SiR ² ₂ —Y ¹ —Si (R ¹ ) _{3 -n} (X ² ) _n (2)
(In the formula (2), R ³ represents an alkyl group having 10 or less carbon atoms or —Y ¹ —Si (R ¹ ) _3-n (X ² ) _n group, and R ² each independently represents a carbon atom. An alkyl group having a number of 3 or less, Y ¹ is independently an alkylene group having 2 to 4 carbon atoms, R ¹ is independently a monovalent hydrocarbon group, and X ² is independently hydrolyzed. Represents a decomposable group, k is an integer of 10 to 200, and n is an integer of 1 to 3.) The underlayer-forming composition includes the component (A) and the component (C) composed of a compound represented by the following formula (3) and / or a partial hydrolysis condensate thereof, or the component (A) The substrate with a water-repellent film according to claim 1, comprising a partial hydrolysis cocondensate of a component and the component (C) (however, the component (A) and / or the component (C) may be included).
Si (X ³ ) ₄ (3)
(However, in formula (3), X ³ each independently represents a halogen atom, an alkoxy group or an isocyanate group.)   The content ratio of the compound-derived component represented by the formula (1) and the compound-derived component represented by the formula (3) in the composition for forming an underlayer is [the compound-derived component represented by the formula (1) The substrate with a water-repellent film according to claim 2, wherein the mass ratio represented by: the compound-derived component represented by the formula (3)] is 0.1: 0.9 to 0.9: 0.1.   The content ratio of the compound-derived component represented by the formula (1) and the compound-derived component represented by the formula (3) in the composition for forming an underlayer is [the compound-derived component represented by the formula (1) The substrate with a water repellent film according to claim 3, wherein the mass ratio represented by: the compound-derived component represented by the formula (3)] is 0.1: 0.9 to 0.6: 0.4. In the formula (1), X ¹ is an alkoxy group or an isocyanate group, m is an integer of 1 to 3, the water-repellent film-coated substrate of any one of claims 1-4. In the formula (2), R ² is 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 an integer of 10 to 150. , N is 3, The substrate with a water-repellent film according to claim 1.   The composition for forming an undercoat layer has a total solid content substantially consisting of only the compound-derived component represented by the formula (1), or the compound-derived component represented by the formula (1) and the formula (3). The substrate with a water-repellent film according to any one of claims 1 to 6, comprising only a compound-derived component represented by formula (1).   The substrate with a water-repellent film according to claim 1, wherein the composition for forming a water-repellent layer has a total solid content substantially consisting only of the component (B).   The substrate with a water-repellent film according to claim 1, wherein the substrate is made of glass.   An article for transport equipment comprising the substrate with a water-repellent film according to any one of claims 1 to 9.