JP2014144551A - Substrate with water-repellent film, and article for transportation equipment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate with a water-repellent film which film has durability such as moisture resistance, is excellent in both of static water repellency and dynamic water repellency, and particularly has a high level of dynamic water repellency and to provide an article for transportation equipment, which article comprises the substrate with the water-repellent film.SOLUTION: The substrate with the water-repellent film includes: the substrate; an underlying layer which is formed on at least a part of the surface of the substrate, is based on silicon oxide, and includes an oxide of an element M having the electronegativity lower than that of a silicon atom; and a water repellent layer which is formed above the underlying layer by using a water repellent layer formation composition containing straight-chain polyorganosiloxane having a hydrolyzable silyl group at the terminal and/or a partially-hydrolyzed condensate thereof. The article for transportation equipment, which article comprises the substrate with the water-repellent film.

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, as a composition for forming a water-repellent film excellent in dynamic water repellency in addition to static water repellency, a fluoroalkyl group and a long-chain alkyl are combined with a hydrolyzable group. A composition using an organosilane having a group is known. The water-repellent film obtained by such a composition is a water-repellent film excellent in both static water repellency and dynamic water repellency, but in recent years, there has been a higher demand for dynamic water repellency. For example, the dynamic water repellency is generally considered to be better as the drop angle of the water droplet is smaller, but in addition to this, for example, the property that the sliding speed of the minute water droplet is fast is required.

  On the other hand, when forming such a water-repellent film, a technique is known in which an underlayer such as silica is formed between the surface of the substrate and the water-repellent film in order to increase the durability of the water-repellent film. As such an underlayer, for example, Patent Document 1 describes an underlayer formed of a composition containing silicon alkoxide and a chelate of an alkoxide of a metal other than silicon. According to the underlayer described in Patent Document 1, the effect of enhancing the durability of the water-repellent film obtained using the organosilane having a fluoroalkyl group is obtained, but the dynamic water-repellent property of the water-repellent film is obtained. Is not raised to a higher level.

JP 2001-205187 A

  The present invention was made from the above viewpoint, and is a water-repellent film having durability such as moisture resistance and excellent in both static and dynamic water repellency, and has a particularly high level of dynamic water repellency. It is an object of the present invention to provide a substrate with a water-repellent film having the water-repellent film and 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 containing an oxide of element M mainly composed of silicon oxide and having a lower electronegativity than silicon atoms, and
A water repellent layer formed using a water repellent layer-forming composition comprising a component (A) comprising a compound represented by the following formula (1) and / or a partially hydrolyzed condensate thereof,
A substrate with a water repellent film.
R ³ — (SiR ² ₂ O) _k —SiR ² ₂ —Y ¹ —Si (R ¹ ) _{3 -n} (X ¹ ) _n (1)
(In the formula (1), R ³ represents an alkyl group having 10 or less carbon atoms or —Y ¹ —Si (R ¹ ) _3-n (X ¹ ) _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 ¹ 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 has a component (B) composed of a compound represented by the following formula (2) and / or a partially hydrolyzed condensate thereof, and a hydrolyzable group bonded to the element M and the element M. A component (C1) comprising a compound and / or a partial hydrolysis condensate thereof and / or a component (C) comprising a component (C2) comprising a salt of the element M and a chelating agent capable of chelating with the element M; Or a partially hydrolyzed cocondensate of the component (B) and the component (C) (however, the component (B) and / or the component (C) may be included) The substrate with a water-repellent film according to [1], which is an underlayer formed using the composition.
Si (X ² ) ₄ (2)
(However, in formula (2), each X ² independently represents a halogen atom, an alkoxy group or an isocyanate group.)

[3] The underlayer-forming composition further includes a component (D) composed of a compound represented by the following formula (3) and / or a partial hydrolysis condensate thereof, or the component (B), Partially hydrolyzed cocondensate by at least two types selected from component (C) and component (D) (however, each of component (B), component (C) and component (D) may be included alone) The substrate with a water repellent film according to [2].
^{_{X 3 3 Si- (CH 2)}} m -SiX 3 3 ... (3)
(However, in Formula (3), X < ³ > shows a hydrolysable group or a hydroxyl group each independently, and m is an integer of 1-8.)

[4] In the underlayer forming composition, the content of the element M derived from the component (C) includes silicon derived from the component (B), the element M derived from the component (C), The substrate with a water-repellent film according to [2] or [3], which is 3 to 50 mol% with respect to 100 mol% of the total amount of silicon derived from component D).

[5] The substrate with a water-repellent film according to [3] or [4], wherein in the formula (3), X ³ is an alkoxy group or an isocyanate group, and m is an integer of 1 to 3.

[6] In the formula (1), R ² is a methyl group, R ³ is a linear alkyl group having 5 or less carbon atoms, and X ¹ is a chlorine atom or an alkoxy group having 3 or less carbon atoms. The substrate with a water-repellent film according to any one of [1] to [5], wherein k is an integer of 10 to 150, and n is 3.
[7] The substrate with a water-repellent film according to any one of [1] to [6], wherein the element M is one or more elements selected from Al, Zr, Hf, Ti, Y, and Ce.
[8] The element M is Al, and the component (C) includes acetylacetonate of Al and / or a partial hydrolysis condensate thereof, and / or a mixture of an Al salt and acetylacetone [2] to [6 ] The base | substrate with a water-repellent film in any one of.
[9] The composition for forming an underlayer has a total solid content substantially consisting of only the component derived from the component (B), the component derived from the component (C), and the component derived from the component (D). ] The substrate with a water-repellent film according to any one of [8] to [8].

