JP2014024288A - Substrate with water-repellent film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate with a water-repellent film which imposes little load on environment, possesses sufficient water repellency, excellent antiweatherability, and at the same time sufficient alkali resistance.SOLUTION: A substrate with a water-repellent film comprises a substrate and a water-repellent layer. The water-repellent layer comprises a middle layer and an outermost layer formed in this order from the substrate side on at least a part of a principal surface of the substrate. The middle layer is formed using a coating composition for the middle layer, which contains a silane compound (a) as a main component of a total solid, the compound (a) having a perfluoroalkyl group having 1 to 6 carbon atoms and a group not having a perfluoroalkylene group as a linking group. The outermost layer is formed using a coating composition for the outermost layer, which contains a silane compound (b) in an amount of 70 mass% or more with respect to the total solid, the compound (b) having a perfluoropolyether group having a terminal perfluoroalkyl group having 1 to 6 carbon atoms.

Description

  The present invention relates to a substrate with a water-repellent film, and in particular, a substrate with a water-repellent film having a water-repellent film that has a small environmental load, has sufficient water repellency, excellent weather resistance, and excellent alkali resistance. About.

  As a method for imparting water repellency to the surface of a substrate, a water repellent composition in which a fluorine-containing silane compound having both a perfluoroalkyl group or a perfluoropolyether group and a hydrolyzable silyl group is dissolved in a solvent is applied to the substrate. A method of forming a water-repellent film by drying is known.

  The water-repellent film is used for various articles whose surface is required to have water repellency, but for characteristics other than the water repellency, the characteristics required according to the environment in which each article is used are given. . For example, a water-repellent film in an article used in the transportation and transportation field such as automobile glass is required to have high water repellency and to be given weather resistance. Furthermore, the provision of alkali resistance is also required in order to protect the water-repellent film from adhesion of foreign substances and cleaning treatment using a detergent.

  As a water-repellent film that satisfies the above requirements, for example, in Patent Document 1, a fluorine-containing silane compound having a perfluoroalkyl group and a hydrolyzable silyl group, a fluorine-containing compound having a perfluoropolyether group and a hydrolyzable silyl group. Articles formed using a composition for forming a water repellent film in combination with a silane compound are described.

  However, recently, a compound having a perfluoroalkyl group having 8 or more carbon atoms, which has been generally used in the production of the water-repellent film, has a high environmental load, and its use is subject to legal regulation and self-regulation. It is coming. In addition, higher alkali resistance is required for the water-repellent film.

  Here, in the composition for forming a water-repellent film described in Patent Document 1, when a compound having a perfluoroalkyl group having 8 or more carbon atoms is used, it is possible to cope with a higher level of alkali resistance. is there. However, when using a fluorine-containing compound having a perfluoroalkyl group having 6 or less carbon atoms that has a low environmental impact, using a compound having a perfluoroalkyl group having 8 or more carbon atoms for water repellency and weather resistance. However, the alkali resistance is not sufficient.

International Publication No. 2011-016458

  An object of the present invention is to provide a substrate with a water repellent film having a water repellent film that has a small environmental load, has sufficient water repellency, is excellent in weather resistance, and has sufficient alkali resistance.

The present invention is a substrate with a water repellent film comprising a substrate, and a water repellent film having an intermediate layer and an outermost layer formed in order from the substrate side on at least a part of the main surface of the substrate,
The intermediate layer includes a hydrolyzable silane compound represented by the following general formula (a1) and / or a fluorine-containing silane compound (a) that is a partial hydrolysis condensate thereof as a main component of the total solid content. Formed using a coating composition;
The outermost layer comprises a hydrolyzable silane compound having a perfluoropolyether group having 1 to 6 carbon atoms in the terminal perfluoroalkyl group and / or a fluorine-containing silane compound (b) which is a partial hydrolysis condensate thereof. Provided is a substrate with a water-repellent film formed using an outermost layer coating composition containing 70% by mass or more based on the total solid content.
R ^F1 -Q ¹ -SiR ¹ _(3-m1) X ¹ _m1 (a1)
However, the symbols in the formula (a1) are as follows.
R ^F1 represents a perfluoroalkyl group containing no etheric oxygen atom between carbon-carbon atoms having 1 to 6 carbon atoms.
Q ¹ represents a divalent organic group not containing a fluorine atom having 1 to 6 carbon atoms.
X ¹ : an alkoxy group having 1 to 10 carbon atoms, an oxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a halogen atom or an isocyanate group Indicates. The m1 X ¹ may be the same as or different from each other.
R ^{1 represents a} hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms that does not contain a fluorine atom that may be partially or wholly substituted. 3-m1 R ^{1 s} may be the same as or different from each other.
m1: An integer of 1 to 3 is shown.

  ADVANTAGE OF THE INVENTION According to this invention, the load with respect to an environment is small, it has sufficient water repellency, it is excellent in a weather resistance, and while providing the water repellent film | membrane provided with the water repellent film | membrane which has sufficient alkali resistance, it can provide.

It is sectional drawing which shows an example of embodiment of the board | substrate with a water repellent film of this invention. It is sectional drawing which shows another example of embodiment of the board | substrate with a water repellent film of this invention.

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 (a1) in this specification is referred to as compound (a1), and the group represented by formula (1) is referred to as group (1). The same applies to other compounds and groups.

The substrate with a water-repellent film of the present invention includes a substrate and a water-repellent film having the following intermediate layer and outermost layer formed in order from the substrate side on at least a part of the main surface of the substrate.
The intermediate layer includes a hydrolyzable silane compound represented by the general formula (a1) and / or a fluorine-containing silane compound (a) that is a partial hydrolysis condensate thereof as a main component of the total solid content. Formed using the composition.
The outermost layer is composed of a hydrolyzable silane compound having a perfluoropolyether group having 1 to 6 carbon atoms in the terminal perfluoroalkyl group and / or a fluorine-containing silane compound (b) which is a partial hydrolysis condensate thereof. It is formed using the coating composition for outermost layers containing 70 mass% or more with respect to solid content.

  In the present specification, “containing a specific component as a main component of the total solid content” means containing the specific component in excess of 50 mass% of the total solid content. Moreover, solid content means the component which remains in the coating composition for each layer as a structural component of the layer formed using this itself or in the form of a reaction product.

  The water-repellent film of the substrate with a water-repellent film of the present invention is such that the outermost layer is formed by using the outermost layer coating composition, so that sufficient water repellency and alkali resistance can be expressed. By forming the intermediate layer coating composition, excellent weather resistance can be exhibited. The outermost layer coating composition and the intermediate layer coating composition are both mainly composed of a fluorine-containing compound having a perfluoroalkyl group having 6 or less carbon atoms, and have a small impact on the environment.

In the substrate with a water-repellent film of the present invention, a tetrafunctional hydrolyzable silane compound and / or a hydrolyzable silane compound (c) that is a partial hydrolysis condensate thereof is completely solid between the substrate and the intermediate layer. You may have the base layer formed using the coating composition for base layers which contains as a main component. By having an underlayer formed using the above coating composition for an underlayer, a substrate with a water-repellent film that is further excellent in terms of weather resistance can be obtained.
The substrate with a water-repellent film of the present invention includes a substrate and the water-repellent film formed on at least a part of the main surface of the substrate. The formation region of the water-repellent film on the substrate is not particularly limited as long as it is on the main surface of the substrate, and is preferably formed on the entire surface of one main surface or, for example, the entire region excluding the end portion.

  FIG. 1 shows a cross-sectional view of an example of an embodiment of a substrate with a water-repellent film of the present invention. FIG. 1 is a cross-sectional view of a water-repellent film-equipped substrate 1 </ b> A including a water-repellent film 3 having an intermediate layer 32 and an outermost layer 31 formed in order from the substrate 2 side on one main surface of the substrate 2. FIG. 2 shows a cross-sectional view of another example of the embodiment of the substrate with a water-repellent film of the present invention. FIG. 2 is a cross-sectional view of a substrate 1B with a water-repellent film provided with a water-repellent film 3 having a base layer 33, an intermediate layer 32, and an outermost layer 31 formed on one main surface of the substrate 2 in this order from the substrate 2 side. .

Hereafter, each component which comprises the board | substrate with a water repellent film of embodiment of this invention is demonstrated taking board | substrate 1A, 1B with a water repellent film as an example.
[substrate]
The substrate 2 used for the substrate with a water-repellent film according to the embodiment 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 A substrate made of (composite material, laminated material, etc.) is preferably used. A transparent substrate such as glass or plastic is preferable, and glass is particularly preferable. 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 2 may be a flat plate, or the entire surface or a part thereof may have a curvature. Although the thickness of the board | substrate 2 can be suitably selected according to the use of a board | substrate with a water-repellent film, generally it is preferable that it is 1-10 mm.

  As the substrate 2 used in the embodiment of the present invention, acid treatment (treatment using diluted hydrofluoric acid, sulfuric acid, hydrochloric acid or the like) or alkali treatment (aqueous sodium hydroxide solution or the like) is used on the surface according to the purpose. Treatment) or discharge treatment (plasma irradiation, corona irradiation, electron beam irradiation, etc.) or the like may be used. The substrate 2 may be provided with various films formed on its surface by a vapor deposition film, a sputtered film, a wet method, or the like. When the substrate 2 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 2 is glass manufactured by the float process, it is preferable in terms of durability to provide the water repellent film 3 on the top surface with a small amount of surface tin.

