JPWO2018021339A1 - Method for producing thin film liquid repellent layer and thin film liquid repellent layer - Google Patents

Abstract

Step (1): A cured film is formed using a liquid repellent composition containing a component (A) which is a tetrafunctional silane compound having a specific structure and a component (B) which is a trifunctional silane compound having a specific structure. Step of forming and step (2): A method for producing a thin film liquid repellent layer, which comprises the steps of removing the surface of the cured film obtained in the step (1) to form a thin film in this order, and the production method The present invention relates to a thin film liquid repellent layer, a cured product of component (A) and component (B), and having a thickness of less than 8 nm.

Description

  The present invention relates to a method for producing a thin film liquid repellent layer and a thin film liquid repellent layer.

In general, it is installed in windshields for buildings, windshields for automobiles, windshields for vehicles, aircraft, ships, etc., water tanks, bottom windows, films for preventing marine organisms from sticking to the bottom, road panels such as soundproof walls, bathrooms, etc. In addition, it is desirable that the surface of a molded product such as a mirror, a glass container, or a glass decorative article does not adhere to the surface such as water droplets, scratches, and dirt.
By covering the surface of such a molded product with a film made of a liquid repellent material, or by attaching a liquid repellent sheet, liquid repellency such as water repellency, oil repellency, synovial fluid, etc. Has been done.
For example, Patent Document 1 discloses a substrate such as glass by a laminate having a base layer formed of an inorganic compound and a water-repellent film that covers the surface of the base layer and is formed of a fluorine-containing compound. A water-repellent film-coated article coated with a material is disclosed.

JP 2010-285574 A

However, since the water-repellent coated article described in Patent Document 1 has a water-repellent film formed from a fluorine-containing compound, it is not preferable from the viewpoint of environmental protection.
Therefore, a liquid repellent material with less environmental load is demanded.
When transparency is required for an object imparting liquid repellency, excellent transparency is also required for the liquid repellent layer provided on the surface thereof. In addition, even when the object is colored or printed and / or printed on the surface of the object, the surface of the object is not affected so as not to affect the color of the object or the print information. The liquid repellent layer provided on the substrate is also required to have excellent transparency (visibility).
An object of the present invention is to provide a method for producing a thin film liquid repellent layer having liquid repellency and excellent visibility, and a thin film liquid repellent layer.

The present inventors use a liquid repellent composition containing a component (A) which is a tetrafunctional silane compound having a specific structure and a component (B) which is a trifunctional silane compound having a specific structure. It was found that a very thin liquid repellent layer obtained by forming a part of the cured film and removing a part of the cured film can solve the above-mentioned problems.
That is, the present invention provides the following [1] to [17].
[1] A method for producing a thin film liquid repellent layer, comprising the following step (1) and the following step (2) in this order.
Step (1): Process component (A) for forming a cured film using a liquid repellent composition containing the following component (A) and the following component (B): tetrafunctional represented by the following general formula (a) Silane-based compounds Si (OR ¹ ) _p (X ¹ ) _4-p (a)
[In General Formula (a), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and X ¹ represents a halogen atom. When R ¹ and ^{X 1} there are a plurality, the plurality of ^{R 1} and ^{X 1} are also identical to each other or may be different. p represents an integer of 0 to 4. ]
Component (B): Trifunctional silane compound represented by the following general formula (b) R ² Si (OR ³ ) _q (X ² ) _3-q (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. If R ³ and ^{X 2} there are a plurality, the plurality of ^{R 3} and ^{X 2} are either identical to one another or may be different. q represents an integer of 0 to 3. ]
Step (2): Step of removing the surface of the cured film obtained in the step (1) by thinning [2] In step (2), the thinning is performed using an adhesive tape, [1] The manufacturing method of the thin film liquid repellent layer of description.
[3] The method for producing a thin film liquid repellent layer according to [1] or [2], wherein in the step (1), the component (B) contains at least one of the following components (B-1).
Component (B-1): Trifunctional silane compound represented by the following general formula (b-1) R ⁴ Si (OR ⁵ ) _r (X ³ ) _3-r (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. If R ⁵ and ^{X 3} there are a plurality, the plurality of ^{R 5} and ^{X 3} are either identical to one another or may be different. r represents an integer of 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): Trifunctional silane compound represented by the following general formula (b-2) R ⁶ Si (OR ⁷ ) _s (X ⁴ ) _3-s (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. If R ⁷ and ^{X 4} there are a plurality, a plurality of ^{R 7} and ^{X 4,} are identical to each other or may be different. s represents an integer of 0 to 3. ]
[5] The method for producing a thin film liquid repellent layer according to [4], further satisfying the following condition (II) in the step (1).
Condition (II): Ratio of molar amount of component (B-1) to total molar amount of component (B-1) and component (B-2) [(B-1) / {(B-1) + (B -2)}] (molar ratio) is 0.020 or more [6] In step (1), the thin film repellent according to any one of [1] to [5], which further satisfies the following condition (I): A method for producing a liquid layer.
Condition (I): Ratio of molar amount of component (A) to molar amount of component (B) [(A) / (B)] (molar ratio) is 0.01 or more and 50.00 or less [7] Step ( In 1), an acid catalyst is further included as component (C), and the content of component (C) is 0.010 mol% or more with respect to 100 mol% in total of components (A) and (B). The manufacturing method of the thin film liquid repellent layer in any one of said [1]-[6] which is 0.00000 mol% or less.
[8] The method [1] to [1], wherein the method for forming the cured film includes at least one application step and drying step selected from the group consisting of dip coating, curtain coating, spray coating, gravure coating, and bar coating. 7] The method for producing a thin film liquid repellent layer according to any one of [7].
[9] The method for producing 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 cured film formed in the step (1) is 8 nm or more.
[11] A thin film liquid repellent layer produced by the production method according to any one of [1] to [10].
[12] A thin film liquid repellent layer which is a cured product of the following component (A) and the following component (B) and has a thickness of less than 8 nm.
Component (A): Tetrafunctional silane compound represented by the following general formula (a) Si (OR ¹ ) _p (X ¹ ) _4-p (a)
[In General Formula (a), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and X ¹ represents a halogen atom. When R ¹ and ^{X 1} there are a plurality, the plurality of ^{R 1} and ^{X 1} are also identical to each other or may be different. p represents an integer of 0 to 4. ]
Component (B): Trifunctional silane compound represented by the following general formula (b) R ² Si (OR ³ ) _q (X ² ) _3-q (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. If R ³ and ^{X 2} there are a plurality, the plurality of ^{R 3} and ^{X 2} are either identical to one another or may be different. q represents an integer of 0 to 3. ]
[13] The thin film liquid repellent layer according to [12], wherein the component (B) includes at least one of the following components (B-1).
Component (B-1): Trifunctional silane compound represented by the following general formula (b-1) R ⁴ Si (OR ⁵ ) _r (X ³ ) _3-r (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. If R ⁵ and ^{X 3} there are a plurality, the plurality of ^{R 5} and ^{X 3} are either identical to one another or may be different. r represents an integer of 0 to 3. ]
[14] The thin film liquid repellent layer according to [12] or [13], wherein the component (B) includes at least one of the following components (B-2).
Component (B-2): Trifunctional silane compound represented by the following general formula (b-2) R ⁶ Si (OR ⁷ ) _s (X ⁴ ) _3-s (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. If R ⁷ and ^{X 4} there are a plurality, a plurality of ^{R 7} and ^{X 4,} are identical to each other or may be different. s represents an integer of 0 to 3. ]
[15] The thin film liquid repellent layer according to [14], further satisfying the following condition (IV).
Condition (IV): Ratio of molar amount of (B-1p) to total molar amount of structure (B-1p) derived from component (B-1) and structure (B-2p) derived from component (B-2) [ (B-1p) / {(B-1p) + (B-2p)}] (molar ratio) satisfies the following condition (III) of 0.020 or more and [16] of the above [12] to [15] The thin film liquid repellent layer according to any one of the above.
Condition (III): The ratio [(Ap) / (Bp)] (molar ratio) of the molar amount of the structure (Ap) derived from the component (A) to the molar amount of the structure (Bp) derived from the component (B) is 0. .01 or more and 50.00 or less [17] Any one of the above [12] to [16], which is obtained by removing the surface of the cured product with the component (A) and the component (B) and thinning the cured product The thin film liquid repellent layer described in 1.