[10] The substrate with a water repellent film according to any one of [1] to [9], wherein the composition for forming a water repellent layer has a total solid content substantially consisting only of the component (A).
[11] The substrate with a water-repellent film according to any one of [1] to [10], wherein the substrate is made of glass.
[12] An article for transportation equipment comprising the substrate with a water-repellent film according to any one of [1] to [11].

  According to the present invention, it is a water-repellent film that has durability such as moisture resistance and is excellent in both static and dynamic water repellency. A substrate with a water-repellent film having a water-repellent film having a small and small water droplet sliding speed and a transport device article comprising the substrate with the water-repellent film can be provided.

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. In the present specification, “component derived from component (B)” is used as a generic term for units derived from component (B) in the partially hydrolyzed cocondensate of component (B) and other hydrolyzable components. 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 of the present invention is a substrate with a water-repellent film having a substrate and a water-repellent film on at least a part of the surface of the substrate, and the water-repellent film has the following configuration in order from the substrate side. It has a foundation layer and a water repellent layer.

Underlayer; a layer containing an oxide of element M mainly composed of silicon oxide and having a lower electronegativity than silicon atoms.
Water repellent layer; a layer formed using a water repellent layer forming composition comprising a component (A) comprising a compound represented by the following formula (1) 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 ¹ ) _n (1)
(In the formula (1), R ³ represents an alkyl group having 10 or less carbon atoms or —Y ¹ —Si (R ¹ ) _3-n (X ¹ ) _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 ¹ 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 water-repellent film of the substrate with a water-repellent film of the present invention is formed using a linear silicone compound having a hydrolyzable silyl group at the terminal represented by the above formula (1) on the base layer having the above structure. The structure has a water repellent layer. The component derived from the compound (1) constituting the water repellent layer is electrically neutral as a whole, but partially, specifically, a repeating unit represented by (SiR ² ₂ O) in the formula (1) The oxygen atom inside is negatively charged. In the present invention, since the underlayer contains an oxide of the element M having an electronegativity lower than that of the silicon atom, the element M is positively charged and the compound (1) in the negatively charged water repellent layer It is easy to electrically draw the oxygen atom from the origin. Accordingly, it is considered that the entire component (1) -derived component, in other words, the entire water-repellent layer can be stably covered with almost no gap formed on the underlayer. In the present invention, such a mechanism makes it possible for the entire water-repellent layer to cover the base layer stably and almost without gaps, and to achieve both static and dynamic water repellency inherent to the water-repellent layer. It is considered that a substrate with a water-repellent film that is excellent, in particular, has a high speed at which minute water droplets slide down, that is, has excellent water droplet sliding properties.
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 in the substrate with a water-repellent film of the present invention contains an oxide of element M mainly composed of silicon oxide and having an electronegativity lower than that of silicon atoms. The term “underlayer is mainly composed of silicon oxide” means that silicon atoms are contained in an amount of 50 mol% or more and 100 mol% or less with respect to 100 mol% of the total molar amount of silicon atoms and elements M as constituent components of the underlayer. .

  As such an underlayer, a structure in which silicon oxide in a silicon oxide matrix bonded with siloxane is partially replaced with an oxide of element M is preferable. In addition, when the element M is an element that forms an oxide with the same valence as a silicon atom when forming an oxide, the silicon atom of the silicon oxide matrix bonded with siloxane is partially replaced by the element M. A structure is preferred. The element M is not particularly limited as long as it has an electronegativity lower than that of a silicon atom.

  Here, the electronegativity of the silicon atom is 1.74, and as the element M having a lower electronegativity than the silicon atom, specifically, Al (1.47), Zr (1.22), Hf ( 1.23), Ti (1.32), Y (1.11), Ce (1.06) and the like. The number in parentheses after the element symbol is the electronegativity. Among these, as the element M, Al and Zr are preferable from the viewpoint of the coating property of the composition for forming a water repellent layer, and Al is particularly preferable in view of durability such as moisture resistance of the water repellent film. Such an element M may be used alone or in combination of two or more.

  The content ratio of element M to the total amount of silicon atoms and element M in the underlayer is mol% of element M with respect to the total molar amount of silicon atoms and element M, preferably 3 to 50 mol%, 35 mol% is more preferable. By making the content ratio of element M with respect to the total amount of silicon atoms and element M in the underlayer within the above range, the resulting substrate with a water repellent film has sufficient durability such as moisture resistance and static water repellency. And dynamic water repellency, in particular, small water droplet slidability.

  The underlayer in the substrate with a water-repellent film of the present invention contains the following components (B) and (C), or a partially hydrolyzed cocondensate of (B) and (C) components (however, The layer formed using the composition for base layer formation containing (B) component and / or (C) component) is preferable.

Component (B): a compound represented by the following formula (2) and / or a partially hydrolyzed condensate thereof.
Si (X ² ) ₄ (2)
(However, in formula (2), each X ² independently represents a halogen atom, an alkoxy group or an isocyanate group.)
Component (C): The above-mentioned element M and a compound having a hydrolyzable group bonded to the element M and / or a partial hydrolysis condensate thereof (C1) and / or a salt of the element M and the element M and a chelate It consists of (C2) component which consists of a chelating agent which can be couple | bonded.