[Water repellent film]
In the embodiment of the present invention, the water repellent film 3 formed on the substrate 2 is formed from an intermediate layer 32 and an outermost layer 31 formed in order from the substrate 2 side, like the substrate 1A with a water repellent film shown in FIG. It may be composed of a base layer 33, an intermediate layer 32, and an outermost layer 31 that are sequentially formed from the substrate 2 side, like a substrate 1B with a water repellent film shown in FIG.

(Middle layer)
The intermediate layer 32 is a layer mainly formed in the water repellent film 3 that contributes to the weather resistance, and is formed in the region where the water repellent film 3 is formed on the substrate 2 by using the intermediate layer coating composition described below. It is. When the water repellent film 3 has the base layer 33 like the substrate 1B with the water repellent film shown in FIG. 2, it is formed on the base layer 33 formed on the substrate 2, and the substrate with the water repellent film shown in FIG. When the base layer 33 is not provided as in 1A, it is formed directly on the substrate 2.

The intermediate layer coating composition for forming the intermediate layer 32 comprises a hydrolyzable silane compound represented by the following general formula (a1) and / or a fluorine-containing silane compound (a) which is a partial hydrolysis condensate thereof. It is a composition containing as a main component of the total solid content.
R ^F1 -Q ¹ -SiR ¹ _(3-m1) X ¹ _m1 (a1)
However, the symbols in the formula (a1) are as follows.
R ^F1 represents a perfluoroalkyl group containing no etheric oxygen atom between carbon-carbon atoms having 1 to 6 carbon atoms.
Q ¹ represents a divalent organic group not containing a fluorine atom having 1 to 6 carbon atoms.
X ¹ : an alkoxy group having 1 to 10 carbon atoms, an oxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a halogen atom or an isocyanate group Indicates. The m1 X ¹ may be the same as or different from each other. In addition, these groups couple | bonded with a silicon atom are hydrolysable groups which can produce | generate the hydroxyl group (silanol group) couple | bonded with a silicon atom by hydrolyzing.
R ^{1 represents a} hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms that does not contain a fluorine atom that may be partially or wholly substituted. 3-m1 R ^{1 s} may be the same as or different from each other.
m1: An integer of 1 to 3 is shown.

Compound (a1) is a fluorine-containing organic group (R ^F1 -Q ^1- ) group, 3-m1 hydrocarbon group (R ¹ ), and m1 (m1 is an integer of 1 to 3) ^per silicon atom. ) Fluorinated hydrolyzable silane compound bonded to ^one hydrolyzable group (X ¹ ).
In group, R ^F1 carbon number of 1 to 6 carbon atoms which may have a ring structure ^- - R ^{F1 -Q} 1 shows a perfluoroalkyl group containing no etheric oxygen atom between carbon atoms. R ^F1 may have a straight chain structure, a branched structure, a cyclic structure, or a structure partially having a branched structure and a cyclic structure as long as the above conditions are satisfied. Good. Among these, as R ^F1 , a linear structure or a branched structure is preferable, and a linear structure is more preferable. R ^F1 preferably has 3 to 6 carbon atoms.

Q ¹ represents a divalent organic group not containing a fluorine atom having 1 to 6 carbon atoms. Q ¹ has 1 to 6 carbon atoms, and 1 to 3 is particularly preferable. Q ¹ is preferably — (CH ₂ ) _f (f is an integer from 1 to 6), —CONH (CH ₂ ) _g (g is an integer from 1 to 5) and —CONH (CH ₂ ) a divalent organic group selected from _h NH (CH ₂ ) _5-h (h is an integer of 1 to 4), more preferably — (CH ₂ ) ₂ , —CONH (CH ₂ ) ₃ , —CONH (CH ₂ ) ₂ NH (CH ₂ ) _{3 and the} like.

The R ^F1 -Q ¹ -group is a fluorine-containing group consisting of the above-mentioned perfluoroalkyl group having 1 to 6 carbon atoms (R ^F1 ) and a divalent organic group having 1 to 6 carbon atoms not containing a fluorine atom (Q ¹ ). Organic group. Since the R ^F1 -Q ¹ -group having such a chemical structure does not generate a compound having a perfluoroalkyl group having 8 or more carbon atoms as a decomposition product, the environmental load is small.

X ¹ in the compound (a1) is an alkoxy group having 1 to 10 carbon atoms, an oxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms. Represents a halogen atom or an isocyanate group.

Specifically, X ¹ is preferably an alkoxy group having 1 to 10 carbon atoms, an isocyanate group or a halogen atom from the viewpoint of the balance between the stability of the compound (a1) and the ease of hydrolysis. As the halogen atom, a chlorine atom is preferable. As an alkoxy group, a C1-C4 alkoxy group is preferable, and a methoxy group or an ethoxy group is more preferable. X ¹ in the compound (a1) is particularly preferably a chlorine atom, an isocyanate group, a methoxy group, or an ethoxy group. These are appropriately selected and used according to the purpose of manufacture, application and the like. When a plurality of X ¹ are present in the compound (a1), X ¹ may be the same group or different groups, and the same group is preferable from the viewpoint of availability.

m1 represents the number of hydrolyzable groups (X ¹ ) in the compound (a1), and the number is an integer of 1 to 3. When m1 is 1 or more, the adhesion between the obtained intermediate layer 32, the outermost layer 31, and the underlayer 33 or the substrate 2 is good. m1 is preferably 2 or 3, and particularly preferably 3, from the viewpoint of adhesion between the obtained intermediate layer 32 and each of the above layers and the substrate 2.

R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms that does not contain a fluorine atom which may be partially or wholly substituted. From the viewpoint of easy acquisition and handling of raw materials, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is particularly preferable. The number of R ^{1 in} the compound (a1) is 3-m1. When the compound (a1) R ¹ in the presence plurality may be in R ¹ are different even in the same group group, in terms of it is ease to obtain the same group.
In this invention, a compound (a1) may be used individually by 1 type, and may use 2 or more types together.

The compound (a1) is represented by the following formulas (a11) to (a16) from the viewpoint of the magnitude of contribution to improving the weather resistance of the water-repellent film 3 in the obtained intermediate layer 32 and the ease of synthesis. Compounds.
F (CF ₂ ) _e (CH ₂ ) _f SiX ¹ ₃ (a11)
F (CF ₂ ) _e (CH ₂ ) _f Si (R ¹ ) X ¹ ₂ (a12)
F (CF ₂ ) _e CONH (CH ₂ ) _g SiX ¹ ₃ (a13)
F (CF ₂ ) _e CONH (CH ₂ ) _g Si (R ¹ ) X ¹ ₂ (a14)
F (CF ₂ ) _e CONH (CH ₂ ) _h NH (CH ₂ ) _5-h SiX ¹ ₃ (a15)
F (CF ₂ ) _e CONH (CH ₂ ) _h NH (CH ₂ ) _5-h Si (R ¹ ) X ¹ ₂ (a16)
(In the formulas (a11) to (a16), e is an integer of 1 to 6, f is an integer of 1 to 6, g is an integer of 1 to 5, and h is 1 to 4. The meanings and preferred embodiments of X ¹ and R ¹ are the same as those in the above formula (a1).)

Compounds (a11) to (a16) can be used alone or in combination of two or more. In the present invention, among these, the compound (a11) is preferable, and F (CF ₂ ) ₆ (CH ₂ ) ₂ SiX ¹ ₃ (wherein, the meaning and preferred embodiment of X ¹ are the above-described formula (a1)). And the like is more preferable. Specifically, F (CF ₂ ) ₆ (CH ₂ ) ₂ SiCl ₃ , F (CF ₂ ) ₆ (CH ₂ ) ₂ Si (NCO) ₃ , F (CF ₂ ) ₆ (CH ₂ ) ₂ Si (OCH) ₃ ) ₃ and F (CF ₂ ) ₆ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ . Among these, F (CF ₂ ) ₆ (CH ₂ ) ₂ SiCl _{3 in} which all three X ¹ are chlorine atoms is more preferable.
The compound (a1) used in the present invention can be produced by a general method. Moreover, since there exists a commercial item as a compound (a1), such a commercial item can also be used for this invention.

  The fluorine-containing silane compound (a) contained in the intermediate layer coating composition comprises the compound (a1) and / or a partial hydrolysis condensate thereof. A partially hydrolyzed condensate of a hydrolyzable silane compound such as the compound (a1) is all or one of the hydrolyzable groups of the compound in the presence of a catalyst such as an acid catalyst or an alkali catalyst and water in a solvent. An oligomer (multimer) produced by hydrolysis of a part followed by dehydration condensation. However, the degree of condensation (degree of multimerization) of this partially hydrolyzed condensate needs to be such that the product is dissolved in the solvent. Compound (a) may be compound (a1) or a partially hydrolyzed condensate of compound (a1), and a mixture of compound (a1) and the partially hydrolyzed condensate thereof, for example, It may be a partial hydrolysis-condensation product of the compound (a1) containing the reaction compound (a1).

