JPWO2019240093A1 - Antifouling article and its manufacturing method - Google Patents

Abstract

Provided is an antifouling article having excellent antifouling property and durability such as abrasion resistance for the antifouling property. An antifouling article having a base material whose surface is at least partially made of metal, a primer layer provided on the surface, and an antifouling layer provided on the primer layer, and the primer layer is hydrolyzable. A layer formed by using a first silane compound containing a silyl group in a proportion of 30% by mass or more, containing no fluorine atom, and having a weight average molecular weight of 500 to 200,000. The antifouling layer is a layer. , An antifouling article, characterized in that it is a layer formed by using a second silane compound having a perfluoropolyether group and a hydrolyzable silyl group.

Description

The present invention relates to an antifouling article having excellent antifouling property and durability such as abrasion resistance for the antifouling property, and a method for producing the same.

By having a coating with low surface tension on the surface of the base material in order to impart water and oil repellency to the surface of various base materials, the property of suppressing the adhesion of dirt and facilitating the removal of the attached dirt. That is, an antifouling article having improved antifouling property is known.

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

Here, in an antifouling article in which an antifouling coating (antifouling layer) is provided on the surface of a base material using a fluorine-containing compound, particularly when at least a part of the surface of the base material is made of metal, the antifouling property is applied. Repeated cleaning and rubbing of the layer surface may reduce the antifouling property. In order to solve this, in Patent Document 1, the metal surface is treated with a primer composition containing a second or third amino functional compound having at least two independently selected silane groups to treat the metal surface. A method of forming an undercoat layer on the surface and forming an antifouling layer on the undercoat layer by using a fluorine-containing compound has been proposed.

Japan Special Table 2017-515650

However, in the method of Patent Document 1, it cannot be said that the antifouling layer formed on the metal surface always has sufficient durability such as wear resistance.

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

The present invention has the following aspects.
[1] An antifouling article having a base material whose surface is at least partially 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, does not contain a fluorine atom, and has a weight average molecular weight of 500 to 200,000, and is hydrolyzable. A layer formed by using the first silane compound containing a group in a proportion of 30% by mass or more with respect to the entire silane compound.
The antifouling article is characterized in that 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 in which the main chain is formed by 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). ) The _b -unit may be a straight chain or a branched chain, and is represented by two or more kinds _{of- (Ca} F 2a O) _b -units having different carbon atoms). To [1] or [2], which is a silane compound having a poly (oxyperfluoroalkylene) chain and having a hydrolyzable silyl group at at least one end of the poly (oxyperfluoroalkylene) chain via a linking group. The listed antifouling article.
[4] The second silane compound is the antifouling article according to [3] represented by the following formula (S3).
[A-O- (C _a F _2a O) _b- ] Q [-SiL _m R _3-m ] _p (S3)
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}} .
(C _a F _2a O) In _b , a is an integer of 1 to 6, b is an integer of 2 or more, and-(C _a F _2a O) _b- is branched even if the unit is linear. It may be a chain and may have two or more kinds of − (C _a F _2a O) _b − units having different carbon numbers.
Q is a (1 + p) valence linking group.
Q ¹⁰ is a divalent linking group.
p is an integer of 1-10.
L is a hydrolyzable group.
R is a hydrogen atom or a monovalent hydrocarbon group.
m is an integer of 1-3.
[5] The antifouling article according to any one of [1] to [4], wherein the thickness of the primer layer is 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 base material whose surface is at least partially made of metal, a primer layer provided on the surface, and an antifouling layer provided on the primer layer.
The surface of the silane compound has a hydrolyzable silyl group in which a hydrolyzable group is bonded to a silicon atom, does not contain a fluorine atom, and has a weight average molecular weight of 500 to 200,000, and is the hydrolyzable group. A composition for a primer layer containing a first silane compound containing 30% by mass or more with respect to the entire silane compound and a first solvent is applied, and the first silane compound is reacted to cause a primer. A layer is obtained, and a composition for an antifouling layer containing a second silane compound having a perfluoropolyether group and a hydrolyzable silyl group is attached onto the primer layer, and the second silane compound is reacted. A method for producing an antifouling article, which comprises obtaining an antifouling layer.
[8] The production method according to [7], wherein the first silane compound is a silane compound in which the main chain is formed by a siloxane bond.
[9] The production method according to [7] or [8], wherein the first solvent contains a non-fluorine-based organic solvent or a non-fluorine-based organic solvent and water.
[10] The production method according to any one of [7] to [9], wherein the composition for a primer layer is applied so that the amount of the first silane compound adhered 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 based on the total amount of the composition. The manufacturing method 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). ) The _b -unit may be a straight chain or a branched chain, and is represented by two or more kinds _{of- (Ca} F 2a O) _b -units having different carbon atoms). [7] to [11], which are silane compounds having a poly (oxyperfluoroalkylene) chain and having a hydrolyzable silyl group at at least one end of the poly (oxyperfluoroalkylene) chain via a linking group. The manufacturing method according to any one.
[13] The production method according to any one of [7] to [12], wherein the antifouling layer composition is adhered so that the amount of the second silane compound adhered is 30 to 80 mg / m ^2.
[14] The production method according to any one of [7] to [13], wherein the antifouling layer composition further contains a second solvent, and the method of adhering to the primer layer is coating.
[15] The production method according to [14], wherein the second silane compound is contained in a proportion 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 by using a fluorine-containing compound on a metal surface, the antifouling property is excellent, and the antifouling property is wear resistance and the like. Has 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 resistance. It is possible to manufacture antifouling articles having excellent durability such as.

The meanings and description methods of the terms in the present specification are as follows.
The compound or group represented by the formula is also referred to as the compound or group numbered by the formula. For example, "compound represented by formula (1)" is also referred to as "compound (1)".
"~" Representing a numerical range includes a lower limit value and an upper limit value. When the unit of the lower limit value and the upper limit value is the same, the unit of the lower limit value may be omitted.

The notation "(meth) acryloxy" is used as a general term for acryloxy and methacryloxy.

[Anti-fouling article]
The antifouling article of the present invention has an antifouling article having a base material whose surface is at least partially made of metal, a primer layer provided on the surface made of the metal, and an antifouling layer provided on the primer layer. Is. The primer layer is formed on at least a part of the surface made of metal, 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, does not contain a fluorine atom, and has a weight average molecular weight of 500 to 100,000, and is hydrolyzable. It is a layer formed by using the first silane compound containing a group in a proportion of 30% by mass or more with respect to the whole compound.

