TW201816066A - Method of producing thin-film liquid-repelling layer and thin-film liquid-repelling layer - Google Patents

Abstract

The present invention pertains to a method for producing a thin-film liquid-repelling layer, the method comprising the following steps, in the stated order: (1) a step for forming a cured film using a liquid-repellent composition containing component (A), which is a tetrafunctional silane compound having a specific structure, and component (B), which is a trifunctional silane compound having a specific structure; and (2) a step for thinning by removing the surface of the cured film obtained in (1). The present invention also pertains to a thin-film liquid-repelling layer produced using the production method, and a thin-film liquid-repelling layer having a thickness of less than 8 nm, said layer being a cured product of component (A) and the component (B).

Description

Method for manufacturing film liquid-repellent layer, and film liquid-repellent layer

[0001] The present invention relates to a method for manufacturing a thin film liquid repellent layer, and a thin film liquid repellent layer.

[0002] In general, windshields for construction, windowpanes for automobiles, windshields for automobiles, aviation equipment, ships, etc., water tanks, bottom windows, road panels, installations for preventing the adhesion of marine organisms to the bottom film, soundproof walls, etc. On the surface of a molded article such as a mirror, a glass container, a glass ornament, or the like in a bathroom, it is desirable that there is no object that obstructs vision such as water droplets, scars, and dirt. The surface of such a molded product is coated with a film made of a liquid-repellent substance or a liquid-repellent sheet is attached to impart liquid-repellency such as water-repellency, oil-repellency, and liquid-slip property. For example, Patent Document 1 discloses a water-repellent film-coated article which covers a glass by a laminate having a base layer formed of an inorganic compound and a water-repellent film covering the surface of the base layer and formed of a fluorine-containing compound. And other substrates. [Prior Art Document] [Patent Document] [0003] [Patent Document 1] Japanese Patent Laid-Open No. 2010-285574

[Problems to be Solved by the Invention] [0004] However, the water-repellent coating article described in Patent Document 1 has a water-repellent film formed of a fluorine-containing compound, which is not good from the viewpoint of environmental protection. Therefore, a liquid-repellent material with less environmental load is sought. When transparency is required for a liquid-repellent object, the liquid-repellent layer provided on the surface is also required to have excellent transparency. In addition, when the object is colored, or the surface of the object is printed or printed, etc., in order not to affect the color of the object or the printing information, etc., it is set on the surface of the object The liquid layer is also required to have excellent transparency (visibility). An object of the present invention is to provide a method for manufacturing a thin film liquid repellent layer having liquid repellency and excellent visibility, and a thin film liquid repellent layer. [Means for Solving the Problem] [0005] The present inventors have found that the liquid repellency using the component (A) containing a tetrafunctional silane-based compound having a specific structure and the component (B) containing a trifunctional silane-based compound having a specific structure The composition forms a hardened film, and a very thin liquid-repellent layer obtained by removing a part of the hardened film can solve the aforementioned problems and complete the present invention. That is, the present invention provides the following [1] to [17]. [1] A method for manufacturing a thin-film liquid-repellent layer, which has the following steps (1) and (2) in sequence, and step (1): using the following component (A) and the following component (B) Step of forming a cured film of a liquid-repellent composition, Component (A): a tetrafunctional silane-based compound represented by the following general formula (a), In [general formula (a), R ¹ represents an alkyl group having 1 to 6 carbon atoms of, X ¹ represents a halogen atom; R ¹ and when plural X ¹ is present, plural R ¹ and X ¹ may be the same as each other or may be different ; P represents an integer of 0 to 4], component (B): a trifunctional silane-based compound represented by the following general formula (b), [In general formula (b), R ² represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent. R ³ represents an alkyl group having 1 to 6 carbon atoms, and X ² represents a halogen atom. When plural R ³ and X ² exist, plural R ³ and X ² may be the same as or different from each other. q represents an integer of 0 to 3], step (2): a step of removing the surface of the cured film obtained in the step (1) to form a thin film. [2] The method for producing a thin film liquid-repellent layer according to [1], wherein in the step (2), the thin film is formed using an adhesive tape. [3] The method for producing a thin film liquid-repellent layer according to [1] or [2], wherein in step (1), the component (B) contains at least one of the following components (B-1), and the component ( B-1): a trifunctional silane-based compound represented by the following general formula (b-1), [In general formula (b-1), R ⁴ represents an alkyl group having 6 to 24 carbon atoms, and the alkyl group may have a substituent; R ⁵ represents an alkyl group having 1 to 6 carbon atoms, and X ³ represents a halogen atom; R ⁵ When there are a plurality of X ³ , the plurality of R ⁵ and X ³ may be the same as or different from each other. r represents an integer from 0 to 3]. [4] The method for producing a thin-film liquid-repellent layer according to any one of [1] to [3], wherein in step (1), the component (B) contains at least one of the following components (B-2) Component (B-2): a trifunctional silane compound represented by the following general formula (b-2), [In general formula (b-2), R ⁶ represents an alkyl group having 1 to 3 carbon atoms, and the alkyl group may have a substituent; R ⁷ represents an alkyl group having 1 to 6 carbon atoms, and X ⁴ represents a halogen atom; R ⁷ When there is a plurality of X ⁴ , the plural R ⁷ and X ⁴ may be the same as or different from each other; s represents an integer of 0 to 3]. [5] The method for producing a thin film liquid-repellent layer as described in [4] above, wherein in step (1), the following condition (II) is further satisfied, and condition (II): the molar amount of the component (B-1) The ratio [(B-1) / {(B-1) + (B-2)}] to the total molar amount of component (B-1) and component (B-2) is 0.020 the above. [6] The method for producing a thin-film liquid-repellent layer according to any one of [1] to [5], wherein in step (1), the following condition (I) is further satisfied, and condition (I): component (A The molar ratio [(A) / (B)] (molar ratio) of the molar amount of) to the molar amount of component (B) is 0.01 or more and 50.00 or less. [7] The method for producing a thin-film liquid-repellent layer according to any one of the above [1] to [6], wherein in step (1), an acid catalyst is further included as a component (C), with respect to the component (A) And the total content of component (B) is 100 mol%, the content of component (C) is 0.010 mol% or more and 1.000 mol% or less. [8] The method for producing a thin-film liquid-repellent layer according to any one of the above [1] to [7], wherein the method for forming the hardened film is selected from the group consisting of dip coating, curtain coating, spray coating, gravure coating and rod A coating step and a drying step of coating at least one of the groups formed. [9] The method for manufacturing a thin-film liquid-repellent layer according to any one of [1] to [8], wherein the thickness of the thin-film liquid-repellent layer is less than 8 nm. [10] The method for producing a thin-film liquid-repellent layer according to any one of [1] to [9], wherein the thickness of the hardened film formed in step (1) is 8 nm or more. [11] A thin-film liquid-repellent layer, which is manufactured by the manufacturing method according to any one of [1] to [10]. [12] A thin film liquid-repellent layer, which is a hardened product of the following component (A) and the following component (B), whose thickness is less than 8 nm, and the component (A): 4 shown in the following general formula (a) Functional silane compounds In [general formula (a), R ¹ represents an alkyl group having 1 to 6 carbon atoms of, X ¹ represents a halogen atom; R ¹ and when plural X ¹ is present, plural R ¹ and X ¹ may be the same as each other or may be different ; P