  The fluorine-containing silane compound (a) contained in the intermediate layer coating composition is a main component of the total solid content in the composition, and is a component contained in the total solid content in excess of 50% by mass. The content of the fluorine-containing silane compound (a) in the total solid content of the intermediate layer coating composition is more than 50% by mass and 100% by mass, preferably 80 to 100% by mass, and 100% by mass from the viewpoint of weather resistance. More preferred.

  When the coating composition for the intermediate layer contains the fluorinated silane compound (a) in the above range, the obtained intermediate layer 32 is a layer in which the fluorinated silane compound (a) is mainly hydrolytically condensed to form a siloxane bond. Thus, sufficient weather resistance can be imparted to the water repellent film 3. The coating composition for intermediate | middle layers can contain hydrolysable silane compounds other than a fluorine-containing silane compound (a) as a component which forms a siloxane bond in solid content in the range which does not impair the effect of this invention. Furthermore, the coating composition for intermediate | middle layers may also contain the functional additive according to various objectives as solid content other than a hydrolysable silane compound in the range which does not impair the effect of this invention.

  The hydrolyzable silane compound other than the fluorine-containing silane compound (a) is preferably a perfluoropolyether group (however, the terminal perfluoroalkyl group has 1 to 1 carbon atoms contained in the outermost layer coating composition). 6) and / or a fluorine-containing silane compound (b) which is a partial hydrolysis-condensation product thereof. Here, when the intermediate layer coating composition contains the fluorine-containing silane compound (a) and the fluorine-containing silane compound (b), the portion of the fluorine-containing silane compound (a) and the fluorine-containing silane compound (b) Hydrolysis cocondensates may also be included. Hereinafter, “including the fluorinated silane compound (a) and the fluorinated silane compound (b)” includes including these partially hydrolyzed cocondensates.

  In the intermediate layer coating composition, the hydrolyzable silane compound other than the fluorine-containing silane compound (a) is a compound that substantially forms a compound having a perfluoroalkyl group having 8 or more carbon atoms as a decomposition product. Not included. Regarding the fluorine-containing silane compound (a) which is an essential component in the coating composition for intermediate layer and the fluorine-containing silane compound (b) preferably used as a hydrolyzable silane compound other than the fluorine-containing silane compound (a), The number of carbon atoms in the perfluoroalkyl group is 6 or less, and the burden on the environment is low.

  Here, the partially hydrolyzed cocondensate of the fluorine-containing silane compound (a) and the fluorine-containing silane compound (b) is the same as described above in the presence of a catalyst such as an acid catalyst or an alkali catalyst in a solvent. The oligomer (multimer) produced | generated by hydrolyzing all or one part of the hydrolysable group which this compound has, and carrying out dehydration condensation then. Here, since it is obtained by hydrolytic condensation of the fluorine-containing silane compound (a) and the fluorine-containing silane compound (b), it is called a partially hydrolyzed “co” condensate. The degree of condensation (degree of multimerization) of this partially hydrolyzed cocondensate must be such that the product is soluble in the solvent.

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

  By using the partial hydrolysis cocondensate, an intermediate layer having higher performance can be formed. For example, in the case of an intermediate layer formed from a fluorine-containing silane compound (a) and a fluorine-containing silane compound (b), the intermediate layer is composed of hydrolysis cocondensates of both compounds, so that the units derived from both compounds are uniform. It is considered that the layer is preferably distributed. Since the hydrolysis cocondensate of both compounds is formed in a relatively short time, units derived from both compounds in the layer formed directly from the fluorine-containing silane compound (a) and the fluorine-containing silane compound (b) There is a risk that the uniformity of the distribution of the material will decrease. It is considered that this uniformity is improved by preparing in advance a partially hydrolyzed cocondensate containing units derived from both compounds.

  The composition ratio of the hydrolyzable silane compound in the coating composition for intermediate layers is such that the hydrolyzable silane compound is composed of, for example, a fluorine-containing silane compound (a) and a fluorine-containing silane compound (b). The composition ratio can be determined by the ratio of both compounds used for the purpose. However, when the intermediate layer coating composition contains the partially hydrolyzed cocondensate, it is difficult to measure the proportion of units in the partially hydrolyzed cocondensate. In this case, in this invention, the composition ratio of an active ingredient shall be determined with the raw material composition before manufacturing a partial hydrolysis cocondensate. That is, the composition ratio is determined from the amounts of the fluorine-containing silane compound (a) and the fluorine-containing silane compound (b) used as the raw material for the partially hydrolyzed cocondensate.

  The hydrolyzable silane compound contained in the intermediate layer coating composition is mainly composed of the fluorine-containing silane compound (a), and the hydrolyzable silane compound other than the fluorine-containing silane compound (a) is a fluorine-containing silane compound (b). ) Is preferable in terms of water repellency and durability. The content ratio of the fluorine-containing silane compound (a) and the fluorine-containing silane compound (b) in the intermediate layer coating composition is a mass ratio represented as fluorine-containing silane compound (a) / fluorine-containing silane compound (b). 51 / 49-100 / 0 is preferable, and 80 / 20-100 / 0 is more preferable.

  The functional additive optionally contained in the coating composition for the intermediate layer is preferably selected in consideration of the reactivity or compatibility with essential components, such as one-end reactive polydimethylsiloxane, both-end reactive Non-fluorinated water repellent materials such as polydimethylsiloxane, ultrafine particles of metal oxides such as silica, alumina, zirconia, and titania, coloring materials such as dyes or pigments, antifouling materials, curing catalysts, and various resins are preferred Can be mentioned. As for the addition amount of a functional additive, 0.01-20 mass parts is preferable with respect to 100 mass parts of total mass of the hydrolysable silane compound which the coating composition for intermediate | middle layers contains. Excessive addition of the functional additive to the composition may cause a decrease in the performance of the resulting intermediate layer.

  The coating composition for the intermediate layer may be composed only of the solid content containing the fluorine-containing silane compound (a) as a main component, but it is economical, easy to work, and easy to control the thickness of the resulting intermediate layer. In general, an organic solvent is included. The organic solvent is not particularly limited as long as it dissolves a solid content containing essential components. As the organic solvent, alcohols, ethers, ketones, aromatic hydrocarbons, paraffin hydrocarbons, acetate esters and the like are preferable, and organic solvents containing fluorine atoms (for example, fluoroalcohols, fluorohydrocarbons) are particularly preferable. Is preferred. The organic solvent is not limited to one kind, and two or more kinds of organic solvents having different polarities and evaporation rates may be mixed and used.

  When the coating composition for an intermediate layer contains a partial hydrolysis condensate or a partial hydrolysis cocondensate, it may contain a solvent used for producing these, and the solvent and the coating composition for the intermediate layer may be included. The same organic solvent may be used. Furthermore, the coating composition for intermediate | middle layers may contain components, such as a catalyst used by the partial hydrolysis-condensation. In particular, the intermediate layer coating composition containing the partially hydrolyzed cocondensate is preferably a solution of the partially hydrolyzed cocondensate obtained in the production of the partially hydrolyzed cocondensate.

  The proportion of the organic solvent in the intermediate layer coating composition is preferably 100,000 parts by mass or less, particularly preferably 10,000 parts by mass or less, with respect to 100 parts by mass of the total mass of the hydrolyzable silane compound. If an amount exceeding 100,000 parts by mass is used, uneven processing may occur in the resulting intermediate layer.

  The amount of the organic solvent used in the intermediate layer coating composition is preferably 3,500 parts by mass or less with respect to 100 parts by mass of the total mass of the hydrolyzable silane compound contained in the composition. More preferably, it is not more than 1,000 parts by mass. Thus, in the coating composition for an intermediate layer, by reducing the amount of the organic solvent relative to the solid content contained, the film thickness of the intermediate layer formed using this can be easily increased, and the water repellent film It becomes possible to contribute to the improvement of the weather resistance. The lower limit of the amount of the organic solvent used in the intermediate layer coating composition is not particularly limited, but as described above, considering the economy, workability, ease of controlling the thickness of the treatment layer, etc., the composition Preferably, the lower limit is about 500 parts by mass with respect to 100 parts by mass of the total mass of the hydrolyzable silane compound contained in the product.

  Further, in the coating composition for the intermediate layer, the fluorine-containing silane compound (a) and the fluorine-containing silane used as necessary may be used even if they do not contain a partial hydrolysis condensate or a partial hydrolysis cocondensate. In order to accelerate the hydrolysis condensation reaction and hydrolysis cocondensation reaction of the compound (b), it is also preferable to incorporate a catalyst such as the same acid catalyst as used in the same 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. The presence of the catalyst makes it possible to form an intermediate layer that can contribute to improving the wear resistance and weather resistance of the water repellent film. As a quantity of a catalyst, 0.01-5 mass parts is preferable with respect to 100 mass parts of total mass of a fluorine-containing hydrolysable silane compound component.

  The coating composition for intermediate | middle layer may contain the water for the hydrolysis condensation reaction and hydrolysis cocondensation reaction of a hydrolysable silane compound. As for content of the water in the coating composition for intermediate | middle layers, 1-50 mass parts is preferable with respect to 100 mass parts of the total mass of a hydrolysable silane compound. Even if the coating composition for the intermediate layer does not contain water, the hydrolysis condensation and hydrolysis co-condensation reaction of the hydrolyzable silane compound are performed using the moisture in the atmosphere in the process of forming the following intermediate layer. Can be made.