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

The antifouling layer is a layer formed by using a second silane compound having a perfluoropolyether group and a hydrolyzable silyl group.
The hydrolyzable silyl group contained in 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 hydrolyzing reaction. It is a group that can be formed. A hydrolyzable group is a group that is decomposed by water.

In the antifouling article of the present invention, a silanol group (Si-OH) is formed by hydrolyzing the hydrolyzable silyl group of the first silane compound when forming the primer layer. This silanol group reacts with the 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 the 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, or the like is preferable, and a hydroxyl group is particularly preferable.

In the present invention, the first silane compound has the above-mentioned predetermined Mw and has a hydrolyzable group that binds to the above-mentioned predetermined amount of silicon atoms, so that the metal surface of the base material and the primer layer, the inside of the primer layer, and the primer It is considered that the above bonds are formed in a well-balanced and sufficient amount between the layer and the antifouling layer. As a result, it is considered that the metal surface of the base material and the primer layer, and the primer layer and the antifouling layer are firmly bonded.

The antifouling layer is bonded to the primer layer by a Si—O—Si bond as described above, and the silanol group formed from the hydrolyzable silyl group of the second silane compound is a molecule in the antifouling layer. It reacts between them to form a Si—O—Si bond. On the other hand, the perfluoropolyether group contained in the second silane compound does not participate in the above reaction and exists on the surface layer of the antifouling layer, so that excellent antifouling property is exhibited.

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

Hereinafter, the constituent members of the antifouling article of the present invention will be described.
(Base material)
There is no particular limitation as long as the base material has at least a part of the surface made of metal. The entire surface of the base material may be made of metal, or a part of the base material may be made of metal. Further, the entire surface may be made of the same metal, or may be made of different metals.

The base material may be, for example, composed entirely of a single metal, or may be a laminated body in which a plurality of layers made of metal (hereinafter, also referred to as metal layers) are laminated. Further, it is a laminate of a metal layer, 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). , A laminated body in which one layer of the surface layer is a metal layer may be used. Alternatively, the surface of the base material may have a region made of a metal and a region made of an inorganic material other than the metal and / or an organic material in the same plane. It may be a base material in which at least a part of the surface of the metal layer or the organic material layer is metal-plated.

The shape of the base material is not particularly limited, and examples thereof include a plate shape, a film (thin film) shape, a rod shape, and a tubular shape. When the base material has a plate shape, it may be a flat plate, or may have a shape in which a part or all of the main surface has a curvature. 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 base material include metals and alloys that are solid at room temperature without 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, cupronickel, tan copper, red copper, western silver, duralumin, and solder. Further, examples of the metal surface include surfaces such as nickel-chrome plating, nickel plating, chrome plating, and zinc plating.

(Primer layer)
The primer layer is formed using the first silane compound. The primer layer is configured to contain the reactant of the first silane compound as described above, but may contain any component other than the reactant of the first silane compound. The ratio of the reaction product of the first silane compound to the entire primer layer is preferably 80 to 100% by mass, preferably 95 to 100% by mass, from the viewpoint of further excellent adhesion between the antifouling layer, the primer layer, and the primer layer and the surface of the substrate. More preferably by mass.

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

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

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

If the content of the hydrolyzable group in the first silane compound is less than 30% by mass, the bond between the formed primer layer and the metal surface is not sufficient, and the desired antifouling article can be obtained with the desired durability. I can't. The content of the hydrolyzable group is 30% by mass or more, preferably 50% by mass or more, and more preferably 80% by mass or more.
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, more preferably 90% by mass or less.

As the first silane compound, specifically, a compound having a main chain formed by a siloxane bond and satisfying (i-1) and (i-2) (hereinafter, also referred to as compound (I)). ), A compound having a main chain formed mainly of a carbon-carbon bond and satisfying (i-1) and (i-2) (hereinafter, also referred to as a compound (II)) can be mentioned. ..

In the case of compound (I), the hydrolyzable silyl group has a structure in which a hydrolyzable group is bonded to a 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 the adhesion to the 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) in which the main chain has a three-dimensional network structure include a compound obtained by partially hydrolyzing (co) condensing a low molecular weight silane compound containing a trifunctional or higher hydrolyzable group silyl group.
Examples of the low molecular weight silane compound for obtaining the compound (I) in which the 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) in which the main chain has a three-dimensional network structure, the compound (S1) having a trifunctional or higher hydrolyzable silyl group is indispensable, and monofunctional or bifunctional hydrolysis is required as necessary. Partial hydrolysis condensation is carried out using the sex silane compound (S1) so as to satisfy (i-1) and (i-2). The monofunctional, bifunctional, and trifunctional are all the number of hydrolyzable groups 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-d-e ... (S1)
However, the symbols in the equation (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: Integer from 1 to 4 d + e: 2 to 4
When a ^{plurality of R 11} , R ¹² , and L ¹¹ exist, they may be the same or different from each other.

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 configuration having a linking group and a hydrolyzable group, and a reaction other than the linking group and the hydrolyzable group. It is either a structure having a sex group or a structure which is a reactive group other than a hydrolyzable group. The linking group means a group that binds a silicon atom to a hydrolyzable group or a non-hydrolyzable reactive group. The hydrolyzable group is, for example, 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 also referred to simply as reactive group together a reactive group other than the hydrolyzable group and a hydrolyzable group in R ^11.
As used herein, the term "reactive organic group" is used in the same meaning as described in R ^11.

Specific examples of the reactive group of R ¹¹ 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 addition, in this specification, an amino group means -NHR ¹³ (R ¹³ is an H or monovalent hydrocarbon group). As the ^{monovalent hydrocarbon group indicated by R 13} , an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 10 carbon atoms is preferable. When R ¹¹ has an amino group and an isocyanate group as reactive groups, R ^{11 also} has a linking group that binds these reactive groups to a silicon atom.

The carbon number of R ¹¹ is preferably 2 to 10, and more preferably 2 to 9. The preferable carbon number of R ¹¹ depends on the reactive group.
When the reactive group is a vinyl group, the number of carbon atoms 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 the vinyl group (-CH = CH ₂ ) itself.

