TW202000849A - Fouling-resistant article and production method therefor - Google Patents

Abstract

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

Description

Anti-fouling article and its manufacturing method

The present invention relates to an anti-fouling article excellent in anti-fouling property and having durability against the anti-fouling property such as abrasion resistance and a method for manufacturing the same.

Background of the invention In order to impart water and oil repellency to the surface of various substrates, there is a well-known anti-fouling article that is coated on the surface of the substrate with low surface tension to enhance the property of inhibiting the adhesion of dirt or easily removing the attached dirt. That is antifouling.

Fluorine-containing compounds have conventionally been used to prepare coating compositions having the aforementioned antifouling properties. For example, a coating composition for imparting oil repellency and/or water repellency to the surface of a substrate composed of inorganic materials such as glass, ceramics, etc., has conventionally used one or more fluorine-containing groups (such as perfluoroalkyl , Perfluoroether group and perfluoropolyether group) fluorine-containing silane compounds.

Here, in an antifouling article in which an antifouling coating (antifouling layer) is provided on the surface of a substrate using a fluorine-containing compound, especially when at least a part of the surface of the substrate is composed of metal, as long as the cleaning or rubbing is repeated On the surface of the anti-fouling layer, the anti-fouling property will be reduced. In order to solve the above problems, the method proposed in Patent Document 1 is to treat a metal surface with a primer composition to form an undercoat layer on the metal surface, and use a fluorine-containing compound on the undercoat layer to form an antifouling layer. The coating composition contains a second or third amine functional compound having at least two independently selectable silane groups.

Prior technical literature Patent Literature Patent Literature 1: Japanese Special Publication No. 2017-515650

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

The present invention is based on the above viewpoint, and aims to provide an antifouling article and a method for efficiently manufacturing the antifouling article. The antifouling article has an antifouling layer formed of a fluorine-containing compound on a metal surface. The antifouling article has excellent antifouling properties, and has durability such as abrasion resistance against the antifouling properties.

Means for Solving the Problems The present invention has the following aspects. [1] An antifouling article, characterized by having: a base material, at least a part of the surface of which is composed of metal; an undercoat layer, which is provided on the aforementioned surface; and an antifouling layer, which is provided on the undercoat layer The aforementioned undercoat layer is a layer formed by using a first silane compound, which is a silane compound having a weight average molecular weight of 500 to 200,000, has a hydrolyzable group bonded to a silicon atom, and does not have a fluorine atom, And contains the hydrolyzable group at a ratio of 30% by mass or more relative to the entire silane compound; the antifouling layer is a layer formed using a second silane compound, the second silane compound having a perfluoropolyether group and hydrolyzable silicon base. [2] The antifouling article according to [1], wherein the first silane compound is a silane compound whose main chain is formed by a siloxane bond. [3] The antifouling article according to [1] or [2], wherein the second silane compound has a poly(oxyperfluoroalkylene) chain and the poly(oxyperfluoroalkylene) chain A silane compound having a hydrolyzable silicon group through at least one end through a linking group, and the poly(oxyperfluoroalkylene) chain system is represented by -(C _a F _2a O) _b- (where a is 1 to 6 Integer, b is an integer of 2 or more,-(C _a F _2a O) _b -unit may be linear or branched, and may have two or more different carbon numbers-(C _a F _2a O) _b -unit). [4] The antifouling article according to [3], wherein the second silane compound is represented by the following formula (S3); [AO-(C _a F _2a O) _b -]Q[-SiL _m R _{3- m} ] _p …(S3) The notation in formula (S3) is as follows: A is a perfluoroalkyl group with 1 to 6 carbon atoms or -Q ¹⁰ -SiL _m R _3-m ; in (C _a F _2a O) _b , A is an integer of 1~6, b is an integer of 2 or more, -(C _a F _2a O) _b -unit may be a straight chain or a branched chain, and may have two or more different carbon numbers -( C _a F _2a O) _b -unit; Q is a (1+p) valent linking group; Q ¹⁰ is a divalent linking group; p is an integer from 1 to 10; L is a hydrolyzable group; R is a hydrogen atom or monovalent Hydrocarbyl. m is an integer from 1 to 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 thickness of the antifouling layer is 10 to 100 nm. [7] A method for manufacturing an anti-fouling article, which is a method for manufacturing the following anti-fouling article, the anti-fouling article having: a substrate, at least a part of the surface of which is composed of metal; an undercoat layer, which is provided in the foregoing On the surface; and an anti-fouling layer, which is provided on the aforementioned undercoat layer; the aforementioned manufacturing method is characterized by comprising the following steps: applying the composition for the undercoat layer containing the first silane compound and the first solvent to the aforementioned surface and making The first silane compound is reacted to obtain an undercoat layer. The first silane compound is a silane compound having a weight average molecular weight of 500 to 200,000. The hydrolyzable silicon group has a hydrolyzable group bonded to a silicon atom and does not have a fluorine atom. The hydrolyzable group is contained at a ratio of 30% by mass or more of the entire silane compound; and the composition for the antifouling layer containing the second silane compound is attached to the undercoat layer and the second silane compound is reacted to obtain In the dirty layer, the second silane compound has a perfluoropolyether group and a hydrolyzable silicon group. [8] The production method according to [7], wherein the first silane compound is a silane compound whose main chain is formed by a siloxane bond. [9] The production method according to [7] or [8], wherein the first solvent includes a non-fluorine-based organic solvent or a non-fluorine-based organic solvent and water. [10] The manufacturing method as described in any one of [7] to [9], wherein the undercoat layer composition is applied in such a manner that the adhesion amount of the first silane compound is 50 to 1000 mg/m ² Thing. [11] The production method according to any one of [7] to [10], wherein the composition for an undercoat layer contains the first in a ratio of 0.1 to 3.0% by mass relative to the total amount of the composition Silane compounds. [12] The production method as described in any one of [7] to [11], wherein the second silane compound has a poly(oxyperfluoroalkylene) chain and the poly(oxyperfluoroalkylene) ) A silane compound having a hydrolyzable silane group through at least one end of the chain through a linking group, and the poly(oxyperfluoroalkylene) chain system is represented by -(C _a F _2a O) _b- (where a is 1 Integer of ~6, b is an integer of 2 or more, -(C _a F _2a O) _b -unit may be linear or branched, and may have two or more different carbon numbers -(C _a F _2a O) _b -unit). [13] The production method as described in any one of [7] to [12], which adheres the composition for the antifouling layer such that the adhesion amount of the second silane compound is 30 to 80 mg/m ² . [14] The production method according to any one of [7] to [13], wherein the composition for the antifouling layer further contains a second solvent, and the method of attaching to the undercoat layer is coating. [15] The production method according to [14], which contains the second silane compound in a ratio of 0.1 to 0.5% by mass relative to the total amount of the antifouling layer composition.