  ADVANTAGE OF THE INVENTION According to this invention, it has liquid repellency and can provide the manufacturing method of a thin film liquid repellent layer which is excellent in visibility, and a thin film liquid repellent layer.

[Method for producing thin liquid repellent layer]
The manufacturing method of the thin film liquid repellent layer which is 1 aspect of this invention has the following process (1) and the following process (2) in this order.
Step (1): Process component (A) for forming a cured film using a liquid repellent composition containing the following component (A) and the following component (B): tetrafunctional represented by the following general formula (a) Silane-based compounds Si (OR ¹ ) _p (X ¹ ) _4-p (a)
[In General Formula (a), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and X ¹ represents a halogen atom. When R ¹ and ^{X 1} there are a plurality, the plurality of ^{R 1} and ^{X 1} are also identical to each other or may be different. p represents an integer of 0 to 4. ]
Component (B): Trifunctional silane compound represented by the following general formula (b) R ² Si (OR ³ ) _q (X ² ) _3-q (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. If R ³ and ^{X 2} there are a plurality, the plurality of ^{R 3} and ^{X 2} are either identical to one another or may be different. q represents an integer of 0 to 3. ]
Step (2): A step of removing a part of the cured film obtained in the step (1) and performing a thin film treatment

In the thin film liquid repellent layer obtained by the production method of the present invention, the condensation reaction of the silane compounds in the liquid repellent composition described in the step (1) proceeds to form a polymer, thereby forming a cured film. Is done.
The present inventors further form a thin liquid-repellent layer having a very thin thickness by removing the surface of the cured film obtained in the step (1) and thinning it in the step (2). Found that is possible.
By reducing the thickness of the liquid repellent layer, the liquid repellent property is imparted to an object to be coated with the liquid repellent composition (hereinafter referred to as “coated body”) while having excellent visibility. The present inventors have found that a thin liquid-repellent layer that can be formed can be formed and completed the present invention.
The thin film liquid repellent layer is excellent in liquid repellency, preferably water repellency and liquid slidability.
Further, since the thin film liquid repellent layer is a very thin layer, the liquid repellent property can be imparted to the coated object while utilizing the texture of the surface of the coated object protected by the thin film liquid repellent layer. This is also useful from the viewpoint of. For example, when the thin film liquid-repellent layer is provided on an object to be coated having a high surface hardness, good liquid repellency can be imparted to the object to be coated while utilizing the excellent surface hardness of the object to be coated. .
Hereinafter, the manufacturing method of the thin film liquid repellent layer of this invention is demonstrated.

<< Step (1) >>
Step (1) is a step of forming a cured film using a liquid repellent composition containing component (A) and component (B).

<Liquid repellent composition>
The liquid repellent composition used in step (1) is a tetrafunctional silane compound represented by the general formula (a) as the component (A) and a trifunctional compound represented by the general formula (b) as the component (B). Contains silane compounds.
In addition, it is preferable that the said liquid repellent composition contains an acid catalyst as a component (C), and contains other additives other than a component (A)-(C) in the range which does not impair the effect of this invention. May be.
Hereinafter, each component contained in the liquid repellent composition used in the step (1) will be described.

(Component (A): tetrafunctional silane compound represented by general formula (a))
The component (A) is a tetrafunctional silane compound represented by the following general formula (a).
Si (OR ¹ ) _p (X ¹ ) _4-p (a)
In general formula (a), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and X ¹ represents a halogen atom. When R ¹ and ^{X 1} there are a plurality, the plurality of ^{R 1} and ^{X 1} are also identical to each other or may be different. p represents an integer of 0 to 4.

The carbon number of the alkyl group that can be selected as R ¹ is preferably 4 or less, more preferably 3 or less, and still more preferably 2 or less.
Examples of the alkyl group that can be selected as R ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, Examples thereof include an n-hexyl group, a neopentyl group, and a methylpentyl group. 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 preferable, and a methyl group or an ethyl group is more preferable.
The alkyl group that can be selected as R ¹ may be either linear or branched, but is preferably linear.

The halogen atom that can be selected as X ¹ is preferably a chlorine atom, a bromine atom, or an iodine atom, and more preferably a chlorine atom.
In addition, you may use the silane type compound represented by the said general formula (a) individually or in combination of 2 or more types.
Moreover, as a component (A), it is preferable to contain the silane type compound whose p in the said general formula (a) is 4.

(Component (B): Trifunctional silane compound represented by the general formula (b))
Component (B) is a trifunctional silane compound represented by the following general formula (b).
R ² Si (OR ³ ) _q (X ² ) _3-q (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. If R ³ and ^{X 2} there are a plurality, the plurality of ^{R 3} and ^{X 2} are either identical to one another or may be different. q represents an integer of 0 to 3.

Number of carbon atoms in the alkyl group may be selected as R ² is 1 to 24.
When the carbon number of the alkyl group exceeds 24, the reactivity of the component (B) is poor. Further, as the carbon number of the alkyl group increases, the liquid repellent composition is easily gelled, and the surface state of the coating film formed from the liquid repellent composition 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.
The carbon number of the alkyl group that can be selected as R ² 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 of occurrence of repelling of the formed coating film.

Examples of the alkyl group that can be selected as R ² include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n -Nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n -Nonadecyl group, n-icosyl group, n-henicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group , Tert-pentyl group, methylpentyl group, isohexyl group, pentylhexyl group, butylpentyl group, and 2-ethylhexyl Groups and the like.
The alkyl group that can be selected as R ² may be either a straight chain or a branched chain, but the reactivity of the component (B) and the surface state of the coating film formed from the liquid repellent composition From the viewpoint of improvement, it is preferably a straight chain.