When the reactive group is an epoxy group, a glycidyloxy group and an epoxycyclohexyl group are preferable as the reactive group containing the epoxy 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 silicon atom to a glycidyloxy group or an epoxycyclohexyl group, 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 end, the reactive group and the silicon atom are bonded via a linking group. As the linking group for bonding the amino group and the silicon atom, an alkylene group having 1 to 10 carbon atoms, which may have a nitrogen atom between carbon atoms, is preferable, and − (CH ₂ ) _{2 or 3} −NH- (CH). ₂ ) _{2 or 3-} , ethylene group or propylene group is particularly preferable.

When R ¹¹ has a reactive group other than a vinyl group, an epoxy group, and an amino group, it may have a linking group that bonds the reactive group and a silicon atom, and if it has a linking group, carbon. 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, L ^11, preferably an alkoxy group having 1 to 4 carbon atoms, a methoxy group or an ethoxy group is particularly preferred.

R ¹² is a monovalent saturated hydrocarbon group or aryl group. The monovalent saturated hydrocarbon group may be linear or may contain a branched or ring structure. The carbon number of R ¹² is preferably 1 to 6, and more preferably 1 to 4. 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 a methyl group is particularly preferable.

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.
The compound (S1) ^{preferably has R 11} from the viewpoint of water resistance. Specific examples of the compound (S1) having R ^{11 are as follows.}

Examples of the compound (S1) having a vinyl group as a reactive group include vinyldimethylmonomethoxysilane, vinyldimethylmonoethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and N-2. -(N-Vinylbenzylaminoethyl) -3-aminopropyltrimethoxysilane and the like can be mentioned.

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

As the compound (S1) having a (meth) acryloxy group as a reactive group, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyl Examples thereof 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 can be mentioned.

Examples of the compound (S1) having an isocyanate group or a mercapto group as a reactive group include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and the like. Can be mentioned.
Specific examples of the compound (S1) having R ¹² without R ¹¹ include trimethoxy (methyl) silane and benzyl trimethoxysilane.

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) whose main chain has a three-dimensional network structure is preferably formed only from the tetrafunctional compound (S1).
Further, the tetrafunctional compound (S1) and the compound (S1) ^{having R 11} are used in the obtained partially hydrolyzed (co) condensate in a composition satisfying (i-1) and (i-2). Is also preferable.

A commercially available product may be used as the compound (I) in which the main chain has a three-dimensional network structure. As commercially available products, all of them are trade names manufactured by Corcote Co., Ltd., and the solid content of Corcote PX (Mw; 1,000 to 100,000 as compound (I), content of hydrolyzable group; 80% by mass or more). (Solution contained at a concentration of 2% by mass) Corcote N-103X (as compound (I), Mw; 20,000 to 30,000, content of hydrolyzable group; 80% by mass or more, solid content concentration of 2% by mass. The solution contained in (1) and the like.

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

In the formula (S2), L ¹¹ is a hydrolyzable group, and a specific embodiment is the same as that ^{of L 11 in the above formula (S1).} R ¹ represents ^{an organic substituent other than L 11} , and specifically, a reactive organic group (R ¹¹ ) in the above formula (S1), a non-reactive monovalent organic group, 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 compound (S2) is adjusted to a satisfactory range of (i-1) and (i-2). m may be 0.

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

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 radically polymerizable monomers are copolymerized with each other. The compound obtained by the above can be mentioned. The compound is a copolymer satisfying (i-1) and (i-2). Examples of the radically polymerizable monomer used include (meth) acrylate, styrene, vinyl ester, vinyl chloride, ethylene and propylene.

Further, 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, a polyolefin-based polymer having a hydrolyzable silyl group in the side chain can be obtained. can get. Examples of the compound (II) include compounds in which the graft polymer obtained by the above-mentioned 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 it satisfies (i-1) and (i-2). Specific examples of the organic substituent include a reactive organic group (R ¹¹ ) in the above formula (S1) and a non-reactive monovalent organic group, for example, a group such as ^{R 12} in the above formula (S1). .. Examples of the reactive group in the reactive organic group include a group similar to the reactive group ^{of R 11 in the compound (S1).}

As such compound (II), a commercially available product may be used. Commercially available products include X-12-1048 (manufactured by Shinetsu Chemical Industry Co., Ltd., trade name, Mw; 1000, content of methoxy group as hydrolyzable group; 31% by mass, acryloxy group as side chain reactive group. Content; 14% by mass) and the like.

For the formation of the primer layer, one kind of the first silane compound may be used alone, or two or more kinds may be used in combination. Further, when the first silane compound is composed of two or more kinds of silane compounds, the requirement of (i-2) needs to be satisfied by each silane compound, but the requirement of (i-1) is two kinds. It suffices to be satisfied when the above are combined, and it is not always necessary that each silane compound is satisfied. However, it is preferable that each silane compound satisfies the requirements of (i-1) and (i-2).

Examples of the component that can be arbitrarily 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 arbitrary component, the ratio of the optional component to the entire primer layer is preferably 0 to 20% by mass, 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 a reactant of the second silane compound as described above, but may contain an arbitrary component other than the reactant of the second silane compound. The ratio of the reaction product of the second silane compound to the entire antifouling layer is preferably 90 to 100% by mass, more preferably 95 to 100% by mass.

If the thickness of the antifouling layer is a single molecule thickness of the second silane compound, the adhesion between the antifouling layer and the primer layer is excellent, and the antifouling durability of the antifouling article is excellent. If the antifouling layer is too thick, the utilization efficiency may be lowered and the transparency of the antifouling layer may be impaired. Specifically, the thickness of the antifouling layer is preferably 10 to 100 nm, 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 which is a divalent group. The proportion of the hydrolyzable group of the second silane compound is preferably 10% by mass or less based on the total amount of the compound.

Specifically, as the second silane compound, − (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) The _b − unit may be a straight chain or a branched chain, and may have two or more kinds of − (C _a F _2a O) _b − groups having different carbon atoms). A silane compound having a poly (oxyperfluoroalkylene) chain and a hydrolyzable silyl group at at least one end of the poly (oxyperfluoroalkylene) chain via a linking group (hereinafter, also referred to as silane compound (A)). (Note) can be mentioned.

Specific examples of the silane compound (A) include compounds represented by the following formula (S3).
[A-O- (C _a F _2a O) _b- ] Q [-SiL _m R _3-m ] _p (S3)
However, the symbols in the equation (S3) are as follows.
A is a perfluoroalkyl group having 1 to 6 carbon atoms or ^{_{-Q 10 -SiL m R 3-m}} .
(C _a F _2a O) In _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) valence linking group.
Q ¹⁰ is a divalent linking group.
p is an integer of 1-10.
L is a hydrolyzable group.
R is a hydrogen atom or a monovalent hydrocarbon group.
m is an integer of 1-3.