Invention effect According to the anti-fouling article of the present invention, an anti-fouling article having an anti-fouling layer formed using a fluorine-containing compound on a metal surface is excellent in anti-fouling property, and has excellent abrasion resistance for the anti-fouling property Equal durability. According to the manufacturing method of the present invention, the method for manufacturing an antifouling article having an antifouling layer formed using a fluorine-containing compound on a metal surface can produce an excellent antifouling property and has excellent abrasion resistance for the antifouling property Durable anti-fouling articles.

Forms for carrying out the invention The meaning and description of the terms in this manual are as follows. The compound or group represented by the chemical formula is also represented by the compound or group appended with the number of the formula. For example, "the compound represented by formula (1)" is also expressed as "compound (1)". The symbol "~" indicating the numerical range includes the lower limit and the upper limit. Moreover, when the unit of the lower limit and the upper limit is the same, the unit of the lower limit may be omitted.

The expression "(meth)acryloyloxy" is used as a general term for acryloyloxy and methacryloyloxy.

[Antifouling article] The antifouling article of the present invention is an antifouling article having a substrate, an undercoat layer, and an antifouling layer, at least a part of the surface of the substrate is made of metal, and the undercoat layer is provided on the metal On the surface, the antifouling layer is provided on the undercoat layer. The undercoat layer is formed on at least a part of the surface composed of metal, and includes an area where an antifouling layer can be formed.

The above-mentioned undercoat layer is a layer formed by using a first silane compound. The first silane compound is a silane compound having a weight average molecular weight of 500 to 100,000, and has a hydrolyzable group bonded to a silicon atom without a fluorine atom. In addition, the hydrolyzable group is contained at a ratio of 30% by mass or more relative to the entire compound.

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

The antifouling layer is a layer formed using a second silane compound having a perfluoropolyether group and a hydrolyzable silicon group. The hydrolyzable silane group possessed by the first silane compound and the second silane compound is a group in which a hydrolyzable group directly bonds with a silicon atom, that is, a group that can form a silanol group (Si-OH) by a hydrolysis reaction. The hydrolyzable group is a group decomposed by water.

In the antifouling article of the present invention, when forming the undercoat layer, the silanol group (Si-OH) can be formed by the hydrolysis reaction of the hydrolyzable silicon group of the first silane compound. The 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 Si-O-Si bonds. In addition, the silanol group may react with the silanol group generated from the hydrolyzable silan group of the second silane compound used to form the antifouling layer to form a Si-O-Si bond. In addition, the polar group on the surface of the metal is a group that can form a hydrogen bond, specifically a hydroxyl group, a carboxyl group, an amine group, etc., and a hydroxyl group is particularly preferable.

We believe that in the present invention, the first silane compound having the above-mentioned predetermined Mw and having the above-mentioned predetermined amount of hydrolyzable groups bonded to the silicon atom can be used as a primer between the metal surface of the substrate and the primer layer A balanced and sufficient amount of the above-mentioned bonds are formed inside the layer and between the undercoat layer and the antifouling layer, respectively. We believe that by this, the metal surface of the substrate and the undercoat layer, and the undercoat layer and the antifouling layer can be firmly joined.

As described above, the antifouling layer can be bonded to the undercoat layer through Si-O-Si bonding. At the same time, in the antifouling layer, the silanol group formed by the hydrolyzable silicon group of the second silane compound will be between the molecules. The reaction proceeds to form Si-O-Si bonds. On the other hand, the perfluoropolyether group of the second silane compound does not participate in the reaction and exists on the surface layer of the antifouling layer, so it can exhibit excellent antifouling properties.

Therefore, in the antifouling article of the present invention, the undercoat layer contains the reactant of the first silane compound in a state where part or all of the hydrolyzable groups of the first silane compound have undergone hydrolysis reaction. Similarly, the antifouling layer contains the reactant of the second silane compound in a state in which the hydrolyzable group of the second silane compound is partially or completely hydrolyzed.

The constituent members of the antifouling article of the present invention will be individually described below. (Substrate) There is no particular limitation as long as at least a part of the surface is made of metal. The base material may be entirely composed of metal on the surface, or partially composed of metal. Moreover, all the surfaces may be composed of the same metal, or they may be composed of different metals.

The base material may be, for example, a structure composed of a single metal as a whole, or may be a laminate in which a plurality of layers composed of metals (hereinafter also referred to as metal layers) are laminated. In addition, it may be a layer composed of a metal layer and an inorganic material other than metal (hereinafter also referred to as an inorganic material layer) and/or a layer composed of an organic material (hereinafter also referred to as an organic material layer), and One layer of the surface layer is a laminate of metal layers. Alternatively, the surface of the base material may be a structure having a region composed of a metal and a region composed of an inorganic material and/or an organic material other than metal on the same surface. It may be a base material to which metal plating is applied on at least a part of the surface of the metal layer or the organic material layer.

The shape of the substrate is not particularly limited, and examples thereof include a plate shape, a film (film) shape, a rod shape, and a tube shape. When the substrate is plate-shaped, it may be a flat plate or a shape having a curvature in part or all of the main surface. In addition, the surface shape may be smooth or uneven. In the substrate, the metal constituting the surface on which the undercoat layer can be formed may be a metal or an alloy that is solid at room temperature, and is not particularly limited.

Specific examples of the aforementioned metals include chromium, iron, aluminum, copper, nickel, zinc, tin, carbon steel, lead, titanium, gold, silver, alloys of these, and the like. Examples of alloys include stainless steel such as SUS304, SUS316, SUS303, SUS317, and SUS403, brass, bronze, cupronickel, red brass, red copper, German silver, Duralumin, solder, and the like. The metal surface may include nickel, chromium plating, nickel plating, chromium plating, zinc plating, and the like.

(Undercoat) The undercoat layer is formed using the first silane compound. As described above, the undercoat layer is composed of the reactant containing the first silane compound, and may contain any component other than the reactant of the first silane compound. From the viewpoint that the adhesion between the antifouling layer and the undercoat layer and the surface of the undercoat layer is more excellent, the ratio of the reactant of the first silane compound in the entire undercoat layer should be 80 to 100 mass %, and 95~100 mass% is better.

