WO2019240093A1 - Fouling-resistant article and production method therefor - Google Patents

Abstract

Provided is a fouling-resistant article that has superior fouling-resistant properties and durability, such as wear resistance, with regard to the fouling-resistant properties.　Specifically provided is a fouling-resistant article comprising: a substrate, at least a part of a surface of which comprises a metal; a primer layer provided on the surface; and an antifouling layer provided upon the primer layer, the fouling-resistant article being characterized in that: the primer layer is formed using a first silane compound having a weight-average molecular weight of 500 to 200,000 that contains hydrolyzable silyl groups in the proportion of at least 30 mass% and does not contain a fluorine atom; and the antifouling layer is formed using a second silane compound that has a perfluoropolyether group and a hydrolyzable silyl group.

Description

Antifouling article and method for producing the same

The present invention relates to an antifouling article having excellent antifouling properties and having durability such as wear resistance with respect to the antifouling properties and a method for producing the same.

In order to impart water and oil repellency to the surface of various base materials, it has the property of having a low surface tension coating on the surface of the base material to suppress the adhesion of dirt and make it easier to remove the attached dirt. That is, an antifouling article having an improved antifouling property is known.

Fluorine-containing compounds have heretofore been used for coating compositions for obtaining the above antifouling coating. For example, the coating composition for imparting oil repellency and / or water repellency to the surface of a substrate made of an inorganic material such as glass or ceramic has one or more fluorine-containing groups (for example, perfluoroalkyl groups, perfluoroalkyl groups, Fluorine-containing silane compounds having an ether group and a perfluoropolyether group) have been used.

Here, in the antifouling article in which the antifouling coating (antifouling layer) is provided on the surface of the substrate using the fluorine-containing compound, particularly when at least a part of the substrate surface is made of metal, the antifouling agent is used. When the surface of the layer was repeatedly washed and rubbed, the antifouling property sometimes deteriorated. In order to solve this, in Patent Document 1, a metal surface is treated with a primer composition containing a second or third amino functional compound having at least two independently selected silane groups. A method has been proposed in which an undercoat layer is formed on the undercoat layer, and an antifouling layer is formed on the undercoat layer using a fluorine-containing compound.

Japan Special Table 2017-515650

However, in the method of Patent Document 1, it is difficult to say that the antifouling layer formed on the metal surface necessarily has sufficient durability such as wear resistance.

The present invention has been made from the above viewpoint, and in an antifouling article having an antifouling layer formed on a metal surface using a fluorine-containing compound, the antifouling property is excellent, and the antifouling property is An object of the present invention is to provide an antifouling article having durability such as wear and a method for efficiently producing the antifouling article.

The present invention has the following aspects.
[1] An antifouling article comprising a base material having at least a part of a surface made of metal, a primer layer provided on the surface, and an antifouling layer provided on the primer layer,
The primer layer is a silane compound having a hydrolyzable silyl group in which a hydrolyzable group is bonded to a silicon atom, containing no fluorine atom, and having a weight average molecular weight of 500 to 200,000, A layer formed using a first silane compound containing a group at a ratio of 30% by mass or more with respect to the entire silane compound;
The antifouling layer is a layer formed by using a second silane compound having a perfluoropolyether group and a hydrolyzable silyl group.
[2] The antifouling article according to [1], wherein the first silane compound is a silane compound having a main chain formed of a siloxane bond.
[3] The second silane compound is — (C _a F _2a O) _b — (a is an integer of 1 to 6, b is an integer of 2 or more, and — (C _a F _2a O _B ) unit may be linear or branched, and may be represented by-(C _a F _2a O) _b -units having two or more different carbon numbers). [1] or [2], which is a silane compound having a poly (oxyperfluoroalkylene) chain and having a hydrolyzable silyl group via a linking group at at least one terminal of the poly (oxyperfluoroalkylene) chain The antifouling article as described.
[4] The antifouling article according to [3], wherein the second silane compound is represented by the following formula (S3).
[AO- (C _a F _2a O) _b- ] Q [-SiL _m R _3-m ] _p (S3)
Symbols in the formula (S3) are as follows.
A is a perfluoroalkyl group having 1 to 6 carbon atoms or -Q ¹⁰ -SiL _m R _3-m .
In (C _a F _2a O) _b , a is an integer of 1 to 6, b is an integer of 2 or more, and the — (C _a F _2a O) _b — unit is linear or branched. It may be a chain and may have two or more — (C _a F _2a O) _b — units having different carbon numbers.
Q is a (1 + p) -valent linking group.
Q ¹⁰ is a divalent linking group.
p is an integer of 1 to 10.
L is a hydrolyzable group.
R is a hydrogen atom or a monovalent hydrocarbon group.
m is an integer of 1 to 3.
[5] The antifouling article according to any one of [1] to [4], wherein the primer layer has a thickness of 3 to 200 nm.
[6] The antifouling article according to any one of [1] to [5], wherein the antifouling layer has a thickness of 10 to 100 nm.
[7] A method for producing an antifouling article having a substrate comprising at least a part of a surface of a metal, a primer layer provided on the surface, and an antifouling layer provided on the primer layer,
A silane compound having a hydrolyzable silyl group in which a hydrolyzable group is bonded to a silicon atom on the surface, no fluorine atom, and a weight average molecular weight of 500 to 200,000, wherein the hydrolyzable group A primer layer composition containing a first silane compound containing 30% by mass or more of the silane compound and a first solvent is applied, and the first silane compound is allowed to react with the primer. Obtaining a layer, and depositing a composition for an antifouling layer comprising a second silane compound having a perfluoropolyether group and a hydrolyzable silyl group on the primer layer, and reacting the second silane compound. A method for producing an antifouling article, comprising: obtaining an antifouling layer.
[8] The method according to [7], wherein the first silane compound is a silane compound having a main chain formed of a siloxane bond.
[9] The production method according to [7] or [8], wherein the first solvent includes a non-fluorine organic solvent, or a non-fluorine organic solvent and water.
[10] The production method according to any one of [7] to [9], wherein the primer layer composition is applied so that the adhesion amount of the first silane compound is 50 to 1000 mg / m ² .
[11] Any of [7] to [10], wherein the primer layer composition contains the first silane compound in a proportion of 0.1 to 3.0% by mass with respect to the total amount of the composition. The manufacturing method as described in.
[12] The second silane compound is — (C _a F _2a O) _b — (a is an integer of 1 to 6, b is an integer of 2 or more, and — (C _a F _2a O _B ) unit may be linear or branched, and may be represented by-(C _a F _2a O) _b -units having two or more different carbon numbers). [7] to [11], wherein the silane compound has a poly (oxyperfluoroalkylene) chain and has a hydrolyzable silyl group via a linking group at at least one end of the poly (oxyperfluoroalkylene) chain. The manufacturing method in any one.
[13] The production method according to any one of [7] to [12], wherein the antifouling layer composition is adhered such that the adhesion amount of the second silane compound is 30 to 80 mg / m ² .
[14] The method according to any one of [7] to [13], wherein the composition for an antifouling layer further contains a second solvent, and the method for adhering to the primer layer is coating.
[15] The production method according to [14], wherein the second silane compound is contained at a ratio of 0.1 to 0.5% by mass with respect to the total amount of the antifouling layer composition.

According to the antifouling article of the present invention, in an antifouling article having an antifouling layer formed on a metal surface using a fluorine-containing compound, the antifouling property is excellent, and the antifouling property has abrasion resistance and the like. Excellent durability.
According to the production method of the present invention, in a method for producing an antifouling article having an antifouling layer formed on a metal surface using a fluorine-containing compound, the antifouling property is excellent, and the antifouling property is wear resistant. Thus, an antifouling article having excellent durability can be produced.

The meaning of terms in this specification and the way of description are as follows.
A compound or group represented by the formula is also expressed as a compound or group with the number of the formula. For example, “the compound represented by the formula (1)” is also referred to as “compound (1)”.
“˜” representing a numerical range includes a lower limit value and an upper limit value. In addition, when the unit of the lower limit value and the upper limit value is the same, the unit for the lower limit value may be omitted.

“(Meth) acryloxy” is used as a general term for acryloxy and methacryloxy.

[Anti-fouling article]
The antifouling article of the present invention is an antifouling article comprising a base material having at least a part of the surface made of metal, a primer layer provided on the surface made of the metal, and an antifouling layer provided on the primer layer. It is. The primer layer is formed on at least a part of the metal surface including the region where the antifouling layer is formed.

The primer layer is a silane compound having a hydrolyzable silyl group in which a hydrolyzable group is bonded to a silicon atom, containing no fluorine atom, and having a weight average molecular weight of 500 to 100,000. This is a layer formed using a first silane compound containing a group in a proportion of 30% by mass or more based on the entire compound.

In the present specification, the content (% by mass) of the hydrolyzable group in the first silane compound is determined by analysis by a nuclear magnetic resonance spectroscopy (NMR) method. The weight average molecular weight (hereinafter also referred to as Mw) of the first silane compound is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

The antifouling layer is a layer formed using a second silane compound having a perfluoropolyether group and a hydrolyzable silyl group.
The hydrolyzable silyl group possessed by the first silane compound and the second silane compound is a group in which a hydrolyzable group is directly bonded to a silicon atom, and a silanol group (Si—OH) is formed by a hydrolysis reaction. It is a group that can be formed. The hydrolyzable group is a group that decomposes with water.

In the antifouling article of the present invention, when forming the primer layer, the hydrolyzable silyl group of the first silane compound undergoes a hydrolysis reaction to form a silanol group (Si—OH). This silanol group reacts with a polar group on the metal surface to form a metal-O-Si bond. In addition, the silanol group reacts between molecules to form a Si—O—Si bond. Further, the silanol group reacts with a silanol group generated from a hydrolyzable silyl group of the second silane compound used for forming the antifouling layer to form a Si—O—Si bond.
The polar group on the metal surface is a group that forms a hydrogen bond. Specifically, a hydroxyl group, a carboxyl group, an amino group, and the like are preferable, and a hydroxyl group is particularly preferable.