The alkyl group that can be selected as R ² may have a substituent.
Examples of such substituents include halogen atoms such as chlorine atom, bromine atom and iodine atom; hydroxyl group; nitro group; amino group; cyano group; mercapto group; epoxy group; glycidoxy group; A cycloalkyl group having 3 to 12 ring carbon atoms (preferably 6 to 10 ring carbon atoms); an aryl group having 6 to 12 ring carbon atoms; a heteroatom selected from a nitrogen atom, an oxygen atom, and a sulfur atom And a heteroaryl group having 6 to 12 ring atoms, an alkoxy group having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms), an aryloxy group having 6 to 12 ring carbon atoms, and the like. The substituent may be further substituted.
However, the alkyl group that can be selected as R ² is preferably an alkyl group having no substituent.

The alkyl group that can be selected as R ³ and the halogen atom that can be selected as X ² are the same as the alkyl group that can be selected as R ¹ and the halogen atom that can be selected as X ^{1 in} the general formula (a). Is mentioned.
In addition, you may use the trifunctional silane type compound represented by the said general formula (b) individually or in combination of 2 or more types.
The component (B) preferably includes a trifunctional silane compound in which q in the general formula (b) is 3.

(Condition (I))
In the relationship between the component (A) and the component (B), a liquid repellent composition satisfying the following condition (I) is preferable.
Condition (I): The ratio of the content (molar amount) of component (A) to the content (molar amount) of component (B) [(A) / (B)] (molar ratio) is 0.01 or more and 50 0.00 or less When the [(A) / (B)] (molar ratio) is 0.01 or more, the synovial properties of the resulting thin film liquid repellent layer and the adhesion to the coated body are improved. From such a viewpoint, the [(A) / (B)] (molar ratio) is more preferably 0.10 or more, still more preferably 0.50 or more, still more preferably 0.80 or more, and even more preferably. Is 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, the thin film liquid repellent layer obtained by the presence of the alkyl group represented by R ² in the component (B) It has better water repellency and synovial properties. From such a viewpoint, the [(A) / (B)] (molar ratio) is more preferably 30.00 or less, still more preferably 25.00 or less, still more preferably 20.00 or less, and even more preferably. Is 10.00 or less, more preferably 5.00 or less.
In addition, content of a component (A) and a component (B) can also be computed from the compounding quantity at the time of mix | blending each component.

  In addition, the content (molar amount) of the component (A) is 100 in total from the viewpoint of obtaining a thin film liquid repellent layer having better synovial properties (molar amount). Preferably, it is 0.50 mol% or more, more preferably 10.00 mol% or more, still more preferably 20.00 mol% or more, still more preferably 30.00 mol% or more, and still more preferably with respect to mol%. It is 45.00 mol% or more. 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 even more preferably 80.00 mol% or less. More preferably, it is 70.00 mol% or less.

[Component (B-1): Trifunctional Silane Compound Represented by General Formula (b-1)]
The component (B) preferably contains at least one component (B-1) which is a trifunctional silane compound represented by the following general formula (b-1).
R ⁴ Si (OR ⁵ ) _r (X ³ ) _3-r (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. If R ⁵ and ^{X 3} there are a plurality, the plurality of ^{R 5} and ^{X 3} are either identical to one another or may be different. r represents an integer of 0 to 3.

Number of carbon atoms in the alkyl group may be selected as R ⁴ is 6 to 24.
It is preferable that the alkyl group represented by R ⁴ has 6 or more carbon atoms because a thin liquid-repellent layer having good water repellency can be obtained. From such a viewpoint, R ⁴ is preferably 8 or more. Further, the preferable upper limit value of the carbon number of the alkyl group represented by R ⁴ is the same as the preferable upper limit value of R ² described above, preferably 22 or less, more preferably 20 or less, and still more preferably 18 or less. . Setting reasons of each of upper preferable values are also as described above for R ^2.
The carbon number of the alkyl group that can be selected as R ⁴ does not include the carbon number of any substituent that the alkyl group may have.

Examples of the alkyl group that can be selected as R ⁴ include n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n- Tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, n-henicosyl group, n-docosyl group, n- Tricosyl group, n-tetracosyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, methylpentyl group, isohexyl group, pentylhexyl group, butylpentyl Group, 2-ethylhexyl group and the like.
The alkyl group that can be selected as R ⁴ may be either a straight chain or a branched chain, but is preferably a straight chain from the viewpoint of improving the reactivity of the component (B-1). As an alkyl group that can be selected as R ⁴ , an n-nonyl group, an n-decyl group, or an n-dodecyl group is preferable from the same viewpoint.
The alkyl group that can be selected as R ⁴ may have a substituent. In addition, the substituent which the alkyl group which can be selected as R < ⁴ > has has the same thing as what was mentioned above about the substituent which the alkyl group which can be selected as R < ² > has.
However, the alkyl group that can be selected as R ⁴ is preferably an alkyl group having no substituent.

The alkyl group that can be selected as R ⁵ and the halogen atom that can be selected as X ³ are the same as the alkyl group that can be selected as R ¹ and the halogen atom that can be selected as X ^{1 in} the general formula (a). Is mentioned.
In addition, you may use the trifunctional silane type compound represented by general formula (b-1) individually or in combination of 2 or more types.
Moreover, as a component (B-1), it is preferable to contain the trifunctional silane type compound whose r in general formula (b-1) is 3.

[Component (B-2): Trifunctional silane compound represented by formula (b-2)]
The component (B) preferably contains at least one component (B-2) which is a trifunctional silane compound represented by the following general formula (b-2).
R ⁶ Si (OR ⁷ ) _s (X ⁴ ) _3-s (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. If R ⁷ and ^{X 4} there are a plurality, a plurality of ^{R 7} and ^{X 4,} are identical to each other or may be different. s represents an integer of 0 to 3.

The number of carbon atoms of the alkyl group that can be selected as R ⁶ is 1 to 3.
The reactivity of a component (B-2) is excellent in the carbon number of the said alkyl group being this range. The carbon number of the alkyl group that can be selected as R ⁶ does not include the carbon number of any substituent that the alkyl group may have.
Examples of the alkyl group that can be selected as R ⁶ include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. From the viewpoint of improving the reactivity of the component (B-2), a methyl group or an ethyl group And a methyl group is more preferable.
The alkyl group that can be selected as R ⁶ may have a substituent. Incidentally, a substituent having alkyl groups may be selected as R ⁶ may be the same as those described above for the substituent having alkyl groups may be selected as R ^2.
However, the alkyl group that can be selected as R ⁶ is preferably an alkyl group having no substituent.