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

Specific examples of the case where A is a perfluoroalkyl group having 1 to 6 carbon atoms 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.
_{Among them, CF 3} − or CF ₃ CF ₂ − is preferable as A from the viewpoint of sufficiently imparting the initial water / oil repellency and stain removing property to the antifouling layer.

When A is −Q ¹⁰ −SiL _m R _3-m , Q ¹⁰ is, for example, a divalent linking group represented by 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)
However, in the 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 between the terminal or carbon atom-carbon atom, an ester bond, an ether bond, an amide bond, a urethane bond, a phenylene group, -S-, and a divalent amino. It may have a group, a silalkylene structure, a silarylene structure, a siloxane structure (including a cyclic siloxane structure), and the hydrogen atom of the 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 hydroxyl groups to be substituted is preferably 1 to 5. The hydrocarbon group may be linear or branched. The number of carbon atoms in Q is preferably 1 to 20, more preferably 1 to 10.

L is a hydrolyzable group. Examples of L include an alkoxy group, a halogen atom, an acyl group, an isocyanate group (-NCO) and the like. As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable.
As L, an alkoxy group or a halogen atom having 1 to 4 carbon atoms is preferable from the viewpoint of easy industrial production. As the halogen atom, a chlorine atom is particularly preferable. As L, an alkoxy group having 1 to 4 carbon atoms is preferable because there is little outgassing during coating and the compound (S3) is excellent in storage stability, and when long-term storage stability of the compound (S3) is required. The ethoxy group is particularly preferable, and the methoxy group is particularly preferable 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, an allyl group and the like. As R, a monovalent hydrocarbon group is preferable, and a monovalent saturated hydrocarbon group is particularly preferable. The monovalent saturated hydrocarbon group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms. R is an alkyl group having preferably 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. The presence of a plurality of L in the molecule strengthens the bond with the surface of the base material. When m is 2 or more, a plurality of Ls existing in one molecule may be the same as each other or may be different from each other. From the viewpoint of availability of raw materials and ease of production, they are preferably the same.

Hydrolyzable silyl groups (-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 preferable. _{-Si (OCH 3} ) ₃ is particularly preferable from the viewpoint of ease of handling in industrial manufacturing.

In the silane compound (S3),-(C _a F _2a O) _b -is, 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 perfluoroalkylene group having 1 carbon number, R ^f2 is a perfluoroalkylene group having 2 carbon atoms, R ^f3 is a perfluoroalkylene group having 3 carbon atoms, and R ^f4 is a perfluoroalkylene group having 4 carbon atoms. The perfluoroalkylene group, R ^f5 is a perfluoroalkylene group having 5 carbon atoms, R ^f6 is a perfluoroalkylene group having 6 carbon atoms, and x1, x2, x3, x4, x5 and x6 are independently integers of 0 or more. The sum of x1, x2, x3, x4, x5 and x6 is 2 or more, and each repeating unit may exist in blocks, alternating or random).

As a specific example of the silane compound (S3), the following compounds are preferable because they are industrially easy to manufacture, easy to handle, and can sufficiently impart initial water and oil repellency and stain removal properties to the antifouling layer.
^{_{A 1 -O- (CF 2 CF 2}} OCF 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}} OCF 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}} OCF 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}} OCF 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}} OCF 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 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 equation, 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 equation, 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 indicates CF ₃ CF ₂ O (CF ₂ CF ₂ O) _n (CF ₂ O) _m CF ₂ CH ₂ −. However, n and m are independently integers 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 equation, 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 equation, 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), and (1-5a) can be prepared, for example, by the method described in WO 2013/121984. it can.

For the formation of the antifouling layer, one kind of the second silane compound may be used alone, or two or more kinds may be used in combination. Examples of the components that can be arbitrarily 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 catalyst, various resins and the like. When the antifouling layer contains an arbitrary component, the ratio of the optional component is preferably 15% by mass or less, more preferably 10% by mass or less. The ratio of the arbitrary component to the entire antifouling layer can be, for example, 1 to 10% by mass.

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

(Anti-fouling article)
The antifouling article of the present invention has a base material whose surface is made of at least a metal, and the primer layer and the antifouling layer on the surface made of the metal in that order. The antifouling article of the present invention may have other members, if necessary. The primer layer is formed on at least a part of the surface of the base material made of metal. The region for forming the primer layer may include the region for forming the antifouling layer, and may be formed in a region wider than the region for forming the antifouling layer, if necessary.
In the antifouling article of the present invention, a primer layer is formed on the metal surface of the base material using the first silane compound, and an antifouling layer is formed on the primer layer using the second silane compound. It can be obtained by.

[Manufacturing method of antifouling articles]
The method for producing an antifouling article of the present invention has the following steps (I) and (II).
(I) A step of applying a composition for a primer layer containing a first silane compound and a first solvent to a surface made of a metal of a base material, and reacting the first silane compound to obtain a primer layer (hereinafter). , Also referred to as a primer layer forming step)
(II) A step of adhering a composition for an antifouling layer containing a second silane compound on a 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, the first silane compound related to the primer layer satisfies the requirements of (i-1) and (i-2), so that the uniform primer layer adheres sufficiently to the metal surface. Can be formed with.

The production method of the present invention may include additional steps in addition to the steps (I) and (II). As an additional step, it is preferable to have a step (hereinafter, (Ib) step) of activating the metal surface of the base material on which the primer layer is formed, which is performed before the step (I). Further, in the production method of the present invention, after the (II) antifouling layer forming step, there may be a step (hereinafter, (IIa) step) of performing a post-treatment on the antifouling layer. Hereinafter, each step will be described.

Step (Ib) Step (Ib) is a step of activating the metal surface. The activation treatment of a metal surface means modification to a state in which a reactive group is present on the surface. This makes it easier for the first silane compound to bond to the metal surface.
In the present invention, as the activation treatment of the metal surface, a dry or wet treatment usually used for the activation treatment of the metal surface can be applied without particular limitation. As the dry treatment, a treatment of irradiating the surface with active energy rays such as ultraviolet rays, electron beams, and X-rays, a corona treatment, a plasma treatment, a flame treatment, an itro treatment, and the like can be used. As the wet treatment, a treatment in which the surface is brought into contact with an acid or alkaline solution can be exemplified. 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 in which polar groups are generated on the metal surface to roughen the surface. As the corona treatment, a known method can be adopted, 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, and gas treatment containing fluorine and ions. It also includes ion implantation treatment using a source, treatment using the PBII method, flame treatment exposed to thermal plasma, and itro treatment. Among these, RF plasma treatment in vacuum, microwave plasma treatment, and atmospheric pressure plasma treatment are preferable.