In the present invention, the first silane compound has the predetermined Mw and has a hydrolyzable group bonded to the predetermined amount of silicon atoms, so that the metal surface of the base material and the primer layer, the primer layer, and the primer It is considered that a sufficient amount of the above bonds are formed in a balanced manner between the layers and the antifouling layer. Thereby, it is thought that the metal surface and primer layer of a base material, and a primer layer and an antifouling layer are joined firmly.

The antifouling layer is bonded to the primer layer by Si—O—Si bonds as described above, and in the antifouling layer, silanol groups formed from hydrolyzable silyl groups of the second silane compound are molecules. React with each other to form Si—O—Si bonds. On the other hand, the perfluoropolyether group of the second silane compound does not participate in the above reaction and is present on the surface layer of the antifouling layer, and therefore exhibits excellent antifouling properties.

Therefore, in the antifouling article of the present invention, the primer layer contains a reaction product of the first silane compound in a state in which a part or all of the hydrolyzable groups of the first silane compound is hydrolyzed. Similarly, the antifouling layer contains a reaction product of the second silane compound in a state in which a part or all of the hydrolyzable groups of the second silane compound is hydrolyzed.

Below, the structural member of the antifouling | stain-proof article of this invention is each demonstrated.
(Base material)
There is no particular limitation as long as at least a part of the surface is a base material made of metal. The whole surface of the substrate may be made of metal, or part of the substrate may be made of metal. Further, the entire surface may be made of the same metal or different metals.

The base material may be composed of, for example, a single metal as a whole, or may be a laminate in which a plurality of layers made of metal (hereinafter also referred to as metal layers) are stacked. Furthermore, it is a laminate of a metal layer and a layer made of an inorganic material other than metal (hereinafter also referred to as an inorganic material layer) and / or a layer made of an organic material (hereinafter also referred to as an organic material layer). Further, a laminate in which one surface layer is a metal layer may be used. Or the structure which has the area | region which consists of an area | region which consists of a metal, and inorganic materials and / or organic materials other than a metal in the same surface may be sufficient. The base material which gave metal plating to at least one part of the surface of a metal layer or an organic material layer may be sufficient.

The shape of the substrate is not particularly limited, and examples thereof include a plate shape, a film (thin film) shape, a rod shape, and a cylindrical shape. When a base material is plate shape, a flat plate may be sufficient and the shape in which a part or all of a main surface has a curvature may be sufficient. Further, the surface shape may be smooth or uneven.
Examples of the metal constituting the surface on which the primer layer is formed in the substrate include metals and alloys that are solid at room temperature without any particular limitation.

Specific examples of the metal include chromium, iron, aluminum, copper, nickel, zinc, tin, carbon steel, lead, titanium, gold, silver, and alloys thereof. Examples of the alloy include stainless steel such as SUS304, SUS316, SUS303, SUS317, and SUS403, brass (brass), bronze, white bronze, red copper, bronze, silver, duralumin, solder, and the like. Examples of the metal surface include nickel / chrome plating, nickel plating, chromium plating, and zinc plating.

(Primer layer)
The primer layer is formed using the first silane compound. As described above, the primer layer includes a reaction product of the first silane compound, but may include an optional component other than the reaction product of the first silane compound. The proportion of the reaction product of the first silane compound in the entire primer layer is preferably 80 to 100% by mass, because the adhesion between the antifouling layer and the primer layer and between the primer layer and the substrate surface is further excellent. The mass% is more preferable.

If the thickness of the primer layer is a monomolecular thickness of the first silane compound, the antifouling layer and the primer layer and the adhesion between the primer layer and the substrate surface are excellent, and the antifouling property of the antifouling article is excellent. Is preferable. When the thickness of the primer layer is too thick, the primer layer becomes brittle and durability is lowered. Specifically, the thickness of the primer layer is preferably 3 to 200 nm, and more preferably 5 to 80 nm. The thickness of the primer layer is determined by, for example, obtaining an interference pattern of reflected X-rays by the X-ray reflectivity method using an X-ray diffractometer ATX-G for thin film analysis (manufactured by Rigaku), and the vibration period of the interference pattern. It can be calculated from

<First silane compound>
The first silane compound is not particularly limited as long as it satisfies the following requirements (i-1) and (i-2).
(I-1) It has a hydrolyzable silyl group, and the ratio of the hydrolyzable group of the hydrolyzable silyl group to the total amount of the compound is 30% by mass or more. Moreover, it does not contain a fluorine atom.
(I-2) Mw is 500 to 200,000.

When the Mw in the first silane compound is less than 500, there is a problem in terms of adhesion to the second silane compound, and when it exceeds 200,000, there is a problem in terms of film formability. The Mw is preferably 700 or more, and more preferably 1,000 or more. The Mw is preferably 150,000 or less, and more preferably 100,000 or less.

When the content of the hydrolyzable group in the first silane compound is less than 30% by mass, the primer layer to be formed and the metal surface are not sufficiently bonded, and the expected durability is obtained in the obtained antifouling article. I can't. Content of a hydrolysable group is 30 mass% or more, 50 mass% or more is preferable and 80 mass% or more is more preferable.
The content of the hydrolyzable group in the first silane compound is preferably as high as possible in terms of molecular design. Specifically, the content of the hydrolyzable group is preferably 95% by mass or less, and more preferably 90% by mass or less.

Specifically, the first silane compound is a compound having a main chain formed of a siloxane bond and satisfying (i-1) and (i-2) (hereinafter also referred to as compound (I)). )), A compound whose main chain is mainly composed of a carbon-carbon bond and satisfying (i-1) and (i-2) (hereinafter also referred to as compound (II)). .

In the case of compound (I), the hydrolyzable silyl group has a structure in which the hydrolyzable group is bonded to the silicon atom constituting the main chain. The main chain formed by the siloxane bond may be a straight chain, a branched chain, or a three-dimensional network structure. As the first silane compound, the compound (I) is preferable from the viewpoint of improving adhesion to metal, and the compound (I) having a three-dimensional network structure is particularly preferable from the viewpoint of increasing the film strength.

Examples of the compound (I) whose main chain has a three-dimensional network structure include compounds obtained by partial hydrolysis (co) condensation of low molecular weight silane compounds containing a trifunctional or higher functional hydrolyzable silyl group.
Examples of the low molecular weight silane compound for obtaining the compound (I) whose main chain has a three-dimensional network structure include a compound represented by the following formula (S1). The compound (S1) includes a monofunctional or bifunctional hydrolyzable silane compound. In order to obtain the compound (I) whose main chain has a three-dimensional network structure, the compound (S1) having a trifunctional or higher functional hydrolyzable silyl group is essential, and monofunctional or bifunctional hydrolysis as necessary. Using the functional silane compound (S1), partial hydrolysis condensation is performed so that (i-1) and (i-2) can be satisfied. Monofunctional, bifunctional, and trifunctional are the numbers of hydrolyzable groups that are directly bonded to the silicon atom in the molecule. That is, it is e in the following formula (S1).

R ¹¹ _d SiL ¹¹ _e R ¹² _4- de (S1)
However, the symbols in the formula (S1) are as follows.
R ¹¹ : reactive organic group R ¹² : monovalent saturated hydrocarbon group or aryl group L ¹¹ : hydrolyzable group d: 0, 1 or 2
e: an integer from 1 to 4 d + e: 2 to 4
When there are a plurality of R ¹¹ , R ¹² and L ¹¹ , they may be the same or different.

R ¹¹ is a group having a linking group and a reactive group, or a reactive group other than a hydrolyzable group. That is, when the reactive group is classified into a hydrolyzable group and a reactive group other than the hydrolyzable group, R ¹¹ has a structure having a linking group and a hydrolyzable group, a reaction other than the linking group and the hydrolyzable group. The structure which has a reactive group, or the structure which is reactive groups other than a hydrolysable group. The linking group means a group that bonds a silicon atom to a hydrolyzable group or a reactive group other than hydrolyzable. Examples of the hydrolyzable group include an alkoxy group, a halogen atom, an acyl group, an isocyanate group (—NCO), an amino group, and the like, and an amino group and an isocyanate group are more preferable. Hereinafter, the hydrolyzable group and the reactive group other than the hydrolyzable group in R ¹¹ are also simply referred to as a reactive group.
In the present specification, the term “reactive organic group” is used in the same meaning as described for R ¹¹ .

Specific examples of the reactive group that R ¹¹ has include a vinyl group, an epoxy group, a (meth) acryloxy group, an amino group, an isocyanate group, a mercapto group, and a styryl group. In this specification, an amino group means —NHR ¹³ (R ¹³ is H or a monovalent hydrocarbon group). The monovalent hydrocarbon group represented by R ¹³ is preferably an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 10 carbon atoms. When R ¹¹ has an amino group or an isocyanate group as a reactive group, R ^{11 also} has a linking group for bonding these reactive groups to a silicon atom.

R ¹¹ preferably has 2 to 10 carbon atoms, more preferably 2 to 9 carbon atoms. A preferable number of carbon atoms in R ¹¹ is different from the reactive groups.
When the reactive group is a vinyl group, the carbon number is preferably 2 to 4, and 2 is more preferable. When the reactive group is a vinyl group and R ¹¹ has 2 carbon atoms, R ¹¹ is a vinyl group (—CH═CH ₂ ) itself.

When the reactive group is an epoxy group, the reactive group containing an epoxy group is preferably a glycidyloxy group or an epoxycyclohexyl group. When R ¹¹ has a reactive group at the end, the reactive group and the silicon atom are bonded via a linking group. As a linking group for bonding a glycidyloxy group or an epoxycyclohexyl group to a silicon atom, an alkylene group having 1 to 6 carbon atoms is preferable, and an ethylene group or a propylene group is particularly preferable.