The alkyl group that can be selected as R ⁷ and the halogen atom that can be selected as X ⁴ are the same as the alkyl group that can be selected as R ¹ and the halogen atom that can be selected as X ^{1 in} the general formula (a). Is mentioned.
In addition, you may use the trifunctional silane type compound represented by general formula (b-2) individually or in combination of 2 or more types.
In addition, as the component (B-2), it is preferable to include a trifunctional silane compound in which s in the general formula (b-2) is 3.

(Condition (II))
When the component (B-1) and the component (B-2) are used as the component (B), it is preferable to satisfy the following condition (II) in the relationship between the component (B-1) and the component (B-2). .
Condition (II): Ratio of content (molar amount) of component (B-1) to total content (molar amount) of component (B-1) and component (B-2) [(B-1) / { (B-1) + (B-2)}] (molar ratio) is 0.020 or more The [(B-1) / {(B-1) + (B-2)}] (molar ratio) is , 0.020 or more, the resulting thin film liquid repellent layer has better water repellency and synovial properties due to the presence of the alkyl group represented by R ⁴ in the component (B-1). From such a viewpoint, the [(B-1) / {(B-1) + (B-2)}] (molar ratio) is more preferably 0.035 or more, still more preferably 0.045 or more. Still more preferably, it is 0.050 or more, More preferably, it is 0.100 or more, More preferably, it is 0.150 or more, More preferably, it is 0.250 or more, More preferably, it is 0.500 or more.
And the upper limit of the said [(B-1) / {(B-1) + (B-2)}] (molar ratio) becomes like this. Preferably it is 0.995 or less, More preferably, it is 0.990 or less, More preferably It is 0.980 or less, More preferably, it is 0.950 or less, More preferably, it is 0.850 or less.
In addition, content of a component (B-1) and a component (B-2) can also be computed from the compounding quantity at the time of mix | blending each component.

  In addition, the liquid repellent composition of this invention contains a component (B-1) and a component (B-2) as a trifunctional silane type compound so that the said conditions (I) and conditions (II) may be satisfy | filled. The thin film liquid repellent layer obtained is preferable because it can have better water repellency. Moreover, the improvement of the surface state of the coating film formed from a liquid repellent composition can be anticipated by including a component (B-2).

When the component (B-1) and the component (B-2) are used as the component (B), the content (molar amount) of the component (B-1) is the water repellency and synovial fluid of the thin film repellent layer to be obtained. From the viewpoint of improving the properties, the content (molar amount) of the component (A), the component (B-1) and the component (B-2) is preferably 100% by mol or more, more preferably 0.30 mol% or more. Preferably it is 0.50 mol% or more, More preferably, it is 1.00 mol% or more, More preferably, it is 5.00 mol% or more, More preferably, it is 15.00 mol% or more, More preferably, it is 30.00 mol% That's it. And the said content (molar amount) becomes like this. Preferably it is 45.00 mol% or less, More preferably, it is 40.00 mol% or less.
Moreover, when using a component (B-1) and a component (B-2) as a component (B), content (molar amount) of a component (B-2) is the coating formed from a liquid repellent composition. From the viewpoint of improving the surface state of the film, the content (molar amount) of the component (A), the component (B-1) and the component (B-2) is preferably 0.50 mol% with respect to the total of 100 mol%. More preferably, it is 0.80 mol% or more, More preferably, it is 1.00 mol% or more, More preferably, it is 1.30 mol% or more, More preferably, it is 5.00 mol% or more, More preferably, it is 8. It is 00 mol% or more. And the said content (molar amount) becomes like this. Preferably it is 40.00 mol% or less, More preferably, it is 30.00 mol% or less, More preferably, it is 20.00 mol% or less.

In addition, when the component (B-1) and the component (B-2) are used as the component (B), the content of the component (B-1) in the relationship between the component (A) and the component (B-1) ( The ratio ((A) / (B-1)) (molar ratio) of the content (molar quantity) of the component (A) to the molar quantity is from the viewpoint of improving the synovial properties of the resulting thin film liquid repellent layer. Preferably it is 0.5 or more, More preferably, it is 0.8 or more, More preferably, it is 1.0 or more, More preferably, it is 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, the thin film repellent obtained can be obtained by the presence of the alkyl group represented by R ⁴ in the component (B-1). The liquid layer has better water repellency and synovial properties. From such a viewpoint, the [(A) / (B-1)] (molar ratio) is more preferably 200.0 or less, still more preferably 150.0 or less, still more preferably 100.0 or less, and more. More preferably, it is 90.0 or less, More preferably, it is 50.0 or less, More preferably, it is 10.0 or less, More preferably, it is 5.0 or less.
In addition, when the component (B-1) and the component (B-2) are used in combination as the component (B), the content of the component (B-2) in the relationship between the component (A) and the component (B-2) The ratio of the content (molar amount) of the component (A) to the amount (molar amount) [(A) / (B-2)] (molar ratio) is not particularly limited and is preferably 1.0 or more. . The [(A) / (B-2)] (molar ratio) is preferably 70.0 or less, more preferably 50.0 or less, still more preferably 20.0 or less, and still more preferably. 10.0 or less.

Moreover, when using a component (B-1) and a component (B-2) together as a component (B), in a relationship of a component (A), a component (B-1), and a component (B-2), a component ( Ratio of content (molar amount) of component (A) to total content (molar amount) of B-1) and 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 even 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, and even more preferably 20.00 or less. More preferably, it is 10.00 or less, More preferably, it is 5.0 or less.
In addition, when using together a component (B-1) and a component (B-2) as a component (B), the total content of the component (B-1) in a component (B) and a component (B-2) Is preferably 50% by mass or more, more preferably 65% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, relative to 100% by mass of the total content of the component (B). More preferably, it is 95 mass% or more, More preferably, it is 99 mass% or more, and Preferably it is 100 mass% or less. Further, the content is more preferably 100% by mass.

(Component (C): acid catalyst)
The liquid repellent composition used in the present invention preferably further contains an acid catalyst as component (C) from the viewpoint of further improving the reactivity of each of the silane compounds.
By containing an acid catalyst in the liquid repellent composition, hydrolysis of the reactive functional group of each silane compound is promoted. As a result, the condensation polymerization reaction between the silane compounds to be used is further promoted, and the curability is improved. The “reactive functional group” refers to a functional group represented by (OR ¹ ) or (X ¹ ) in the general formula (a) and the general formula (b) in the silane compound, The functional group etc. which are represented by OR < ³ >) or (X < ² >) are pointed out.
The acid catalyst is not particularly limited as long as it has a function of promoting hydrolysis of the reactive functional group of each silane compound. For example, from the viewpoint of further improving the reactivity of each silane-based compound, 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. It is preferable to include one or more selected from the above, and it is more preferable to include hydrochloric acid.
In addition, as said component (C), you may use individually or in combination of 2 or more types.