If the thickness of the undercoat layer is the monomolecular thickness of the first silane compound, the adhesion between the antifouling layer and the undercoat layer and the surface of the undercoat layer is good, and the durability of the antifouling property of the antifouling article Excellent, it is suitable. If the thickness of the undercoat layer is too thick, the undercoat layer will become brittle and the durability will be reduced. The thickness of the undercoat layer is preferably 3 to 200 nm, and preferably 5 to 80 nm. In addition, for the thickness of the undercoat layer, for example, the X-ray diffractometer ATX-G (manufactured by RIGAKU) for thin-film analysis can be used. After obtaining the interference pattern of the reflected X-ray by the X-ray reflectance method, the vibration period of the interference pattern Figure it out.

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

If the Mw of the first silane compound is less than 500, there will be a problem with the adhesion to the second silane compound; if it is greater than 200,000, there will be a problem with the film forming property. The Mw is preferably 700 or more, preferably 1,000 or more. The Mw is preferably 150,000 or less, preferably 100,000 or less.

When the content of the hydrolyzable group of the first silane compound is less than 30% by mass, the combination of the formed undercoat layer and the metal surface will be insufficient, and the expected durability cannot be obtained in the resulting antifouling article. The content of the hydrolyzable group is 30% by mass or more, and preferably 50% by mass or more, preferably 80% by mass or more. The content of the hydrolyzable group of the first silane compound should be as high as possible in the molecular design. Specifically, the content of the hydrolyzable group is preferably 95% by mass or less, preferably 90% by mass or less.

Specific examples of the first silane compound include compounds whose main chain is formed of siloxane bonds and satisfy (i-1) and (i-2) (hereinafter also referred to as compound (I)), and whose main chain is carbon-carbon The bond is a compound formed mainly and satisfying (i-1) and (i-2) (hereinafter also referred to as compound (II)).

In the case of compound (I), a hydrolyzable silicon-based hydrolyzable group is bonded to the silicon atom constituting the main chain. The main chain formed by the siloxane bond may be a straight chain or a branched chain, or a 3-dimensional mesh structure. From the viewpoint of improving adhesion to metals, the first silane compound is preferably compound (I); from the viewpoint of improving film strength, compound (I) with a three-dimensional mesh structure is particularly preferable.

The compound (I) having a three-dimensional mesh structure in the main chain can be exemplified by a compound having a partially hydrolyzed (co)condensate of a low-molecular-weight silane compound containing a hydrolyzable silicon group having more than 3 functions. The low-molecular-weight silane compound used for obtaining the compound (I) having a three-dimensional mesh structure in the main chain may be a compound represented by the following formula (S1). In addition, the compound (S1) contains a monofunctional or bifunctional hydrolyzable silane compound. In order to obtain a compound (I) having a three-dimensional mesh structure in the main chain, a compound (S1) having a hydrolyzable silicon group of more than 3 functions is necessary, and a monofunctional or difunctional hydrolyzable silane compound (S1) is used as required ) And (i-1) and (i-2) are satisfied to perform partial hydrolysis and condensation. In addition, monofunctional, bifunctional, and trifunctional are all hydrolyzable groups directly bonded to silicon atoms in the molecule. That is, e in the following formula (S1).

R ¹¹ _d SiL ¹¹ _e R ¹² _4-de …(S1) However, the notation in formula (S1) is 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 R ¹¹ , R ¹² , when there a plurality of L ¹¹ may be the same or different from each individual.

R ¹¹ is a group having a linking group and a reactive group or a reactive group other than a hydrolyzable group. That is, if the reactive group is classified into a reactive group other than a hydrolyzable group and a hydrolyzable group, R ¹¹ is any one of the following constitutions: a composition having a linking group and a hydrolyzable group, a linking group and a hydrolyzable group The composition of the reactive group other than the group, or the composition of the reactive group other than the hydrolyzable group. The linking group refers to a group that links a silicon atom to a hydrolyzable group or a reactive group other than hydrolyzable group. The hydrolyzable group is, for example, an alkoxy group, a halogen atom, an acetyl group, an isocyanate group (-NCO), an amine group, and the like, and preferably an amine group and an isocyanate group. Hereinafter, the hydrolyzable group in R ¹¹ and reactive groups other than the hydrolyzable group are integrated and referred to only as a reactive group. In this specification, the term "reactive organic group" is used in the same meaning as explained in R ¹¹ .

Specific examples of the reactive group included in R ¹¹ include a vinyl group, an epoxy group, a (meth)acryloyloxy group, an amine group, an isocyanate group, a mercapto group, and a styryl group. In this specification, the amine group refers to -NHR ¹³ (R ¹³ is H or a monovalent hydrocarbon group). The monovalent hydrocarbon group represented by R ^{13 is} preferably an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 10 carbon atoms. In addition, when R ¹¹ has an amine group or an isocyanate group as a reactive group, R ¹¹ also has a linking group that links these reactive groups and silicon atoms.

The carbon number of R ¹¹ is preferably from 2 to 10, preferably from 2 to 9. In addition, the ideal carbon number of R ¹¹ differs depending on the reactive group. When the reactive group is a vinyl group, the carbon number is preferably 2 to 4, and 2 is preferred. When the reactive group is vinyl and R ^{11 has} a carbon number of 2, R ^{11 is} vinyl (-CH=CH ₂ ) itself.

When the reactive group is an epoxy group, the epoxy group-containing reactive group is preferably a glycidoxy group or an epoxycyclohexyl group. When R ¹¹ has a reactive group at the end, the reactive group and the silicon atom system are linked through a linking group. The linking group which connects the glycidoxy group or epoxycyclohexyl group and the silicon atom is preferably an alkylene group having 1 to 6 carbon atoms, and ethyl or propyl group is particularly preferred.

When the reactive group is an amine group and R ¹¹ has an amine group at the end, the reactive group and the silicon atom system are connected through a linking group. The linking group connecting the amine group and the silicon atom is preferably an alkylene group having a carbon number of 1 to 10, which may also have a nitrogen atom between carbon-carbon atoms, and -(CH ₂ ) _{2 or 3-} NH-(CH ₂ ) _{2 or 3} -, ethyl or propyl is particularly preferred.