When the reactive group is an amino group and R ¹¹ has an amino group at the terminal, the reactive group and the silicon atom are bonded via a linking group. As the linking group for bonding an amino group and a silicon atom, an alkylene group having 1 to 10 carbon atoms which may have a nitrogen atom between carbon and carbon atoms is preferable, and — (CH ₂ ) _{2 or 3} —NH— (CH ₂ ) _{2 or 3-} , ethylene or propylene are particularly preferred.

When R ¹¹ has a reactive group other than a vinyl group, an epoxy group, or an amino group, it may have a linking group that binds the reactive group and the silicon atom. An alkylene group having a number of 1 to 10 is preferable, and an ethylene group or a propylene group is particularly preferable.

L ¹¹ is a hydrolyzable group. Specific examples of L ¹¹ include an alkoxy group, a halogen atom, an acyl group, an isocyanate group (—NCO), and an amino group. As the alkoxy group, an alkoxy group having 1 to 5 carbon atoms is preferable. As the halogen atom, a chlorine atom is preferable. Among these, as L ¹¹ , an alkoxy group having 1 to 4 carbon atoms is preferable, and a methoxy group or an ethoxy group is particularly preferable.

R ¹² is a monovalent saturated hydrocarbon group or aryl group. The monovalent saturated hydrocarbon group may be a straight chain or may contain a branched or ring structure. R ¹² preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. As the aryl group, an aryl group having 6 to 10 carbon atoms is preferable, and a phenyl group is particularly preferable. R ¹² is more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

In the compound (S1), the compound in which e is 4 is a tetrafunctional compound. Specific examples of the tetrafunctional compound include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, and tetrapropoxysilane.
Compound (S1) preferably has R ¹¹ from the viewpoint of water resistance. Specific examples of the compound (S1) having R ¹¹ are as follows.

As the compound (S1) having a vinyl group as a reactive group, vinyldimethylmonomethoxysilane, vinyldimethylmonoethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N-2 -(N-vinylbenzylaminoethyl) -3-aminopropyltrimethoxysilane and the like.

As the compound (S1) having an epoxy group as a reactive group, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3 -Glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and the like.

As the compound (S1) having a (meth) acryloxy group as a reactive group, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyl Examples include triethoxysilane and 3-acryloxypropyltrimethoxysilane.

As the compound (S1) having an amino group as a reactive group, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -N ′-(2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3 -Aminopropylmethyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and the like.

Examples of the compound (S1) having an isocyanate group or a mercapto group as a reactive group include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and the like. Can be mentioned.
Specific examples of the compound (S1) having R ¹² but not R ¹¹ include trimethoxy (methyl) silane and benzyltrimethoxysilane.

As the low molecular weight silane compound for obtaining the compound (I) having a three-dimensional network structure, a tetrafunctional compound (S1) is preferable. The low molecular weight silane compound for obtaining the compound (I) having a main chain having a three-dimensional network structure is preferably formed from only the tetrafunctional compound (S1).
In addition, the tetrafunctional compound (S1) and the compound (S1) having R ¹¹ are used in a composition satisfying (i-1) and (i-2) in the resulting partially hydrolyzed (co) condensate. Is also preferable.

A commercially available product may be used as the compound (I) whose main chain has a three-dimensional network structure. Commercially available products are trade names manufactured by Colcoat Co., Ltd., Colcoat PX (compound (I), Mw: 1,000 to 100,000, hydrolyzable group content: 80% by mass or more, solid content Solution containing a concentration of 2% by mass) Colcoat N-103X (as compound (I), Mw; 20,000 to 30,000, hydrolyzable group content; 80% by mass or more, solid content concentration of 2% by mass And the like).

Examples of the compound (I) having a linear main chain include compounds represented by the following formula (S2).

In the formula (S2), L ¹¹ is a hydrolyzable group, and a specific embodiment is the same as L ¹¹ in the above formula (S1). R ¹ represents an organic substituent other than L ¹¹ , specifically, a reactive organic group (R ¹¹ ) in the above formula (S1), a monovalent organic group having no reactivity, for example, in the above formula (S1) It includes groups of R ¹² or the like. R ² is independently L ¹¹ or R ¹ . n and m are integers, and the compound (S2) is adjusted to a range that satisfies (i-1) and (i-2). m may be 0.

A commercially available product may be used as the compound (S2). Commercially available products are trade names manufactured by Shin-Etsu Chemical Co., Ltd., and include KR-517, X-41-1059A, KR-518, X-41-1818, KR-519, and the like. Table 1 shows the molecular structure, Mw and the like of these compounds. In Table 1, the organic substituents are, for example, shows a reactive group and ^{R 12} in ^{R 11} of the compound (S2).

Incidentally, the compound (I) having a branched main chain can also be used as the first silane compound without particular limitation as long as it satisfies (i-1) and (i-2).

As the compound (II), for example, a compound (S1) having a group having an unsaturated double bond such as a vinyl group, a (meth) acryloxy group, or a styryl group as a reactive group, and various radical polymerizable monomers are copolymerized. And the resulting compound. The compound is a copolymer satisfying (i-1) and (i-2). Examples of the radical polymerizable monomer to be used include (meth) acrylate, styrene, vinyl ester, vinyl chloride, ethylene, propylene and the like.

Also, a polyolefin polymer having a hydrolyzable silyl group in the side chain can be obtained by grafting the compound (S1) having a vinyl group with an aliphatic olefin polymer such as polyethylene or polypropylene in the presence of an organic peroxide. can get. Examples of compound (II) include compounds in which the graft polymer obtained by the grafting reaction satisfies (i-1) and (i-2).

The compound (II) may have an organic substituent other than the hydrolyzable silyl group in the side chain as long as (i-1) and (i-2) are satisfied. Specific examples of the organic substituent include a reactive organic group (R ¹¹ ) in the above formula (S1) and a monovalent organic group having no reactivity, for example, a group such as R ¹² in the above formula (S1). . Examples of the reactive group in the reactive organic group include the same groups as the reactive groups possessed by R ¹¹ in the compound (S1).

Commercial products may be used as such compound (II). As a commercially available product, X-12-1048 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, Mw: 1000, methoxy group content as a hydrolyzable group; 31% by mass, acryloxy group as a side chain reactive group) Content; 14 mass%).

In forming the primer layer, one type of the first silane compound may be used alone, or two or more types may be used in combination. When the first silane compound is composed of two or more silane compounds, the requirement (i-2) needs to satisfy each silane compound, but the requirement (i-1) What is necessary is just to be satisfied when the above is put together, and each silane compound is not necessarily satisfied. However, it is preferable that each silane compound satisfies the requirements (i-1) and (i-2).

Examples of the component that can be optionally contained in the primer layer include a reaction product of a hydrolyzable silane compound other than the first silane compound. When the primer layer contains an optional component, the proportion of the optional component in the entire primer layer is preferably 0 to 20% by mass, and more preferably 0 to 5% by mass.

(Anti-fouling layer)
The antifouling layer is formed using the second silane compound. The antifouling layer is configured to contain the second silane compound reactant as described above, but may contain an optional component other than the second silane compound reactant. The ratio of the reaction product of the second silane compound in the entire antifouling layer is preferably 90 to 100% by mass, and more preferably 95 to 100% by mass.

If the thickness of the antifouling layer is a monomolecular thickness of the second silane compound, the adhesion between the antifouling layer and the primer layer is excellent, and the antifouling property of the antifouling article is excellent. When the thickness of the antifouling layer is too thick, the utilization efficiency is lowered, and the transparency of the antifouling layer may be impaired. Specifically, the thickness of the antifouling layer is preferably 10 to 100 nm, and more preferably 10 to 50 nm. The thickness of the antifouling layer can be measured in the same manner as the method for measuring the thickness of the primer layer.

<Second silane compound>
The second silane compound is a compound having a perfluoropolyether group and a hydrolyzable silyl group. The perfluoropolyether group may be a monovalent group or a poly (oxyperfluoroalkylene) chain that is a divalent group. The ratio of the hydrolyzable group of the second silane compound is preferably 10% by mass or less based on the whole compound.

As the second silane compound, specifically, — (C _a F _2a O) _b — (a is an integer of 1 to 6, b is an integer of 2 or more, and — (C _a F _2a O) _b — unit may be linear or branched, and may have two or more — (C _a F _2a O) _b — groups having different carbon numbers). A silane compound having a poly (oxyperfluoroalkylene) chain having a hydrolyzable silyl group via a linking group at at least one terminal of the poly (oxyperfluoroalkylene) chain (hereinafter also referred to as silane compound (A)) Note).

Specific examples of the silane compound (A) include compounds represented by the following formula (S3).
[AO- (C _a F _2a O) _b- ] Q [-SiL _m R _3-m ] _p (S3)
However, the symbols in the formula (S3) are as follows.
A is a perfluoroalkyl group having 1 to 6 carbon atoms or -Q ¹⁰ -SiL _m R _3-m .
In (C _a F _2a O) _b , a is an integer of 1 to 6, b is an integer of 2 or more, and each —C _a F _2a O— unit may be the same or different.
Q is a (1 + p) -valent linking group.
Q ¹⁰ is a divalent linking group.
p is an integer of 1 to 10.
L is a hydrolyzable group.
R is a hydrogen atom or a monovalent hydrocarbon group.
m is an integer of 1 to 3.

A is preferably a perfluoroalkyl group having 1 to 3 carbon atoms from the viewpoint of friction resistance. The perfluoroalkyl group may be linear or branched.

Specific examples when A is a C 1-6 perfluoroalkyl group include the following.
CF _3- ,
CF ₃ CF _2- ,
CF ₃ (CF ₂ ) _2- ,
CF ₃ (CF ₂ ) _3- ,
_{CF 3 (CF 2) 4 -} ,
CF ₃ (CF ₂ ) _5- ,
CF ₃ CF (CF ₃ ) -etc.
Of these, CF ₃ — or CF ₃ CF ₂ — is preferable as A from the viewpoint of sufficiently imparting initial water and oil repellency and stain removability to the antifouling layer.