represents an integer of 0 to 4], component (B): a trifunctional silane-based compound represented by the following general formula (b), [In general formula (b), R ² represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent; R ³ represents an alkyl group having 1 to 6 carbon atoms, and X ² represents a halogen atom; R ³ and X ^When there are plurals, R ³ and X ² may be the same as or different from each other; q represents an integer of 0 to 3]. [13] The thin film liquid-repellent layer according to [12], wherein the component (B) contains at least one of the following components (B-1), and the component (B-1): the following general formula (b-1) ) Is a trifunctional silane compound, [In general formula (b-1), R ⁴ represents an alkyl group having 6 to 24 carbon atoms, and the alkyl group may have a substituent; R ⁵ represents an alkyl group having 1 to 6 carbon atoms, and X ³ represents a halogen atom; R ⁵ When there is a plurality of X ³ , the plural R ⁵ and X ³ may be the same as or different from each other; r represents an integer of 0 to 3]. [14] The thin film liquid-repellent layer according to [12] or [13], wherein the component (B) contains at least one of the following components (B-2), and the component (B-2): the following general formula (b-2) a trifunctional silane compound, [In general formula (b-2), R ⁶ represents an alkyl group having 1 to 3 carbon atoms, and the alkyl group may have a substituent; R ⁷ represents an alkyl group having 1 to 6 carbon atoms, and X ⁴ represents a halogen atom; R ⁷ When there is a plurality of X ⁴ , the plural R ⁷ and X ⁴ may be the same as or different from each other; s represents an integer of 0 to 3]. [15] The thin film liquid-repellent layer according to [14], which further satisfies the following condition (IV), condition (IV): the molar amount of (B-1p) relative to the component (B-1) The ratio of the total moles of the structure (B-1p) and the structure (B-2p) derived from the component (B-2) [(B-1p) / {(B-1p) + (B-2p)} ] (Molar ratio) is 0.020 or more. [16] The thin film liquid-repellent layer described in any one of the above [12] to [15], which satisfies the following condition (III), and condition (III): Mo derived from the structure (Ap) of the component (A) The ratio [(Ap) / (Bp)] (molar ratio) of the ear amount to the mole amount of the structure (Bp) derived from the component (B) is 0.01 or more and 50.00 or less. [17] The thin film liquid-repellent layer according to any one of the above [12] to [16], which is obtained by removing the surface of the hardened material of the component (A) and the component (B) and thinning the hardened material. By. [Effects of the Invention] According to the present invention, a method for manufacturing a thin film liquid repellent layer having liquid repellency and excellent visibility, and a thin film liquid repellent layer can be provided.

[0007] [Manufacturing method of thin-film liquid-repellent layer] A method for manufacturing a thin-film liquid-repellent layer according to one aspect of the present invention includes the following steps (1) and (2) in this order. Step (1): A step of forming a cured film using a liquid-repellent composition containing the following component (A) and the following component (B): Component (A): a tetrafunctional silane represented by the following general formula (a) Department of compounds, [In general formula (a), R ¹ C1-C6 alkyl group, X ¹ Represents a halogen atom; R ¹ And X ¹ When there are plurals, the plural R ¹ And X ¹ They may be the same as or different from each other; p represents an integer of 0 to 4], component (B): a trifunctional silane-based compound represented by the following general formula (b), [In general formula (b), R ² Represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent; R ³ C1-C6 alkyl group, X ² Represents a halogen atom; R ³ And X ² When there are plurals, the plural R ³ And X ² Each may be the same or different; q represents an integer of 0 to 3], step (2): a step of removing a part of the cured film obtained in the foregoing step (1) and performing a thin film treatment. [0008] The thin-film liquid-repellent layer obtained by the production method of the present invention is polymerized to form a polymer through the condensation reaction of the silane-based compounds in the liquid-repellent composition described in the step (1). . The present inventors have discovered that by removing the surface of the cured film obtained in step (1) in the above step (2) and forming a thin film, an extremely thin film liquid-repellent layer can be formed. It has been found that by forming the liquid-repellent layer into a thin film, it is possible to form a film having excellent visibility and capable of imparting liquid-repellency to an object to be coated with the liquid-repellent composition (hereinafter referred to as a "coated body"). The liquid repellent layer completes the present invention. In addition, the film liquid-repellent layer is liquid-repellent, and preferably has excellent water-repellency and synovial properties. In addition, since the thin film liquid-repellent layer is a very thin layer, from the viewpoint of imparting liquid-repellency to the coated body by generating the texture of the surface of the coated body protected by the thin-film liquid-repellent layer. Also useful. For example, in a case where the thin film liquid-repellent layer is provided on an object to be coated having a high surface hardness, excellent surface hardness of the object to be coated can be generated, and a good liquid-repellent property can be imparted to the object to be coated. Hereinafter, the manufacturing method of the thin film liquid-repellent layer of this invention is demonstrated. [0009] << Step (1) >> Step (1) is a step of forming a cured film using a liquid-repellent composition containing the component (A) and the component (B). [Liquid-repellent composition] The liquid-repellent composition used in step (1) includes a tetrafunctional silane-based compound represented by the general formula (a) as a component (A), and includes the general formula (b) The trifunctional silane compound shown is used as the component (B). In addition, the liquid-repellent composition preferably further contains an acid catalyst as the component (C), and may contain other additives other than the components (A) to (C) within a range that does not impair the effect of the present invention. Hereinafter, each component contained in the liquid repellent composition used in step (1) will be described. [0011] (ingredient (A): tetrafunctional silane compound represented by general formula (a)) The aforementioned component (A) is a tetrafunctional silane compound represented by the following general formula (a). In general formula (a), R ¹ C1-C6 alkyl group, X ¹ Represents a halogen atom. R ¹ And X ¹ When there are plurals, the plural R ¹ And X ¹ They may be the same as or different from each other. p represents an integer from 0 to 4. [0012] can be selected as R ¹ The carbon number of the alkyl group is preferably 4 or less, more preferably 3 or less, and even more preferably 2 or less. As optional as R ¹ Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tertiary butyl, n-pentyl, n-hexyl, Neopentyl, methylpentyl, etc. Among these, from the viewpoint of further improving the reactivity of the component (A), a methyl group, an ethyl group or an n-propyl group is preferred, and a methyl group or an ethyl group is more preferred. Optional as R ¹ Although the alkyl group may be either a straight chain or a branched chain, a straight chain is preferred. [0013] As an alternative to X ¹ The halogen atom is preferably a chlorine atom, a bromine atom or an iodine atom, and more preferably a chlorine atom. The silane-based compound represented by the general formula (a) may be used alone or in combination of two or more kinds. The component (A) preferably contains a silane-based compound in which p is 4 in the general formula (a). [Component (B): Trifunctional silane compound represented by general formula (b)] Component (B) is a trifunctional silane compound represented by general formula (b) below. In general formula (b), R ² It represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent. R ³ C1-C6 alkyl group, X ² Represents a halogen atom. R ³ And X ² When there are plurals, the plural R ³ And X ² They may be the same as or different from each other. q represents an integer from 0 to 3. [0015] can be selected as R ² The carbon number of the alkyl group is 1 to 24. When the carbon number of this alkyl group exceeds 24, the reactivity of a component (B) will worsen. Moreover, as the carbon number of the alkyl group increases, the liquid-repellent composition is more likely to gel, and the surface state of the coating film formed from the liquid-repellent composition also