The content (molar amount) of the component (C) in the liquid repellent composition is the total content (molar amount) of the component (A) and the component (B) from the viewpoint of further improving the reactivity of each silane compound. The amount) is preferably 0.010 mol% or more, more preferably 0.030 mol% or more, still more preferably 0.050 mol% or more, and still more preferably 0.060 mol% or more with respect to 100 mol%. . And the said content becomes like this. Preferably it is 1.000 mol% or less, More preferably, it is 0.500 mol% or less, More preferably, it is 0.100 mol% or less, More preferably, it is 0.075 mol% or less.
In addition, the said content can also be computed from the compounding quantity at the time of mix | blending each component.

(Other additives)
In addition to the components described above, the liquid repellent composition may contain other additives as long as the effects of the present invention are not impaired.
Examples of other additives include a resin component, a metal catalyst, a curing agent, an anti-aging agent, a light stabilizer, a flame retardant, a conductive agent, an antistatic agent, and a plasticizer.
The content of these additives is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, still more preferably 0 to 5% by mass, based on the total amount of the liquid repellent composition solution. Still more preferably, it is 0-2 mass%.
In addition, the said content can also be computed from the compounding quantity at the time of mix | blending each component.

The total content of component (A) and component (B) in the liquid repellent composition is preferably 50% by mass or more, more preferably 100% by mass relative to all the active ingredients in the liquid repellent composition. 65% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 99% by mass or more, and preferably 100% by mass or less. It is.
In addition, the said content can also be computed from the compounding quantity at the time of mix | blending each component.
In the present invention, the active ingredient in the liquid repellent composition is a liquid component excluding a solvent (water or an organic solvent) not directly involved in the reaction, among the components contained in the liquid repellent composition, and A component that is solid at room temperature.

Moreover, 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 based on 100% by mass of all effective components in the liquid repellent composition. , Preferably 50% by mass or more, more preferably 65% by mass or more, further preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, and even more preferably 99% by mass or more. And preferably 100% by mass or less. Further, the content is more preferably 100% by mass.
In addition, the said content can also be computed from the compounding quantity at the time of mix | blending each component.

  In step (1), a cured film is formed using the liquid-repellent composition. When the cured film is formed, an application step of applying the liquid-repellent composition to an object to be coated; It is preferable to have a drying step of drying the coating film formed on the coated body.

{Coating process}
In the case of applying the liquid repellent composition, it is preferably dissolved on a solvent and applied on the substrate as a solution form.
Examples of the solvent include methanol, ethanol, propanol, butanol, isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, toluene and other organic solvents, water, and the like.

  The application method can be appropriately selected depending on the shape of the object to be applied, but for example, dip coating, curtain coating, spray coating, die coating, knife coating, blade coating, roll knife coating, roll coating, spin coating, etc. And at least one selected from the group consisting of coating, gravure coating and bar coating, preferably at least one selected from the group consisting of dip coating, curtain coating, spray coating, spin coating, gravure coating and bar coating Preferably the group consisting of dip coating, curtain coating, spray coating, gravure coating and bar coating At least one selected, more preferably include dip coating.

The coated body to which the liquid repellent composition is applied is not particularly limited as long as it requires liquid repellency, but glass, metal, alloy, semiconductor, rubber, cloth, plastic, ceramics, wood, It can be suitably used for paper, fiber and the like, and can be more suitably used for glass, metal and plastic. Moreover, it can be used suitably also for a metal oxide film or a resin coating surface.
There is no restriction | limiting in particular in the shape of a to-be-coated body, For example, planar things, such as a film and a sheet | seat, may be three-dimensional. As a three-dimensional thing, three-dimensional objects, such as display bodies, such as a bottle container, a roof, a signboard (three-dimensional signboard), a traffic signal, a building material, a wall, a floor, a shelf, a vehicle, a ship, and an airplane, are mentioned, for example.
Further, the shape of the surface to be coated is not particularly limited, and can be applied to a flat surface, a three-dimensional shape surface (including a curved surface, an uneven surface, etc.), a porous surface, and the like.

{Drying process}
In the coating step, after the coating film is formed on the coated body, the drying temperature and drying time when the coated film is dried are not particularly limited, and the heat resistance and liquid repellency of the coated body are not limited. It can be set as appropriate according to the type of the solution in which the composition is dissolved.
In addition, the liquid repellent composition used in the present invention can be cured at room temperature and room temperature (5-35 ° C.). For example, the liquid repellent composition used in an object to be coated using a material having low heat resistance such as vinyl chloride. Even in such a case, deformation at a high temperature such as heat shrinkage of the coated body can be suppressed. On the other hand, it can be cured even at a high temperature (50 to 200 ° C.), and the reaction of each silane compound can be promoted to improve the productivity.
Therefore, from the above viewpoint, the drying temperature is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, still more preferably 15 ° C. or higher, and preferably 200 ° C. or lower, more preferably 150 ° C. or lower, more More preferably, it is 130 degrees C or less, More preferably, it is 110 degrees C or less.
The drying may be natural drying, 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.

  The thickness of the cured film formed in the step (1) is not particularly limited, but is preferably 8 nm or more, more preferably 20 nm or more, still more preferably 100 nm or more, and preferably 3000 nm or less, more preferably It is 2000 nm or less, More preferably, it is 1800 nm or less.

<< Step (2) >>
Step (2) is a step of removing the surface of the cured film obtained in the step (1) to reduce the thickness.
As a method of thinning the surface of the cured film by removing the surface, preferably one or more selected from a method of thinning using an adhesive tape and a method of thinning using an organic solvent, more preferably an adhesive tape. A method of forming a thin film using it is mentioned.

Examples of the method of thinning using the pressure-sensitive adhesive tape include a method of attaching the pressure-sensitive adhesive tape on the surface of the cured film obtained in the step (1) and then peeling the pressure-sensitive adhesive tape.
The adhesive strength of the adhesive tape is not particularly limited as long as it can be thinned, but it is attached to a stainless steel plate (SUS304 steel plate, No. 360 polishing) in an environment of 23 ° C. and 50% RH (relative humidity). The adhesive strength after 24 hours has passed is preferably 1 N / 25 mm or more, more preferably 2 N / 25 mm or more, still more preferably 3 N / 25 mm or more, and preferably 30 N / 25 mm or less, more preferably It is 20 N / 25 mm or less, More preferably, it is 10 N / 25 mm or less.
The adhesive strength of the adhesive tape refers to a value measured according to JIS Z0237: 2000, and specifically refers to a value measured by the following method and conditions.
In an environment of 23 ° C. and 50% RH (relative humidity), an adhesive tape is applied to a stainless steel plate (SUS304 steel plate, No. 360 polishing) as an adherend and left to stand for 24 hours in the same environment. Then, under the same environment, the adhesive strength after 24 hours from pasting is measured at a pulling speed of 300 mm / min by a 180 ° peeling method in accordance with JIS Z0237: 2000.
Examples of the adhesive tape include “Scotch (registered trademark)” (product name, manufactured by 3M), “Cello Tape (registered trademark)” (product name, manufactured by Nichiban Co., Ltd.), and the like.