When A is -Q ¹⁰ -SiL _m R _3-m , Q ¹⁰ is a divalent linking group represented by, for example, the following formulas (2-1) to (2-6). In the formulas (2-1) to (2-6), Si is bonded to the right side.
-R ^f7 CX ₂ O (CH ₂ ) _3- (2-1),
—R ^f7 CX ₂ OCH ₂ CH (CH ₃ ) — (2-2),
—R ^f7 C (═O) NHC _k H _2k − (2-3),
-R ^f7 (CH ₂ ) _2- (2-4),
—R ^f7 (CH ₂ ) ₃ — (2-5),
-R ^f7 (2-6)
In formulas (2-1) to (2-6), R ^f7 represents a perfluoroalkylene group having 1 to 20 carbon atoms, X represents a hydrogen atom or a fluorine atom, and k represents an integer of 1 or more.

when p is 1, Q is a divalent linking ^group, which is the same as ^{Q 10.}
When p is 2 or more, Q is, for example, a hydrocarbon group, and has an ester bond, an ether bond, an amide bond, a urethane bond, a phenylene group, —S—, divalent amino group at the terminal or between carbon atoms. Group, a silalkylene structure, a silarylene structure, a siloxane structure (including a cyclic siloxane structure), and a hydrogen atom of a hydrocarbon group may be substituted with a fluorine atom. The hydrogen atom of the hydrocarbon group may be substituted with a hydroxyl group, but the number of substituted hydroxyl groups is preferably 1 to 5. The hydrocarbon group may be linear or branched. The number of carbon atoms in Q is preferably 1-20, and more preferably 1-10.

L is a hydrolyzable group. Examples of L include an alkoxy group, a halogen atom, an acyl group, and an isocyanate group (—NCO). As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable.
L is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom from the viewpoint of easy industrial production. As the halogen atom, a chlorine atom is particularly preferable. L is preferably an alkoxy group having 1 to 4 carbon atoms from the viewpoint of low outgassing during coating and excellent storage stability of the compound (S3), and when long-term storage stability of the compound (S3) is required. Is particularly preferably an ethoxy group, and a methoxy group is particularly preferred when the reaction time after coating is short.

R is a hydrogen atom or a monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, and an allyl group. R is preferably a monovalent hydrocarbon group, particularly preferably a monovalent saturated hydrocarbon group. The number of carbon atoms of the monovalent saturated hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2. R is preferably an alkyl group having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms from the viewpoint of easy synthesis.

M is an integer of 1 to 3, preferably 2 or 3, and particularly preferably 3. By the presence of a plurality of L in the molecule, the bond with the surface of the substrate becomes stronger. When m is 2 or more, the plurality of L present in one molecule may be the same as or different from each other. From the viewpoint of availability of raw materials and ease of production, it is preferable that they are the same.

Examples of the hydrolyzable silyl group (—SiL _m R _3-m ) include —Si (OCH ₃ ) ₃ , —SiCH ₃ (OCH ₃ ) ₂ , —Si (OCH ₂ CH ₃ ) ₃ , —SiCl ₃ , —Si (OCOCH ₃ ) ₃ or —Si (NCO) ₃ is preferred. From the viewpoint of easy handling in industrial production, —Si (OCH ₃ ) ₃ is particularly preferable.

In the silane compound (S3), — (C _a F _2a O) _b — represents, for example, — (R ^f1 O) _x1 (R ^f2 O) _x2 (R ^f3 O) _x3 (R ^f4 O) _x4 (R ^f5 O) ) _X5 (R ^f6 O) _x6 — (R ^f1 is a C 1 perfluoroalkylene group, R ^f2 is a C 2 perfluoroalkylene group, R ^f3 is a C ³ perfluoroalkylene group, and R ^f4 is a C ⁴ carbon atom) A perfluoroalkylene group, R ^f5 is a C ⁵ perfluoroalkylene group, R ^f6 is a C 6 perfluoroalkylene group, x 1, x 2, x 3, x 4, x 5 and x 6 are each independently an integer of 0 or more, (The total of x1, x2, x3, x4, x5, and x6 is 2 or more, and each repeating unit may exist in any of block, alternating, and random) It is shown.

As specific examples of the silane compound (S3), the following compounds are preferable because they are easy to produce industrially, are easy to handle, and can sufficiently impart initial water and oil repellency and stain removability to the antifouling layer.
A ¹ —O— (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _n —CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CH ₂ O (CH ₂ ) ₃ —SiL _m R _3-m ... (1-1Ha),
A ¹ —O— (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _n —CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O (CH ₂ ) ₃ —SiL _m R _3-m ... (1-1Fa),
A ¹ —O— (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _n —CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ C (═O) NH (CH ₂ ) ₃ —SiL _m R _{3 -m} ... (1-3a),
A ¹ —O— (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _n —CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ (CH ₂ ) ₂ —SiL _m R _3-m (1- 4a),
A ¹ —O— (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _n —CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ (CH ₂ ) ₃ —SiL _m R _3-m (1- 5a).
However, A ¹ is CF _3- , CF ₃ CF _2- , CF ₃ CF ₂ OCF ₂ CF ₂ CF ₂ CF _2- , CF ₃ OCF ₂ CF _2- , CF ₃ OCF ₂ CF ₂ OCF ₂ CF ₂ -or CF ₃ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ —. n is an integer of 2 or more. SiL _m R _3-m is the same as described above.

　式中、ｎおよびｍはそれぞれ独立に１以上の整数であり、ｎおよびｍの合計は２以上である。

In the formula, n and m are each independently an integer of 1 or more, and the sum of n and m is 2 or more.

　式中、ｎおよびｍはそれぞれ独立に１以上の整数であり、ｎおよびｍの合計は２以上である。

In the formula, n and m are each independently an integer of 1 or more, and the sum of n and m is 2 or more.

　式中ＰＦＰＥは、ＣＦ_３ＣＦ_２Ｏ（ＣＦ_２ＣＦ_２Ｏ）_ｎ（ＣＦ_２Ｏ）_ｍＣＦ_２ＣＨ_２－を示す。ただし、ｎおよびｍはそれぞれ独立に１以上の整数であり、ｎおよびｍの合計は２以上である。

In the formula, PFPE represents CF ₃ CF ₂ O (CF ₂ CF ₂ O) _n (CF ₂ O) _m CF ₂ CH ₂ —. However, n and m are each independently an integer of 1 or more, and the sum of n and m is 2 or more.

　式中、ｎおよびｍはそれぞれ独立に１以上の整数であり、ｎおよびｍの合計は２以上である。

In the formula, n and m are each independently an integer of 1 or more, and the sum of n and m is 2 or more.

　式中、ｎおよびｍはそれぞれ独立に１以上の整数であり、ｎおよびｍの合計は２以上である。

In the formula, n and m are each independently an integer of 1 or more, and the sum of n and m is 2 or more.

　式中、ｎは２以上の整数である。

In the formula, n is an integer of 2 or more.

　式中、ｎは２以上の整数、ｍは１～１０の整数、Ｍｅはメチル基である。

In the formula, n is an integer of 2 or more, m is an integer of 1 to 10, and Me is a methyl group.

Compounds (1-1Ha), (1-1Fa), (1-3a), (1-4a), (1-5a) can be produced, for example, by the method described in International Publication No. 2013/121984. it can.

In forming the antifouling layer, one type of the second silane compound may be used alone, or two or more types may be used in combination. Examples of components that can be optionally contained in the antifouling layer include hydrolyzable silane compounds other than the second silane compound, fine particles of metal oxides such as silica, alumina, zirconia, and titania, dyes, pigments, and antifouling materials. , Curing catalysts, various resins and the like. When the antifouling layer contains an optional component, the ratio of the optional component is preferably 15% by mass or less, and more preferably 10% by mass or less. The ratio of the optional component in the entire antifouling layer can be, for example, 1 to 10% by mass.

Moreover, the antifouling layer may contain impurities as an optional component. An impurity means an inevitable compound in the production of the second silane compound. Specifically, it is a by-product generated in the manufacturing process of the second silane compound and a component mixed in the manufacturing process. When the antifouling layer contains impurities, the proportion of impurities in the entire antifouling layer is preferably 5% by mass or less, and more preferably 2% by mass or less.

(Anti-fouling article)
The antifouling article of the present invention has a base material in which at least a part of the surface is made of metal, and the primer layer and the antifouling layer in that order on the surface made of the metal. The antifouling article of the present invention may have other members other than these as required. The primer layer is formed on at least a part of the surface of the substrate made of metal. The primer layer forming region only needs to include the antifouling layer forming region, and may be formed in a region wider than the antifouling layer forming region as necessary.
In the antifouling article of the present invention, a primer layer is formed on the metal surface of the substrate using the first silane compound, and the antifouling layer is formed on the primer layer using the second silane compound. Can be obtained.

[Method for producing antifouling article]
The method for producing an antifouling article of the present invention includes the following steps (I) and (II).
(I) The process of apply | coating the composition for primer layers containing the 1st silane compound and the 1st solvent to the surface which consists of a metal of a base material, and making a 1st silane compound react, and obtaining a primer layer (following) Also referred to as a primer layer forming step.)
(II) A step of depositing a composition for an antifouling layer containing a second silane compound on the primer layer and reacting the second silane compound to obtain an antifouling layer (hereinafter also referred to as an antifouling layer forming step).

Here, the first silane compound is the first silane compound that satisfies the requirements (i-1) and (i-2) described above. The second silane compound is the second silane compound having a perfluoropolyether group and a hydrolyzable silyl group described above.

According to the production method of the present invention, since the first silane compound related to the primer layer satisfies the requirements (i-1) and (i-2), the uniform primer layer has sufficient adhesion on the metal surface. Can be formed.