  As a method for forming the intermediate layer 32 using the intermediate layer coating composition, a known method in a film forming composition containing a hydrolyzable silane compound can be used. For example, the composition is applied to the surface of the substrate 2 or the underlayer 33 by a method such as brush coating, flow coating, spin coating, dip coating, squeegee coating, spray coating, wipe coating, or hand coating. In the atmosphere, the intermediate layer 32 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. Depending on the treatment method, an excess component may be generated and the appearance quality may be impaired. However, the appearance may be adjusted by removing the excess component by solvent wiping or empty wiping. The thickness of the intermediate layer 32 formed from the intermediate layer coating composition is not particularly limited, but considering the economy, a thickness of 50 nm or less is preferable, and the lower limit is the thickness of the monomolecular layer. The thickness of the intermediate layer 32 can be appropriately controlled depending on the solid content concentration of the intermediate layer coating composition to be used, coating conditions, heating conditions, and the like.

(Outermost layer)
The outermost layer 31 is a layer formed on the surface of the intermediate layer 32 on the substrate 2 using the outermost layer coating composition described below. The outermost layer 31 is a layer located on the outermost layer of the water-repellent film 3 that mainly imparts excellent water repellency and alkali resistance to the water-repellent film 3.

  The outermost layer coating composition for forming the outermost layer 31 is a hydrolyzable silane compound having a perfluoropolyether group having 1 to 6 carbon atoms in the terminal perfluoroalkyl group (hereinafter referred to as “ Perfluoropolyether group-containing hydrolyzable silane compound) and / or a fluorine-containing silane compound (b) that is a partially hydrolyzed condensate thereof is a composition containing 70% by mass or more based on the total solid content.

  When the fluorinated silane compound (b) is composed of a partially hydrolyzed condensate of the perfluoropolyether group-containing hydrolyzable silane compound, the degree of condensation (degree of multimerization) is such that the product is dissolved in the solvent. Adjusted to The fluorine-containing silane compound (b) may be a perfluoropolyether group-containing hydrolyzable silane compound or a partially hydrolyzed condensate thereof, or a mixture of both, for example, an unreacted perfluoropolyether group. The partial hydrolysis-condensation product containing the containing hydrolyzable silane compound may be sufficient.

Examples of the perfluoropolyether group-containing hydrolyzable silane compound include at least one selected from a compound represented by the following formula (b1) and a compound represented by the following formula (b2).
_{^{A 2 -Q 2 -SiX 2 m2 R}} 2 3-m2 ... (b1)
^{_{A 3 -Q 3 - {CH 2}} CH (SiX 3 m3 R 3 3-m3)} n -H ... (b2)
However, the symbols in formula (b1) and formula (b2) are as follows independently for each formula.
A ² and A ³ are groups represented by the following formula (1).

(In Formula (1), R ^F2 represents a perfluoroalkyl group having 1 to 6 carbon atoms. A, b, c and d each independently represents 0 or an integer of 1 or more, and a + b + c + d is The order of existence of each repeating unit that is at least 1 and is a, b, c, d is not limited in the formula.
Q ² , Q ³ : —C (═O) NH—, —C (═O) N (CH ₃ ) —, —C (═O) N (C ₆ H ₅ ) — selected from amide bond and urethane bond , An ether bond, an ester bond, a —CF ₂ — group, and a divalent organic compound having 2 to 12 carbon atoms composed of repeating —CH ₂ — units, which may contain one or two selected from a —CF ₂ — group and a phenylene group A group (wherein one hydrogen atom of the —CH ₂ — group may be substituted with an —OH group).
X ² and X ³ : an alkoxy group having 1 to 10 carbon atoms, an oxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen atom Or an isocyanate group is shown. m2 amino ^{X 2} and m3 pieces of ^{X 3} may each be the same or different from each other.
R ² and R ³ : each represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms that does not contain a fluorine atom that may be partially or wholly substituted. 3-m2 R ² and 3-m3 R ³ may be the same as or different from each other.
m2, m3: An integer of 1 to 3 is shown.
n represents an integer of 1 to 10.

The compound (b1) and the compound (b2) are both a perfluoroether group represented by the above formula (1) and 3-m2 and 3-m3 hydrocarbon groups (R ² , R ³ ) on the silicon atom, respectively. When a m2, m3 (m2, m3 is an integer of 1 to 3) number of hydrolyzable groups ^(X 2, ^{X 3)} and has a structure bound, fluorinated hydrolyzable silane compound.

The terminal R ^F2 in the perfluoroether group (1) represents a perfluoroalkyl group that does not contain an etheric oxygen atom between carbon-carbon atoms having 1 to 6 carbon atoms which may have a ring structure. R ^F2 may have a straight chain structure, a branched structure, a cyclic structure, or a structure partially having a branched structure and a cyclic structure as long as the above conditions are satisfied. Good. Among these, as R ^F2 , a linear structure or a branched structure is preferable, and a linear structure is more preferable. R ^F2 preferably has 1 to 3 carbon atoms.

Thus, in the perfluoroether group (1) of the compound (b1) and the compound (b2), the terminal perfluoroalkyl group R ^F2 has 1 to 6 carbon atoms, and the decomposition product has 8 or more carbon atoms. Therefore, the compound (b1) and the compound (b2) have a low environmental load.

In A ² and A ³ each having compound (b1) and compound (b2), that is, in the perfluoroether group (1), the upper limit of a, b, c and d is each independently preferably 200, more preferably 50 preferable. Further, the upper limit of a + b + c + d is preferably 200, and more preferably 100. Moreover, ^{A 2} and ^{A 3} compound (b1) and the compound (b2) having respectively, each preferably a group represented by any one of the following formulas (11) to (15).
CF _3- (OCF ₂ ) _c- (11)
CF ₃ — (OCF ₂ CF ₂ ) _a — (OCF ₂ ) _c − (12)
CF ₃ CF _2- (OCF ₂ CF ₂ ) _a- (13)
CF ₃ CF ₂ CF ₂ — (OCF ₂ CF ₂ CF ₂ ) _d − (14)
CF ₃ CF ₂ CF ₂ — {OCF (CF ₃ ) CF ₂ } _b − (15)
(However, the symbols a, b, c, and d in the formulas (11) to (15) are independent for each formula, and the meaning and preferred embodiment are the same as those in the formula (1).)

As Q ² and Q ³ in the compound (b1) and the compound (b2), specifically, — (CH ₂ ) _n1 — (n1 represents an integer of 2 to 4), —CONH (CH ₂ ) _n2 — (N2 represents an integer of 2 to 4)-(CF ₂ ) _n3 —, —O— (CF ₂ ) _n3 — (n3 represents an integer of 2 to 4), —CH ₂ OCONHC ₃ H ₆ — , —COCH ₂ CH (OH) CH ₂ OC ₃ H ₆ —, —CH ₂ OCH ₂ CH (OH) CH ₂ OC ₃ H ₆ —, —CH ₂ OC ₃ H ₆ —, —CF ₂ OC ₃ H ₆ — Etc. Among these, —CONHC ₃ H ₆ —, —CONHC ₂ H ₄ —, —CH ₂ OCONHC ₃ H ₆ —, —COCH ₂ CH (OH) CH ₂ OC ₃ H ₆ —, —CH ₂ OCH ₂ CH ( _{OH) CH 2 OC 3 H 6} -, - CH 2 OC 3 H 6 -, - CF 2 OC 3 H 6 -, - C 2 H 4 -, - C 3 H 6 -, - C 2 F 4 - and - Any divalent organic group selected from OC ₂ F ₄ — is preferred. _{Furthermore, -CONHC 3 H 6 -, -} CONHC 2 H 4 -, - C 2 H 4 - is preferable.

Specific hydrolyzable groups represented by the symbols X ² and X ³ in the compound (b1) and the compound (b2) include specific hydrolyzable groups represented by X ¹ in the compound (a1) and preferred embodiments. And similar. From the viewpoint of adhesion to the intermediate layer, m2 and m3 are preferably 2 or 3, and 3 is particularly preferable. Where a compound (b1) and the compound (b2) respectively in X ² and X ³ are plurally present, availability is X ² and X ³ in each compound may be either different groups in the same group, the same group It is preferable in terms of ease.

Specific monovalent hydrocarbon groups represented by symbols R ² and R ³ in compound (b1) and compound (b2) include a specific monovalent hydrocarbon group represented by R ¹ in compound (a1), and preferred embodiments The same can be done including When there are a plurality of R ² and R ³ in each of the compound (b1) and the compound (b2), R ² and R ³ may be the same or different in each compound, and it is obtained that they are the same group Moreover, n in a compound (b2) shows the integer of 1-10, 1-5 are preferable and 1-2 are more preferable.