tends to deteriorate. From such a viewpoint, the carbon number of the alkyl group is preferably 22 or less, more preferably 20 or less, and still more preferably 18 or less. Also selectable as R ² The carbon number of the alkyl group does not include the carbon number of any substituent that the alkyl group may have. Here, the "surface state" refers to the surface state of the coating film, such as the degree to which shrinkage cracking of the formed coating film occurs. [0016] As an alternative to R ² Examples of the alkyl group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl , N-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl , N-octadecyl, n-nonadecyl, n-icosyl, n-tecosyl, n-tcosyl, n-tcosyl, n-tecosyl, iso Propyl, isobutyl, sec-butyl, tertiary butyl, isopentyl, neopentyl, tert-pentyl, methylpentyl, isohexyl, pentylhexyl, butylpentyl and 2-ethyl Kihexyl and others. Also, as optional as R ² Although the alkyl group may be either straight or branched, it is straight from the viewpoint of reactivity of the component (B) and improvement of the surface state of the coating film formed of the liquid-repellent composition. The chain is better. Can be selected as R ² The alkyl group may have a substituent. Examples of such a substituent include a halogen atom such as a chlorine atom, a bromine atom, and an iodine atom; a hydroxyl group; a nitro group; an amine group; a cyano group; a mercapto group; an epoxy group; a glycidyloxy group; ; Methacrylfluorenyloxy; cycloalkyl having 3 to 12 carbons (preferably 6 to 10 carbons forming ring); aryl having 6 to 12 carbons forming ring; Heteroatoms of nitrogen, oxygen, and sulfur atoms forming heteroaryl groups having 6 to 12 atoms in the ring; alkoxy groups having 1 to 6 carbon atoms (preferably 1 to 3 in carbon atoms); carbons forming the ring The aryloxy group of 6 to 12 and the like may further be substituted. However, as optional R ² The alkyl group is preferably an alkyl group having no substituent. [0018] As an alternative to R ³ Alkyl and optional as X ² The halogen atom can be exemplified as the one selected in the general formula (a) as R ¹ Alkyl, selectable as X ¹ The same halogen atom. The trifunctional silane-based compound represented by the general formula (b) may be used alone or in combination of two or more kinds. In addition, as the component (B), a trifunctional silane-based compound containing q in the general formula (b) of 3 is preferable. [About Condition (I)] Among the relationship between the component (A) and the component (B), a liquid-repellent composition that satisfies the following condition (I) is preferable. Condition (I): The ratio of the content (molar amount) of the component (A) to the content (molar amount) of the component (B) [(A) / (B)] (molar ratio) is 0.01 or more and 50.00 or less If this [(A) / (B)] (molar ratio) is 0.01 or more, the obtained liquid-repellent layer will have good liquid-sliding properties and adhesion to the object to be coated. From such a viewpoint, the [(A) / (B)] (molar ratio) is more preferably 0.10 or more, even more preferably 0.50 or more, even more preferably 0.80 or more, and even more preferably 0.90 or more. . The [(A) / (B)] (molar ratio) is preferably 50.00 or less. When the [(A) / (B)] (molar ratio) is 50.00 or less, according to R in the component (B) ² In the presence of the alkyl group shown, the obtained film liquid-repellent layer has better water-repellency and synovial properties. From such a viewpoint, the [(A) / (B)] (molar ratio) is more preferably 30.00 or less, even more preferably 25.00 or less, still more preferably 20.00 or less, and even more preferably 10.00 or less. And further more preferably 5.00 or less. In addition, the content of the component (A) and the component (B) can be calculated from the blending amount when each component is blended. [0020] The content (molar amount) of the component (A) is from the viewpoint of obtaining a thin film liquid-repellent layer having better liquid-sliding properties, with respect to the compounded amount of the component (A) and the component (B). (Molar amount) 100 mol% in total, preferably 0.50 mol% or more, more preferably 10.00 mol% or more, even more preferably 20.00 mol% or more, and even more preferably 30.00 mol% The above and further more preferably 45.00 mole% or more. Then, the content (molar amount) is preferably 98.00 mol% or less, more preferably 94.00 mol% or less, still more preferably 90.00 mol% or less, and still more preferably 80.00 mol% or less, and further more More preferably, it is 70.00 mol% or less. [Component (B-1): trifunctional silane compound represented by general formula (b-1)] Component (B) contains at least one trifunctional silane compound represented by general formula (b-1) The component (B-1) of the compound is preferred. In general formula (b-1), R ⁴ It represents an alkyl group having 6 to 24 carbon atoms, and the alkyl group may have a substituent. R ⁵ C1-C6 alkyl group, X ³ Represents a halogen atom. R ⁵ And X ³ When there are plurals, the plural R ⁵ And X ³ They may be the same as or different from each other. r represents an integer from 0 to 3. [0022] can be selected as R ⁴ The carbon number of the alkyl group is 6 to 24. The R ⁴ When the carbon number of the alkyl group represented is 6 or more, it is preferable to obtain a thin film liquid-repellent layer having good water-repellency. From this point of view, as the R ⁴ , Preferably 8 or more. Again, R ⁴ The preferred upper limit of the carbon number of the alkyl group indicated is the same as the aforementioned R ² The preferred upper limit value is the same, preferably 22 or less, more preferably 20 or less, and still more preferably 18 or less. The reason for setting each of the preferred upper values is also the same as described above for R ² As described. Alternatively, as the aforementioned R ⁴ The carbon number of the alkyl group does not include the carbon number of any substituent which the alkyl group may have. [0023] As an alternative to R ⁴ Examples of the alkyl group include n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecane N-tetradecyl, n-pentadecyl, n-hexadecyl, n-hexadecyl, n-octadecyl, n-nonadecyl, n-icosyl, n- twenty-one, n- twenty-two, n- twenty-three, n-tetrakisyl, isopropyl, isobutyl, sec-butyl, tertiary butyl, isopentyl, Neopentyl, tert-pentyl, methylpentyl, isohexyl, pentylhexyl, butylpentyl, and 2-ethylhexyl. Also, as optional as R ⁴ Although the alkyl group may be either a straight chain or a branched chain, it is preferably a straight chain from the viewpoint of improving the reactivity of the component (B-1). As optional as R ⁴ As the alkyl group, from the same viewpoint, n-nonyl, n-decyl or n-dodecyl is preferred. Optional as R ⁴ The alkyl group may have a substituent. Also selectable as R ⁴ Examples of the substituents of the alkyl group include the same as the above-mentioned optional R ² The alkyl group has the same substituents as described above. However, as optional R ⁴ The alkyl group is preferably an alkyl group having no substituent. [0024] As an alternative to R ⁵ Alkyl and optional as X ³ The halogen atom can be exemplified as the one selected in the general formula (a) as R ¹ Alkyl, selectable as X ¹ The same halogen atom. The trifunctional silane compound represented by the general formula (b-1) may be used alone or in combination of two or more kinds. In addition, as the component (B-1), a trifunctional silane-based compound containing r in general formula (b-1) of 3 is preferable. [Component (B-2): trifunctional silane compound represented by general formula (b-2)] Component (B) contains at least one trifunctional silane represented by general formula (b-2) The component (B-2) of the compound is preferred. In general formula (b-2), R ⁶ It represents an alkyl group having 1 to 3 carbon atoms, and the alkyl group may have a substituent. R ⁷ C1-C6 alkyl group, X ⁴ Represents a halogen atom. R ⁷ And X ⁴ When there are plurals, the plural R ⁷ And X ⁴ They may be the same as or different from each other. s represents an integer from 0 to 3. Can be selected as R ⁶ The carbon number of the alkyl group is 1 to 3. When the carbon number of this alkyl group is this range, the reactivity of a component (B-2) will be excellent. Also selectable as R ⁶ The carbon number of the alkyl group does not include the carbon number of any substituent which the alkyl group may have. As optional as R ⁶ Examples of the alkyl group include methyl, ethyl, n-propyl, and isopropyl. From the viewpoint of improving the reactivity of the component (B-2), methyl or ethyl is preferred, and methyl is more preferred. . Optional as R ⁶ The alkyl group may have a substituent. Also selectable as R ⁶ Examples of the substituents of the alkyl group include the same as the above-mentioned optional R ² The alkyl group has the same