The manufacturing method of the present invention may have additional steps in addition to the steps (I) and (II). As an additional step, it is preferable to have a step (hereinafter referred to as (Ib) step) of activating the metal surface of the substrate on which the primer layer is formed, which is performed before the step (I). Moreover, in the manufacturing method of this invention, you may have the process (henceforth (IIa) process) which performs the post-process with respect to this antifouling layer after the (II) antifouling layer formation process. Hereinafter, each step will be described.

(Ib) Step (Ib) Step is a step of activating the metal surface. Activation treatment of a metal surface means modification to a state in which a reactive group exists on the surface. This makes it easier for the first silane compound to bind to the metal surface.
In the present invention, the activation treatment of the metal surface is usually applicable to a dry or wet treatment used for activating the metal surface without any particular limitation. As the dry process, a process of irradiating the surface with active energy rays such as ultraviolet rays, electron beams, and X-rays, a corona process, a plasma process, a flame process, an intro process, and the like can be used. Examples of the wet treatment include a treatment in which the surface is brought into contact with an acid or alkali solution. In the present invention, the activation treatment preferably used is a corona treatment or a plasma treatment, and it is preferable to combine the corona treatment or the plasma treatment with a wet alkali treatment.

The corona treatment is a treatment for generating a polar group on the metal surface to roughen the surface. As the corona treatment, a known method can be employed, and examples thereof include a method of discharging in normal pressure air using a corona treatment machine.
The plasma treatment is not particularly limited, but includes RF plasma treatment in vacuum, microwave plasma treatment, microwave ECR plasma treatment, atmospheric pressure plasma treatment, corona treatment, etc., gas treatment containing fluorine, ion Includes ion implantation using a source, treatment using PBII, flame treatment exposed to thermal plasma, and intro treatment. Among these, RF plasma treatment, microwave plasma treatment, and atmospheric pressure plasma treatment in vacuum are preferable.

Appropriate conditions for the plasma treatment include oxygen plasma, plasma containing fluorine such as CF ₄ , C ₂ F _{6 and the} like, which are known to have a high etching effect, such as Ne, Ar, Kr, and Xe. It is desirable to use a plasma treatment that has a high effect of physically etching the metal surface by applying physical energy. It is also preferable to add CO ₂ , CO, H ₂ , N ₂ , NH ₄ , CH ₄ and a mixed gas thereof, and further water vapor. In addition to these, OH, N ₂ , N, CO, CO ₂ , H, H ₂ , O ₂ , NH, NH ₂ , NH ₃ , COOH, NO, NO ₂ , He, Ne, Ar, Kr, Xe, At least selected from the group consisting of CH ₂ O, Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , C ₃ H ₇ Si (OCH ₃ ) ₃ and C ₃ H ₇ Si (OC ₂ H ₅ ) ₃ It is also preferable to add a plasma containing one or more components as a gas or as a decomposition product in the plasma.

When aiming for processing in a short time, a plasma with high plasma energy density and high kinetic energy of ions in the plasma is desirable. However, since surface smoothness is required, there is a limit to increasing the energy density. . When oxygen plasma is used, surface oxidation proceeds, a surface with poor adhesion to the substrate itself is likely to be formed, and surface roughness (roughness) increases, resulting in poor adhesion.
In addition, in the plasma using Ar gas, the influence of pure physical collision occurs on the surface, and in this case, the roughness of the surface becomes large. Considering these comprehensively, microwave plasma treatment, microwave ECR plasma treatment, plasma irradiation with an ion source that easily implants high-energy ions, a PBII method, and the like are also desirable.

The above activation treatment cleans the metal surface and further generates reactive groups on the metal surface. The generated reactive group is bonded to the first silane compound by hydrogen bonding or chemical reaction, and the metal surface of the substrate and the primer layer can be firmly bonded. In the plasma treatment, an effect of etching the metal surface can also be obtained.

The activation treatment may be performed at least on the metal surface on which the primer layer is formed. For example, in the case where a primer layer is formed on one main surface of a plate-like base material made entirely of metal, and plasma processing is performed only on the main surface, the following plasma processing is performed. Just do it.
That is, in plasma processing with parallel plate electrodes, by placing a base material on one side of the electrode so as to contact the main surface opposite to the main surface on which plasma processing is desired, the side that is not in contact with the base electrode Plasma treatment can be performed only on the main surface. In plasma processing with parallel plate electrodes, plasma processing can be performed on both main surfaces if the substrate is placed in a state where it is electrically floated in the space between the two electrodes. Moreover, single-sided processing becomes possible by performing plasma processing in the state which stuck the protective film on the single side | surface of the base material. In addition, as a protective film, a PET film with adhesive or a polyolefin film can be used.

(I) Primer layer forming step The primer layer forming step is a primer layer composition comprising a first silane compound and a first solvent on the metal surface of the substrate, preferably the metal surface after the step (Ib). Is a step of reacting the first silane compound.
The primer layer composition includes a first silane compound and a first solvent. The first silane compound is as described above.

The content of the first silane compound in the composition for the primer layer is preferably 0.1 to 3.0% by mass with respect to the total amount of the composition from the viewpoint that the primer layer is easily formed uniformly. 1 to 2.5% by mass is more preferable, and 0.1 to 2.0% by mass is particularly preferable.
The first solvent is not particularly limited as long as it can dissolve the first silane compound. As the first solvent, a solvent having high compatibility with the hydrolyzate of the first silane compound in which the hydrolyzable silyl group of the first silane compound is hydrolyzed to form a silanol group is preferable.

As described above, the primer layer is bonded to the antifouling layer formed on the primer layer by a siloxane bond at the interface. Therefore, in the primer layer formed in the primer layer forming step, a considerable amount of the silanol group contained in the hydrolyzate of the first silane compound exists stably while partially reacting between molecules. It is preferable. In this respect, the primer layer obtained in the primer layer forming step is combined with the antifouling layer in the following (II) antifouling layer forming step.

Specific examples of the first solvent include water and organic solvents. Water is used to hydrolyze the hydrolyzable silyl group of the first silane compound. The first solvent may be composed of a single compound or a mixed solvent composed of two or more compounds. From the viewpoint of compatibility, the first solvent is preferably a non-fluorinated organic solvent or a mixed solvent of a non-fluorinated organic solvent and water.

As the non-fluorine organic solvent, a compound consisting only of a hydrogen atom and a carbon atom and a compound consisting only of a hydrogen atom, a carbon atom and an oxygen atom are preferable. Examples thereof include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents, ester organic solvents, and chlorine solvents.

As the hydrocarbon organic solvent, hexane, heptane, cyclohexane, toluene and the like are preferable. As the alcohol organic solvent, methanol, ethanol, propanol, isopropanol (IPA) and the like are preferable. As the ketone organic solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone and the like are preferable. As the ether organic solvent, diethyl ether, tetrahydrofuran, tetraethylene glycol dimethyl ether and the like are preferable. As the ester organic solvent, ethyl acetate, butyl acetate and the like are preferable.

Chlorinated solvents include 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane 1,1-dichloroethylene, (Z) -1,2-dichloroethylene, (E) -1,2-dichloroethylene, trichloroethylene, tetrachloroethylene, chloroform, carbon tetrachloride, dichloromethane and the like are preferable.

Here, the water for hydrolyzing the hydrolyzable silyl group of the first silane compound can be covered by moisture in the atmosphere, but the first solvent contains water, and the water is hydrolyzed. It is preferable to be used.
The content of water in the primer layer composition is preferably 0.5 to 2.0 moles per mole of hydrolyzable group bonded to the silicon atom of the first silane compound, and 0.8 to 1. 3 moles is more preferred. In addition, the content ratio of water in the first solvent is preferably 1 to 30% by mass, and more preferably 5 to 10% by mass with respect to the total amount of the first solvent.

The content ratio of the first solvent in the primer layer composition is preferably 97.0 to 99.9% by mass, and more preferably 97.5 to 99.9% by mass. The solid content (solid content concentration) in the primer layer composition is preferably from 0.1 to 3.0 mass%, particularly preferably from 0.1 to 2.5 mass%. The solid content concentration of the primer layer composition is a value calculated from the mass of the primer layer composition before heating and the mass after heating for 4 hours in a convection dryer at 120 ° C.

As described above, the primer layer composition may contain an optional component in a proportion of 20% by mass or less, preferably 5% by mass or less, based on the entire solid content. Moreover, as other components, you may contain well-known additives, such as an acid catalyst and a basic catalyst which accelerate | stimulate the hydrolysis and condensation reaction of a hydrolysable silyl group, for example. Examples of the acid catalyst include sulfonic acids such as hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, methanesulfonic acid, and p-toluenesulfonic acid. Examples of the basic catalyst include sodium hydroxide, potassium hydroxide, ammonia and the like. The content of other components in the primer layer composition is preferably 10% by mass or less, particularly preferably 1% by mass or less, based on the total amount of the composition.

The primer layer composition is desirably applied uniformly and smoothly to the metal surface of the substrate in order to form the primer layer uniformly. After the primer layer composition is applied, the first silane compound reacts as described above to form a primer layer. That is, the first silane compound is hydrolyzed to generate a silanol group, and the silanol group and the metal surface react to form a chemical bond. Further, silanol groups are condensed to form an intermolecular bond. Furthermore, the silanol group is also subjected to a condensation reaction with the silanol group generated from the second silane compound in the (II) antifouling layer forming step.

The composition for primer layers can be manufactured by mixing the above-mentioned components. For applying the primer layer composition to the metal surface of the base material, a known method can be appropriately used.
Application methods include spin coating method, wipe coating method, spray coating method, squeegee coating method, dip coating method, die coating method, ink jet method, flow coating method, roll coating method, casting method, Langmuir-Blodgett method or gravure coating. The method is preferred. In addition, it is also possible to apply by a simple method such as hand coating or brush coating.