As the compound (b1), compounds represented by the following formulas (b11) to (b16) are preferable from the viewpoint of water repellency and alkali resistance of the water-repellent layer 31 to be obtained and ease of synthesis.
_{CF 3 - (OCF 2 CF 2} ) a -OCF 2 -CONHC 3 H 6 Si (OCH 3) 3 ... (b11)
_{CF 3 - (OCF 2 CF 2} ) a -OCF 2 -CONHC 3 H 6 Si (OC 2 H 5) 3 ... (b12)
_{CF 3 - (OCF 2 CF 2} ) a -OCF 2 -CONHC 2 H 4 Si (OCH 3) 3 ... (b13)
_{CF 3 - (OCF 2 CF 2} ) a -OCF 2 -CONHC 2 H 4 Si (OC 2 H 5) 3 ... (b14)
_{CF 3 - (OCF 2 CF 2} ) a -OCF 2 -C 2 H 4 Si (OCH 3) 3 ... (b15)
_{CF 3 - (OCF 2 CF 2} ) a -OCF 2 -C 2 H 4 Si (OC 2 H 5) 3 ... (b16)
(However, in formulas (b11) to (b16), a = 7 to 8 and average value: 7.3 are shown independently for each formula.)
Compounds (b11) to (b16) can be used alone or in combination of two or more.

As the compound (b2), compounds represented by the following formulas (b21) to (b25) are preferable from the viewpoint of water repellency and alkali resistance of the water-repellent layer 31 to be obtained, and ease of synthesis.
^{_{CF 3 - (OCF 2) c}} -Q 3 - {CH 2 CH (SiX 3 m3 R 3 3-m3)} n -H ... (b21)
_{CF 3 - (OCF 2 CF 2} ) a - (OCF 2) c -Q 3 - {CH 2 CH (SiX 3 m3 R 3 3-m3)} n -H ... (b22)
_{CF 3 CF 2 - (OCF 2} CF 2) a -Q 3 - {CH 2 CH (SiX 3 m3 R 3 3-m3)} n -H ... (b23)
_{CF 3 CF 2 CF 2 - (} OCF 2 CF 2 CF 2) d -Q 3 - {CH 2 CH (SiX 3 m3 R 3 3-m3)} n -H ... (b24)
_{CF 3 CF 2 CF 2 - {} OCF (CF 3) CF 2} b -Q 3 - {CH 2 CH (SiX 3 m3 R 3 3-m3)} n -H ... (b25)
(However, in the formulas (b21) to (b25), the symbols a, b, c, d, Q ³ , X ³ , R ³ , m3 and n are each independently represented by the formula (b2). And preferred embodiments are the same as above.)
Compounds (b21) to (b25) can be used alone or in combination of two or more.

In the present invention, among these, the compound (b11) is particularly preferable.
The compound (b1) and the compound (b2) can be produced by a known method. For example, the compound (b1) can be specifically produced by the method described in WO2009-008380. Compound (b2) can be produced, for example, by the method described in JP-A-9-157388.

  The fluorine-containing silane compound (b) contained in the outermost layer coating composition is a component contained in an amount of 70% by mass or more based on the total solid content in the composition. The content of the fluorine-containing silane compound (b) in the total solid content of the outermost layer coating composition is 70 to 100% by mass, preferably 90 to 100% by mass, and 100 from the viewpoint of imparting alkali resistance to the water-repellent film. The mass% is more preferable.

  When the coating composition for outermost layer contains the fluorine-containing silane compound (b) in the above range, the outermost layer 31 to be obtained is mostly hydrolyzed and condensed with the fluorine-containing silane compound (b) to form a siloxane bond. A layer having a perfluoropolyether group (wherein the terminal perfluoroalkyl group has 1 to 6 carbon atoms) can impart sufficient water repellency and alkali resistance to the water repellent film 3. It becomes. The outermost layer coating composition can contain a hydrolyzable silane compound other than the fluorine-containing silane compound (b) as a component for forming a siloxane bond in the solid content within a range not impairing the effects of the present invention. Furthermore, the coating composition for outermost layers may contain a functional additive according to various purposes as a solid content other than the hydrolyzable silane compound as long as the effects of the present invention are not impaired.

  The hydrolyzable silane compound other than the fluorine-containing silane compound (b) is preferably the fluorine-containing silane compound (a) contained in the intermediate layer coating composition. Here, when the outermost layer coating composition contains the fluorine-containing silane compound (b) and the fluorine-containing silane compound (a), the portion of the fluorine-containing silane compound (b) and the fluorine-containing silane compound (a) Hydrolysis cocondensates may also be included. In addition, the partial hydrolysis cocondensate of the fluorine-containing silane compound (a) and the fluorine-containing silane compound (b) is as described in the intermediate layer coating composition.

  In the outermost layer coating composition, the hydrolyzable silane compound other than the fluorine-containing silane compound (b) is a compound that substantially forms a compound having a perfluoroalkyl group having 8 or more carbon atoms as a decomposition product. Not included. The fluorine-containing silane compound (b) that is an essential component in the outermost layer coating composition and the fluorine-containing silane compound (a) that is preferably used as a hydrolyzable silane compound other than the fluorine-containing silane compound (b) are as described above. The number of carbon atoms in the perfluoroalkyl group they have is 6 or less, and the burden on the environment is low.

  The hydrolyzable silane compound contained in the outermost layer coating composition contains the fluorine-containing silane compound (b) in the above-mentioned proportion with respect to the total solid content, and is hydrolyzable other than the fluorine-containing silane compound (b). What contains only the fluorine-containing silane compound (a) as a silane compound is preferable at the point of water repellency. The content ratio of the fluorine-containing silane compound (b) and the fluorine-containing silane compound (a) in the outermost layer coating composition is a mass ratio expressed as fluorine-containing silane compound (b) / fluorine-containing silane compound (a). 70/30 to 100/0, preferably 80/20 to 100/0, and more preferably 90/10 to 100/0. The composition ratio of the hydrolyzable silane compound in the outermost layer coating composition can also be calculated in the same manner as in the intermediate layer coating composition. For example, when a partially hydrolyzed cocondensate of a fluorine-containing silane compound (b) and a fluorine-containing silane compound (a) is used, the fluorine-containing silane compound (b) and fluorine-containing silane compound (a) used as raw materials The composition ratio is determined from the amount of

  Examples of the functional additive optionally contained in the outermost layer coating composition include the same functional additives as those optionally contained in the intermediate layer coating composition. It can be similar to the coating composition. Moreover, the coating composition for outermost layers usually contains an organic solvent, and the kind and addition amount of the organic solvent can be the same as those for the intermediate layer coating composition. Furthermore, the coating composition for outermost layers can contain a catalyst and water similarly to the coating composition for intermediate | middle layers.

  The method of forming the outermost layer 31 using the outermost layer coating composition is a method of forming the intermediate layer 32 using the intermediate layer coating composition except that the coated surface is the surface of the intermediate layer 32. The same can be done. The thickness of the outermost layer 31 formed from the outermost layer coating composition is not particularly limited. However, in consideration of economy, the thickness is preferably 50 nm or less, and the lower limit is the thickness of the monomolecular layer. The thickness of the outermost layer 31 can be appropriately controlled by the solid content concentration of the outermost layer coating composition to be used, coating conditions, heating conditions, and the like.

(Underlayer)
The underlayer 33 has a tetrafunctional hydrolyzable silane compound and / or a hydrolyzable silane compound (c), which is a partially hydrolyzed condensate thereof, as a main component of the total solids between the substrate 2 and the intermediate layer 32. It is a layer arbitrarily formed using the coating composition for foundation | substrate layers containing. By having the base layer 33, the adhesion between the water repellent film 3 and the substrate 2 is increased, and the denseness of the water repellent film 3 as a whole is increased, thereby improving the durability such as wear resistance and weather resistance. Is possible.

Specific examples of the tetrafunctional hydrolyzable silane compound include compounds represented by the following formula (c1).
Si (X ⁴ ) ₄ (c1)
In the above formula (c1), X ⁴ is an alkoxy group having 1 to 10 carbon atoms, an oxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, or an alkenyl having 2 to 10 carbon atoms. An oxy group, a halogen atom or an isocyanate group is shown. The four X ⁴ may be the same as or different from each other. Among these, X ⁴ is preferably a chlorine atom, an alkoxy group having 1 to 4 carbon atoms or an isocyanate group, and more preferably a methoxy group, an ethoxy group or an isocyanate group. Moreover, it is preferable that ^four X4 is the same. Specific examples of the compound (c1) include SiCl ₄ , Si (NCO) ₄ , Si (OCH ₃ ) ₄ , and Si (OC ₂ H ₅ ) ₄ . Of these, Si (NCO) ₄ is particularly preferable as the compound (c1).

When the hydrolyzable silane compound (c) is composed of a partial hydrolysis condensate of a tetrafunctional hydrolyzable silane compound, the degree of condensation (degree of multimerization) is adjusted so that the product is dissolved in a solvent. The The hydrolyzable silane compound (c) may be a tetrafunctional hydrolyzable silane compound or a partially hydrolyzed condensate thereof, and a mixture of both, for example, an unreacted tetrafunctional hydrolyzable silane. It may be a partially hydrolyzed condensate containing the compound. There are commercially available tetrafunctional hydrolyzable silane compounds such as compound (c1) and partial hydrolysis condensates thereof, and such commercially available products can be used in the present invention.
Moreover, 1 type of a hydrolysable silane compound (c) may be used independently for the said coating composition for base layers, and 2 or more types may be used together.