Moreover, as a method of thinning using the said organic solvent, the method of wash | cleaning the said cured film surface with an organic solvent is mentioned, for example.
Although there is no restriction | limiting in particular as the said cleaning method, Preferably ultrasonic cleaning is mentioned.
The organic solvent is not particularly limited as long as it can dissolve the surface of the cured film, and for example, methanol, ethanol, propanol, butanol, isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate. , At least one selected from the group consisting of organic solvents such as toluene, water and the like.

The thickness of the thin film liquid repellent layer produced through the steps (1) and (2) is preferably less than 8 nm, more preferably less than 7 nm, still more preferably less than 6 nm, still more preferably 5.8 nm or less, More preferably, it is 5.5 nm or less, More preferably, it is 5 nm or less. The thickness of the thin film liquid repellent layer is preferably 0.5 nm or more, more preferably 0.8 nm or more, still more preferably 1 nm or more, and even more preferably 2 nm or more. The thickness of the thin film liquid repellent layer is For example, it can measure using the method as described in the Example mentioned later.

[Thin liquid repellent layer]
The thin film liquid repellent layer which is 1 aspect of this invention is a hardened | cured material with the following component (A) and the following component (B), Comprising: It is a thin film liquid repellent layer which is less than 8 nm in thickness.
Component (A): Tetrafunctional silane compound represented by the following general formula (a) Si (OR ¹ ) _p (X ¹ ) _4-p (a)
[In General Formula (a), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and X ¹ represents a halogen atom. When R ¹ and ^{X 1} there are a plurality, the plurality of ^{R 1} and ^{X 1} are also identical to each other or may be different. p represents an integer of 0 to 4. ]
Component (B): Trifunctional silane compound represented by the following general formula (b) R ² Si (OR ³ ) _q (X ² ) _3-q (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. If R ³ and ^{X 2} there are a plurality, the plurality of ^{R 3} and ^{X 2} are either identical to one another or may be different. q represents an integer of 0 to 3. ]

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. And the thickness of the said thin film liquid repellent layer becomes like this. Preferably it is 0.5 nm or more, More preferably, it is 0.8 nm or more, More preferably, it is 1 nm or more, More preferably, it is 2 nm or more.
The thickness of the thin film liquid repellent layer can be measured using, for example, the method described in Examples described later.

Component (A) and component (B) are the same as component (A) and component (B) described above, respectively, and their preferred embodiments are also the same.
Moreover, when a component (B) contains at least 1 sort (s) chosen from the group which consists of the above-mentioned component (B-1) and a component (B-2), a component (B-1) and a component (B-2) are These are the same as the component (B-1) and the component (B-2) described above, respectively, and the preferred embodiments thereof are also the same.

(Condition (III))
In the cured product with the component (A) and the component (B), the following condition (III) is preferably satisfied.
Condition (III): Ratio of content (molar amount) of structure (Ap) derived from component (A) to content (molar amount) of structure (Bp) derived from component (B) in the cured product [(Ap) / (Bp)] (molar ratio) is 0.01 or more and 50.00 or less When the [(Ap) / (Bp)] (molar ratio) is 0.01 or more, the resulting thin film liquid repellent layer Synovial fluidity and adhesion to the coated body are improved.
Here, the content (molar amount) of the structure (Ap) in the cured product and the content (molar amount) of the structure (Bp) are, for example, in the liquid repellent composition before forming the cured product, respectively. It can also be considered that it is the same as content of a component (A) and a component (B).
Therefore, the content of the structure (Ap) in the cured product, the content of the structure (Bp), and the preferred range of the [(Ap) / (Bp)] (molar ratio) are the contents of the component (A) described above. It is the same as each preferable range of the amount, the content of component (B), and [(A) / (B)] (molar ratio).

(Condition (IV))
As a component (B), when it is a cured product using the component (B-1) and the component (B-2) in combination, the structure (B-1p) and the component (B-2) derived from the component (B-1) In the relationship of the structure (B-2p), the following condition (IV) is preferably satisfied.
Condition (IV): Content (molar amount) of the structure (B-1p) derived from the component (B-1) in the cured product and content (molar) of the structure (B-2p) derived from the component (B-2) (B-1p) / {(B-1p) + (B-2p)}] (molar ratio) of the molar amount of (B-1p) to the total content (molar amount) of 020 or more When the [(B-1p) / {(B-1p) + (B-2p)}] (molar ratio) is 0.020 or more, the thin film liquid repellent layer has better water repellency and smoothness. It has liquidity.
Here, the content (molar amount) of the structure (B-1p) and the content (molar amount) of the structure (B-2p) in the cured product are, for example, liquid repellency before forming the cured product, respectively. It can also be considered as content of the component (B-1) and a component (B-2) in a composition.
Therefore, the content (molar amount) of the structure (B-1p) in the cured product, the content (molar amount) of the structure (B-2p), and the [(B-1p) / {(B-1p) + The preferred range of (B-2p)}] (molar ratio) is the content of component (B-1), the content of component (B-2), and [(B-1) / {(B- 1) + (B-2)}] (molar ratio).

In the case of a cured product using the component (B-1) and the component (B-2) as the component (B), in the relationship between the structure (Ap) and the structure (B-1p) in the cured product, the structure (B −1p) content (molar amount) to structure (Ap) content (molar amount) ratio [(Ap) / (B-1p)] (molar ratio) is the same as [(A) / (B -1)] (molar ratio) is the same as the preferred range.
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 preferred range of [(A) / (B-2)] (molar ratio) described above.
In addition, in the relationship between the structure (Ap), the structure (Bp), and the structure (B-1p), the content of the structure (Ap) with respect to the total content (molar amount) of the structure (B-1p) and the structure (B-2p) The ratio [(Ap) / {(B-1p) + (B-2p)}] (molar ratio) of the amount (molar amount) is [(A) / {(B-1) + (B-2 )}] (Molar ratio) is the same as the preferred range.
In addition, when it is a cured product using the component (B-1) and the component (B-2) as the component (B), the structure (B-1p) and the structure (B-2p) in the structure (Bp) The total content is preferably 50 mol% or more, more preferably 65 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol%, based on 100 mol% of the total content of the structure (Bp). More preferably, it is 95 mol% or more, still more preferably 99 mol% or more, and preferably 100 mol% or less. The content is more preferably 100 mol%.

The thin film liquid repellent layer which is one embodiment of the present invention is preferably a thin film liquid repellent layer obtained by removing the surface of the cured product of the component (A) and the following component (B) to form a thin film.
Examples of the method for removing the surface of the cured film to form a thin film include the method described above in the step (2) of the method for producing the thin film liquid repellent layer, and the preferred embodiment thereof is also the same.
Moreover, as a suitable one aspect | mode of the thin film liquid repellent layer of this invention, it is a thin film liquid repellent layer obtained by the manufacturing method of the thin film liquid repellent layer of this invention mentioned above.