Suitable conditions for plasma treatment include oxygen plasma, plasma _{containing fluorine such as CF 4} , C ₂ F _6, and plasma known to have a high etching effect, or Ne, Ar, Kr, Xe, and the like. Treatment with plasma, which has a high effect of physically etching by applying physical energy to the metal surface, is desirable. It is _{also preferable to add CO 2} , CO, H ₂ , N ₂ , NH ₄ , CH _4, a mixed gas thereof, or 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 plasma containing one or more components as a gas or as a decomposition product in plasma.

When aiming for processing in a short time, it is desirable that the plasma has a high energy density and the kinetic energy of the ions in the plasma is high, but since surface smoothness is required, there is a limit to increasing the energy density. .. When oxygen plasma is used, surface oxidation progresses, a surface having poor adhesion to the base material itself is likely to be formed, and the surface roughness (roughness) becomes large, so that the adhesion also deteriorates.
Further, in plasma using Ar gas, the influence of purely physical collision occurs on the surface, and in this case as well, the surface roughness becomes large. Considering all of these, microwave plasma treatment, microwave ECR plasma treatment, plasma irradiation with an ion source that can easily shoot high-energy ions, PBII method, and the like are also desirable.

The activation treatment cleans the metal surface and further produces reactive groups on the metal surface. The generated reactive group is bonded to the first silane compound by a hydrogen bond or a chemical reaction, and the metal surface of the base material and the primer layer can be firmly adhered to each other. In the plasma treatment, the effect of etching the metal surface can also be obtained.

The activation treatment may be applied to at least the metal surface on which the primer layer is formed. For example, when a primer layer is formed on one main surface of a plate-shaped base material whose entire base material is made of metal, and when plasma treatment is performed only on the main surface, the following plasma treatment is performed. Just do it.
That is, in the plasma treatment with the parallel plate type electrode, the base material is placed on one side of the electrode so as to be in contact with the main surface on the opposite side to the main surface to be subjected to the plasma treatment, so that the side not in contact with the electrode of the base material is placed. Plasma treatment can be applied only to the main surface of the. In the plasma treatment with the parallel plate type electrodes, if the base material is placed in a state of being electrically floated in the space between the two electrodes, the plasma treatment can be performed on both main surfaces. In addition, one-sided treatment is possible by performing plasma treatment with a protective film attached to one side of the base material. As the protective film, a PET film with an adhesive, a polyolefin film, or the like can be used.

(I) Primer layer forming step The primer layer forming step is a composition for a primer layer containing a first silane compound and a first solvent on the metal surface of the base material, preferably the metal surface after the above step (Ib). Is a step of applying and reacting the first silane compound.
The composition for the primer layer contains a first silane compound and a first solvent. The first silane compound is as described above.

The content ratio 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 can be 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, which is obtained by hydrolyzing the hydrolyzable silyl group of the first silane compound 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 silanol groups contained in the hydrolyzate of the first silane compound is stably present while a part of the silanol groups reacts between the molecules. Is preferable. In this respect, the primer layer obtained in the primer layer forming step binds to the antifouling layer in the next (II) antifouling layer forming step.

Specific examples of the first solvent include water, organic solvents and the like. Water is used to hydrolyze the hydrolyzable silyl group of the first silane compound. The first solvent may be a simple substance of one kind of compound, or may be a mixed solvent composed of two or more kinds of compounds. From the viewpoint of compatibility, the first solvent is preferably a non-fluorine-based organic solvent or a mixed solvent of a non-fluorine-based organic solvent and water.

As the non-fluorine-based 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-based organic solvents, alcohol-based organic solvents, ketone-based organic solvents, ether-based organic solvents, ester-based organic solvents, and chlorine-based solvents.

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

Examples of chlorine-based solvents include 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, and pentachloroethane. , 1,1-dichloroethylene, (Z) -1,2-dichloroethylene, (E) -1,2-dichloroethylene, trichlorethylene, tetrachlorethylene, 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 the water in the atmosphere, but the first solvent contains water, and the water is hydrolyzed. It is preferably used.
The content ratio of water in the composition for the primer layer is preferably 0.5 to 2.0 mol, preferably 0.8 to 1 mol, with respect to 1 mol of the hydrolyzable group bonded to the silicon atom of the first silane compound. 3 mol is more preferred. The water content in the first solvent is preferably 1 to 30% by mass, more preferably 5 to 10% by mass, based on the total amount of the first solvent.

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

As described above, the composition for the primer layer may contain an arbitrary component in a proportion of 20% by mass or less, preferably 5% by mass or less, based on the total solid content. Further, as the other component, for example, a known additive such as an acid catalyst or a basic catalyst that promotes the hydrolysis and condensation reaction of the hydrolyzable silyl group may be contained. 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 composition for the primer layer is preferably 10% by mass or less, particularly preferably 1% by mass or less, based on the total amount of the composition.

It is desirable that the composition for the primer layer is uniformly and smoothly applied to the metal surface of the base material in order to form the primer layer uniformly. After coating, the composition for a primer layer forms a primer layer by reacting the first silane compound as described above. That is, the first silane compound is hydrolyzed to form a silanol group, and the silanol group reacts with the metal surface to form a chemical bond. In addition, silanol groups undergo a condensation reaction to form an intermolecular bond. Further, the silanol group is also subjected to a condensation reaction with a silanol group produced from the second silane compound in the step (II) of forming an antifouling layer.

The composition for the primer layer can be produced by mixing each of the above components. A known method can be appropriately used for applying the primer layer composition to the metal surface of the base material.
As the coating method, spin coating method, wipe coating method, spray coating method, squeegee coating method, dip coating method, die coating method, inkjet method, flow coating method, roll coating method, casting method, Langmuir Brodget method or gravure coating method. The method is preferred. In addition, it is also possible to apply by a simple method such as hand coating or brush coating.