  The hydrolyzable silane compound (c) contained in the coating composition for an underlayer is a main component of the total solid content in the composition, and is a component included in the total solid content in excess of 50% by mass. The content of the hydrolyzable silane compound (c) in the total solid content of the coating composition for the underlayer is more than 50% by mass and 100% by mass, preferably 80 to 100% by mass, and 100% by mass from the viewpoint of weather resistance. Is more preferable.

  When the coating composition for the underlayer contains the hydrolyzable silane compound (c) in the above range, the resulting underlayer 33 mainly forms a siloxane bond by hydrolytic condensation of the hydrolyzable silane compound (c). Thus, the water repellent film 3 can be given further durability such as wear resistance and weather resistance. The coating composition for underlayers can contain a hydrolyzable silane compound other than the hydrolyzable silane compound (c) as a component that forms a siloxane bond in the solid content as long as the effects of the present invention are not impaired. Furthermore, the coating composition for underlayers may contain a functional additive according to various purposes as a solid content other than the hydrolyzable silane compound as long as the effects of the present invention are not impaired.

  The hydrolyzable silane compound other than the hydrolyzable silane compound (c) is preferably the fluorine-containing silane compound (a) contained in the intermediate layer coating composition. Here, in the case where the coating composition for the underlayer includes the hydrolyzable silane compound (c) and the fluorine-containing silane compound (a), the hydrolyzable silane compound (c), the fluorine-containing silane compound (a), The partially hydrolyzed cocondensate may be included. The fluorine-containing silane compound (a) and the hydrolyzable silane compound (c) partially hydrolyzed cocondensate are the fluorine-containing silane compound (a) and the fluorine-containing silane compound described in the intermediate layer coating composition. The partially hydrolyzed cocondensate (b) is a partially hydrolyzed cocondensate obtained by replacing the fluorinated silane compound (b) with a hydrolyzable silane compound (c).

  In the coating composition for the underlayer, the hydrolyzable silane compound other than the hydrolyzable silane compound (c) substantially produces a compound having a perfluoroalkyl group having 8 or more carbon atoms as a decomposition product. Contains no compounds. In addition, as above-mentioned, the fluorine-containing silane compound (a) has 6 or less carbon atoms of the perfluoroalkyl group which these have, and the load given to an environment is low.

  The hydrolyzable silane compound contained in the coating composition for the underlayer includes a hydrolyzable silane compound (c) as a main component, and a fluorine-containing silane compound as a hydrolyzable silane compound other than the hydrolyzable silane compound (c). What contains only (a) is preferable at the point of a weather resistance. As a content ratio of the hydrolyzable silane compound (c) and the fluorine-containing silane compound (a) in the coating composition for the underlayer, the mass shown as hydrolyzable silane compound (c) / fluorine-containing silane compound (a). The ratio is preferably 51/49 to 100/0, and more preferably 80/20 to 100/0. The composition ratio of the hydrolyzable silane compound in the underlayer coating composition can also be calculated in the same manner as in the intermediate layer coating composition. For example, when a partially hydrolyzed cocondensate of a hydrolyzable silane compound (c) and a fluorine-containing silane compound (a) is used, the hydrolyzable silane compound (c) and fluorine-containing silane compound ( The composition ratio is determined from the amount of a).

  Examples of the functional additive optionally contained in the coating composition for the underlayer include those similar to the functional additive optionally contained in the coating composition for the intermediate layer. It can be similar to the coating composition. The underlayer coating composition usually contains an organic solvent, and the type and amount of the organic solvent can be the same as in the intermediate layer coating composition. Furthermore, the coating composition for underlayers can contain a catalyst and water similarly to the coating composition for intermediate layers.

  The method of forming the underlayer 33 using the underlayer coating composition is the same as the method of forming the intermediate layer 32 using the intermediate layer coating composition except that the coating surface is the surface of the substrate 2. And can. The thickness of the underlayer 33 formed from the underlayer coating composition is not particularly limited, but considering the economy, a thickness of 50 nm or less is preferable, and the lower limit is the thickness of the monomolecular layer. The thickness of the underlayer 33 can be appropriately controlled depending on the solid content concentration of the underlayer coating composition to be used, coating conditions, heating conditions, and the like.

  As described above, in the substrates 1 </ b> A and 1 </ b> B with the water-repellent film according to the embodiment of the present invention, the manufacturing method of the base layer 33, the intermediate layer 32, and the outermost layer 31 constituting the water-repellent film 3 formed on the substrate 2 is adjusted. explained. Here, in the case of manufacturing the substrate 1B with a water repellent film, when forming the base layer 33, the intermediate layer 32, and the outermost layer 31, the base layer coating composition is applied to the substrate surface and kept for a certain period of time. After forming a film, coating the intermediate layer coating composition on the surface and holding for a certain period of time to form a coating film, further coating the outermost layer forming coating composition on the surface to form a coating film, By performing the curing process under appropriate conditions, it is possible to simultaneously perform the curing process for forming the base layer, the curing process for forming the intermediate layer, and further the curing process for forming the outermost layer. The same applies to the substrate 1A with a water repellent film.

  In addition, in the coating composition for forming each layer, when it is stored for a long time in a state containing a catalyst, the hydrolysis of the hydrolyzable silane compound gradually proceeds to polymerize the silane compound, etc. It may be a problem in terms of storage stability. Accordingly, each coating composition is prepared to a composition that does not substantially contain a catalyst, and after applying the outermost layer-forming coating composition to form a coating film and drying it, a surface treatment liquid containing a catalyst and a solvent is prepared. It is also possible to take a method in which each layer is cured by infiltrating from the surface.

  The surface treatment liquid used in this case is not particularly limited as long as it is a surface treatment liquid containing a catalyst that catalyzes the hydrolysis reaction of the hydrolyzable silane compound contained in the coating composition for each layer and a solvent that dissolves the catalyst. . Specific examples of the catalyst include acids and alkalis. As the acid catalyst, hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, paratoluenesulfonic acid and the like can be used. As the alkali catalyst, sodium hydroxide, potassium hydroxide, ammonia or the like can be used. Among these, the catalyst is preferably an acid, and the acid is preferably at least one selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, paratoluenesulfonic acid and methanesulfonic acid. As a quantity of the catalyst which a surface treatment liquid contains, the ratio from which a catalyst will be 0.01-5 mass% with respect to the whole surface treatment liquid is preferable.

  Since the solvent of the surface treatment liquid needs to be finally removed, the boiling point thereof is preferably in the range of 60 to 160 ° C, more preferably 60 to 120 ° C. Specific examples of the solvent include alcohols, ethers, ketones, and acetates. Specific examples of the solvent that satisfies the above boiling point conditions include isopropyl alcohol, ethanol, propylene glycol monomethyl ether, 2- Examples include butanone. These may be used alone or in combination of two or more. The amount of the solvent in the surface treatment liquid is preferably 2,000 to 1,000,000 parts by mass with respect to 100 parts by mass of the catalyst.

  The surface treatment liquid may further contain water. This water acts as water for hydrolytic condensation of the hydrolyzable silane compound in each layer to be treated. Therefore, when the surface treatment liquid contains water, the water is distinguished from the solvent. The amount of water in the surface treatment liquid is preferably 50 to 15,000 parts by mass with respect to 100 parts by mass of the catalyst. Even if the surface treatment liquid does not contain water, if each layer contains water or if there is sufficient moisture in the atmosphere, hydrolytic condensation of the hydrolyzable silane compound is performed using such water. Can be done.

  The board | substrate with a water-repellent film of this invention is used suitably for the use as articles | goods for transport equipment which comprises this. Preferred examples of the article for transportation equipment include bodies in trains, automobiles, ships, aircrafts, window glass (front glass, side glass, rear glass), mirrors, bumpers, and the like.

  The substrate with a water-repellent film of the present invention or an article for transport equipment comprising this substrate has an excellent water repellency on the surface of the water-repellent film, and there is little adhesion of water droplets to the surface, and the adhered water droplets are immediately repelled. It is. 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. Further, since the water-repellent film is also excellent in alkali resistance and weather resistance, for example, 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. it can.

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

Examples of the present invention are shown below, but the present invention is not limited to these examples. Examples 1 to 6 are examples, and examples 7 to 10 are comparative examples. Example 11 is a reference example.
The following compounds were used as hydrolyzable silane compounds to be blended in the coating composition for each layer.
Compound (a11-1) as fluorine-containing silane compound (a): F (CF ₂ ) ₆ (CH ₂ ) ₂ SiCl ₃ (manufactured by Synquest)
Compound (b11) as the fluorine-containing silane compound (b): CF ₃ — (OCF ₂ CF ₂ ) _a —OCF ₂ —CONHC ₃ H ₆ Si (OCH ₃ ) ₃ (produced in Synthesis Example 1 below, provided that the compound ( b11), a = 7 to 8, average value: 7.3.)
As the hydrolyzable silane compound (c), the compound (c1-1): Si (NCO) ₄ (Orgatech SI-400, trade name, manufactured by Matsumoto Fine Chemical Co., Ltd.)
Fluorine-containing silane compound (S) having 8 carbon atoms in the perfluoroalkyl group used in Reference Example: F (CF ₂ ) ₈ (CH ₂ ) ₂ SiCl ₃ (manufactured by Synquest)

[Synthesis of Compound (b11)]
The abbreviations of the compounds used in the synthesis examples indicate the following compounds.
R-225: Dichloropentafluoropropane R ^F6 : —CF (CF ₃ ) OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₃
R-113: CCl ₂ FCClF ₂

In the flask, 25 g of CH ₃ O (CH ₂ CH ₂ O) _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 thoroughly 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 the 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 (b11) which was liquid at room temperature.