The component (B) is a raw material component of silicon oxide contained in the underlayer, which is composed of the compound represented by the above formula (2) and / or a partial hydrolysis condensate thereof. In the above formula (2), X ² is chlorine atom, is preferably an alkoxy group or an isocyanate group having 1 to 4 carbon atoms, preferably further four X ² are identical.

As such a compound represented by the above formula (2), specifically, Si (NCO) ₄ , Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) _{4 and the} like are preferably used. In this invention, a compound (2) may be used individually by 1 type, and may use 2 or more types together.

  The component (B) contained in the underlayer-forming composition may be a partial hydrolysis condensate of compound (2). The partially hydrolyzed condensate of a hydrolyzable silicon compound such as compound (2) is the whole 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. Component (B) may be compound (2) as described above, or a partial hydrolysis condensate of compound (2), or a mixture of compound (2) and its partial hydrolysis condensate, For example, a partially hydrolyzed condensate of compound (2) containing unreacted compound (2) may be used.

  There are commercially available compounds as the compound represented by the above formula (2) and partially hydrolyzed condensates thereof, and such commercially available products can be used in the present invention.

  The component (C) is a raw material component of the oxide of the element M having a lower electronegativity than the silicon atom contained in the underlayer. As the component (C), the component M and a compound having a hydrolyzable group bonded to the element M (hereinafter referred to as a hydrolyzable compound (Z)) and / or a partially hydrolyzed condensate thereof (C1) component, It consists of at least one of the component (C2) consisting of the salt of the element M and a chelating agent capable of chelating with the element M.

In the component (C1), the hydrolyzable group bonded to the element M of the hydrolyzable compound (Z) is a group that can form M-OH by hydrolysis of the group. Specific examples of the hydrolyzable group include an alkoxy group, an acyloxy group, a ketoxime group, an alkenyloxy group, an amino group, an aminoxy group, an amide group, an isocyanate group, a halogen atom, and a β-diketonate group. From the viewpoint of the balance between the stability of the hydrolyzable compound (Z) and the ease of hydrolysis, the hydrolyzable group is preferably an alkoxy group, a β-diketonate group or the like, and a β-diketonate group is particularly preferable. Specifically, as the β-diketonate group, (—O—C (CH ₃ ) ═CH—C (═O) —CH ₃ ) group, (—O—C (CH ₃ ) ═CH—C (═O ) _-O-CH 2 -CH ₃₎ group and the like.

  The number of hydrolyzable groups bonded to the element M of the hydrolyzable compound (Z) depends on the valence of the element M. The elements M preferably used in the present invention exemplified above are all trivalent or tetravalent elements. The hydrolyzable groups bonded to these elements M are 1 to 3 or 1 to 4, and preferably have 3 or 4 hydrolyzable groups, respectively. When the hydrolyzable compound (Z) has a plurality of hydrolyzable groups, they may be the same group or different groups, and the same group is preferable in terms of availability.

  Examples of the hydrolyzable compound (Z) having a preferable hydrolyzable group include β-diketonates of the element M. Examples of the β-diketone that reacts with the element M to form a β-diketonate include acetylacetone and ethylacetoacetate, and acetylacetone is preferred. The hydrolyzable compound (Z) is preferably a β-diketonate of the element M exemplified above. Specific examples of such β-diketonates of element M include aluminum (III) acetylacetonate, zirconium dibutoxybis (ethylacetoacetate), hafnium (IV) acetylacetonate), and titanium (IV) acetylacetonate. ) And the like. Of these, Al β-diketonates are preferred, and Al acetylacetonates such as aluminum (III) acetylacetonate are particularly preferred.

  The component (C1) may be a hydrolyzable compound (Z) or a partially hydrolyzed condensate of the hydrolyzable compound (Z). The hydrolyzable compound (Z) and its partially hydrolyzed condensation For example, it may be a partially hydrolyzed condensate of hydrolyzable compound (Z) containing unreacted hydrolyzable compound (Z). The hydrolyzable compound (Z) partially hydrolyzed condensate means that all or part of the hydrolyzable group of the compound is hydrolyzed in the presence of a catalyst such as an acid catalyst or an alkali catalyst and water in a solvent. Then, it refers to an oligomer (multimer) produced by dehydration condensation, and can be produced by a conventional method. The degree of condensation (degree of multimerization) of the partially hydrolyzed condensate is appropriately adjusted to such an extent that the product is dissolved in the solvent. There are commercially available products as the hydrolyzable compound (Z) and its partially hydrolyzed condensate, and such a commercially available product can be used in the present invention.

The component (C2) includes a salt of the element M and a chelating agent capable of chelating with the element M. Examples of the salt of the element M include carboxylate, inorganic salt, alkoxide and the like.
Examples of carboxylates include acetates, oxalates, citrates, inorganic salts include nitrates, sulfates, halides, etc., and alkoxides include alkoxy groups having 1 to 4 carbon atoms. Is mentioned. Of these, hydrochloride, nitrate, alkoxide having 1 to 4 carbon atoms, and the like are preferable. Examples of chelating agents capable of chelating with the element M include β-diketones. Examples of β-diketone include acetylacetone and ethylacetoacetate, and acetylacetone is preferred. Among these, (C2) is preferably a combination of Al nitrate and acetylacetone.