[Applications of thin-film liquid repellent layer]
The thin film liquid repellent layer of the present invention includes, for example, architectural window glass, automotive window glass, windshield glass for vehicles, aircraft, ships, etc., water tanks, ship bottom windows, films for preventing adhesion of marine organisms to the ship bottom, soundproof walls, etc. It can be suitably used to prevent adhesion of objects that obstruct visibility such as water droplets, scratches, and dirt on the surface of molded articles such as road panels, mirrors installed in bathrooms, glass containers, glass ornaments, etc. .

[Preparation of liquid repellent composition solution]
Examples 1-5
<Step (1)>
Ingredient (A), ingredient (B-1) and ingredient (B-2) are blended in the types and blending ratios (mol%) shown in Table 1, and diluted by adding ethanol as a solvent to give a concentration of 1.30M. A solution of the liquid composition was obtained.
To this solution, hydrochloric acid (excluding dilution water) as the acid catalyst (C) is further blended so as to be 0.067 mol% with respect to 100 mol% in total of component (A) and component (B). The coating solution was obtained by stirring for a period of time.
A slide glass (product name “Micro Slide Glass S1111”, manufactured by Matsunami Glass Industrial Co., Ltd., plasma-cleaned under the conditions of 100 W and 1 minute) was prepared as an object to be coated. Silicone slightly adhesive tape (product name “REPOP RE505S”, manufactured by Lintec Corporation) was applied to a part of the slide glass as a masking tape for masking. The coating solution was dip-coated on the masked slide glass to form a coating film, and dried at room temperature (23 ° C.) for 24 hours to form a cured film on the slide glass.

<Step (2)>
“Cello tape (registered trademark)” (manufactured by Nichiban Co., Ltd.) was attached as an adhesive tape to the surface of the cured film formed in the step (1). Next, the applied tape was peeled off from the surface of the cured film, and the surface of the cured film was removed to prepare a thin film liquid repellent layer.

Comparative Example 1
A comparative cured film was produced in the same manner as in Example 1 except that a coating solution containing only the component (A) was prepared in the step (1).

Comparative Example 2
A comparative cured film was produced in the same manner as in Example 1 except that a coating solution containing only the component (B-1) was prepared in the step (1).

Comparative Example 3
A comparative cured film was produced in the same manner as in Example 1 except that the thinning treatment in the step (2) was not performed.

The detail of each component described in Table 1 is as follows.
<Component (A): Tetrafunctional Silane Compound Represented by General Formula (a)>
"TEOS": Tetraethoxysilane, a tetrafunctional silane compound in which p = 4 and R ¹ = ethyl group (carbon number: 2) in the general formula (a).
<Component (B-1): Trifunctional silane compound represented by general formula (b-1)>
“Decyltrimethoxysilane”: a trifunctional silane in which r = 3, R ⁴ = n-decyl group (carbon number: 10), and R ⁵ = methyl group (carbon number: 1) in the general formula (b) Compounds.
<Component (B-2): Trifunctional silane compound represented by the general formula (b-2)>
“Methyltrimethoxysilane”: trifunctional silane in the above general formula (b-2) where s = 3, R ⁶ = methyl group (carbon number: 1), and R ⁷ = methyl group (carbon number: 1) Compounds.
<Component (C): Acid catalyst>
"Hydrochloric acid": 0.01M hydrochloric acid.

  The characteristics of the thin film liquid repellent layer and the comparative cured film prepared in each Example and each Comparative Example were evaluated based on the following methods.

<Thickness of cured film formed in step (1) and thin film liquid repellent layer prepared in step (2)>
The thickness of the cured film formed in the step (1) and the thin film liquid repellent layer prepared in the step (2) were measured using the following method. The results are shown in Tables 1 and 2.
・ Measuring equipment: Optical interference type film thickness meter “Wyko NT9100” (product name, manufactured by Veeco)
The masking tape on the slide glass having the thin liquid-repellent layer or the slide glass having a comparative cured film (hereinafter, simply referred to as “evaluation sample”) prepared in each Example and each Comparative Example was peeled off. The thickness (X) of the evaluation sample in the portion where the thin film liquid repellent layer or the cured film is formed and the thickness (Y) of the evaluation sample in the portion where the thin film liquid repellent layer or the cured film is not formed, respectively The measurement was performed using the above-described measuring equipment and conditions. From the difference (X)-(Y) between the obtained thickness (X) and thickness (Y), the thickness of the thin film liquid repellent layer and the cured film was calculated.

<Tape peelability of the cured film formed in step (1)>
When the film was thinned in the step (2), the peelability of the cured film surface with cello tape (registered trademark) was evaluated according to the following criteria. The results are shown in Table 1.
-A: The cured film surface of the whole range which stuck the tape was able to be peeled.
-B: The part which cannot peel was produced in a part of cured film surface of the range which stuck the tape.
C: The area where the tape was applied could not be peeled at all.

<Liquid repellency>
As an index of liquid repellency, water contact angle and water sliding angle were evaluated based on the following methods.
(Water contact angle)
The water contact angle of the thin liquid-repellent layer or comparative cured film was prepared in each example and each comparative example using a fully automatic contact angle measuring device (product name “DM-701”, manufactured by Kyowa Interface Science Co., Ltd.). The contact angle with respect to 2 μL of water was measured on the surface of the thin liquid repellent layer or the comparative cured film surface. The results are shown in Table 2. It shows that it is excellent in water repellency, so that a value is large.

(Water sliding angle)
The evaluation samples prepared in each Example and each Comparative Example were placed on a sample table (glass plate) with an inclination angle of 0 ° by water filling. Next, 14 μL of pure water was dropped on the surface of the thin film liquid repellent layer or comparative cured film to form a droplet, and then the sample when the receding angle of the droplet moved when the sample stage was tilted The inclination angle of the table was the water sliding angle. The results are shown in Table 2. It shows that it is excellent in water sliding property, so that a value is small.

<Visibility>
The haze of the evaluation sample and the slide glass alone produced in each example and each comparative example was measured using a haze meter (product name “NDH-2000”, manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS K7136: 2000. did. Table 2 shows the result of the value obtained by subtracting the haze of the slide glass alone from the haze of the evaluation sample. The smaller the value, the higher the transparency and the better the visibility.

From Table 1 and Table 2, it was confirmed that the thin film liquid repellent layers of Examples 1 to 5 have good water contact angle and water sliding angle as liquid repellency and excellent visibility.
On the other hand, the cured film of Comparative Example 1 is a cured product composed of only the component (A), and the surface of the cured film cannot be peeled off with cello tape (registered trademark), and the water contact angle of the cured film is also inferior. As a result.
And the comparative example 2 was inferior in the surface state of the coating film formed at the process (1), and could not form the cured film which can endure each evaluation.
Moreover, in Comparative Example 3, since the cured film formed in the step (1) was not thinned, the cured film was thick and the visibility was poor.