The composition for the primer layer is applied so that the coating amount (adhesion amount) of the first silane compound is 50 to 1000 mg / m ^{2 in order to make the thickness of the obtained primer layer the above-mentioned preferable thickness.} preferable. The coating amount of the first silane compound is more preferably ^{50~500mg / m 2, 50~300mg / m} 2 is particularly preferred.

After applying the composition for the primer layer, the first silane compound is reacted. Specifically, the first silane compound is reacted by heating the coating film-like composition for the primer layer. The heating temperature is preferably 80 to 120 ° C, preferably 90 to 120 ° C. Prior to the reaction, the first solvent is removed by drying, for example, heating, if necessary. The heating for the reaction of the first silane compound and the drying (heating) for removing the first solvent may be performed at the same time.

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

When the second silane compound is blended into the antifouling layer composition, the second silane compound may be blended as it is, or may be blended as an oligomer (partially hydrolyzed condensate) thereof. Good. Further, it may be blended in the composition for the primer layer as a mixture of the second silane compound and its oligomer.
When two or more kinds of second silane compounds are used in combination, each compound may be blended in the primer layer composition as it is, each may be blended as an oligomer, and further. It may be blended as a co-oligomer (partially hydrolyzed copolymer) of two or more compounds.

Further, it may be a mixture of these compounds, an oligomer (partially hydrolyzed condensate), and a co-oligomer (partially hydrolyzed cocondensate). The oligomers and co-oligomers also have hydrolyzable silyl groups (including hydrolyzed silanol groups) and perfluoropolyether groups. Hereinafter, the fact that the composition for an antifouling layer contains a second silane compound means that such an oligomer and a co-oligomer are comprehensively contained in addition to the second silane compound itself.

(Dry coating method)
In the dry coating method, a component for forming an antifouling layer, that is, a composition for an antifouling layer for dry coating containing a second silane compound and a component arbitrarily contained in the antifouling layer can be used as it is. The antifouling layer composition for dry coating may be composed of only the second silane compound.

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

The film forming conditions when the vacuum deposition method is used differ depending on the type of vacuum 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 1 × 10 ^-3 Pa. The following are particularly preferred. The heating temperature of the vapor deposition source is not particularly limited as long as the vapor deposition source (composition for antifouling layer for dry coating) has a sufficient vapor pressure. Specifically, 30 to 400 ° C. is preferable, and 50 to 300 ° C. is particularly preferable.

When 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 not more than the upper limit of the above range, the desired water and oil repellency and stain removing property can be imparted to the metal surface of the base material without decomposing the second silane compound. During 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 heat resistant temperature, the film formation rate is good. The base material temperature is more preferably the heat resistant temperature of −50 ° C. or lower.

Also in the case of the dry coating method and the wet coating method described later, in the present invention, the composition for the antifouling layer is attached to the primer layer with the second silane in order to make the thickness of the obtained antifouling layer the above preferable thickness. It is preferable that the amount of the compound adhered is 30 to 80 mg / m ^2. Deposition of the second silane compound is more preferably ^{35~80mg / m 2, 55~70mg / m} 2 is particularly preferred.

In the dry coating method, the reaction of the second silane compound proceeds substantially simultaneously by adjusting the substrate temperature as described above at the time of the film formation. At this time, a part of the silanol group generated by the hydrolysis reaction from the hydrolyzable silyl group of the second silane compound undergoes a condensation reaction to bond between 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 contained in the primer layer, and the primer layer and the antifouling layer are bonded by a siloxane bond. By performing the post-treatment step, which is an arbitrary step described later, a strong bond is formed by the antifouling layer.

(Wet coating method)
In the wet coating method, a composition for an antifouling layer for wet coating (hereinafter, also referred to as a coating liquid) containing a second solvent in the composition for an antifouling layer for dry coating is prepared.
In the wet coating method, a coating liquid is applied to the surface of the primer layer, and a 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 coating method include the same method as the coating of the primer layer composition, including preferred embodiments. The coating liquid can be applied in the same manner as the amount of the second silane compound applied, including the amount of adhesion in the case of the above dry coating method and a preferred embodiment.

After applying the coating liquid, the second silane compound is reacted. Specifically, the coating film-like coating liquid is left at a predetermined reaction temperature for a predetermined time to react the second silane compound. The reaction temperature is preferably in the range of 10 ° C. to the heat resistant temperature of the base material, and more preferably in the range of 20 ° C. to the heat resistant temperature of the base material. Prior to the reaction, the second solvent is removed by drying, if necessary. The reaction of the second silane compound and the drying for removing the second solvent may be carried out at the same time.

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

<Coating liquid>
The antifouling layer composition (coating liquid) for wet coating used in the wet coating method contains a second silane compound and a second solvent. The coating liquid may contain a second silane compound as a solid component, and may contain impurities such as by-products produced in the manufacturing process of the compound in the above ratio. Further, the above-mentioned arbitrary solid component may be contained in the above-mentioned ratio. The coating liquid can be produced by mixing the second silane compound, the second solvent and any component in a suitable mixing vessel.

The second solvent is preferably liquid. The coating liquid may be a liquid, a solution, or a dispersion.
The content ratio of the second silane compound in the coating liquid is preferably 0.1 to 0.5% by mass, particularly preferably 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 fluorine-based organic solvent, a non-fluorine-based organic solvent, or both solvents. Further, the second solvent may be one kind of compound or a mixture of two or more kinds.
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. Commercially available products include, for example, 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 CHFC CHFCF ₃ (Bertrel: product name, manufactured by DuPont) and the like can be mentioned. In addition, 1,1,1,3,3-pentafluorobutane, 1,1,1,2,2,3,4,5,5-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.

Examples of the fluorinated alkene 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, alkyl perfluoroalkenyl ethers (wherein described by the following formula, ^{R 3} _is, CH _3, C 2 _{H 5} or may be a mixture thereof, y1 and y2 are , Independently 0, 1, 2 or 3, y1 + y2 = 0, 1, 2 or 3) and the like.

CF ₃ (CF ₂ ) _y1 CF = CFCF (OR ³ ) (CF ₂ ) _y2 CF ₃ ,
CF ₃ (CF ₂ ) _y1 C (OR ³ ) = CFCF ₂ (CF ₂ ) _y2 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. And so on.
As the fluoroalkyl ether, a compound having 4 to 12 carbon atoms is preferable. Commercially available products include, for example, CF ₃ CH ₂ OFF 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 Co., Ltd.), C ₄ Examples include 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-butyl tetrahydrofuran), and the like. ..