  In addition, it is considered that the salt of element M and the chelating agent used in the underlayer-forming composition as the component (C2) form a chelate compound of element M in the underlayer-forming composition. In the component (C2), the mixing ratio of the salt of the element M and the chelating agent is not limited as long as the salt of the element M is sufficiently a chelate compound. The composition for forming the underlayer includes the component (C2) composed of the salt of the element M and the chelating agent as the component (C). When the composition for forming the underlayer is prepared, the salt of the element M and the chelating agent are used. Are separately mixed in the underlayer forming composition to form a chelate compound of element M in the underlayer forming composition, and a salt of element M and a chelating agent are mixed in advance to It includes both cases where the chelate compound is formed and blended into the underlayer-forming composition.

  The component (C) may be composed of only the component (C1), may be composed only of the component (C2), or may be composed of the component (C1) and the component (C2). In any case, the element M may be one type or two or more types.

  The content ratio of the component (B) and the component (C) in the underlayer forming composition is such that the content ratio of the element M to the total amount of silicon atoms and the element M in the underlayer forming composition is silicon. A ratio of 3 to 50 mol% is preferable and 5 to 35 mol% is more preferable as the mol% of the element M with respect to the total molar amount of the atom and the element M.

  Moreover, when the composition for base layer formation contains (B) component and (C1) component, it is preferable to use these partial hydrolysis cocondensates, and compound (2) and hydrolyzable compound (Z) It is more preferable to use a partially hydrolyzed 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. In addition, when the composition for base layer formation contains the partial hydrolysis cocondensate of a compound (2) and a hydrolyzable compound (Z), it contains (B) component and / or (C1) component separately from this. But you can. Further, the component (C2) may be further included as necessary.

The composition for forming the underlayer comprises a compound represented by the following formula (3) and / or a partially hydrolyzed condensate thereof in addition to the above component (B) as a raw material component of silicon oxide contained in the underlayer ( It is preferable that D) component is included.
^{_{X 3 3 Si- (CH 2)}} m -SiX 3 3 ... (3)
(However, in Formula (3), X < ³ > shows a hydrolysable group or a hydroxyl group each independently, and m is an integer of 1-8.)

In the formula (3), X ³ 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 ³ group.
Examples of the hydrolyzable group represented by X ³ 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. X ³ is preferably an alkoxy group or an isocyanate group, more preferably an alkoxy group, from the viewpoint of the balance between the stability of the compound (3) and the ease of hydrolysis. As an alkoxy group, a C1-C4 alkoxy group is preferable, and a methoxy group or an ethoxy group is more preferable. X ³ in the compound (3) is particularly preferably a methoxy group or an ethoxy group. These are appropriately selected and used according to the purpose of manufacture, application and the like. A plurality of X ³ present in the compound (3) may be the same group or different groups, and the same group is preferable from the viewpoint of availability.

  In the formula (3), 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.

Specifically, as the compound (3), (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 (3) may be used individually by 1 type, and may use 2 or more types together.

  Component (D) contained in the underlayer forming composition may be a partial hydrolysis condensate of compound (3), or a mixture of compound (3) and its partial hydrolysis condensate, for example, unreacted A partially hydrolyzed condensate of the compound containing the compound (3) may be used. The partially hydrolyzed condensate of compound (3) refers to an oligomer (multimer) of compound (3) obtained in the same manner as the partially hydrolyzed condensate of compound (2). The degree of condensation (degree of multimerization) of the partially hydrolyzed condensate is appropriately adjusted to such an extent that the product is dissolved in the solvent.

  In combination with the compound (2), the compound (3) preferably has a hydrolyzable group that is the same group or atom as the hydrolyzable group of the compound (2). There are commercially available compounds as the compound represented by the above formula (3) and partially hydrolyzed condensates thereof, and such commercially available products can be used in the present invention.

  In this case, the composition for forming the underlayer may contain the component (B) and the component (D) alone as a raw material component of silicon oxide, or may contain these partially hydrolyzed cocondensates. . When the composition for base layer formation contains the partial hydrolysis cocondensate of (B) component and (D) component, you may contain (B) component and / or (D) component separately from this.

  In addition to the component (B) derived component (which is the same as the component derived from the compound (2)), the composition for forming the base layer is agreed with the component derived from the component (D) (the component derived from the compound (3)). It is preferable that the water-repellent film obtained has improved durability such as moisture resistance. The content ratio of the component derived from the component (B) and the component derived from the component (D) in the composition for forming the underlayer is 0 as a mass ratio represented by [(B) component derived component: (D) component derived component]. 0.1: 0.9 to 0.9: 0.1 is preferable, and 0.9: 0.1 to 0.4: 0.6 is more preferable. When the composition for forming an underlayer contains the component (B) component-derived component and the component (D) component at such a mass ratio, the resulting water-repellent film is improved in moisture resistance and is slid against fine water droplets. It is possible to improve the performance.

  In addition, the content ratio of the component derived from the component (B) and the component derived from the component (D) in the composition for forming the base layer is determined when a partially hydrolyzed condensate or a partially hydrolyzed cocondensate is used. It can be calculated from the amounts of the compound (2) and the compound (3) used in the above.