When R ¹¹ has a reactive group other than a vinyl group, an epoxy group, and an amine group, it may also have a linking group that links the reactive group and a silicon atom, and when it has a linking group, the carbon number extends from 1 to 10. Alkyl groups are preferred, and ethyl or propyl groups are particularly preferred.

L ¹¹ is a hydrolyzable group. Specific examples of L ¹¹ include alkoxy groups, halogen atoms, amide groups, isocyanate groups (-NCO), and amine groups. The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms. The halogen atom is preferably a chlorine atom. Among these, L ^{11 is} preferably an alkoxy group having 1 to 4 carbon atoms, particularly preferably methoxy or ethoxy.

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

In the compound (S1), the compound in which e is 4 is a tetrafunctional compound. Specific examples of the 4-functional compound include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, and tetrapropoxysilane. If the compound (S1) has R ¹¹ , it is preferable 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 vinyl dimethyl monomethoxy silane, vinyl dimethyl monoethoxy silane, vinyl methyl dimethoxy silane, and vinyl methyl diethoxy Silane, vinyltrimethoxysilane, vinyltriethoxysilane, N-2-(N-vinylbenzylaminoethyl)-3-aminopropyltrimethoxysilane, etc.

Examples of the compound (S1) having an epoxy group as a reactive group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-epoxy Propoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, etc.

Examples of the compound (S1) having (meth)acryloyloxy as a reactive group include 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxy Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-propenyloxypropyltrimethoxysilane, etc.

Examples of the compound (S1) having an amine group as a reactive group include N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane and N-(2-aminoethyl)-3-amine Propyltrimethoxysilane, N-(2-aminoethyl)-N'-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Triethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, etc.

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-mercaptopropylmethyl Based on dimethoxysilane and so on. In addition, the compound (S1) that does not have R ¹¹ and has R ¹² specifically includes trimethoxy(methyl)silane, benzyltrimethoxyane, and the like.

The low-molecular-weight silane compound used to obtain the compound (I) having a three-dimensional mesh structure is preferably a 4-functional compound (S1). The low-molecular-weight silane compound used to obtain the compound (I) having a three-dimensional mesh structure in the main chain is preferably formed of only the 4-functional compound (S1). In addition, it is also preferable to use a tetrafunctional compound (S1) and a compound (S1) having R ¹¹ in the prepared partially hydrolyzed (co)condensate to satisfy the composition of (i-1) and (i-2).

As the compound (I) having a three-dimensional mesh structure in the main chain, commercially available products can also be used. Commercially available products can be exemplified by Colcoat Co., Ltd. under the trade name Colcoat PX (a solution containing a solid content concentration of 2% by mass, and the solution contains Mw: 1,000 to 100,000 and a content of hydrolyzable groups: 80% by mass The above compound (I)), Colcoat N-103X (a solution containing a solid content concentration of 2% by mass, and the solution contains a compound (I) of Mw: 20,000 to 30,000 and a content of hydrolyzable groups: 80% by mass or more) Wait.

The compound (I) whose main chain is linear can be exemplified by the compound represented by the following formula (S2).

[Chemical Formula 1]

In formula (S2), L ¹¹ is a hydrolyzable group, particularly the same aspects as in the above-described formula (S1) L ^11. R ¹ represents an organic substituent other than L ¹¹ , specifically, a reactive organic group (R ¹¹ ) of the above formula (S1), a non-reactive monovalent organic group such as R ^{12 of the} above formula (S1), etc. . R ² L ¹¹ independently based or R ^1. n and m are integers, and can be adjusted within the range that the compound (S2) can satisfy (i-1) and (i-2). m can also be 0.

The compound (S2) can also use a commercial item. The commercially available products may be trade names KR-517, X-41-1059A, KR-518, X-41-1818, KR-519, etc., all manufactured by Shin-Etsu Chemical Industry Co., Ltd. The molecular composition and Mw of these compounds are listed in Table 1. In Table 1, the organic substituent represents, for example, the reactive group in R ¹¹ and R ¹² in the compound (S2).

[Table 1]

In addition, the compound (I) whose main chain is branched is also not particularly limited as long as it satisfies (i-1) and (i-2), and can be used as the first silane compound.

The compound (II) includes, for example, a compound (S1) having a group having an unsaturated double bond such as a vinyl group, (meth)acryloyloxy group, and styryl group as a reactive group and various radical polymerizable monomers Compound obtained by copolymerization. In addition, this compound is a copolymer satisfying (i-1) and (i-2). Radical polymerizable monomers used include (meth)acrylate, styrene, vinyl ester, vinyl chloride, ethylidene, propylidene and the like.

In addition, by grafting the compound (S1) having a vinyl group with aliphatic olefin polymers such as polyethylene and polypropylene in the presence of an organic peroxide, a hydrolyzable silicon group in the side chain can be obtained Of polyolefin polymers. As the compound (II), a graft polymer produced by the above-mentioned grafting reaction may be a compound that satisfies (i-1) and (i-2).

In addition, as long as the compound (II) satisfies (i-1) and (i-2), it may have an organic substituent other than the hydrolyzable silicon group in the side chain. The organic substituent specifically includes a reactive organic group (R ¹¹ ) in the above formula (S1) and a non-reactive monovalent organic group such as R ¹² in the above formula (S1). The reactive group in the reactive organic group may be the same group as the reactive group possessed by R ¹¹ in the compound (S1).

As the compound (II), commercially available products can also be used. Commercial products include X-12-1048 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, Mw: 1000, methoxy content as a hydrolyzable group: 31% by mass, and propylene acetyl content as a side chain reactive group) : 14% by mass) etc.

When forming the undercoat layer, the first silane compound may be used alone or in combination of two or more. In addition, when the first silane compound is composed of two or more kinds of silane compounds, each silane compound must satisfy the necessary condition of (i-2), and the necessary condition of (i-1) is to be satisfied when combining two or more kinds, Not all silane compounds need to be satisfied. However, it is preferable that each silane compound satisfies the necessary conditions of (i-1) and (i-2).

Examples of components that the undercoat layer may optionally contain include reactants of hydrolyzable silane compounds other than the first silane compound. When the undercoat layer contains any components, the ratio of the arbitrary components in the entire undercoat layer is preferably 0 to 20% by mass, and preferably 0 to 5% by mass.

(Antifouling layer) The antifouling layer is formed using the second silane compound. As described above, the antifouling layer is composed of the reactant containing the second silane compound, and may contain any components other than the reactant of the second silane compound. The proportion of the reactant of the second silane compound in the entire antifouling layer is preferably 90 to 100% by mass, and preferably 95 to 100% by mass.