By using the method for producing a thin film liquid repellent layer which is one embodiment of the present invention, a thin film liquid repellent layer having excellent visibility and liquid repellency (preferably water repellency and synovial fluid) can be produced. The thin film liquid repellent layer which is one embodiment of the present invention is excellent in visibility and liquid repellency.
Therefore, the thin film liquid repellent layer is, for example, windshield glass for buildings, window glass for automobiles, vehicles, airplanes, ships, etc., water tank, ship bottom window, film for preventing attachment of marine organisms to the ship bottom, soundproof wall, etc. In order to provide liquid repellency to prevent adhesion of objects that obstruct visibility such as water droplets and dirt on the surface of molded products such as road panels, mirrors installed in bathrooms, glass containers, glass ornaments, etc. Is preferred. And, for example, water repellency and liquid slidability that can efficiently slide down water drops and snow that has fallen on windshield glass of automobile window glass, vehicles, airplanes, ships, etc., and excellent visibility are required. It is more suitable for the application used below.

Claims (17)

The manufacturing method of a thin film liquid repellent layer which has the following process (1) and the following process (2) in this order.
Step (1): Process component (A) for forming a cured film using a liquid repellent composition containing the following component (A) and the following component (B): tetrafunctional represented by the following general formula (a) Silane-based compounds Si (OR ¹ ) _p (X ¹ ) _4-p (a)
[In General Formula (a), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and X ¹ represents a halogen atom. When R ¹ and ^{X 1} there are a plurality, the plurality of ^{R 1} and ^{X 1} are also identical to each other or may be different. p represents an integer of 0 to 4. ]
Component (B): Trifunctional silane compound represented by the following general formula (b) R ² Si (OR ³ ) _q (X ² ) _3-q (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. If R ³ and ^{X 2} there are a plurality, the plurality of ^{R 3} and ^{X 2} are either identical to one another or may be different. q represents an integer of 0 to 3. ]
Step (2): Step of removing the surface of the cured film obtained in the step (1) to form a thin film   The manufacturing method of the thin film liquid repellent layer of Claim 1 which performs the said thin film formation using an adhesive tape at a process (2). The manufacturing method of the thin film liquid repellent layer of Claim 1 or 2 with which a component (B) contains at least 1 sort (s) of the following component (B-1) at a process (1).
Component (B-1): Trifunctional silane compound represented by the following general formula (b-1) R ⁴ Si (OR ⁵ ) _r (X ³ ) _3-r (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. If R ⁵ and ^{X 3} there are a plurality, the plurality of ^{R 5} and ^{X 3} are either identical to one another or may be different. r represents an integer of 0 to 3. ] The manufacturing method of the thin film liquid repellent layer of any one of Claims 1-3 in which a component (B) contains at least 1 sort (s) of the following component (B-2) at a process (1).
Component (B-2): Trifunctional silane compound represented by the following general formula (b-2) R ⁶ Si (OR ⁷ ) _s (X ⁴ ) _3-s (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. If R ⁷ and ^{X 4} there are a plurality, a plurality of ^{R 7} and ^{X 4,} are identical to each other or may be different. s represents an integer of 0 to 3. ] The method for producing a thin film liquid repellent layer according to claim 4, further satisfying the following condition (II) in the step (1).
Condition (II): Ratio of molar amount of component (B-1) to total molar amount of component (B-1) and component (B-2) [(B-1) / {(B-1) + (B -2)}] (molar ratio) is 0.020 or more The manufacturing method of the thin film liquid repellent layer of any one of Claims 1-5 which satisfy | fills the following conditions (I) further at a process (1).
Condition (I): Ratio of molar amount of component (A) to molar amount of component (B) [(A) / (B)] (molar ratio) is 0.01 or more and 50.00 or less   In step (1), an acid catalyst is further contained as component (C), and the content of component (C) is 0.010 mol% or more with respect to 100 mol% in total of component (A) and component (B) The manufacturing method of the thin film liquid repellent layer of any one of Claims 1-6 which is 1.000 mol% or less.   The method for forming the cured film includes at least one application step and drying step selected from the group consisting of dip coating, curtain coating, spray coating, gravure coating, and bar coating. The manufacturing method of the thin film liquid repellent layer of claim | item.   The manufacturing method of the thin film liquid repellent layer of any one of Claims 1-8 whose thickness of the said thin film liquid repellent layer is less than 8 nm.   The manufacturing method of the thin film liquid repellent layer of any one of Claims 1-9 whose thickness of the said cured film formed at the process (1) is 8 nm or more.   The thin film liquid repellent layer manufactured with the manufacturing method of any one of Claims 1-10. A thin film liquid repellent layer which is a cured product of the following component (A) and the following component (B) and has a thickness of less than 8 nm.
Component (A): Tetrafunctional silane compound represented by the following general formula (a) Si (OR ¹ ) _p (X ¹ ) _4-p (a)
[In General Formula (a), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and X ¹ represents a halogen atom. When R ¹ and ^{X 1} there are a plurality, the plurality of ^{R 1} and ^{X 1} are also identical to each other or may be different. p represents an integer of 0 to 4. ]
Component (B): Trifunctional silane compound represented by the following general formula (b) R ² Si (OR ³ ) _q (X ² ) _3-q (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. If R ³ and ^{X 2} there are a plurality, the plurality of ^{R 3} and ^{X 2} are either identical to one another or may be different. q represents an integer of 0 to 3. ] The thin film liquid repellent layer according to claim 12, wherein the component (B) contains at least one of the following components (B-1).
Component (B-1): Trifunctional silane compound represented by the following general formula (b-1) R ⁴ Si (OR ⁵ ) _r (X ³ ) _3-r (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. If R ⁵ and ^{X 3} there are a plurality, the plurality of ^{R 5} and ^{X 3} are either identical to one another or may be different. r represents an integer of 0 to 3. ] The thin film liquid repellent layer according to claim 12 or 13, wherein the component (B) contains at least one of the following components (B-2).
Component (B-2): Trifunctional silane compound represented by the following general formula (b-2) R ⁶ Si (OR ⁷ ) _s (X ⁴ ) _3-s (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. If R ⁷ and ^{X 4} there are a plurality, a plurality of ^{R 7} and ^{X 4,} are identical to each other or may be different. s represents an integer of 0 to 3. ] Furthermore, the thin film liquid repellent layer of Claim 14 which satisfy | fills following condition (IV).
Condition (IV): Ratio of molar amount of (B-1p) to total molar amount of structure (B-1p) derived from component (B-1) and structure (B-2p) derived from component (B-2) [ (B-1p) / {(B-1p) + (B-2p)}] (molar ratio) is 0.020 or more. The thin film liquid repellent layer according to any one of claims 12 to 15, which satisfies the following condition (III).
Condition (III): The ratio [(Ap) / (Bp)] (molar ratio) of the molar amount of the structure (Ap) derived from the component (A) to the molar amount of the structure (Bp) derived from the component (B) is 0. .01 or more and 50.00 or less   The thin film liquid repellent layer according to any one of claims 12 to 16, which is obtained by removing a surface of a cured product of the component (A) and the component (B) and thinning the cured product.