[Preparation of coating composition (X) for underlayer]
The preparation example of coating composition (X) for base layers used for the manufacture example of the board | substrate with a water repellent film is shown below.
(Preparation Example 1)
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.) and 0.30 g of compound (c1-1) are added and stirred at 25 ° C. for 30 minutes. Coating composition (X1) was obtained.

[Preparation of intermediate layer coating composition (Y)]
An example of preparing the intermediate layer coating composition (Y) used in the production example of the substrate with a water-repellent film is shown below.
(Preparation Example 2)
In a glass container in which a stirrer and a thermometer are set, 1.90 g of butyl acetate (manufactured by Junsei Chemical Co., Ltd.), 7.60 g of AE3000 (trade name, manufactured by Asahi Glass Co., Ltd., hydrofluoroether), compound (a11-1) In an amount of 0.40 g and 0.10 g of the compound (b11) were stirred at 25 ° C. for 30 minutes to obtain an intermediate layer coating composition (Y1).

(Preparation Example 3)
In a glass container in which a stirrer and a thermometer are set, 1.90 g of butyl acetate (manufactured by Junsei Chemical Co., Ltd.), 7.60 g of AE3000 (trade name, manufactured by Asahi Glass Co., Ltd., hydrofluoroether), compound (a11-1) Was added and stirred at 25 ° C. for 30 minutes to obtain an intermediate layer coating composition (Y2).
(Preparation Example 4)
In a glass container in which a stirrer and a thermometer are set, 1.90 g of butyl acetate (manufactured by Junsei Chemical Co., Ltd.), 7.60 g of AE3000 (trade name, manufactured by Asahi Glass Co., Ltd., hydrofluoroether), and 0 of compound (b11) .50 g was added and stirred at 25 ° C. for 30 minutes to obtain an intermediate layer coating composition (Ycf3) for Comparative Example.

[Preparation of outermost layer coating composition (Z)]
A preparation example of the outermost layer coating composition (Y) used in the production example of the substrate with a water-repellent film is shown below.
(Preparation Example 5)
In a glass container in which a stirrer and a thermometer are set, 9.90 g of AC-6000 (trade name, manufactured by Asahi Glass Co., Ltd., hydrofluorocarbon) and 0.10 g of compound (b11) are placed and stirred at 25 ° C. for 30 minutes. Thus, a coating composition for outermost layer (Z1) was obtained.
(Preparation Example 6)
In a glass container in which a stirrer and a thermometer are set, 9.90 g of AC-6000 (trade name, manufactured by Asahi Glass Co., Ltd., hydrofluorocarbon), 0.01 g of compound (a11-1), and 0.8 g of compound (b11). 09 g was added and stirred at 25 ° C. for 30 minutes to obtain an outermost layer coating composition (Z2).

(Preparation Example 7)
In a glass container in which a stirrer and a thermometer are set, 9.90 g of AC-6000 (trade name, manufactured by Asahi Glass Co., Ltd., hydrofluorocarbon), 0.02 g of compound (a11-1) and 0.02 g of compound (b11) are added. 08 g was added and stirred at 25 ° C. for 30 minutes to obtain an outermost layer coating composition (Z3).
(Preparation Example 8)
In a glass container in which a stirrer and a thermometer are set, 9.90 g of AC-6000 (trade name, manufactured by Asahi Glass Co., Ltd., hydrofluorocarbon), 0.03 g of compound (a11-1) and 0.03 g of compound (b11) are added. 07 g was added and stirred at 25 ° C. for 30 minutes to obtain an outermost layer coating composition (Z4).
(Preparation Example 9)
In a glass container in which a stirrer and a thermometer are set, 9.50 g of butyl acetate (manufactured by Junsei Chemical Co., Ltd.) and 0.50 g of compound (a11-1) are added and stirred at 25 ° C. for 30 minutes. A coating composition for outermost layer (Zcf5) was obtained.
(Preparation Example 10)
In a glass container in which a stirrer and a thermometer are set, 9.50 g of butyl acetate (manufactured by Junsei Chemical Co., Ltd.) and 0.5 g of compound (S) are added and stirred at 25 ° C. for 30 minutes. The outermost layer coating composition (Zs6) was obtained.

[Preparation of surface treatment liquid (W)]
A preparation example of the surface treatment liquid (W) used in the production example of the substrate with the water repellent film is shown below.
(Preparation Example 11)
In a glass container in which a stirrer and a thermometer are set, 0.01 g of paratoluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries), 0.30 g of pure water and 2-propanol (manufactured by Junsei Chemical Co., Ltd.) 9.69 g was added and stirred at 25 ° C. for 30 minutes to obtain a surface treatment liquid (W1).

Table 1 shows the composition of the coating composition of each layer.

[Examples 1 to 11] Production and Evaluation of Substrate with Water-Repellent Film Using the coating composition of each layer obtained in each of the above preparation examples, a water-repellent film was formed on a glass substrate as follows. An attached substrate was manufactured. The obtained substrate with a water-repellent film was evaluated by the following evaluation method. Table 2 shows the types of coating compositions for each layer used in each example and the results obtained in each evaluation.
For each example other than Example 1 shown in Table 2, using 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 as the substrate. Then, 2 g of the coating composition (X1) for the underlayer obtained in the above preparation example was applied to the surface of the glass substrate by a squeegee coating method and held at 25 ° C. for 1 minute to form an underlayer.

  Then, the coating for intermediate layer obtained in the above-mentioned preparation example was applied to each of the examples as shown in Table 2 on the surface of the base layer formed above for Examples 2 to 9, and on the surface of the glass substrate for Example 1. 2 g of the compositions Y1 to Ycf3 were applied by a squeegee coating method. Thereafter, an intermediate layer is formed by holding for 1 hour in a constant temperature and humidity chamber set at 25 ° C. and 80% RH, and a base layer in which the intermediate layer is formed on the substrate (Example 1), and the base layer in order from the substrate side And the board | substrate (Example 2-Example 9) in which the intermediate | middle layer was formed was obtained. In Examples 10 and 11, the outermost layer was formed on the base layer without forming the intermediate layer.

Furthermore, for each of the examples shown in Table 2 (Examples 1 to 7, 10, 11), the outermost layer coating composition Z1 obtained in the preparation example was applied to the intermediate layer surface or the underlayer surface on the substrate. Using a cloth soaked with 2 g of Zs6, the composition was applied by wipe coating, and then dried at 25 ° C. for 10 minutes. Thereby, about Example 1, the board | substrate with which the intermediate | middle layer and the outermost layer were formed in order from the board | substrate side was obtained. About Examples 2-7, the board | substrate with which the base layer, the intermediate | middle layer, and the outermost layer were formed in order from the board | substrate side was obtained. In Examples 8 and 9, the outermost layer was not formed, and a substrate on which an underlayer and an intermediate layer were formed in order from the substrate side was obtained. About Example 10 and Example 11, the board | substrate with which the base layer and the outermost layer were formed in order from the board | substrate side was obtained.
In each of the examples (1 to 11) obtained above, each substrate with each layer laminated on the glass substrate in the above order is wiped with a cloth containing 2 g of the surface treatment liquid (W1), The substrate was finished with a water-repellent film.

Evaluation of the substrate with a water-repellent film in each example was performed as follows.
<Water repellency>
Water repellency was evaluated by the value of water contact angle (CA) measured by the following method. First, initial values were measured before each of the following tests. If the water contact angle (CA) is 100 degrees or more at the initial value, it can be said that the water repellency is sufficiently high for practical use.

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

<Alkali resistance>
After performing a test (alkali resistance test) of immersing the substrate with a water-repellent film in a 0.1N sodium hydroxide aqueous solution (pH 13) with the surface of the water-repellent film facing up for 24 hours, and then washing with pure water, the above method Was used to measure the water contact angle. If the water contact angle (CA) maintains a value of 80 degrees or more after performing the alkali resistance test, it is evaluated that the alkali resistance of water repellency is practically sufficient.

<Weather resistance>
An outdoor exposure test was conducted according to JISZ2381. That is, after performing a test (outdoor exposure test) in which the substrate with a water-repellent film is installed outdoors so that the surface of the water-repellent film faces southward at an angle of 30 degrees with respect to the horizontal, the above method is performed. Was used to measure the water contact angle. In addition, if the water contact angle (CA) maintains a value of 100 degrees or more after the outdoor exposure test, it is evaluated that the weather resistance of the water repellency is practically sufficient.