  When the composition for forming the underlayer contains the component (B), the component (C1), and the component (D), it is preferable to use these partially hydrolyzed cocondensates, and the compound (2) and the hydrolyzable compound It is more preferable to use a partially hydrolyzed cocondensate of (Z) and compound (3). The partially hydrolyzed cocondensate is a combination of two partially hydrolyzed cocondensates selected from the compound (2), hydrolyzable compound (Z) and compound (3), and the component (B) and the component (C1) , (D) component may be included, but it is particularly preferable to use a three-part partial hydrolysis cocondensate. By using the partially hydrolyzed cocondensate, it is considered that the underlayer can be formed as a layer in which units derived from these compounds are uniformly distributed. In addition, when the composition for base layer formation contains the partial hydrolysis cocondensate of a compound (2), a hydrolyzable compound (Z), and a compound (3), (B) component separately from this, (C1) A component and (D) component may be included. Further, the component (C2) may be further included as necessary.

  In addition, when the composition for base layer formation contains (B) component, (C2) component, and (D) component, these partial hydrolysis is carried out about (B) component and (D) component from a viewpoint similar to the above. It is preferable to use a cocondensate, and it is more preferable to use the component (2) and the partially hydrolyzed cocondensate (C2) component of the compound (3). In this case, the underlayer-forming composition may contain a component (B) and a component (D) separately.

  When the composition for forming the underlayer contains the component (D) in addition to the component (B) and the component (C), the content ratio of each component is the ratio of the component (B) and the component (D). As described above, the content ratio of the element M with respect to the total amount of the silicon atom and the element M in the composition for forming the underlayer is, as a mol% of the element M with respect to the total molar amount of the silicon atom and the element M, A ratio of 3 to 50 mol% is preferable, and 5 to 35 mol% is more preferable.

  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 base layer formation does not contain the component derived from the component (D), it is preferable that the total solid component consists essentially of the component derived from the component (B) and the component derived from the component (C). When the component-derived component is included, it is preferable that the total solid component consists essentially of the component-derived component (B), the component-derived component (C), and the component-derived component (D). 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 component (B) and the component derived from the component (C), the partially hydrolyzed cocondensate of the component (B) and the component (C) When using, it is preferable that the composition for base layer formation is the solution of the partial hydrolysis cocondensate obtained by manufacture of the partial hydrolysis cocondensate of (B) component and (C) component itself. The same applies to the case where the total solid content of the composition for forming the underlayer is substantially composed only of the component (B) component, the component (C), and the component (D).

  As for the ratio of the organic solvent in the composition for base layer formation, 400-100,000 mass parts is preferable with respect to 100 mass parts of total solids. 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 composition for forming an underlayer is more preferably 900 to 3,500 parts by mass, and particularly preferably 1,100 to 2,000 parts by mass with respect to 100 parts by mass of the total solid content.

  Furthermore, in the composition for forming the underlayer, even if it does not contain a partial hydrolysis condensate or a partial hydrolysis cocondensate, the component (B) and the component (C) are added as necessary ( In order to promote the hydrolysis condensation reaction and hydrolysis cocondensation reaction of component D), it is also preferable to incorporate a catalyst such as an acid catalyst similar to that used in the partial hydrolysis condensation reaction above. Even when a partially hydrolyzed condensate or a partially hydrolyzed cocondensate is included, when the catalyst used for the production thereof does not remain in the composition, it is preferable to add a catalyst. As the catalyst, an acid catalyst is preferable. The amount of the catalyst is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total solid content. 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 solid content of the 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 (2), a hydrolyzable compound (Z), a compound in which the hydrolyzable group of the compound (3) is a chlorine atom as the components (B) to (D) When these partially hydrolyzed condensates, partially hydrolyzed cocondensates and the like are contained, it is preferable that they are substantially free of the above catalyst and water in view of storage stability because of their high reactivity. “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 composed of a water repellent layer-forming composition containing a component (A) comprising a compound represented by the following formula (1) 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 ¹ ) _n (1)
(In the formula (1), R ³ represents an alkyl group having 10 or less carbon atoms or —Y ¹ —Si (R ¹ ) _3-n (X ¹ ) _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 ¹ 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 (1) 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 (1) 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 the present invention, it is particularly preferable that the compound (1) is a compound having a hydrolyzable silyl group at one end from the viewpoint of small water droplet sliding property. 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 (1), R ² in the repeating unit of SiR ² ₂ O and —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 (1) is often used as a mixture in which the number of repeating units of SiR ² ₂ O is different. When compound (1) is such a mixture, the number of each repeating unit is shown by an average value. In the case of an average value, the number of repeating units is not necessarily an integer, but a preferable range of numerical values is the same as described above.

X ¹ of the hydrolyzable silyl group (—Si (R ¹ ) _3-n (X ¹ ) _n ) possessed by the terminal of the compound (1) represents a hydrolyzable group. When R ³ represents -Y ¹ -Si (R ¹ ) _3-n (X ¹ ) _n group, the compound (1) 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 compound (1), the hydrolyzable silyl groups at both ends may be the same or different.