Examples of the fluorinated alkylamine include perfluorotripropylamine, perfluorotributylamine, perfluorotripentylamine and the like. Examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol and the like.
As the fluorinated organic solvent, a fluorinated alkane, a fluorinated aromatic compound, and a fluoroalkyl ether are preferable, and a fluoroalkyl ether is particularly preferable, in terms of the solubility of the second silane compound.

As the non-fluorine-based 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-based organic solvents, alcohol-based organic solvents, ketone-based organic solvents, ether-based organic solvents, ester-based organic solvents, and chlorine-based solvents.

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

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

Examples of chlorine-based solvents include 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, and pentachloroethane. , 1,1-dichloroethylene, (Z) -1,2-dichloroethylene, (E) -1,2-dichloroethylene, trichlorethylene, tetrachlorethylene, chloroform, carbon tetrachloride, dichloromethane and the like are preferable.
As the non-fluorine-based organic solvent, a ketone-based organic solvent is particularly preferable in terms 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 of only hydrogen atoms and carbon atoms, and hydrogen atoms and carbon in terms of increasing 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 fluorinated organic solvent selected from fluorinated alkanes, fluorinated aromatic compounds and fluoroalkyl ethers is preferable.

The second solvent consists of a group consisting of fluorinated alkanes, which are fluorinated organic solvents, fluorinated aromatic compounds, fluoroalkyl ethers, hydrogen atoms, which are non-fluorinated organic solvents, and compounds consisting only of carbon atoms and oxygen atoms. It is preferable that at least one selected organic solvent is contained in a total amount of 90% by mass or more of the total amount of the second solvent in terms of increasing the solubility of the second silane compound.

The coating liquid preferably contains the second solvent in an amount of 70 to 99.999% by mass, particularly preferably 80 to 99.99% by mass, based on the total amount of the coating liquid. Specifically, as the second solvent, C ₆ F ₁₃ C ₂ H ₅ (AC-6000: product name, manufactured by Asahi Glass Co., Ltd.), 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), C ₄ F ₉ OC ₂ H ₅ (Novec-7200: product name, manufactured by 3M), C ₆ F ₁₃ OCH ₃ (manufactured by 3M) Novell 7300 (product name, manufactured by 3M) may be mentioned, and these may be used alone or a mixture thereof may be used. 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 Novell-7200, a combination of AC-6000 and Novell-7300, a combination of AE-3000 and Novell-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 and AE-3000 and Novec-7200, AC- Combination of 6000 and 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-7300, combination of AE-3000 and isopropanol, Any combination is possible, such as a combination of AC-6000 and isopropanol, a combination of AE-3000 and isopropanol, and the like.

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

The content ratio (solid content concentration) of the solid content 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 in a convection dryer at 120 ° C. for 4 hours.

Step (IIa) Step (IIa) is a post-treatment step performed on the antifouling layer after the antifouling layer is formed on the surface of the primer layer 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 moist atmosphere, a substrate having a primer layer and an antifouling layer formed on the surface of an organic material in that order is heated to hydrolyze a hydrolyzable silyl group of a second silane compound to a silanol group. Promotes reactions such as reaction, condensation reaction between silanol groups on the surface of the primer layer and silanol groups generated from the second silane compound, and formation of siloxane bonds by condensation reactions between silanol groups generated from the second silane compound. be able to.

Further, after the antifouling layer is formed, the 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 in which a solvent, for example, a second solvent is poured over the antifouling layer, and a method in which the antifouling layer is wiped off with a cloth impregnated with the solvent, for example, the second solvent.

In the examples, a composition for a primer layer and a composition for an antifouling layer for wet coating are prepared, and the obtained composition is used to form a primer layer and an antifouling layer on the main surface of a plate-shaped metal base material. Was formed in that order and evaluated. 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 the base material, the metal substrates shown in Table 2 were prepared, and the test metal substrates 1 to 5 were further washed with ion-exchanged water after being washed with the alkaline aqueous solution shown in Table 2 by the method shown in Table 2. .. The metal substrate used for the test metal substrate 5 is a substrate in which the surface of a metal substrate (iron material, manufactured by SPCC) is nickel-chrome plated (thickness 30 μm).

<First silane compound and silane compound for comparative example>
As the first silane compound, Corcote N-103X, Corcote PX, and KR-517 were prepared.

The following compounds were prepared as silane compounds for comparative examples.
KR-516 (manufactured by Shinetsu Chemical Industry Co., Ltd., trade name, compound whose main chain is formed by a linear siloxane bond, methoxy group as a hydrolyzable group bonded to a silicon atom of the main chain, 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 Industry Co., Ltd., trade name, silane compound in which the main chain is mainly formed of a carbon-carbon bond and has a triethoxysilyl group and an epoxy group in the side chain, Mw; 1000, hydrolyzable. Content of ethoxy group as group; 15% by mass, content of epoxy group as side chain reactive group; 15% by mass)
KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, 3-glycidoxypropyltrimethoxysilane, formula; 236.3)
TEOS (Tetraethoxysilane, formula; 208.3)

<Second silane compound>
The following compounds were produced and used as the second silane compound by the method described in WO 2013/121984.
_{CF 3 -O- (CF 2 CF 2} OCF 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 composition for primer layer)
For each of the first silane compound and the silane compound for comparative example, isopropanol (IPA) was used as a diluting solvent as needed, and in Table 3, the components and the respective contents are shown in the composition for the primer layer. 1 to 7 were prepared. The composition 1 and 2 for the primer layer were used as they were in the commercial product composition (concentration of silane compound; 2.0% by mass).

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

[Examples 1 to 8]
(Activation treatment of test metal substrate)
By carrying out the corona treatment, the contaminated layer on the main surface of the test metal substrate 1 was removed, and the surface of the substrate was imparted with wettability. The corona treatment is a test under a corona discharge with a discharge amount of 80 W ・ min / m ^{2 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. This was done by passing the metal substrate 1 for use.

(Primer layer forming step)
The primer layer compositions 1 to 7 prepared above are coated on one main surface of the test metal substrate 1 after the corona treatment by a spin coating method (coating conditions: 1000 rpm / 30 sec, first silane compound). Adhesion amount: 55 mg / m ² ), heated on a hot plate at 120 ° C. for 10 minutes to dry and remove the solvent, and the first silane compound was reacted to form a primer layer having a thickness of 5 nm.