  The substrates with water repellent films obtained in Examples 1 to 6 corresponding to the examples of the present invention have sufficient water repellency, alkali resistance and weather resistance, and have a low environmental load. In particular, the substrates with water-repellent films obtained in Examples 1, 2 and 6 are excellent in alkali resistance under particularly severe conditions, and are equivalent to the substrates with water-repellent films in Example 11 which is a reference example and has a large environmental load. Has performance. In Comparative Examples 7 to 10, there is no problem in terms of initial water repellency and environmental load, but either alkali resistance or weather resistance is not sufficient.

  The substrate with a water repellent film of the present invention has sufficient water repellency, alkali resistance and weather resistance, and has a low environmental load. The substrate with a water-repellent film of the present invention is suitably used for applications such as bodies, window glass (front glass, side glass, rear glass), mirrors, bumpers and the like in transportation equipment such as trains, automobiles, ships, and aircraft.

DESCRIPTION OF SYMBOLS 1A, 1B ... Substrate with water repellent film, 2 ... Substrate, 3 ... Water repellent film, 31 ... Outermost layer, 32 ... Intermediate layer, 33 ... Underlayer.

Claims (9)

A substrate with a water-repellent film comprising: a substrate; and a water-repellent film having an intermediate layer and an outermost layer formed in order from the substrate side on at least a part of the main surface of the substrate,
The intermediate layer includes a hydrolyzable silane compound represented by the following general formula (a1) and / or a fluorine-containing silane compound (a) that is a partial hydrolysis condensate thereof as a main component of the total solid content. Formed using a coating composition;
The outermost layer comprises a hydrolyzable silane compound having a perfluoropolyether group having 1 to 6 carbon atoms in the terminal perfluoroalkyl group and / or a fluorine-containing silane compound (b) which is a partial hydrolysis condensate thereof. A substrate with a water-repellent film formed using an outermost layer coating composition containing 70% by mass or more based on the total solid content.
R ^F1 -Q ¹ -SiR ¹ _(3-m1) X ¹ _m1 (a1)
However, the symbols in the formula (a1) are as follows.
R ^F1 represents a perfluoroalkyl group containing no etheric oxygen atom between carbon-carbon atoms having 1 to 6 carbon atoms.
Q ¹ represents a divalent organic group not containing a fluorine atom having 1 to 6 carbon atoms.
X ¹ : an alkoxy group having 1 to 10 carbon atoms, an oxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a halogen atom or an isocyanate group Indicates. The m1 X ¹ may be the same as or different from each other.
R ^{1 represents a} hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms that does not contain a fluorine atom that may be partially or wholly substituted. 3-m1 R ^{1 s} may be the same as or different from each other.
m1: An integer of 1 to 3 is shown. The hydrolyzable silane compound having the perfluoropolyether group is at least one selected from a compound represented by the following formula (b1) and a compound represented by the following formula (b2). Substrate with water repellent film.
_{^{A 2 -Q 2 -SiX 2 m2 R}} 2 3-m2 ... (b1)
_{^{A 3 -Q 3 - {CH 2}} CH (SiX 3 m3 R 3 3-m3)} n -H ... (b2)
However, the symbols in formula (b1) and formula (b2) are as follows independently for each formula.
A ² and A ³ are groups represented by the following formula (1).

(In Formula (1), R ^F2 represents a perfluoroalkyl group having 1 to 6 carbon atoms. A, b, c and d each independently represents 0 or an integer of 1 or more, and a + b + c + d is The order of existence of each repeating unit that is at least 1 and is a, b, c, d is not limited in the formula.
Q ² , Q ³ : —C (═O) NH—, —C (═O) N (CH ₃ ) —, —C (═O) N (C ₆ H ₅ ) — selected from amide bond and urethane bond , An ether bond, an ester bond, a —CF ₂ — group, and a divalent organic compound having 2 to 12 carbon atoms composed of repeating —CH ₂ — units, which may contain one or two selected from a —CF ₂ — group and a phenylene group A group (wherein one hydrogen atom of the —CH ₂ — group may be substituted with an —OH group).
X ² and X ³ : an alkoxy group having 1 to 10 carbon atoms, an oxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen atom Or an isocyanate group is shown. m2 amino ^{X 2} and m3 pieces of ^{X 3} may each be the same or different from each other.
R ² and R ³ : each represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms that does not contain a fluorine atom that may be partially or wholly substituted. 3-m2 R ² and 3-m3 R ³ may be the same as or different from each other.
m2, m3: An integer of 1 to 3 is shown.
n represents an integer of 1 to 10. The substrate with a water-repellent film according to claim 2, wherein A ² in the formula (b1) and A ³ in the formula (b2) are groups represented by any of the following formulas (11) to (15), respectively. .
CF _3- (OCF ₂ ) _c- (11)
CF ₃ — (OCF ₂ CF ₂ ) _a — (OCF ₂ ) _c − (12)
CF ₃ CF _2- (OCF ₂ CF ₂ ) _a- (13)
CF ₃ CF ₂ CF ₂ — (OCF ₂ CF ₂ CF ₂ ) _d − (14)
CF ₃ CF ₂ CF ₂ — {OCF (CF ₃ ) CF ₂ } _b − (15)
(However, in formulas (11) to (15), each independently represents a, b, c, d each independently represents 0 or an integer of 1 or more, and a + b + c + d is at least 1 or more. Yes, the existence order of each repeating unit enclosed by a, b, c, d is not limited in the formula.) The substrate with a water-repellent film according to claim 2 or 3, wherein the compound represented by the formula (b1) is at least one selected from compounds represented by the following formulas (b11) to (b16).
_{CF 3 - (OCF 2 CF 2} ) a -OCF 2 -CONHC 3 H 6 Si (OCH 3) 3 ... (b11)
_{CF 3 - (OCF 2 CF 2} ) a -OCF 2 -CONHC 3 H 6 Si (OC 2 H 5) 3 ... (b12)
_{CF 3 - (OCF 2 CF 2} ) a -OCF 2 -CONHC 2 H 4 Si (OCH 3) 3 ... (b13)
_{CF 3 - (OCF 2 CF 2} ) a -OCF 2 -CONHC 2 H 4 Si (OC 2 H 5) 3 ... (b14)
_{CF 3 - (OCF 2 CF 2} ) a -OCF 2 -C 2 H 4 Si (OCH 3) 3 ... (b15)
_{CF 3 - (OCF 2 CF 2} ) a -OCF 2 -C 2 H 4 Si (OC 2 H 5) 3 ... (b16)
(However, in formulas (b11) to (b16), a = 7 to 8 and average value: 7.3 are shown independently for each formula.)   The substrate with a water-repellent film according to claim 4, wherein the compound represented by the formula (b1) is a compound represented by the formula (b11). The hydrolyzable silane compound represented by the general formula (a1) is at least one selected from compounds represented by the following formulas (a11) to (a16), respectively. The substrate with a water-repellent film according to Item.
F (CF ₂ ) _e (CH ₂ ) _f SiX ¹ ₃ (a11)
F (CF ₂ ) _e (CH ₂ ) _f Si (R ¹ ) X ¹ ₂ (a12)
F (CF ₂ ) _e CONH (CH ₂ ) _g SiX ¹ ₃ (a13)
F (CF ₂ ) _e CONH (CH ₂ ) _g Si (R ¹ ) X ¹ ₂ (a14)
F (CF ₂ ) _e CONH (CH ₂ ) _h NH (CH ₂ ) _5-h SiX ¹ ₃ (a15)
F (CF ₂ ) _e CONH (CH ₂ ) _h NH (CH ₂ ) _5-h Si (R ¹ ) X ¹ ₂ (a16)
(In the formulas (a11) to (a16), e is an integer of 1 to 6, f is an integer of 1 to 6, g is an integer of 1 to 5, and h is 1 to 4. X ¹ is independently for each formula, and may be the same or different and each represents an alkoxy group having 1 to 10 carbon atoms, an oxyalkoxy group having 2 to 10 carbon atoms, carbon An acyloxy group having 2 to 10 atoms, an alkenyloxy group having 2 to 10 carbon atoms, a halogen atom or an isocyanate group, wherein R ¹ is independently a hydrogen atom, a part of a hydrogen atom or A monovalent hydrocarbon group having 1 to 8 carbon atoms which does not contain a fluorine atom which may be substituted entirely. The hydrolyzable silane compound represented by the general formula (a1) is F (CF ₂ ) ₆ (CH ₂ ) ₂ SiCl ₃ , F (CF ₂ ) ₆ (CH ₂ ) ₂ Si (NCO) ₃ , F ( _{CF 2) 6 (CH 2)} 2 Si (OCH 3) 3, and _{F (CF 2) 6 (CH} 2) 2 Si (OC 2 H 5) of claims 1 to 6 is at least one selected from ₃ The substrate with a water-repellent film according to any one of the above items.   The water repellent film further contains a tetrafunctional hydrolyzable silane compound and / or a hydrolyzable silane compound (c), which is a partial hydrolysis condensate thereof, between the substrate and the intermediate layer as a main component of the total solid content. The substrate with a water-repellent film according to any one of claims 1 to 7, which has an underlayer formed using a coating composition for an underlayer that is contained as a component. The water repellent according to claim 8, wherein the tetrafunctional hydrolyzable silane compound is at least one selected from SiCl ₄ , Si (NCO) ₄ , Si (OCH ₃ ) ₄ , and Si (OC ₂ H ₅ ) _4. Substrate with film.

Images