Application of the primer layer composition is carried out so that the amount of the first silane compound applied (attachment amount) is 50 to 1000 mg / m ² in order to obtain the above-described preferable thickness of the primer layer. preferable. The coating amount of the first silane compound, more preferably 50 ~ 500mg / ^{m 2,} particularly preferably 50 ~ 300mg / ^{m 2.}

After the primer layer composition is applied, the first silane compound is reacted. Specifically, the first silane compound is allowed to react by heating the coating composition for the primer layer. The heating temperature is preferably from 80 to 120 ° C, more preferably from 90 to 120 ° C. Prior to the reaction, if necessary, the first solvent is removed by drying, for example, heating. Heating for the reaction of the first silane compound and drying (heating) for removing the first solvent may be performed simultaneously.

(II) Antifouling layer forming step In the antifouling layer forming step, an antifouling layer is obtained by attaching a composition for an antifouling layer containing a second silane compound to the primer layer and reacting the second silane compound. . Examples of the method for attaching the antifouling layer composition on the primer layer include the following dry coating method or wet coating method.

In addition, when mix | blending a 2nd silane compound with the composition for antifouling layers, a 2nd silane compound may be mix | blended in the state as it is, and even if it mix | blends as the oligomer (partial hydrolysis-condensation product). Good. Moreover, you may mix | blend with the composition for primer layers as a mixture of a 2nd silane compound and its oligomer.
When two or more kinds of second silane compounds are used in combination, each compound may be blended as it is in the primer layer composition, each may be blended as an oligomer, You may mix | blend as a co-oligomer (partial hydrolysis cocondensate) of 2 or more types of compounds.

Also, a mixture of these compounds, oligomers (partially hydrolyzed condensates), and co-oligomers (partially hydrolyzed cocondensates) may be used. The oligomers and co-oligomers also have hydrolyzable silyl groups (including hydrolyzed silanol groups) and perfluoropolyether groups. Hereinafter, that the composition for an antifouling layer contains the second silane compound means that it contains such oligomers and co-oligomers in addition to the second silane compound itself.

(Dry coating method)
In the dry coating method, the antifouling layer composition for dry coating containing the components that form the antifouling layer, that is, the second silane compound and the components optionally contained in the antifouling layer can be used as they are. The antifouling layer composition for dry coating may be composed of only the second silane compound.

Examples of dry coating methods include vacuum deposition, CVD, and sputtering. From the viewpoint of suppressing the decomposition of the second silane compound and the simplicity of the apparatus, a vacuum deposition method can be suitably used. The vacuum deposition method can be subdivided into resistance heating method, electron beam heating method, high frequency induction heating method, reactive deposition, molecular beam epitaxy method, hot wall deposition method, ion plating method, cluster ion beam method, etc. Any method can be applied. The resistance heating method can be suitably used from the viewpoint of suppressing the decomposition of the second silane compound and the simplicity of the apparatus. The vacuum deposition apparatus is not particularly limited, and a known apparatus can be used.

The film forming conditions when using the vacuum vapor deposition method vary depending on the type of vacuum vapor deposition method to be applied, but in the case of the resistance heating method, the degree of vacuum before vapor deposition is preferably 1 × 10 ⁻² Pa or less, and preferably 1 × 10 ⁻³ Pa. The following are particularly preferred: The heating temperature of the deposition source is not particularly limited as long as the deposition source (antifouling layer composition for dry coating) has a sufficient vapor pressure. Specifically, 30 to 400 ° C is preferable, and 50 to 300 ° C is particularly preferable.

If the heating temperature is equal to or higher than the lower limit of the above range, the film formation rate is good. If it is below the upper limit of the above range, the desired water and oil repellency and dirt removability can be imparted to the metal surface of the substrate without causing the decomposition of the second silane compound. At the time of vacuum deposition, the substrate temperature is preferably in the range from room temperature (20 to 25 ° C.) to the heat resistant temperature of the substrate. When the substrate temperature is equal to or lower than the above heat resistance temperature, the film formation rate is good. The substrate temperature is more preferably the above heat resistant temperature of −50 ° C. or less.

In the present invention also in the case of the dry coating method and the wet coating method to be described later, the adhesion of the antifouling layer composition to the primer layer is carried out by using the second silane It is preferable to carry out such that the adhesion amount of the compound is 30 to 80 mg / m ² . Deposition of the second silane compound is more preferably 35 ~ 80 mg / ^{m 2,} particularly preferably 55 ~ 70mg / ^{m 2.}

In the dry coating method, the reaction of the second silane compound proceeds substantially simultaneously by adjusting the substrate temperature as described above during the film formation. At this time, part of the silanol group produced by the hydrolysis reaction from the hydrolyzable silyl group of the second silane compound undergoes a condensation reaction to bond the molecules. The silanol group generated from the second silane compound undergoes a condensation reaction with the silanol group generated from the first silane compound included in the primer layer, so that the primer layer and the antifouling layer are bonded by a siloxane bond. In addition, a firm bond is formed by the antifouling layer by performing a post-processing step which is an optional step described later.

(Wet coating method)
In the wet coating method, an antifouling layer composition for wet coating (hereinafter also referred to as a coating solution) containing a second solvent in the antifouling layer composition for dry coating is prepared.
In the wet coating method, a coating solution is applied to the surface of the primer layer, and the second silane compound is reacted to form an antifouling layer.

As a method for applying the coating liquid, a known method can be appropriately used. Specific examples of the application method include the same method as the application of the primer layer composition, including preferred embodiments. The coating liquid can be applied in the same manner as the application amount of the second silane compound, including the adhesion amount in the case of the dry coating method and a preferred embodiment.

After the coating liquid is applied, the second silane compound is reacted. Specifically, the second silane compound is allowed to react by leaving the coating liquid in the form of a coating film at a predetermined reaction temperature for a predetermined time. The reaction temperature is preferably in the range from 10 ° C. to the heat resistant temperature of the substrate, and more preferably in the range from 20 ° C. to the heat resistant temperature of the substrate. Prior to the reaction, the second solvent is removed by drying as necessary. The reaction of the second silane compound and the drying for removing the second solvent may be performed simultaneously.

The reaction of the second silane compound in the wet coating method is the same as that in the dry coating method. Similar to the dry coating method, a strong bond is formed by the antifouling layer by performing a post-treatment step which is an optional step described later.

<Coating solution>
The antifouling layer composition (coating solution) for wet coating used in the wet coating method contains a second silane compound and a second solvent. The coating liquid should just contain the 2nd silane compound as a solid component, and may contain impurities, such as a by-product produced | generated at the manufacturing process of this compound, in the said ratio. Furthermore, the said arbitrary solid component may be included in the said ratio. The coating liquid can be produced by mixing the second silane compound, the second solvent and optional components in a suitable mixing vessel.

The second solvent is preferably liquid. The coating liquid may be liquid, may be a solution, or may be a dispersion.
The content ratio of the second silane compound in the coating liquid is preferably from 0.1 to 0.5% by mass, particularly preferably from 0.1 to 0.3% by mass, based on the total amount of the coating liquid.

<Second solvent>
As the second solvent, an organic solvent is preferable. The organic solvent may be a fluorinated organic solvent, a non-fluorinated organic solvent, or may include both solvents. In addition, the second solvent may be one type of compound or a mixture of two or more types.
Examples of the fluorinated organic solvent include fluorinated alkanes, fluorinated alkenes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols, and the like.

As the fluorinated alkane, a compound having 4 to 8 carbon atoms is preferable. Examples of commercially available products include C ₆ F ₁₃ H (AC-2000: product name, manufactured by Asahi Glass Co., Ltd.), C ₆ F ₁₃ C ₂ H ₅ (AC-6000: product name, manufactured by Asahi Glass Co., Ltd.), C ₂ F ₅ CHFCHFCF ₃ (Bertrel: product name, manufactured by DuPont) and the like. In addition, 1,1,1,3,3-pentafluorobutane, 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 1,1,2,2,3, 3,4-heptafluorocyclopentane, 1,1,1,2,2,3,3,4,4-nonafluorohexane and the like can also be used.

Fluorinated alkenes include (E) -1-chloro-3,3,3-trifluoro-1-propene, (Z) -1-chloro-3,3,3-trifluoro-1-propene, 1, 1-dichloro-2,3,3,3-tetrafluoro-1-propene, (E) -1-chloro-2,3,3,3-tetrafluoro-1-propene, (Z) -1-chloro- 2,3,3,3-tetrafluoro-1-propene, (Z) -1,1,1,4,4,4-hexafluoro-2-butene, (E) -1,1,1,4, 4,4-hexafluoro-2-butene, an alkyl perfluoroalkenyl ether described by the following formula (wherein R ³ can be CH ₃ , C ₂ H ₅ or a mixture thereof, and y1 and y2 are , Independently, 0, 1, 2 or 3, y1 + y2 = 0, 1, 2, or 3 is.), And the like.

CF ₃ (CF ₂ ) _{y 1} CF═CFCF (OR ³ ) (CF ₂ ) _{y 2} CF ₃ ,
CF ₃ (CF ₂ ) _{y 1} C (OR ³ ) = CFCF ₂ (CF ₂ ) _{y 2} CF ₃ ,
CF ₃ CF═CFCF (OR ³ ) (CF ₂ ) _y1 (CF ₂ ) _y2 CF ₃ ,
^{_{CF 3 (CF 2) y1 CF}} = C (OR 3) CF 2 (CF 2) y2 CF.

Examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, ortho-bis (trifluoromethyl) benzene, meta-bis (trifluoromethyl) benzene, and para-bis (trifluoromethyl) benzene. Etc.
As the fluoroalkyl ether, a compound having 4 to 12 carbon atoms is preferable. Commercially available products include, for example, CF ₃ CH ₂ OCF ₂ CF ₂ H (AE-3000: product name, manufactured by Asahi Glass Co., Ltd.), C ₄ F ₉ OCH ₃ (Novec-7100: product name, manufactured by 3M Company), C ₄ F ₉ OC ₂ H ₅ (Novec-7200: product name, manufactured by 3M), C ₆ F ₁₃ OCH ₃ (Novec-7300: product name, manufactured by 3M), perfluoro (2-butyltetrahydrofuran), etc. .