(Anti-fouling layer forming process)
The composition for the antifouling layer prepared above was applied by a spray method (adhesion amount of the second silane compound; 64 mg / m ² ) onto the primer layer of the test metal substrate 1 on which the primer layer was formed, and 120 The antifouling article of Examples 1 to 7 was formed by heating in a hot air circulation oven at ° C. for 10 minutes to dry and remove AC-6000 and reacting with a second silane compound to form an antifouling layer having a thickness of 15 nm. Got In Example 8, an antifouling article having a thickness of 15 nm is formed on one main surface of the test metal substrate 1 after the corona treatment in the same manner as described above without forming a primer layer. And said.

[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 corona-treated in the same manner as in Example 9, and the thickness was 15 nm in the same manner as above on one main surface of the test metal substrate 2 after the corona treatment without forming a primer layer. An antifouling layer was formed to obtain an antifouling article of Example 11.

[Examples 12 and 13]
The 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 corona-treated in the same manner as in Example 12, and the thickness was 15 nm in the same manner as above on one main surface of the test metal substrate 3 after the corona treatment without forming a primer layer. An antifouling layer was formed to obtain an 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 corona-treated in the same manner as in Example 14, and the thickness was 15 nm in the same manner as above on one main surface of the test metal substrate 4 after the corona treatment without forming a primer layer. An antifouling layer was formed to obtain an antifouling article of Example 16.

[Examples 17 and 18]
The 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 corona-treated in the same manner as in Example 17, and the thickness was 15 nm in the same manner as above on one main surface of the test metal substrate 5 after the corona treatment without forming a primer layer. An antifouling layer was formed to obtain the antifouling article of Example 18.

(Evaluation)
<Measurement method of water contact angle>
For the antifouling articles of Examples 1 to 18 obtained above, the contact angle of about 2 μL of distilled water placed on the surface of the antifouling layer was measured using a contact angle measuring device DM-500 (manufactured by Kyowa Interface Science Co., Ltd.). Was measured. Measurements were 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 the water contact angle is 100 ° or more, it can be said that it has sufficient antifouling property for actual use.

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

The results are shown in Table 4 for Examples 1-8 and Table 5 for Examples 9-18. In Examples 4 and 5, respectively, in which the primer layer compositions 4 and 5 were used, when the antifouling layer composition was applied onto the primer layer, the antifouling layer composition was repelled and the antifouling layer was formed. I couldn't. In Tables 4 and 5, "-" indicates that the water contact angle was not measured, and the diagonal 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 such as smartphones, home appliances, water-washing metal fittings such as faucets and pipes, and elevator walls.
The entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2018-112799 filed on June 13, 2018 are cited here as disclosure of the specification of the present invention. , Incorporate.

Claims (15)

With a base material whose surface is at least partly 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, does not contain a fluorine atom, and has a weight average molecular weight of 500 to 200,000, and is hydrolyzable. A layer formed by using the first silane compound containing a group in a proportion of 30% by mass or more with respect to the entire silane compound.
The antifouling article is characterized in that 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 in which the main chain is formed by 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 a straight chain or a branched chain, and may have two or more kinds of − ( _Ca F _2a O) _b − units having different carbon numbers (oxy). The antifouling property according to claim 1 or 2, which is a silane compound having a perfluoroalkylene) chain and having a hydrolyzable silyl group at at least one end of the poly (oxyperfluoroalkylene) chain via a linking group. Goods. The second silane compound is the antifouling article according to claim 3, which is represented by the following formula (S3).
[A-O- (C _a F _2a O) _b- ] Q [-SiL _m R _3-m ] _p (S3)
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}} .
(C _a F _2a O) In _b , a is an integer of 1 to 6, b is an integer of 2 or more, and-(C _a F _2a O) _b- is branched even if the unit is linear. It may be a chain and may have two or more kinds of − (C _a F _2a O) _b − units having different carbon numbers.
Q is a (1 + p) valence linking group.
Q ¹⁰ is a divalent linking group.
p is an integer of 1-10.
L is a hydrolyzable group.
R is a hydrogen atom or a monovalent hydrocarbon group.
m is an integer of 1-3. The antifouling article according to any one of claims 1 to 4, wherein the thickness of the primer layer is 3 to 200 nm. The antifouling article according to any one of claims 1 to 5, wherein the thickness of the antifouling layer is 10 to 100 nm. A method for producing an antifouling article having a base material whose surface is at least partially made of metal, a primer layer provided on the surface, and an antifouling layer provided on the primer layer.
The surface of the silane compound has a hydrolyzable silyl group in which a hydrolyzable group is bonded to a silicon atom, does not contain a fluorine atom, and has a weight average molecular weight of 500 to 200,000, and is the hydrolyzable group. A composition for a primer layer containing a first silane compound containing 30% by mass or more with respect to the entire silane compound and a first solvent is applied, and the first silane compound is reacted to cause a primer. A layer is obtained, and a composition for an antifouling layer containing a second silane compound having a perfluoropolyether group and a hydrolyzable silyl group is attached onto the primer layer, and the second silane compound is reacted. A method for producing an antifouling article, which comprises obtaining an antifouling layer. The production method according to claim 7, wherein the first silane compound is a silane compound in which the main chain is formed by a siloxane bond. The production method according to claim 7 or 8, wherein the first solvent is a non-fluorine-based organic solvent, or a non-fluorine-based organic solvent and water. The production method according to any one of claims 7 to 9, wherein the composition for a primer layer is applied so that the amount of the first silane compound adhered is 50 to 1000 mg / m ^2. The one according to any one of claims 7 to 10, wherein the composition for a primer layer contains the first silane compound in a ratio 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 a straight chain or a branched chain, and may have two or more kinds of − ( _Ca F _2a O) _b − units having different carbon numbers (oxy). The item according to any one of claims 7 to 11, which is a silane compound having a perfluoroalkylene) chain and having a hydrolyzable silyl group at at least one end of the poly (oxyperfluoroalkylene) chain via a linking group. The manufacturing method described. The production method according to any one of claims 7 to 12, wherein the composition for an antifouling layer is adhered so that the amount of the second silane compound adhered is 30 to 80 mg / m ^2. The production method according to any one of claims 7 to 13, wherein the composition for an antifouling layer 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 in a proportion of 0.1 to 0.5% by mass with respect to the total amount of the antifouling layer composition.