X ¹ includes the same group or atom as X ³ described above. From the viewpoint of the balance between the stability of the compound (1) 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 the alkoxy group, an alkoxy group having 3 or less carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable. X ¹ in the compound (1) is more preferably a chlorine atom, a methoxy group or an ethoxy group, particularly preferably a chlorine atom or a methoxy group, and most preferably a chlorine atom. These are appropriately selected and used according to the purpose of manufacture, application and the like. When a plurality of X ¹ are present in compound (1), X ¹ may be the same group or different groups, and the same group is preferable from the viewpoint of availability.

n represents the number of hydrolyzable groups (X ¹ ) in the hydrolyzable silyl group of the compound (1), 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 (1) 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 (1), Y ¹ which is a group that links (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 (1), 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 (1), 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 (1), R ² in the formula (1) is preferably a methyl group, R ³ is a linear alkyl group having 5 or less carbon atoms, X ¹ 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 (1) 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 (1) may be used individually by 1 type, and may use 2 or more types together. Of these, as described above, compound (1) having a hydrolyzable silyl group only at one end is preferred. The hydrolyzable group is more preferably a chlorine atom or a methoxy group, and particularly preferably a chlorine atom.

Compound (1) can be produced by a known method.
For example, in the formula (1), 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 _{1) 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 ¹ ) _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 ¹ ) _n is reacted.
The compound (1) 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 (1) in which Y ¹ is —C ₃ H ₆ — is obtained.

Linear polydimethyl having formula (1) having hydrolyzable silyl groups (—Si (R ¹ ) _{3 -n} (X ¹ ) _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. By reacting R ¹ ) _3-n (X ¹ ) _n , (X ¹ ) _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 ¹ ) _n is obtained. Also in this case, the compound (1) 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 1) n, likewise the compound (1) 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. For when X ¹ is a chlorine atom, among these synthetic methods, polydimethyl siloxane and _{^{HSi (R 1) 3-n}} (X 1) synthesis method using an _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 (A) contained in the composition for forming a water repellent layer may be a partially hydrolyzed condensate of compound (1). 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. 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.

  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 (A).

  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 (A), when using the partial hydrolysis condensate of compound (1), the composition for forming the water repellent layer 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. 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.

  Furthermore, 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 component (A), 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 (A) component (compound (1) 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 (A) (component derived from the compound (1)). 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 (A), the compound (1) in which the hydrolyzable group of the compound (1) is a chlorine atom, a partial hydrolysis 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 water repellent film of the substrate with a water repellent film of the present invention thus obtained is a water repellent film having durability such as moisture resistance and excellent in both static and dynamic water repellency. The water repellency of water, specifically, has a property that the water falling angle is small and the sliding speed of small water droplets is fast.

[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. This property is fully expressed even when the water droplets are minute. 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 to 12 and Examples 17 to 24 are examples, and Examples 13 to 16 and Examples 25 to 30 are comparative examples.

As the compound (1) to be blended in the water repellent layer forming composition, the following compounds (11) to (14) were synthesized and used according to the following Synthesis Examples 1 to 4.
(Compound 11); CH ₃ (Si (CH ₃ ) ₂ O) ₆₀ Si (CH ₃ ) ₂ C ₂ H ₄ SiCl ₃
(Compound _{12); CH 3 (Si (} CH 3) 2 O) 39 Si (CH 3) 2 C 2 H 4 SiCl 3
(Compound _{13); CH 3 (Si (} CH 3) 2 O) 120 Si (CH 3) 2 C 2 H 4 SiCl 3
(Compound _{14); CH 3 (Si (} CH 3) 2 O) 58 Si (CH 3) 2 C 2 H 4 Si (OCH 3) 3

[Synthesis Example 1] Synthesis Example of Compound (11) (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. 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): 5.6 to 6.1 (3H, m, H—Si), 0.0 to 0.3 (369H, m, CH ₃ —Si) ).

(Production of Compound (11))
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 (11) represented by the following formula (11) which is 94: 6 as the compound of (1a): the compound of group (1b)] was obtained. The yield was 98%.
_{-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) 60 Si (CH 3) 2 C 2 H 4 SiCl 3 ... (11)

The measurement result of ¹ H-NMR (300.4 MHz, standard: C ₆ D ₆ (= 7.00 ppm)) of the obtained compound (11) 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 2] Synthesis Example of Compound (12) (Production of Hydrogen Polydimethylsiloxane (1-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 volatile components were removed under the condition of 50 ° C./10 mmHg to obtain 25.0 g of the compound (1-A) represented by the following formula (1-A). The yield was 99%.
CH ₃ (Si (CH ₃ ) ₂ O) ₃₉ 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.
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 (12))
In a reactor equipped with a stirrer and a Dimroth (internal volume 50 mL), compound (1-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 (12) represented by the following formula (12), 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 ... (12)

The measurement result of ¹ H-NMR (300.4 MHz, standard: C ₆ D ₆ (= 7.00 ppm)) of the obtained compound (12) 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 (13) (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 (13))
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 (13) represented by the following formula (13) which is 93: 7 as the compound of (1a): the compound of 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 ... (13)

The measurement result of ¹ H-NMR (300.4 MHz, standard: C ₆ D ₆ (= 7.00 ppm)) of the obtained compound (13) 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 4] Synthesis Example of Compound (14) (Production of Hydrogen Polydimethylsiloxane (2-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 a compound (2-A) represented by the following formula (2-A). The yield was 99%.
CH ₃ (Si (CH ₃ ) ₂ O) ₅₈ 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 (357H, m, CH 3 -Si).