If the thickness of the antifouling layer is the thickness of a single molecule of the second silane compound, the adhesion between the antifouling layer and the undercoat layer is good, and the durability of the antifouling properties of the antifouling article is excellent. If the thickness of the antifouling layer is too thick, the use efficiency may be reduced, or the transparency of the antifouling layer may be impaired. Specifically, the thickness of the antifouling layer is preferably 10 to 100 nm, and preferably 10 to 50 nm. In addition, the thickness measurement of the antifouling layer can be performed in the same manner as the thickness measurement method of the undercoat layer.

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

The second silane compound specifically includes a silane compound having a poly(oxyperfluoroalkylene) chain and having a hydrolyzable silane group through a linking group at at least one end of the poly(oxyperfluoroalkylene) chain ( The following is also expressed as a silane compound (A)), and the poly(oxyperfluoroalkylene) chain system is represented by -(C _a F _2a O) _b- (where a is an integer of 1 to 6 and b is 2 The above integer, -(C _a F _2a O) _b -unit may be linear or branched, and may have two or more -(C _a F _2a O) _b -groups with different carbon numbers).

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

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

Specific examples when A is a perfluoroalkyl group of 1 to 6 are as follows. 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. Wherein the initial antifouling layer imparting sufficient water-repellent and oil repellency, soil perspective view of removability, A is suitably CF ₃ - or CF ₃ CF ₂ -.

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 addition, in formulas (2-1) to (2-6), the Si system 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 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 may have an ester bond, an ether bond, an amide bond, an urethane bond, a phenylene group, -S-, or a divalent amine at the terminal or between carbon atoms and carbon atoms. The hydrogen atom of the alkyl group, the silylalkylene structure, the silylarylene structure, the siloxane structure (including the cyclic siloxane structure), or a hydrocarbon group may be replaced by a fluorine atom. Hydrogen atoms of the hydrocarbon group can also be substituted by hydroxyl groups, but the number of substituted hydroxyl groups is preferably 1 to 5. The hydrocarbon group may be linear or branched. The number of carbon atoms of Q is preferably 1-20, preferably 1-10.

L is a hydrolyzable group. Examples of L include an alkoxy group, a halogen atom, an acetyl group, and an isocyanate group (-NCO). The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms. From the viewpoint of easy industrial manufacture, L is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom. The halogen atom is preferably a chlorine atom. From the viewpoint of less outgassing during coating and excellent storage stability of the compound (S3), L is preferably an alkoxy group having 1 to 4 carbon atoms, and when the compound (S3) needs long-term storage stability, Ethoxy is particularly preferred. Methoxy is preferred when the reaction time after coating is to be shortened.

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

m is an integer from 1 to 3, and 2 or 3 is preferred, and 3 is particularly preferred. Due to the presence of multiple Ls in the molecule, it can be more firmly bonded to the surface of the substrate. When m is 2 or more, a plurality of L present in one molecule may be the same as or different from each other. From the viewpoint of the availability and ease of manufacture of raw materials, they should be the same as each other.

Hydrolyzable silicon-based (-SiL _m R _3-m ) should be -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 . From the viewpoint of ease of handling in industrial manufacturing, -Si(OCH ₃ ) _{3 is} particularly preferred.

In the silane compound (S3), -(C _a F _2a O) _b -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}} - represents (R ^f1 is a C perfluorinated alkylene of 1, R ^f2 is a perfluorinated carbon atoms of the 2 alkylene, R ^f3 is a perfluoroalkylene having a carbon number of 3 alkylene, R ^f4 is a C4 perfluoroalkylene group, R ^f5 is a C5 perfluoroalkylene group, R ^f6 is a C6 perfluoroalkylene group, x1, x2, x3, x4, x5 and x6 Each is independently an integer of 0 or more, and x1, x2, x3, x4, x5, and x6 add up to 2, and each repeating unit may exist in any of block, alternation, and random).

From the viewpoint of industrial ease of manufacture, ease of handling, and sufficient water and oil repellency and dirt removability that can be imparted to the antifouling layer, specific examples of the silane compound (S3) are preferably the following compounds. A ¹ -O-(CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _n -CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CH ₂ O(CH ₂ ) ₃ -SiL _m R _3-m … (1-1Ha), A ¹ -O-(CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _n -CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O(CH ₂ ) ₃ -SiL _m R _3-m …(1-1Fa), A ¹ -O-(CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _n -CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ C(=O )NH(CH ₂ ) ₃ -SiL _m R _3-m …(1-3a), A ¹ -O-(CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _n -CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ (CH ₂ ) ₂ -SiL _m R _3-m …(1-4a), A ¹ -O-(CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _n -CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ (CH ₂ ) ₃ -SiL _m R _3-m …(1-5a). However, A ¹ is CF ₃ -, CF ₃ CF ₂ -, CF ₃ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ -, CF ₃ OCF ₂ CF ₂ -, CF ₃ OCF ₂ CF ₂ OCF ₂ CF ₂ -or CF ₃ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ -. n is an integer of 2 or more. SiL _m R _3-m is the same as described above.

式中，n及m分別獨立為1以上之整數，n及m之合計為2以上。[Chemical Formula 2]

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

式中，n及m分別獨立為1以上之整數，n及m之合計為2以上。[Chemical Formula 3]

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

式中，PFPE表示CF₃ CF₂ O(CF₂ CF₂ O)_n (CF₂ O)_m CF₂ CH₂ -。惟，n及m分別獨立為1以上之整數，n及m之合計為2以上。[Chemical Formula 4]

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

式中，n及m分別獨立為1以上之整數，n及m之合計為2以上。[Chemical Formula 5]

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

式中，n及m分別獨立為1以上之整數，n及m之合計為2以上。[Chemical Formula 6]

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

式中，n為2以上之整數。 [化學式8]

[Chemical Formula 7]

In the formula, n is an integer of 2 or more. [Chemical Formula 8]

式中，n為2以上之整數，m為1~10之整數，Me為甲基。[Chemical Formula 9]

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

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

When forming the antifouling layer, the second silane compound may be used alone or in combination of two or more. The anti-fouling layer may optionally contain components such as hydrolyzable silane compounds other than the second silane compound, silica, alumina, zirconia, titania and other metal oxide fine particles, dyes, pigments, anti-fouling materials, Hardening catalyst, various resins, etc. When the antifouling layer contains an arbitrary component, the ratio of the arbitrary component is preferably 15% by mass or less, and preferably 10% by mass or less. The ratio of arbitrary components in the entire antifouling layer can be set to, for example, 1 to 10% by mass.