substituents as described above. However, as optional R ⁶ The alkyl group is preferably an alkyl group having no substituent. [0027] As an alternative to R ⁷ Alkyl and optional as X ⁴ A halogen atom can be exemplified in the aforementioned general formula (a) and can be selected as R ¹ Alkyl, selectable as X ¹ The same halogen atom. The trifunctional silane compound represented by the general formula (b-2) may be used alone or in combination of two or more kinds. In addition, as the component (B-2), a trifunctional silane-based compound containing s of 3 in the general formula (b-2) is preferable. [About Condition (II)] As the component (B), when the component (B-1) and the component (B-2) are used, the relationship between the component (B-1) and the component (B-2) It is preferable to satisfy the following condition (II). Condition (II): The content (molar amount) of the component (B-1) is compared with the total content (molar amount) of the component (B-1) and the component (B-2). [(B-1) / ((B-1) + (B-2)}) (Mole ratio) is 0.020 or more. [(B-1) / {(B-1) + (B-2)}] (Mole ratio) if 0.020 or more, according to R in component (B-1) ⁴ In the presence of the alkyl group shown, the obtained film liquid-repellent layer has better water-repellent and synovial properties. From this point of view, the [(B-1) / {(B-1) + (B-2)}] (molar ratio) is more preferably 0.035 or more, still more preferably 0.045 or more, and even more It is preferably 0.050 or more, still more preferably 0.100 or more, even more preferably 0.150 or more, still more preferably 0.250 or more, and even more preferably 0.500 or more. Then, the upper limit of the [(B-1) / {(B-1) + (B-2)}] (molar ratio) is preferably 0.995 or less, more preferably 0.990 or less, and still more preferably 0.980 or less. It is further more preferably 0.950 or less, and still more preferably 0.850 or less. In addition, the content of the component (B-1) and the component (B-2) can be calculated from the blending amount when each component is blended. [0029] In addition, the liquid-repellent composition of the present invention includes the component (B-1) and the component (B-2) as a trifunctional silane-based compound by satisfying the conditions (I) and (II). It is preferable because the obtained membrane liquid-repellent layer can have better water-repellency. In addition, by including the component (B-2), an improvement in the surface state of the coating film formed of the liquid-repellent composition can be expected. [0030] In the case of using the component (B-1) and the component (B-2) as the component (B), the content (molar amount) of the component (B-1) is determined by making the obtained film liquid-repellent layer From the viewpoint of improvement in water-based and synovial properties, the content (mole amount) of the component (A), the component (B-1), and the component (B-2) is preferably 100 mol%, preferably 0.30. Molar% or more, more preferably 0.50 Molar% or more, even more preferably 1.00 Molar% or more, even more preferably 5.00 Molar% or more, even more preferably 15.00 Molar% or more, and even more preferably It is 30.00 mole% or more. The content (molar amount) is preferably 45.00 mol% or less, and more preferably 40.00 mol% or less. In addition, when the component (B-1) and the component (B-2) are used as the component (B), the content (molar amount) of the component (B-2) is increased from the liquid-repellent composition From the viewpoint of the surface state of the coating film, the content (molar amount) of the component (A), the component (B-1), and the component (B-2) is preferably 100 mol%, preferably 0.50. Molar% or more, more preferably 0.80 Mole% or more, even more preferably 1.00 Mole% or more, even more preferably 1.30 Mole% or more, even more preferably 5.00 Mole% or more, and even more preferably More than 8.00 mole%. Then, the content (molar amount) is preferably 40.00 mol% or less, more preferably 30.00 mol% or less, and even more preferably 20.00 mol% or less. [0031] In the case of using the component (B-1) and the component (B-2) as the component (B), in the relationship between the component (A) and the component (B-1), The ratio [(A) / (B-1)] (mole ratio) of the content (molar amount) to the content (molar amount) of the component (B-1) is obtained by making the synovial liquid of the obtained film liquid-repellent layer From the standpoint of improving the sex, it is preferably 0.5 or more, more preferably 0.8 or more, even more preferably 1.0 or more, and still more preferably 1.2 or more. The [(A) / (B-1)] (molar ratio) is preferably 300.0 or less. When the [(A) / (B-1)] (molar ratio) is 300.0 or less, according to R in the component (B-1) ⁴ In the presence of the alkyl group shown, the obtained film liquid-repellent layer has better water-repellent and synovial properties. From such a viewpoint, the [(A) / (B-1)] (molar ratio) is more preferably 200.0 or less, even more preferably 150.0 or less, still more preferably 100.0 or less, and even more preferably 90.0 or less, still more preferably 50.0 or less, even more preferably 10.0 or less, and even more preferably 5.0 or less. When the component (B) is used in combination with the component (B-1) and the component (B-2), the content of the component (A) in the relationship between the component (A) and the component (B-2) (Mo) The ratio [(A) / (B-2)] (molar ratio) to the content (molar amount) of the component (B-2) is not particularly limited, but it is preferably 1.0 or more. The [(A) / (B-2)] (molar ratio) is preferably 70.0 or less, more preferably 50.0 or less, even more preferably 20.0 or less, and even more preferably 10.0 or less. [0032] When component (B-1) and component (B-2) are used in combination as component (B), the relationship between component (A), component (B-1), and component (B-2) In the ratio of the content (molar amount) of the component (A) to the total content (molar amount) of the component (B-1) and the component (B-2), [(A) / {(B-1) + (B-2)}] (Molar ratio) is preferably 0.01 or more, more preferably 0.10 or more, still more preferably 0.50 or more, still more preferably 0.80 or more, and still more preferably 0.90 or more. The [(A) / {(B-1) + (B-2)}] (molar ratio) is preferably 50.00 or less, more preferably 25.00 or less, even more preferably 20.00 or less, and even more preferably It is 10.00 or less, and still more preferably 5.0 or less. When the component (B) is used in combination with the component (B-1) and the component (B-2), the total content of the component (B-1) and the component (B-2) in the component (B) is relatively With respect to 100% by mass of the total content of the component (B), it is preferably 50% by mass or more, more preferably 65% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more. It is further more preferably 95% by mass or more, still more preferably 99% by mass or more, and further preferably 100% by mass or less. The content is more preferably 100% by mass. (Component (C): acid catalyst) The liquid-repellent composition used in the present invention further contains an acid catalyst as a component (from the viewpoint of further improving the reactivity of each of the silane-based compounds ( C) Better. By including an acid catalyst in the liquid-repellent composition, hydrolysis of the reactive functional group of each of the silane-based compounds is promoted. As a result, the polycondensation reaction of the silane-based compounds used is further promoted, and the hardenability is improved. The "reactive functional group" refers to a silane-based compound such as (OR in the general formula (a)). ¹ ) Or (X ¹ Functional group represented by), and in general formula (b), (OR ³ ) Or (X ² ) And other functional groups. The acid catalyst is not particularly limited as long as it is a component having a function of promoting the hydrolysis of a reactive functional group of each of the silane-based compounds. For example, from the viewpoint of further improving the reactivity of each of the silane-based compounds, it is selected from the group consisting of hydrochloric acid, phosphoric acid, acetic acid, formic acid, sulfuric acid, methanesulfonic acid, oxalic acid, p-toluenesulfonic acid, and trifluoroacetic acid One or more of the groups are preferred, and hydrochloric acid is more preferred. Moreover, as said component (C), it can use individually or in combination of 2 or more types. [0034] The content (molar amount) of the component (C) in the liquid-repellent composition is higher than the component (A) and the component (B) from the viewpoint of improving the reactivity of each of the silane-based compounds. The total content (molar amount) of 100 mole% is preferably 0.010 mole% or more, more preferably 0.030 mole% or more, even more preferably 0.050 mole% or more, and still more preferably 0.060 