Examples of the fluorinated alkylamine include perfluorotripropylamine, perfluorotributylamine, and perfluorotripentylamine. Examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol and the like.
The fluorinated organic solvent is preferably a fluorinated alkane, a fluorinated aromatic compound, or a fluoroalkyl ether, particularly preferably a fluoroalkyl ether, from the viewpoint of the solubility of the second silane compound.

As the non-fluorine organic solvent, a compound consisting only of a hydrogen atom and a carbon atom and a compound consisting only of a hydrogen atom, a carbon atom and an oxygen atom are preferable. Examples thereof include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents, ester organic solvents, and chlorine solvents.

As the hydrocarbon organic solvent, hexane, heptane, cyclohexane, petroleum benzine, toluene, xylene and the like are preferable.
As the alcohol organic solvent, methanol, ethanol, propanol, isopropanol and the like are preferable.

As the ketone organic solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone and the like are preferable.
As the ether organic solvent, diethyl ether, tetrahydrofuran, tetraethylene glycol dimethyl ether and the like are preferable. As the ester organic solvent, ethyl acetate, butyl acetate and the like are preferable.

Chlorinated solvents include 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane 1,1-dichloroethylene, (Z) -1,2-dichloroethylene, (E) -1,2-dichloroethylene, trichloroethylene, tetrachloroethylene, chloroform, carbon tetrachloride, dichloromethane and the like are preferable.
As the non-fluorine organic solvent, a ketone organic solvent is particularly preferable in view of the solubility of the second silane compound.

The second solvent includes a fluorinated alkane, a fluorinated aromatic compound, a fluoroalkyl ether, a compound consisting only of a hydrogen atom and a carbon atom, a hydrogen atom, a carbon atom, in order to enhance the solubility of the second silane compound. At least one organic solvent selected from the group consisting of compounds consisting only of atoms and oxygen atoms is preferred. In particular, a fluorine-based organic solvent selected from a fluorinated alkane, a fluorinated aromatic compound, and a fluoroalkyl ether is preferable.

The second solvent is a group consisting of a fluorinated alkane that is a fluorinated organic solvent, a fluorinated aromatic compound, a fluoroalkyl ether, and a compound that is composed of only a hydrogen atom, a carbon atom, and an oxygen atom that is a non-fluorinated organic solvent. It is preferable to include at least one selected organic solvent in a total of 90% by mass or more of the entire second solvent from the viewpoint of enhancing the solubility of the second silane compound.

The coating liquid preferably contains 70 to 99.999 mass%, particularly preferably 80 to 99.99 mass%, of the second solvent with respect to the total amount of the coating liquid. Specific examples of the second solvent include C ₆ F ₁₃ C ₂ H ₅ (AC-6000: product name, manufactured by Asahi Glass), CF ₃ CH ₂ OCF ₂ CF ₂ H (AE-3000: product name, Asahi Glass) _{Ltd.), C 4 F 9 OCH 3} ( Novec -7100: product name, 3M _{Co.), C 4 F 9 OC 2} H 5 ( Novec -7200: product name, 3M _{Co.), C 6 F 13 OCH 3} ( Novec-7300: product name, manufactured by 3M Corporation), which may be used alone or in combination. Examples of such a mixture include the following combinations by product name.

A combination of AC-6000 and AE-3000, a combination of AC-6000 and Novec-7100, a combination of AC-6000 and Novec-7200, a combination of AC-6000 and Novec-7300, a combination of AE-3000 and Novec-7100, Combination of AE-3000 and Novec-7200, Combination of AE-3000 and Novec-7300, Combination of AC-6000 and AE-3000 and Novec-7100, Combination of AC-6000, AE-3000 and Novec-7200, AC- Combination of 6000, AE-3000 and Novec-7300, Combination of Novec-7100 and Novec-7200, Combination of Novec-7100 and Novec-7300, Combination of Novec-7200 and Novec-730 The combination of the combination of AE-3000 and isopropanol, combinations of AC-6000 and isopropanol, combinations of AE-3000 and isopropanol, etc., any combination is possible.

When AC-6000 and AE-3000 are used in combination, the ratio of AE-3000 to the total amount of AC-6000 and AE-3000 is preferably 5 to 20% by mass.
When AC-6000, AE-3000 and Novec-7100 are used in combination, the ratio of AE-3000 to the total amount of AC-6000, AE-3000 and Novec-7100 is 0.05 to 0.15% by mass. The ratio of Novec-7100 is preferably 95 to 99.5% by mass.

When AC-6000, AE-3000, and Novec-7200 are used in combination, the ratio of AE-3000 to the total amount of AC-6000, AE-3000, and Novec-7200 is 0.05 to 0.15 mass%. The ratio of Novec-7200 is preferably 95 to 99.5% by mass.

When AC-6000, AE-3000, and Novec-7300 are used in combination, the ratio of AE-3000 to the total amount of AC-6000, AE-3000, and Novec-7300 is 0.05 to 0.15 mass%. The ratio of Novec-7300 is preferably 95 to 99.5% by mass.

When AE-3000 and isopropanol are used in combination, the ratio of AE-3000 to the total amount of AE-3000 and isopropanol is preferably 50 to 90% by mass.
When AC-6000 and isopropanol are used in combination, the ratio of AC-6000 to the total amount of AC-6000 and isopropanol is preferably 50 to 90% by mass.

The coating solution may further contain other components as necessary. Examples of the other components include known additives such as an acid catalyst and a basic catalyst that promote hydrolysis and condensation reaction of the hydrolyzable silyl group. Examples of the acid catalyst and the basic catalyst include the same compounds as those described in the primer layer composition. The content of other components in the coating solution is preferably 10% by mass or less, and particularly preferably 1% by mass or less in the coating solution.

The content of solid content (solid content concentration) in the coating liquid is preferably 0.001 to 30% by mass, and particularly preferably 0.01 to 20% by mass. The solid content concentration of the coating liquid is a value calculated from the mass of the coating liquid before heating and the mass after heating for 4 hours in a convection dryer at 120 ° C.

Step (IIa) Step (IIa) is a post-treatment step performed on the antifouling layer after the antifouling layer is formed on the primer layer surface by the dry coating method or the wet coating method.
Examples of the post-treatment include an operation for promoting the reaction between the second silane compound and the primer layer, which is performed to improve the durability of the antifouling layer against friction. Examples of the operation include heating, humidification, and light irradiation. For example, in a moisture atmosphere, the base material in which the primer layer and the antifouling layer are formed in this order on the surface of the organic material is heated to hydrolyze the hydrolyzable silyl group of the second silane compound to the silanol group. Facilitates reactions, such as condensation reaction between silanol groups on the primer layer surface and silanol groups generated from the second silane compound, and formation of siloxane bonds by condensation reaction between silanol groups generated from the second silane compound. be able to.

In addition, after the antifouling layer is formed, compounds in the antifouling layer that are not chemically bonded to other compounds or the primer layer may be removed as necessary. Specific methods include, for example, a method of pouring a solvent such as a second solvent over the antifouling layer, and a method of wiping with a cloth soaked with a solvent such as the second solvent.

In the examples, a primer layer composition and an antifouling layer composition for wet coating were prepared, and using the obtained composition, a primer layer and an antifouling layer were formed on the main surface of a plate-shaped metal substrate. Were formed and evaluated in that order. Examples 1 to 3, 9, 10, 12, 14, 15, and 17 are examples, and examples 4 to 8, 11, 13, 16, and 18 are comparative examples.

<Base material>
As a base material, metal substrates shown in Table 2 were prepared, and after cleaning by the method shown in Table 2 using an alkaline aqueous solution shown in Table 2, test metal substrates 1 to 5 that were further washed with ion-exchanged water were prepared. . The metal substrate used for the test metal substrate 5 is a substrate obtained by treating the surface of a metal substrate (iron material, manufactured by SPCC) with nickel / chrome plating (thickness: 30 μm).

<First Silane Compound and Comparative Example Silane Compound>
As the first silane compound, Colcoat N-103X, Colcoat PX, and KR-517 were prepared.

The following compounds were prepared as silane compounds for comparative examples.
KR-516 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, compound having a main chain formed of a linear siloxane bond, methoxy group as a hydrolyzable group bonded to the main chain silicon atom, epoxy group as an organic substituent, methyl Silane compound having a group, Mw: 1000, content of methoxy group as hydrolyzable group; 17% by mass, content of epoxy group as organic substituent; 15% by mass)
X-12-981S (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, silane compound having a main chain mainly composed of carbon-carbon bonds and having a triethoxysilyl group and an epoxy group in the side chain, Mw; 1000, hydrolyzable Ethoxy group content as a group; 15% by mass, epoxy group content as a side chain reactive group; 15% by mass)
KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, 3-glycidoxypropyltrimethoxysilane, formula weight: 236.3)
TEOS (tetraethoxysilane, formula weight; 208.3)

<Second silane compound>
The following compound was produced by the method described in International Publication No. 2013/121984 and used as the second silane compound.
CF ₃ —O— (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _n —CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ C (═O) NH (CH ₂ ) ₃ —Si (OCH _{3 3} (n = 14)

(Preparation of primer layer composition)
About each of the said 1st silane compound and the silane compound for comparative examples, the composition for primer layers which shows a content component and each content in Table 3 using isopropanol (IPA) as a dilution solvent as needed. 1-7 were prepared. The primer layer compositions 1 and 2 were used as they were on the commercial product (concentration of silane compound; 2.0% by mass).