In addition, the antifouling layer may contain impurities as arbitrary components. Impurities are compounds that cannot be avoided in the manufacture of the second silane compound. Specifically, it is a by-product generated in the manufacturing step of the second silane compound and components mixed in the manufacturing step. When the antifouling layer contains impurities, the proportion of the impurities in the entire antifouling layer is preferably 5% by mass or less, and preferably 2% by mass or less.

(Antifouling article) The antifouling article of the present invention has a base material composed of at least a part of the surface made of metal, and has the above-mentioned undercoat layer and the above-mentioned antifouling layer in this order on the surface made of metal. The anti-fouling article of the present invention may also have other components besides these as required. The undercoat layer may be formed on at least a portion of the surface of the substrate made of metal. The formation area of the undercoat layer only needs to include the formation area including the anti-fouling layer, and can be formed into a wider area than the formation area of the anti-fouling layer according to needs. The antifouling article of the present invention can be produced by forming a primer layer on the metal surface of the aforementioned substrate using a first silane compound, and using the second silane compound on the primer layer to form an antifouling layer.

[Manufacturing method of antifouling article] The method for manufacturing the antifouling article of the present invention has the following steps (I) and (II). (I) is a step of applying a composition for an undercoat layer containing a first silane compound and a first solvent on a surface of a substrate made of metal, and reacting the first silane compound to prepare an undercoat layer (hereinafter also This is called the undercoat layer forming step). (II) is a step of attaching a composition for an antifouling layer containing a second silane compound to the undercoat layer, and reacting the second silane compound to prepare 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 a second silane compound having a perfluoropolyether group and a hydrolyzable silicon group as described above.

According to the manufacturing method of the present invention, by satisfying the requirements of (i-1) and (i-2) with the first silane compound of the undercoat layer, a uniform undercoat layer can be formed on the metal surface with sufficient adhesion .

The manufacturing method of the present invention may have additional steps in addition to the steps (I) and (II). As an additional step, it is preferable to have a step of activating the metal surface of the substrate that can form the undercoat layer (step (Ib) hereinafter) performed before step (I). In addition, in the manufacturing method of the present invention, a step of post-processing the antifouling layer (hereinafter referred to as (IIa) step) may be provided after the (II) antifouling layer forming step. The following describes each step.

(Ib) Step Step (Ib) is the step of activating the metal surface. Activating the metal surface means modifying to a state where reactive groups are present on the surface. In this way, the first silane compound can be more easily bonded to the metal surface. In the present invention, the activation treatment of the metal surface can generally be applied without any limitation to the dry or wet treatment used when the metal surface is activated. For the dry treatment, treatment with active energy rays such as ultraviolet rays, electron beams, and X-rays on the surface, corona treatment, plasma treatment, flame treatment, ITRO treatment, etc. can be used. Examples of wet treatment include treatment in which the surface is contacted with an acidic or alkaline solution. In the present invention, the activation treatment suitably used is corona treatment or plasma treatment, and a combination of corona treatment or plasma treatment and wet acid treatment is suitable.

Corona treatment is the process of forming polar groups on the metal surface and roughening them. A known method can be used for the corona treatment, for example, a method using a corona treatment machine to discharge in atmospheric air. Plasma treatment is not particularly limited, there are RF plasma treatment in vacuum, microwave plasma treatment, microwave ECR plasma treatment, atmospheric piezoelectric plasma treatment, corona treatment, etc., also includes fluorine-containing gas treatment, the use of ion source Ion implantation treatment, treatment using PBII method, flame treatment exposed to thermal plasma, ITRO treatment, etc. Among these, RF plasma treatment, microwave plasma treatment, and atmospheric piezoelectric plasma treatment in vacuum are suitable.

As far as the appropriate conditions for plasma treatment are concerned, it is desirable to use the following plasma treatments: oxygen plasma or plasma containing CF ₄ , C ₂ F ₆ and other fluorine and other well-known plasmas with high chemical etching effect; or Plasma with high physical etching effect, such as Ne, Ar, Kr, Xe, is given to the metal surface. In addition, it is also appropriate to add CO ₂ , CO, H ₂ , N ₂ , NH ₄ , CH ₄ and mixed gas of these, or further add water vapor. In addition to these, it is also suitable to additionally contain selected from 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, 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 At least one or more components in the group constitute the plasma as a gas or as a decomposition product in the plasma.

When the target is processed in a short time, although the plasma has a high energy density and high kinetic energy of the ions in the plasma, it must have surface smoothness, so there is a limit to increasing the energy density. When oxygen plasma is used, it is easy to make a surface with poor adhesion to the substrate itself due to surface oxidation, and the roughness of the surface becomes larger, so the adhesion becomes worse. In addition, the plasma using Ar gas will have a pure physical impact on the surface, and the surface roughness will also increase at this time. In summary, microwave plasma treatment, microwave ECR plasma treatment, plasma irradiation using an ion source that is easy to implant high-energy ions, and the PBII method are also good.

The above activation treatment cleans the metal surface and further generates reactive groups on the metal surface. The generated reactive group is connected to the first silane compound through hydrogen bonding or chemical reaction, so that the metal surface of the substrate and the undercoat layer can be firmly bonded. Plasma treatment can also obtain the effect of etching the metal surface.

The activation treatment may be performed at least on the metal surface that can form the undercoat layer. For example, to form an undercoat layer on one main surface of a plate-shaped base material whose entire substrate is made of metal and perform plasma treatment only on the main surface, the following plasma treatment may be performed. That is, in the plasma treatment with parallel plate electrodes, by placing the substrate on the one-side electrode so as to be in contact with the main surface opposite to the main surface to be subjected to the plasma treatment, only The main surface of the substrate that is not in contact with the electrode is subjected to plasma treatment. In the plasma treatment using parallel plate electrodes, as long as the substrate is placed in a state where the substrate is electrically floated in the space between the two electrodes, the plasma treatment can be performed on both main surfaces. In addition, if plasma treatment is carried out with the protective film attached to one side of the substrate, single-sided treatment can be performed. In addition, the protective film can use PET film or polyolefin film with adhesive.