mole%. Ear%. Then, the content is preferably 1.000 mole% or less, more preferably 0.500 mole% or less, even more preferably 0.100 mole% or less, and still more preferably 0.075 mole% or less. In addition, this content can be calculated from the blending amount when each component is blended. [Other Additives] The liquid-repellent composition may contain other additives in addition to the aforementioned components, as long as the effects of the present invention are not impaired. Examples of other additives include resin components, metal catalysts, hardeners, anti-aging agents, light stabilizers, flame retardants, conductive agents, antistatic agents, and plasticizers. The content of these additives is independent of each other, and is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and even more preferably 0 to 5% by mass relative to the total amount of the liquid-repellent composition solution. , And even more preferably 0 to 2% by mass. In addition, this content can be calculated from the blending amount when each component is blended. [0036] The total content of the component (A) and the component (B) in the liquid-repellent composition is preferably 50% by mass or more relative to 100% by mass of all the active ingredients in the liquid-repellent composition, It is more preferably 65% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and still more preferably 99% by mass or more. It is preferably 100% by mass or less. In addition, this content can be calculated from the blending amount when each component is blended. In addition, in the present invention, an active ingredient in a liquid-repellent composition refers to a liquid component other than a solvent (water or organic solvent) that does not directly participate in the components contained in the liquid-repellent composition, and Components that are solid at room temperature. [0037] The total content of the component (A), the component (B), and the component (C) in the liquid-repellent composition used in the present invention is 100% of the total effective ingredient in the liquid-repellent composition. In terms of mass%, it is preferably 50 mass% or more, more preferably 65 mass% or more, even more preferably 80 mass% or more, still more preferably 90 mass% or more, and even more preferably 95 mass% or more. It is further more preferably 99% by mass or more, and more preferably 100% by mass or less. The content is more preferably 100% by mass. In addition, this content can be calculated from the blending amount when each component is blended. [0038] In step (1), although the cured film is formed using the liquid-repellent composition, when the cured film is formed, there is a coating step of applying the liquid-repellent composition to the object to be coated, and drying the substrate. The drying step of the coating film formed on the coated body is preferred. [0039] {Applying Step} When the liquid-repellent composition is applied, it is preferable to dissolve it in a solvent and apply it to the object as a solution. Examples of the solvent include organic solvents such as methanol, ethanol, propanol, butanol, isopropanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and toluene, and water. [0040] Although the coating method may be appropriately selected depending on the shape of the object to be coated, for example, it may be selected from, for example, dip coating, curtain coating, spray coating, mold coating, knife coating, doctor blade coating, and rollers. At least one selected from the group consisting of knife coating, roll coating, spin coating, gravure coating and bar coating, and is preferably selected from the group consisting of dip coating, curtain coating, spray coating, spin coating, gravure coating and At least one of the groups formed by rod coating, more preferably at least one selected from the group consisting of dip coating, curtain coating, spray coating, gravure coating, and rod coating, and even more preferably dip coating . [0041] Although the object to be coated as a liquid-repellent composition is not particularly limited as long as it is a material that requires liquid-repellency, glass, metal, alloy, semiconductor, rubber, cloth, plastic, ceramic, and wood , Paper, fiber, etc. can be more suitable for use, for glass, metal, plastic can be more suitable for use. It is also suitable for use on metal oxide films or resin-coated surfaces. The shape of the object to be coated is not particularly limited, and it may be a flat object such as a film or a sheet, or a three-dimensional object. Examples of the three-dimensional object include three-dimensional objects such as a bottle container, a roof, a kanban (three-dimensional kanban), a display such as a signal, a building material, a wall, a floor, a shelf, a vehicle, a ship, and an aircraft. The shape of the surface to be coated is not particularly limited, and it can be applied to flat surfaces, three-dimensionally shaped surfaces (including curved surfaces, uneven surfaces, etc.), porous surfaces, and the like. [Drying step] In the aforementioned coating step, there is no particular limitation on the drying temperature and drying time when the coating film is dried after the coating film is formed on the coating body, and corresponds to the heat resistance of the coating body, The type of the solution that dissolves the liquid-repellent composition can be appropriately set. In addition, the liquid-repellent composition used in the present invention can be hardened even at room temperature and normal temperature (5 to 35 ° C). For example, a quilt made of a material having low heat resistance such as vinyl chloride In the case of a coated body, deformation at high temperatures such as thermal contraction of the coated body can also be suppressed. On the other hand, it can harden even at a high temperature (50 to 200 ° C), which can promote the reaction of the aforementioned silane compounds and improve productivity. Therefore, from the foregoing viewpoint, the drying temperature is preferably 5 ° C or higher, more preferably 10 ° C or higher, even more preferably 15 ° C or higher, and then preferably 200 ° C or lower, and more preferably 150 ° C or lower. It is further more preferably 130 ° C or lower, and still more preferably 110 ° C or lower. This drying can be referred to as natural drying, or forced drying using a dryer, an oven, or the like, and can be appropriately selected according to the characteristics of the object to be coated. [0043] Although the thickness of the hardened film formed in step (1) is not particularly limited, it is preferably 8 nm or more, more preferably 20 nm or more, still more preferably 100 nm or more, and then preferably 3000 nm or less, more preferably It is 2000 nm or less, and even more preferably 1800 nm or less. [0042] << Step (2) >> The step (2) is a step of removing the surface of the cured film obtained in the step (1) and thinning it. As a method of removing the surface of the cured film and forming a thin film, for example, one or more methods selected from a method of thin film formation using an adhesive tape and a method of thin film formation using an organic solvent are more preferable. Thin film method. [0045] As the method for forming a thin film using an adhesive tape, for example, a method of attaching an adhesive tape to the surface of the cured film obtained in the step (1), and then peeling off the adhesive tape. Although the adhesive force of the adhesive tape is not particularly limited as long as it can be formed into a thin film, it is attached to a stainless steel plate (SUS304 steel plate, No. 360 grinding) under an environment of 23 ° C and 50% RH (relative humidity). The adhesion after 24 hours is preferably 1N / 25mm or more, more preferably 2N / 25mm or more, even more preferably 3N / 25mm or more, and then preferably 30N / 25mm or less, and more preferably 20N / 25mm or less. More preferably, it is 10N / 25mm or less. The adhesive force of the adhesive tape is a value measured in accordance with JIS Z0237: 2000, and specifically means a value measured by a method and conditions described below. In 23 ° C and 50% RH (relative humidity) environment, the adhesive tape was attached to a stainless steel plate (SUS304 steel plate, No. 360 milled) which is an adherend, and left for 24 hours under the same environment. Then, according to JIS Z0237: 2000, the adhesive force was measured at a tensile speed of 300 mm / min by a 180 ° peel method under the same environment after 24 hours from the application. Examples of the adhesive tape include "Scotch (registered trademark)" (product name, manufactured by 3M Corporation), "Cellotape (registered trademark)" (product name, manufactured by Nichiban Corporation), and the like. [0046] As a method for forming a thin film using the organic solvent, for example, a method of washing