(Production of Compound (14))
In a reactor equipped with a stirrer and a Dimroth (internal volume 50 mL), compound (2-A) (20.0 g), vinyltrimethoxysilane (1.33 g), and Pt catalyst (Pt 1,3-divinyl-1 , 1,3,3-tetramethyldisiloxane complex in 2% by mass xylene) (0.086 g) was added, 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 (14) represented by the following formula (14), wherein [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 ... (14)

The measurement result of ¹ H-NMR (300.4 MHz, standard: C ₆ D ₆ (= 7.00 ppm)) of the obtained compound (14) 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 ).

[Preparation of water repellent layer forming composition]
(Water repellent layer forming compositions 1 to 3)
In a glass container in which a stirrer and a thermometer were set, the compound (11) obtained above was mixed at a ratio of 10% by mass and butyl acetate (manufactured by Junsei Kagaku Co., Ltd.) at 90% by mass. Was stirred for 5 minutes to obtain a water-repellent layer forming composition 1. A water repellent layer forming composition 2 and a water repellent layer forming composition 3 were obtained in the same manner except that the compound (11) was changed to the compound (12) and the compound (13).

(Water repellent layer forming composition 4)
In a glass container in which a stirrer and a thermometer are set, the compound (14) obtained above is 10% by mass, isopropyl alcohol (manufactured by Junsei Kagaku) is 16.7% by mass, and butyl acetate is 68.3% by mass. The mixture was stirred at 25 ° C. for 1 minute, then added with 5% by weight of a 10% by weight nitric acid aqueous solution and stirred at 25 ° C. for 3 hours to obtain a water repellent layer-forming composition 4. In addition, content (mass%) of each component is mass% with respect to the whole quantity of the composition 4 for water-repellent layer formation.

[Preparation of composition for forming underlayer]
The following compounds were prepared in the preparation of the underlayer forming composition.
(B) Component Tetramethoxysilane; Si (OCH ₃ ) ₄ (manufactured by Kanto Chemical Co., Inc.), hereinafter referred to as “TMOS”. Corresponds to compound (2).
(D) component bistrimethoxysilyl ethane; (CH ₃ O) ₃ SiCH ₂ CH ₂ Si (OCH ₃ ) ₃ (manufactured by Kanto Chemical Co., Inc.), hereinafter referred to as “BTME”. Corresponds to compound (3).
Component (C) As a component (C1) and a component (C2), a hydrolyzable compound (Z) of element M shown in Table 1 below or a combination of a salt of element M and a chelating agent was prepared. In Table 1, B contained in boric acid is an element having an electronegativity greater than 1.74 of silicon atoms, and is an element outside the scope of the present invention. A combination of boric acid and acetylacetone was used for comparison.

(Underlayer forming compositions 1-14)
In a glass container in which a stirrer and a thermometer are set, each raw material (g) shown in Table 2 is added and stirred at 25 ° C. for 3 minutes, and then 0.463 g of 0.463 mass% nitric acid aqueous solution is dropped. And the compositions 1-14 for base layer formation were obtained by stirring at 25 degreeC for 3 hours.

(Underlayer forming composition 15-20)
In the same manner as the underlayer forming compositions 1 to 14, the underlayer forming compositions 15 to 20 (for comparative examples) that are not suitable for forming the underlayer according to the present invention were obtained.
In Table 2, the compound of component (C) is indicated by the compound abbreviation shown in Table 1. Component (C) content 1 indicates the charged mass (g), and content 2 is the total molar amount of silicon atoms derived from component (B) and component (D) and element M derived from component (C) 100. The mol% of the element M derived from the component (C) with respect to mol% is shown. Moreover, content 1 at the time of using solutions, such as Zr-1 and Ti-1, as (C) component shows the preparation amount (g) as a solution.

[Examples 1 to 30; Production of substrate with water-repellent film]
As a 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. On the surface of the glass substrate, Tables 3 and 4 were used. As shown in FIG. 5, 0.5 g of any of the liquid compositions 1 to 20 for forming the underlayer obtained above was applied by a squeegee coating method and dried at 25 ° C. for 1 minute to form an underlayer (uncured). Next, 0.5 g of any one of the water-repellent layer-forming compositions 1 to 4 obtained above as shown in Table 3 and Table 4 was applied to the surface of the formed base layer (uncured) by the squeegee coating method. After forming the water-repellent layer by holding it in a thermo-hygrostat set to 50 ° C. and 60% RH for 48 hours, the base layer is cured at the same time, and the surface of the water-repellent layer is soaked with 2-propanol. The substrate with a water repellent film having a water repellent film composed of an underlayer / water repellent layer in order from the substrate side was obtained by wiping with a paper waste.

  Table 3 shows a production example when the composition for forming the underlayer does not contain the component (D), and Table 4 shows a production example when the composition for forming the underlayer contains the component (D). showed that.

[Evaluation]
Evaluation of the substrate with a water repellent film obtained in Examples 1 to 30 was performed as follows. The results are shown in Tables 3 and 4. 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. Further, before the moisture resistance test, the sliding property of small water droplets on the surface of the water-repellent film of the obtained substrate with the water-repellent film was evaluated. The sliding property of small water droplets is a physical property that is preferably possessed particularly in applications for articles for transportation equipment.