(Preparation of antifouling layer composition)
The second silane compound is mixed with AC-6000 (product name, manufactured by Asahi Glass Co., Ltd.), and the content of the second silane compound is 0.1% by mass with respect to the total amount of the composition. A layer composition was prepared.

[Examples 1 to 8]
(Activation treatment of test metal substrate)
By performing the corona treatment, the contamination layer on the main surface of the test metal substrate 1 was removed, and wettability was imparted to the substrate surface. The corona treatment is performed in a state where the electrodes are electrically floated so that the distance between the electrodes and the main surface of the metal substrate is 1 to 2 mm, respectively, under corona discharge with a discharge amount of 80 W · min / m ^2. This was performed by passing the metal substrate 1 for use.

(Primer layer formation process)
The primer layer compositions 1 to 7 prepared above were applied to one main surface of the test metal substrate 1 after the corona treatment by a spin coating method (application conditions: 1000 rpm / 30 sec, the first silane compound Adhesion amount: 55 mg / m ² ), heating for 10 minutes on a 120 ° C. hot plate, drying and removing the solvent, and reacting with the first silane compound, a 5 nm thick primer layer was formed.

(Anti-fouling layer forming process)
On the primer layer of the test metal substrate 1 on which the primer layer was formed, the antifouling layer composition prepared above was applied by a spray method (attachment amount of the second silane compound; 64 mg / m ² ), 120 Antifouling article of Examples 1-7 by heating for 10 minutes in a hot air circulating oven at 0 ° C., drying and removing AC-6000 and reacting with the second silane compound to form a 15 nm thick antifouling layer. Got. In Example 8, an antifouling article was formed by forming an antifouling layer having a thickness of 15 nm on one main surface of the test metal substrate 1 after the corona treatment without forming a primer layer. It was.

[Examples 9 to 11]
The antifouling articles of Examples 9 and 10 were obtained in the same manner except that the test metal substrate 1 was replaced with the test metal substrate 2 in Examples 1 and 2. Further, the test metal substrate 2 was subjected to corona treatment in the same manner as in Example 9, and without forming a primer layer, the test metal substrate 2 having a thickness of 15 nm was formed on one main surface of the test metal substrate 2 after the corona treatment in the same manner as described above. An antifouling layer was formed to obtain the antifouling article of Example 11.

[Examples 12 and 13]
An antifouling article of Example 12 was obtained in the same manner except that the test metal substrate 1 was replaced with the test metal substrate 3 in Example 2. Further, the test metal substrate 3 was subjected to corona treatment in the same manner as in Example 12, and a primer layer was not formed. On the one main surface of the test metal substrate 3 after the corona treatment, a thickness of 15 nm was formed in the same manner as described above. An antifouling layer was formed to obtain the antifouling article of Example 13.

[Examples 14 to 16]
The antifouling articles of Examples 14 and 15 were obtained in the same manner except that the test metal substrate 1 was replaced with the test metal substrate 4 in Examples 1 and 2. Further, the test metal substrate 4 was subjected to corona treatment in the same manner as in Example 14, and without forming a primer layer, the test metal substrate 4 having a thickness of 15 nm was formed on one main surface of the test metal substrate 4 after the corona treatment in the same manner as described above. An antifouling layer was formed to obtain the antifouling article of Example 16.

[Examples 17 and 18]
An antifouling article of Example 17 was obtained in the same manner except that the test metal substrate 1 was replaced with the test metal substrate 5 in Example 2. Further, the test metal substrate 5 was subjected to corona treatment in the same manner as in Example 17, and without forming a primer layer, the test metal substrate 5 having a thickness of 15 nm was formed on one main surface of the test metal substrate 5 after the corona treatment in the same manner as described above. An antifouling layer was formed to obtain the antifouling article of Example 18.

(Evaluation)
<Measurement method of water contact angle>
Using the contact angle measuring device DM-500 (manufactured by Kyowa Interface Science Co., Ltd.), the contact angle of about 2 μL of distilled water placed on the surface of the antifouling layer for the antifouling articles of Examples 1 to 18 obtained above. Measured. Measurement was performed at five different locations on the surface of the antifouling layer, and the average value was calculated. The 2θ method was used to calculate the contact angle. If a water contact angle is 100 degrees or more, it can be said that it has antifouling property sufficient for actual use.

(Abrasion resistance evaluation)
In accordance with JIS L 0849: 2013 (ISO 105-X12: 2001), a reciprocating flat surface wear tester (PA-300A manufactured by Daiei Seiki Co., Ltd.) was used, a gold width (No. 30) was loaded: 1 kg / cm ² , speed: 60 rpm The sample was worn back and forth with an amplitude of 40 mm, and the water contact angle was measured every predetermined number of times. The test was terminated when the water contact angle became 100 ° or less.

The results are shown in Table 4 for Examples 1 to 8, and Table 5 for Examples 9 to 18. In Examples 4 and 5 using the primer layer compositions 4 and 5, respectively, when the antifouling layer composition was applied on the primer layer, the antifouling layer composition was repelled and the antifouling layer was formed. I could not. In Tables 4 and 5, “−” indicates that the water contact angle was not measured, and the hatched line indicates that the wear resistance test was not performed.

The antifouling article of the present invention can be used in a wide range of fields such as housings for smartphones, household appliances, flushing fittings such as faucets and pipes, and elevator walls.
Note that the entire content of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2018-1212799 filed on June 13, 2018 is cited herein as the disclosure of the specification of the present invention. Incorporate.

Claims (15)

A base material having at least a part of a surface made of metal;
An antifouling article having a primer layer provided on the surface and an antifouling layer provided on the primer layer,
The primer layer is a silane compound having a hydrolyzable silyl group in which a hydrolyzable group is bonded to a silicon atom, containing no fluorine atom, and having a weight average molecular weight of 500 to 200,000, A layer formed using a first silane compound containing a group at a ratio of 30% by mass or more with respect to the entire silane compound;
The antifouling layer is a layer formed by using a second silane compound having a perfluoropolyether group and a hydrolyzable silyl group. The antifouling article according to claim 1, wherein the first silane compound is a silane compound having a main chain formed of a siloxane bond. The second silane compound is — (C _a F _2a O) _b — (a is an integer of 1 to 6, b is an integer of 2 or more, and — (C _a F _2a O) _b — The unit may be linear or branched, and may be a poly (oxy) represented by — (C _a F _2a O) _b — units having two or more different carbon numbers). The antifouling property according to claim 1 or 2, which is a silane compound having a perfluoroalkylene) chain and having a hydrolyzable silyl group via a linking group at at least one terminal of the poly (oxyperfluoroalkylene) chain. Goods. The antifouling article according to claim 3, wherein the second silane compound is represented by the following formula (S3).
[AO- (C _a F _2a O) _b- ] Q [-SiL _m R _3-m ] _p (S3)
Symbols in the formula (S3) are as follows.
A is a perfluoroalkyl group having 1 to 6 carbon atoms or -Q ¹⁰ -SiL _m R _3-m .
In (C _a F _2a O) _b , a is an integer of 1 to 6, b is an integer of 2 or more, and the — (C _a F _2a O) _b — unit is linear or branched. It may be a chain and may have two or more — (C _a F _2a O) _b — units having different carbon numbers.
Q is a (1 + p) -valent linking group.
Q ¹⁰ is a divalent linking group.
p is an integer of 1 to 10.
L is a hydrolyzable group.
R is a hydrogen atom or a monovalent hydrocarbon group.
m is an integer of 1 to 3. The antifouling article according to any one of claims 1 to 4, wherein the primer layer has a thickness of 3 to 200 nm. The antifouling article according to any one of claims 1 to 5, wherein the antifouling layer has a thickness of 10 to 100 nm. A method for producing an antifouling article comprising a substrate comprising at least a part of a surface of a metal, a primer layer provided on the surface, and an antifouling layer provided on the primer layer,
A silane compound having a hydrolyzable silyl group in which a hydrolyzable group is bonded to a silicon atom on the surface, no fluorine atom, and a weight average molecular weight of 500 to 200,000, wherein the hydrolyzable group A primer layer composition containing a first silane compound containing 30% by mass or more of the silane compound and a first solvent is applied, and the first silane compound is allowed to react with the primer. Obtaining a layer, and depositing a composition for an antifouling layer comprising a second silane compound having a perfluoropolyether group and a hydrolyzable silyl group on the primer layer, and reacting the second silane compound. A method for producing an antifouling article, comprising: obtaining an antifouling layer. The manufacturing method according to claim 7, wherein the first silane compound is a silane compound having a main chain formed of a siloxane bond. The manufacturing method according to claim 7 or 8, wherein the first solvent includes a non-fluorine organic solvent, or a non-fluorine organic solvent and water. The production method according to any one of claims 7 to 9, wherein the primer layer composition is applied so that the adhesion amount of the first silane compound is 50 to 1000 mg / m ² . The primer layer composition according to any one of claims 7 to 10, wherein the primer layer composition contains the first silane compound in a proportion of 0.1 to 3.0% by mass with respect to the total amount of the composition. Production method. The second silane compound is — (C _a F _2a O) _b — (a is an integer of 1 to 6, b is an integer of 2 or more, and — (C _a F _2a O) _b — The unit may be linear or branched, and may be a poly (oxy) represented by — (C _a F _2a O) _b — units having two or more different carbon numbers). The silane compound according to any one of claims 7 to 11, which is a silane compound having a perfluoroalkylene) chain and having a hydrolyzable silyl group via a linking group at at least one end of the poly (oxyperfluoroalkylene) chain. The manufacturing method as described. The production method according to any one of claims 7 to 12, wherein the antifouling layer composition is adhered such that the adhesion amount of the second silane compound is 30 to 80 mg / m ² . The production method according to any one of claims 7 to 13, wherein the antifouling layer composition further contains a second solvent, and the method of adhering to the primer layer is coating. The production method according to claim 14, wherein the second silane compound is contained at a ratio of 0.1 to 0.5 mass% with respect to the total amount of the antifouling layer composition.