the surface of the cured film with an organic solvent can be exemplified. Although this washing method is not particularly limited, examples thereof include ultrasonic washing. The organic solvent is not particularly limited as long as it is a solvent capable of dissolving and thinning the surface of the cured film, and examples thereof include those selected from the group consisting of methanol, ethanol, propanol, butanol, isopropanol, methyl ethyl ketone, Organic solvents such as methyl isobutyl ketone, acetone, ethyl acetate, toluene, and water are at least one member of the group. [0047] The thickness of the thin-film liquid-repellent layer manufactured through the foregoing steps (1) and (2) is preferably less than 8 nm, more preferably less than 7 nm, even more preferably less than 6 nm, and even more preferably It is 5.8 nm or less, still more preferably 5.5 nm or less, and even more preferably 5 nm or less. Then, the thickness of the thin film liquid-repellent layer is preferably 0.5 nm or more, more preferably 0.8 nm or more, even more preferably 1 nm or more, and even more preferably 2 nm or more. The thickness of the thin film liquid-repellent layer can be measured, for example, by a method described in Examples described later. [Thin Film Repellent Layer] The thin film repellent layer according to one aspect of the present invention is a hardened product of the following component (A) and the following component (B), and is a thin film repellent layer having a thickness of less than 8 nm. . Component (A): a tetrafunctional silane compound represented by the following general formula (a) [In general formula (a), R ¹ C1-C6 alkyl group, X ¹ Represents a halogen atom; R ¹ And X ¹ When there are plurals, the plural R ¹ And X ¹ They may be the same as or different from each other; p represents an integer of 0 to 4], component (B): a trifunctional silane compound represented by the following general formula (b) [In general formula (b), R ² Represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent; R ³ C1-C6 alkyl group, X ² Represents a halogen atom; R ³ And X ² When there are plurals, the plural R ³ And X ² Each may be the same or different; q represents an integer from 0 to 3]. [0049] The thickness of the thin film liquid-repellent layer is preferably less than 7 nm, more preferably less than 6 nm, still more preferably 5.8 nm or less, still more preferably 5.5 nm or less, and even more preferably 5 nm or less. Then, the thickness of the thin film liquid-repellent layer is preferably 0.5 nm or more, more preferably 0.8 nm or more, even more preferably 1 nm or more, and even more preferably 2 nm or more. The thickness of the thin film liquid-repellent layer can be measured, for example, by a method described in Examples described later. [0050] The component (A) and the component (B) are the same as the aforementioned component (A) and the component (B), respectively, and their preferred aspects are also the same. When the component (B) includes at least one selected from the group consisting of the component (B-1) and the component (B-2), the component (B-1) and the component (B-2) are respectively It is the same as the aforementioned component (B-1) and component (B-2), and the preferred aspects thereof are also the same. [About Condition (III)] It is preferable that the cured product of the component (A) and the component (B) satisfy the following condition (III). Condition (III): The ratio of the content (molar amount) of the structure (Ap) derived from the component (A) to the content (molar amount) of the structure (Bp) derived from the component (B) in the hardened material [ (Ap) / (Bp)] (Molar ratio) is 0.01 or more and 50.00 or less. If [(Ap) / (Bp)] (Molar ratio) is 0.01 or more, the liquid-sliding property of the obtained film liquid repellent layer and The adherence of the object to be coated becomes good. Here, the content (molar amount) of the structure (Ap) and the content (molar amount) of the structure (Bp) in the hardened material can be regarded as, for example, the components ( A) and the content of component (B) are the same. Therefore, the content of the structure (Ap), the content of the structure (Bp) in the hardened material, and the preferred range of the [(Ap) / (Bp)] (molar ratio), and the content of the aforementioned component (A), The content of the component (B) and the respective preferable ranges of [(A) / (B)] (Molar ratio) are the same. [About Condition (IV)] When the component (B) is a cured product of the component (B-1) and the component (B-2) in combination, the structure (B) derived from the component (B-1) In the relationship between -1p) and the structure (B-2p) derived from the component (B-2), it is preferable to satisfy the following condition (IV). Condition (IV): the molar amount of (B-1p) in the hardened substance relative to the content (mole amount) of the structure (B-1p) derived from the component (B-1) and the component (B- 2) The ratio of the content (molar amount) of the content (molar amount) of the structure (B-2p) [(B-1p) / {(B-1p) + (B-2p)}] (Mole Ratio) is 0.020 or more. If [(B-1p) / {(B-1p) + (B-2p)}] (Molar ratio) is 0.020 or more, the film liquid repellent layer has better water repellency and slippery properties. Liquid. Here, the content (molar amount) of the structure (B-1p) and the content (molar amount) of the structure (B-2p) in the hardened material can be regarded as, for example, the liquid-repellent composition before the hardened material is formed. Content of component (B-1) and component (B-2). Therefore, the content (molar amount) of the structure (B-1p), the content (molar amount) of the structure (B-2p), and the [(B-1p) / {(B-1p) + (B-2p)}] (Molar ratio), and the content of the aforementioned component (B-1), the content of component (B-2), and [(B-1) / {(B-1 ) + (B-2)}] (Molar ratio) have the same preferred ranges. [0053] As the component (B), when the hardened material of the component (B-1) and the component (B-2) is used, in the relationship between the structure (Ap) and the structure (B-1p) in the hardened material, The ratio of the content (molar amount) of the structure (Ap) to the content (molar amount) of the structure (B-1p) [(Ap) / (B-1p)] (molar ratio) is the same as [(A ) / (B-1)] (Molar ratio) has the same preferable range. In addition, in the relationship between the structure (Ap) and the structure (B-2p), the ratio of the content (molar amount) of the structure (Ap) to the content (molar amount) of the structure (B-2p) [(Ap) / (B-2p)] (molar ratio) is the same as the aforementioned preferred range of [(A) / (B-2)] (molar ratio). In addition, in the relationship between the structure (Ap), the structure (Bp), and the structure (B-1p), the content (molar amount) of the structure (Ap) is larger than that of the structure (B-1p) and the structure (B-2p). The ratio of the total content (molar amount) [(Ap) / {(B-1p) + (B-2p)}] (molar ratio) is the same as [(A) / {(B-1) + (B -2)}] (Molar ratio) The same preferable range. In addition, in the case where a hardened product of the component (B-1) and the component (B-2) is used as the component (B), the total of the structure (B-1p) and the structure (B-2p) in the structure (Bp) The content is preferably 50 mol% or more, more preferably 65 mol% or more, more preferably 80 mol% or more, and further more than 100 mol% of the total content of the structure (Bp). It is preferably 90 mol% or more, further more preferably 95 mol% or more, still more preferably 99 mol% or more, and then more preferably 100 mol% or less. The content is more preferably 100 mol%. [0054] The thin-film liquid-repellent layer according to one aspect of the present invention is preferably a thin-film liquid-repellent layer obtained by removing the surface of the hardened product of the component (A) and the following component (B) and thinning it. As a method of removing the surface of the hardened film and forming a thin film, for example, the method described in step (2) of the aforementioned method for manufacturing a thin-film liquid-repellent layer can be exemplified, and its preferable aspect is also the same. In addition, as a preferred aspect of the thin film liquid-repellent layer of the present invention, the thin film liquid-repellent layer obtained by the aforementioned method for manufacturing a thin-film liquid-repellent layer of the present invention. [Application of the thin film liquid-repellent layer] The thin film liquid-repellent layer of the present invention can be suitably used, for example, in windshields and water tanks for building window glass, automobile window glass, vehicles, aviation equipment, and ships. Bottom windows, road panels to prevent marine organisms from adhering to the bottom of the ship, soundproof walls, etc., and the surface of molded products such as