(I) Step of forming undercoat layer The step of forming the undercoat layer is on the metal surface of the substrate, ideally the metal surface after the step (Ib) above, applying the composition for the undercoat layer containing the first silane compound and the first solvent to make the first silane compound Steps to proceed the reaction. The composition for the undercoat layer contains the first silane compound and the first solvent. The first silane compound is as described above.

From the viewpoint of easy and uniform formation of the undercoat layer, the content ratio of the first silane compound in the undercoat layer composition is preferably 0.1 to 3.0% by mass, and 0.1 to 2.5% by mass relative to the total composition Good, 0.1~2.0% by mass is especially good. The first solvent is not particularly limited as long as it can dissolve the first silane compound. The first solvent should preferably have a high compatibility with the hydrolyzate of the first silane compound which has been hydrolyzed into the silanol group by the hydrolyzable silane group of the first silane compound.

As described above, the undercoat layer and the antifouling layer formed on the undercoat layer are joined by siloxane bonds at the interface. Therefore, in the undercoat layer formed in the undercoat layer forming step, a part of the silanol group included in the hydrolysate of the first silane compound reacts between the molecules and is stably present in a considerable amount. From this viewpoint, the undercoat layer prepared in the undercoat layer forming step will be combined with the antifouling layer in the next (II) antifouling layer forming step.

Specific examples of the first solvent include water and organic solvents. In addition, water is used to hydrolyze the hydrolyzable silicon group of the first silane compound. The first solvent may be composed of monomers of one compound, or may be a mixed solvent composed of two or more 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.

The non-fluorine-based organic solvent is preferably a compound composed of only hydrogen atoms and carbon atoms, and a compound composed of only hydrogen atoms, carbon atoms and oxygen atoms. 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 preferred. The alcohol-based organic solvent is preferably methanol, ethanol, propanol, isopropanol (IPA), or the like. The ketone-based organic solvent is preferably acetone, methyl ethyl ketone, methyl isobutyl ketone, or the like. As the ether-based organic solvent, diethyl ether, tetrahydrofuran, tetraethylene glycol dimethyl ether, etc. are preferred. As the ester-based organic solvent, ethyl acetate, butyl acetate, etc. are preferred.

Chlorine solvents include 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1, 2,2-tetrachloroethane, pentachloroethane, 1,1-dichloroethylene, (Z)-1,2-dichloroethylene, (E)-1,2-dichloroethylene, trichloroethylene, Tetrachloroethylene, chloroform, carbon tetrachloride, methylene chloride, etc. are suitable.

Here, the water used to hydrolyze the hydrolyzable silicon group of the first silane compound may also be supplied by moisture in the atmosphere, but it is preferable that the first solvent contains water and use the water for hydrolysis. The content ratio of water in the undercoat layer composition is preferably 0.5 to 2.0 moles, preferably 0.8 to 1.3 moles relative to 1 mole of the hydrolyzable group bonded to the silicon atom of the first silane compound. In addition, the content ratio of water in the first solvent is preferably 1 to 30% by mass relative to the total amount of the first solvent, and preferably 5 to 10% by mass.

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

The composition for an undercoat layer may contain an arbitrary component in a ratio of 20% by mass or less, preferably 5% by mass or less to the entire solid content as described above. In addition, as for other components, for example, a well-known additive such as an acid catalyst or an alkaline catalyst that promotes the hydrolysis and condensation reaction of the hydrolyzable silicon group may be included. Examples of the acid catalyst include sulfonic acid such as hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, methanesulfonic acid, and p-toluenesulfonic acid. Examples of alkaline catalysts include sodium hydroxide, potassium hydroxide, and ammonia. The content of other components of the composition for the undercoat layer is preferably 10% by mass or less relative to the total composition, and 1% by mass or less is particularly preferable.

In addition, in order to form an undercoat layer uniformly, the composition for the undercoat layer is preferably applied uniformly and smoothly on the metal surface of the substrate. After the undercoat layer composition is applied, the first silane compound reacts as described above to form an undercoat layer. That is, the first silane compound undergoes a hydrolysis reaction to generate a silanol group, and the silanol group reacts with the metal surface to form a chemical bond. Furthermore, the silanol groups undergo condensation reaction with each other to form intermolecular bonds. In addition, the silanol group is also supplied to the condensation reaction with the silanol group generated from the second silane compound in the (II) antifouling layer forming step.

The composition for an undercoat layer can be produced by mixing the above components. To apply the undercoat layer composition to the metal surface of the base material, a well-known method can be suitably used. As for the coating method, the spin coating method, the wipe coating method, the spray coating method, the blade coating method, the dip coating method, the die coating method, the inkjet method, the flow film coating method, the roll coating method, the casting method, and the Langmu- Blodget method or gravure coating method is preferred. Others can also be applied by simple methods such as hand coating and brush coating.

In order to make the thickness of the prepared undercoat layer the above-mentioned ideal thickness, the coating of the undercoat layer composition is preferably performed so that the coating amount (adhesion amount) of the first silane compound becomes 50 to 1000 mg/m ² . The coating amount of the first silane compound is preferably 50 to 500 mg/m ² , and more preferably 50 to 300 mg/m ² .

After the undercoat layer composition is applied, the first silane compound is reacted. Specifically, the coating film-like undercoat composition is heated to react the first silane compound. The heating temperature is preferably 80 to 120°C, and preferably 90 to 120°C. In addition, before the reaction, the first solvent may be removed by drying, such as heating, as necessary. The heating for the reaction of the first silane compound and the drying (heating) for the removal of the first solvent may be performed simultaneously.

(II) Anti-fouling layer forming steps In the antifouling layer forming step, the antifouling layer composition containing the second silane compound is adhered to the undercoat layer, and the second silane compound is reacted to obtain an antifouling layer. The method for attaching the composition for the antifouling layer to the undercoat layer can be exemplified by the following dry coating method or wet coating method.

In addition, when the second silane compound is blended into the composition for the antifouling layer, the second silane compound may be blended as it is, or may be blended in the form of an oligomer (partially hydrolyzed condensate). In addition, the second silane compound and its oligomer may be blended into the undercoat layer composition. In addition, when two or more kinds of second silane compounds are used in combination, each compound may be blended into the composition for the undercoat layer in its original state, or may be separately blended in the form of an oligomer, and more than two kinds of The forms of co-oligomers (partially hydrolyzed co-condensates) of the compounds are blended.