(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).

(Small water slidability)
An evaluation of small water droplet sliding property by placing 6 μL of water droplets on the water repellent film of a substrate with a water repellent film inclined at 70 degrees from the horizontal, calculating the sliding speed (mm / second) by measuring the time when moving 50 mm, and did. Note that the evaluation “does not slide” indicates that the object did not move at all.

<Moisture resistance test>
The substrate with water repellent film obtained in Examples 1 to 6, Example 17 and 18 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) and water falling angle (SA) were measured.
The results of the initial water repellency measured above and the water repellency after the moisture resistance test are shown in Table 3 (Examples 1 to 16) and Table 4 (Examples 17 to 30).

  As can be seen from Tables 3 and 4, the substrate has an underlayer formed using a hydrolyzable silicon compound and a composition for forming an underlayer containing a compound containing an element M having an electronegativity lower than that of a silicon atom. The substrate with the water-repellent film of the example was compared with the substrate with the water-repellent film of the comparative example having the base layer formed using the composition for forming the base layer containing only any of them. Although the corners are the same, the sliding speed of minute water droplets is much faster. Moreover, it turns out that moisture resistance is greatly improved by mix | blending bissilane as a hydrolysable silicon compound.

  The substrate with a water-repellent film of the present invention is a water-repellent film having durability such as moisture resistance and excellent in both static and dynamic water repellency. , Having a water-repellent film having the property that the water falling angle is small and the sliding speed of minute water droplets is high, and the body, window glass (front glass, side glass, Rear glass), mirrors, bumpers and the like.

Claims (12)

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 containing an oxide of element M mainly composed of silicon oxide and having a lower electronegativity than silicon atoms, and
A water repellent layer formed using a water repellent layer-forming composition comprising a component (A) comprising a compound represented by the following formula (1) and / or a partially hydrolyzed condensate thereof,
A substrate with a water repellent film.
R ³ — (SiR ² ₂ O) _k —SiR ² ₂ —Y ¹ —Si (R ¹ ) _{3 -n} (X ¹ ) _n (1)
(In the formula (1), R ³ represents an alkyl group having 10 or less carbon atoms or —Y ¹ —Si (R ¹ ) _3-n (X ¹ ) _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 ¹ 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 comprises a component (B) composed of a compound represented by the following formula (2) and / or a partial hydrolysis condensate thereof, a compound having a hydrolyzable group bonded to the element M and the element M, and / or Or (C1) component consisting of a partially hydrolyzed condensate thereof and / or (C) component consisting of (C2) component consisting of a salt of the element M and a chelating agent capable of chelating with the element M, Or the composition for base layer formation containing the partial hydrolysis cocondensate of the said (B) component and the said (C) component (however, the said (B) component and / or the said (C) component may be included). The substrate with a water-repellent film according to claim 1, wherein the substrate is a base layer formed by using the substrate.
Si (X ² ) ₄ (2)
(However, in formula (2), each X ² independently represents a halogen atom, an alkoxy group or an isocyanate group.) The underlayer-forming composition further includes a component (D) composed of a compound represented by the following formula (3) and / or a partial hydrolysis condensate thereof, or the component (B) and the component (C). A partially hydrolyzed cocondensate comprising at least two components selected from the component and the component (D) (however, the component (B), the component (C), and the component (D) may each be included alone)) The substrate with a water-repellent film according to claim 2.
_{^{X 3 3 Si- (CH 2)}} m -SiX 3 3 ... (3)
(However, in Formula (3), X < ³ > shows a hydrolysable group or a hydroxyl group each independently, and m is an integer of 1-8.)   In the composition for forming an underlayer, the content of the element M derived from the component (C) is silicon derived from the component (B), the element M derived from the component (C), and the component (D). The substrate with a water-repellent film according to claim 2 or 3, which is 3 to 50 mol% with respect to 100 mol% of the total amount of silicon derived therefrom. 5. The substrate with a water-repellent film according to claim 3, wherein in the formula (3), X ³ is an alkoxy group or an isocyanate group, and m is an integer of 1 to 3. 6. In the formula (1), R ² is a methyl group, R ³ is a linear alkyl group having 5 or less carbon atoms, X ¹ is a chlorine atom or an alkoxy group having 3 or less carbon atoms, The substrate with a water-repellent film according to claim 1, wherein k is an integer of 10 to 150 and n is 3.   The substrate with a water-repellent film according to any one of claims 1 to 6, wherein the element M is one or more elements selected from Al, Zr, Hf, Ti, Y, and Ce.   The element M is Al, and the component (C) comprises acetylacetonate of Al and / or a partial hydrolysis condensate thereof, and / or a mixture of an Al salt and acetylacetone. A substrate with a water-repellent film according to Item.   The said composition for base layer formation consists of only the said (B) component origin component, the said (C) component origin component, and the said (D) component origin component substantially in total solid content. The substrate with a water-repellent film according to any one of the above.   The substrate with a water-repellent film according to any one of claims 1 to 9, wherein the water repellent layer-forming composition has a total solid content substantially consisting only of the component (A).   The substrate with a water-repellent film according to claim 1, wherein the substrate is made of glass.   The article for transport equipment provided with the base with a water repellent film according to any one of claims 1 to 11.