mirrors, glass containers, and glass ornaments installed in bathrooms to prevent water droplets, scars, dirt, and other obstacles Attachment of vision. [Examples] [Preparation of liquid-repellent composition solution] Examples 1 to 5 <Step (1)> The components (A) and components ( B-1) and component (B-2), adding ethanol as a solvent and diluting to obtain a solution of a liquid-repellent composition having a concentration of 1.30M. In this solution, hydrochloric acid (excluding the dilution water) of the acid catalyst (C) was further blended so that 100 mol% relative to the total of the component (A) and the component (B) became 0.067 mol%, and stirred for 24 hours A coating solution was obtained. A glass slide (a product name "Micro Slide Glass S1111" using a product name, manufactured by Matsuna Glass Industry Co., Ltd., and washed with a plasma at 100 W for 1 minute) was prepared as a to-be-coated body. A part of the glass slide was attached with a silicone micro-adhesive tape (product name "REPOP RE505S", manufactured by Lindec Corporation) as a masking tape for masking. On the masked glass slide, the coating solution was dip-coated to form a coating film, and it was dried at room temperature (23 ° C.) for 24 hours to form a cured film on the glass slide. [0057] <Step (2)> On the surface of the cured film formed in step (1), "Cellotape (registered trademark)" (manufactured by Nichiban Co., Ltd.) is attached as an adhesive tape. Next, the adhered tape is peeled from the surface of the cured film, and the surface of the cured film is removed to prepare a thin film liquid-repellent layer. Comparative Example 1 A cured film for comparison was produced in the same manner as in Example 1 except that a coating solution in which only the component (A) was prepared in step (1) was prepared. [0059] Comparative Example 2 A cured film for comparison was produced in the same manner as in Example 1 except that a coating solution in which only the component component (B-1) was prepared in step (1). [0060] Comparative Example 3 A cured film for comparison was produced in the same manner as in Example 1 except that the thinning treatment in step (2) was not performed. [0061] The details of each component described in Table 1 are as follows. <Component (A): 4-functional silane compound represented by general formula (a)> ・ "TEOS": Tetraethoxysilane, in the general formula (a), p = 4, R ¹ = Ethyl (carbon number: 2) 4-functional silane-based compound. <Component (B-1): Trifunctional silane compound represented by general formula (b-1)>"Decyltrimethoxysilane": r = 3, R in the general formula (b) ⁴ = n-decyl (carbon number: 10), R ⁵ = Methyl (carbon number: 1) trifunctional silane compound. <Component (B-2): Trifunctional silane compound represented by general formula (b-2)>"Methyltrimethoxysilane": s = 3, R in the general formula (b-2) ⁶ = Methyl (carbon number: 1), R ⁷ = Methyl (carbon number: 1) trifunctional silane compound. <Component (C): Acid catalyst>-"Hydrochloric acid": 0.01M hydrochloric acid. [0062] The characteristics of the thin-film liquid-repellent layer and the comparative cured film produced in the examples and comparative examples were evaluated based on the following methods. [0063] <Thickness of the hardened film formed in step (1) and thin film liquid-repellent layer produced in step (2)> Hardened film formed in step (1) and thin film produced in step (2) The thickness of the liquid-repellent layer was measured using the method shown below. The results are shown in Tables 1 and 2.・ Measuring equipment: Optical interference film thickness meter "Wyko NT9100" (product name, manufactured by Veeco) Peel off the glass slides with the thin-film liquid-repellent layer produced in each Example and each Comparative Example, or those with a comparative cured film Masking tape on a glass slide (hereinafter referred to as "evaluation sample"). The thickness (X) of the evaluation sample of the portion where the thin film liquid-repellent layer or hardened film is formed and the thickness (Y) of the evaluation sample of the portion where the thin-film liquid repellent layer or hardened film is not formed are measured using the aforementioned measurement equipment and conditions. Based on the difference (X)-(Y) between the obtained thickness (X) and the thickness (Y), the thicknesses of the thin film liquid-repellent layer and the cured film were calculated. [0064] <Peelability of Adhesive Tape of Cured Film Formed in Step (1)> The peelability of the surface of the cured film by Cellotape (registered trademark) at the time of performing the thinning in the step (2) is as follows: To benchmark. The results are shown in Table 1.・ A: The entire surface of the cured film where the tape can be peeled off.・ B: A part of the surface of the cured film in the range where the tape is affixed has a part that cannot be peeled off.・ C: The range where the tape is attached cannot be peeled off at all. [0065] <Liquid Repellency> As an index of the liquid repellency, the water contact angle and the water slide angle were evaluated based on the following methods. (Water contact angle) The water contact angle of the thin film liquid-repellent layer or the comparative hardened film is a fully automatic contact angle measuring device (product name "DM-701", manufactured by Kyowa Interface Science Co., Ltd.). The surface of the thin film liquid-repellent layer or the comparative cured film produced in each comparative example was measured at a contact angle of 2 μL with respect to water. The results are shown in Table 2. A larger value indicates better water repellency. [0066] (Water Sliding Angle) The evaluation samples prepared in the examples and comparative examples were placed on a sample table (glass plate) with an inclination angle of 0 ° by being wet with water. Next, 14 μL of pure water was dropped on the surface of the thin film liquid-repellent layer or the comparative hardened film to form droplets. When the sample stage was tilted, the inclination angle of the sample stage when the receding angle of the droplet was moved was taken as the water sliding angle. The results are shown in Table 2. The smaller the value, the better the water-sliding property. [Visibility] According to JIS K7136: 2000, the haze meter (product name "NDH-2000", manufactured by Nippon Denshoku Industries Co., Ltd.) was used to measure the evaluation samples made in the examples and comparative examples. Haze of the glass slide monomer. Table 2 shows the results obtained by subtracting the haze of the glass slide monomer from the haze of the evaluation sample. A smaller value indicates higher transparency and excellent visibility. [0068] [0069] [0070] From Tables 1 and 2, it was confirmed that the thin-film liquid-repellent layers of Examples 1 to 5 had good water contact angles and water-sliding angles as liquid-repellent properties and excellent visibility. On the other hand, the cured film of Comparative Example 1 was a cured product composed of only the component (A). As a result, the surface of the cured film could not be peeled off with Cellotape (registered trademark), and the water contact angle of the cured film was also poor. Then, in Comparative Example 2, the surface state of the coating film formed in step (1) was poor, and a cured film that was resistant to each evaluation could not be formed. Moreover, in Comparative Example 3, since the thinning of the cured film formed in step (1) was not performed, as a result, the thickness of the cured film was thick and the visibility was poor. [Industrial Applicability] [0071] If a method for manufacturing a thin film liquid-repellent layer according to one aspect of the present invention is used, it is possible to produce a film with excellent visibility and good liquid-repellency (preferably water-repellent and synovial properties). Thin film repellent layer. Moreover, the film liquid-repellent layer of one aspect of the present invention is excellent in visibility and liquid-repellency. Therefore, this thin film liquid-repellent layer is suitable for use in, for example, windshields, water tanks, bottom windows, sea-fighting membranes, soundproof walls, etc. for building window glass, automobile window glass, vehicles, aviation equipment, ships, etc. The road surface panel, the surface of a molded product such as a mirror, a glass container, and a glass ornament installed in a bathroom, etc., are provided with liquid repellency to prevent the attachment of objects that obstruct vision such as water droplets and dirt. Then, for example, water repellency and liquid-sliding properties of water droplets or snow that can be efficiently dropped off in windshields such as automotive window glass, windshields of vehicles, aviation equipment, and ships, and excellent visibility are required. It is more suitable for use.

Claims (17)

A method for manufacturing a thin-film liquid-repellent layer, which has the following steps (1) and (2) in sequence, step (1): using a liquid-repellent liquid containing the following component (A) and the following component (B) Step of forming a hardened film from a chemical composition, Component (A): a tetrafunctional silane-based compound represented by the following general formula (a), In [general formula (a), R ¹ represents an alkyl group having 1 to 6 carbon atoms of, X ¹ represents a halogen atom; R ¹ and when plural X ¹ is present, plural R ¹ and X ¹ may be the same as each other or may be different ; P represents an integer of 0 to 4], component (B): a trifunctional silane-based compound represented by the following general formula (b), [In general formula (b), R ² represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent; R ³ represents an alkyl group having 1 to 6 carbon atoms, and X ² represents a halogen atom; R ³ and X ^{2 When} there is a plurality, R ³ and X ² may be the same as or different from each other; q represents an integer of 0 to 3], step (2): removing the surface of the hardened film obtained in the above step (1) and performing Thin film step. For example, the method for manufacturing a thin-film liquid-repellent layer according to claim 1, wherein in the step (2), the aforementioned thin film is formed using an adhesive tape. For example, the method for manufacturing a thin film liquid-repellent layer according to claim 1 or 2, wherein in step (1), the component (B) contains at least one of the following components (B-1), and the component (B-1): the following general A trifunctional silane compound represented by formula (b-1), [In general formula (b-1), R ⁴ represents an alkyl group having 6 to 24 carbon atoms, and the alkyl group may have a substituent; R ⁵ represents an alkyl group having 1 to 6 carbon atoms, and X ³ represents a halogen atom; R ⁵ When there is a plurality of X ³ , the plural R ⁵ and X ³ may be the same as or different from each other; r represents an integer of 0 to 3]. For example, in the method for manufacturing a thin film liquid-repellent layer according to any one of claims 1 to 3, in step (1), the component (B) contains at least one of the following components (B-2) and component (B-2) : A trifunctional silane-based compound represented by the following general formula (b-2), [In general formula (b-2), R ⁶ represents an alkyl group having 1 to 3 carbon atoms, and the alkyl group may have a substituent; R ⁷ represents an alkyl group having 1 to 6 carbon atoms, and X ⁴ represents a halogen atom; R ⁷ When there is a plurality of X ⁴ , the plural R ⁷ and X ⁴ may be the same as or different from each other; s represents an integer of 0 to 3]. For example, the method for manufacturing a thin-film liquid-repellent layer according to claim 4, wherein in step (1), the following condition (II) is further satisfied, and condition (II): the molar amount of the component (B-1) relative to the component (B- 1) The ratio [(B-1) / {(B-1) + (B-2)}] (molar ratio) of the total molar amount of the component (B-2) is 0.020 or more. For example, in the method for manufacturing a thin film liquid-repellent layer according to any one of claims 1 to 5, wherein in step (1), the following condition (I) is further satisfied, (i) condition (I): the molar amount of the component (A) relative to The molar ratio [(A) / (B)] (molar ratio) of the component (B) is 0.01 or more and 50.00 or less. For example, the method for manufacturing a thin film liquid-repellent layer according to any one of claims 1 to 6, wherein step (1) further includes an acid catalyst as a component (C), relative to the total of the components (A) and (B). For 100 mole%, the content of component (C) is 0.010 mole% or more and 1.000 mole% or less. The method for manufacturing a thin film liquid-repellent layer according to any one of claims 1 to 7, wherein the method for forming the aforementioned hardened film is selected from the group consisting of dip coating, curtain coating, spray coating, gravure coating, and bar coating. At least one of a coating step and a drying step. For example, the method for manufacturing a thin-film liquid-repellent layer according to any one of claims 1 to 8, wherein the thickness of the thin-film liquid-repellent layer is less than 8 nm. For example, the method for manufacturing a thin-film liquid-repellent layer according to any one of claims 1 to 9, wherein the thickness of the aforementioned cured film formed in step (1) is 8 nm or more. A thin-film liquid-repellent layer is manufactured by a manufacturing method according to any one of claims 1 to 10. A thin-film liquid-repellent layer is a hardened product of the following component (A) and the following component (B), the thickness of which is less than 8 nm, and the component (A): a tetrafunctional silane system represented by the following general formula (a) Compounds, In [general formula (a), R ¹ represents an alkyl group having 1 to 6 carbon atoms of, X ¹ represents a halogen atom; R ¹ and when plural X ¹ is present, plural R ¹ and X ¹ may be the same as each other or may be different ; P represents an integer of 0 to 4], component (B): a trifunctional silane-based compound represented by the following general formula (b), [In general formula (b), R ² represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent; R ³ represents an alkyl group having 1 to 6 carbon atoms, and X ² represents a halogen atom; R ³ and X ^When there are plurals, R ³ and X ² may be the same as or different from each other; q represents an integer of 0 to 3]. For example, the thin film liquid-repellent layer of claim 12, wherein the component (B) contains at least one of the following components (B-1), and the component (B-1): a trifunctional compound represented by the following general formula (b-1) Silane-based compounds, [In general formula (b-1), R ⁴ represents an alkyl group having 6 to 24 carbon atoms, and the alkyl group may have a substituent; R ⁵ represents an alkyl group having 1 to 6 carbon atoms, and X ³ represents a halogen atom; R ⁵ When there is a plurality of X ³ , the plural R ⁵ and X ³ may be the same as or different from each other; r represents an integer of 0 to 3]. For example, the thin film liquid-repellent layer of claim 12 or 13, wherein the component (B) contains at least one of the following components (B-2), and the component (B-2): as shown in the following general formula (b-2) Trifunctional silane compound [In general formula (b-2), R ⁶ represents an alkyl group having 1 to 3 carbon atoms, and the alkyl group may have a substituent; R ⁷ represents an alkyl group having 1 to 6 carbon atoms, and X ⁴ represents a halogen atom; R ⁷ When there is a plurality of X ⁴ , the plural R ⁷ and X ⁴ may be the same as or different from each other; s represents an integer of 0 to 3]. For example, the thin film liquid-repellent layer of claim 14 further satisfies the following condition (IV) and (4): (B-1p) the molar amount of (B-1p) relative to the structure (B-1p) derived from component (B-1) ) And the ratio of the total moles of the structure (B-2p) derived from the component (B-2) [(B-1p) / {(B-1p) + (B-2p)}] (Mole ratio) It is 0.020 or more. For example, the thin film liquid-repellent layer of any one of claims 12 to 15, which satisfies the following condition (III), condition (III): the molar amount of the structure (Ap) derived from the component (A) relative to the source The molar ratio [(Ap) / (Bp)] (molar ratio) of the structure (Bp) of (B) is 0.01 or more and 50.00 or less. If the thin film liquid-repellent layer according to any one of claims 12 to 16 is obtained by removing the surface of the hardened material of the component (A) and the component (B) and thinning the hardened material.