In addition, it may be a mixture of such compounds, oligomers (partially hydrolyzed condensate), and co-oligomers (partially hydrolyzed cocondensate). The oligomer and co-oligomer may have a hydrolyzable silicon group (including a hydrolyzed silanol group) and a perfluoropolyether group. Hereinafter, the composition for the antifouling layer containing the second silane compound means that in addition to the second silane compound itself, this type of oligomer and co-oligomer are contained.

(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 that contains a second silane compound and an arbitrarily contained component of the antifouling layer can be directly used. The composition for the antifouling layer for dry coating may be composed only of the second silane compound.

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

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

If the heating temperature is equal to or higher than the lower limit of the above range, the film formation rate is preferably. As long as it is below the upper limit of the above range, decomposition of the second silane compound will not occur, and the desired water and oil repellency and detergency can be imparted to the metal surface of the substrate. During vacuum evaporation, the substrate temperature should be in the range of room temperature (20~25℃) to the heat-resistant temperature of the substrate. As long as the substrate temperature is equal to or lower than the above-mentioned heat-resistant temperature, the film-forming speed is preferable. The temperature of the substrate is preferably 50°C or less of the above heat resistance temperature.

In the case of the dry coating method and the wet coating method described later, in the same manner in the present invention, in order to make the thickness of the obtained antifouling layer be the above-mentioned ideal thickness, the adhesion of the antifouling layer composition to the undercoat layer is preferably 30 ~80mg/m ^{2 is performed} as the adhesion amount of the second silane compound. The adhesion amount of the second silane compound is preferably 35 to 80 mg/m ^{2, and more} preferably 55 to 70 mg/m ² .

In the dry coating method, the reaction of the second silane compound is carried out substantially simultaneously while adjusting the substrate temperature in the same manner as described above during the film formation. At this time, a part of the silanol group generated by the hydrolysis reaction from the hydrolyzable silicon group of the second silane compound undergoes a condensation reaction to link the molecules. The silanol group generated from the second silane compound undergoes a condensation reaction with the silanol group generated from the first silane compound included in the above-mentioned undercoat layer, so that the undercoat layer and the antifouling layer are bonded through the siloxane bond. In addition, by performing post-processing steps of any of the steps described later, a stronger bond can be formed by the anti-fouling layer.

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

The application method of the application liquid can be suitably used a well-known method. The coating method specifically includes an ideal aspect, and the same method as the coating of the above-mentioned composition for an undercoat layer may be mentioned. The application amount of the coating liquid is set to the application amount of the second silane compound, and together with the ideal aspect, the adhesion amount is the same as in the case of the dry application method described above.

After applying the coating liquid, the second silane compound is reacted. Specifically, the coating liquid in the form of a film is left at a predetermined reaction temperature for a predetermined time to cause the second silane compound to react. The reaction temperature is preferably in the range of 10°C to the heat-resistant temperature of the substrate, and preferably in the range of 20°C to the heat-resistant temperature of the substrate. In addition, before the reaction, the second solvent may be removed by drying as needed. The reaction of the second silane compound and the drying to remove the second solvent can also be performed simultaneously.

The reaction of the second silane compound in the wet coating method is the same reaction as in the case of the dry coating method described above. In addition, as in the dry coating method, by performing post-processing steps of any of the steps described below, a stronger bond can be formed by the antifouling layer.

>Coating fluid> The composition (coating liquid) for the wet coating antifouling layer used in the wet coating method contains a second silane compound and a second solvent. The coating liquid only needs to contain the second silane compound as a solid component, and may contain impurities such as by-products generated in the production step of the compound in the above ratio. In addition, the above-mentioned arbitrary solid content may be contained in the above ratio. The coating liquid can be produced by mixing the second silane compound with the second solvent and optional components in an appropriate mixing container.

The second solvent is preferably liquid. The coating liquid may be a liquid, and may be 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 relative to the total amount of the coating liquid, and preferably 0.1 to 0.3% by mass.

>Second solvent> The second solvent is preferably an organic solvent. The organic solvent may be a fluorine-based organic solvent or a non-fluorine-based organic solvent, or may contain two solvents. Furthermore, the second solvent may be one kind of compound or a mixture of two or more kinds. Examples of the fluorine-based organic solvent include fluorinated alkanes, fluorinated olefins, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.

Fluorinated alkanes are preferably compounds with 4 to 8 carbon atoms. Commercial products include C ₆ F ₁₃ H (AC-2000: product name, manufactured by Asahi Glass Co., Ltd.), C ₆ F ₁₃ C ₂ H ₅ (AC-6000: product name, manufactured by Asahi Glass Co., Ltd.), C ₂ F ₅ CHFCHFCF ₃ (Vertrel: product name, manufactured by Du Pont), etc. In addition, 1,1,1,3,3-pentafluorobutane, 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 1,1,2 can also be used ,2,3,3,4-heptafluorocyclopentane, 1,1,1,2,2,3,3,4,4-nonafluorohexane, etc.

Examples of fluorinated olefins are (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 ether contained in the following formula (where R ³ can be CH ₃ , C ₂ H ₅ or a mixture of these, y1 and y2 Independently is 0, 1, 2 or 3, and y1+y2=0, 1, 2 or 3), etc.

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 fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, o-bis(trifluoromethyl)benzene, m-bis(trifluoromethyl)benzene, p-bis(trifluoromethyl) Methyl)benzene and so on. The fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms. Commercial products include CF ₃ CH ₂ OCF ₂ CF ₂ H (AE-3000: product name, manufactured by Asahi Glass Co., Ltd.), C ₄ F ₉ OCH ₃ (Novec-7100: product name, manufactured by 3M Company), C ₄ F ₉ OC ₂ H ₅ (Novec-7200: product name, manufactured by 3M Corporation), C ₆ F ₁₃ OCH ₃ (Novec-7300: product name, manufactured by 3M Corporation), perfluoro (2-butyltetrahydrofuran), etc.

Examples of fluorinated alkylamines include perfluorotripropylamine, perfluorotributylamine, and perfluorotriamylamine. Examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol. From the viewpoint of the solubility of the second silane compound, the fluorine-based organic solvent is preferably fluorinated alkane, fluorinated aromatic compound, or fluoroalkyl ether, and fluoroalkyl ether is particularly preferred.

The non-fluorine-based organic solvent is preferably a compound composed of only hydrogen atoms and carbon atoms, and a compound composed of only hydrogen atoms, carbon atoms and oxygen atoms. 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.

The hydrocarbon-based organic solvent is preferably hexane, heptane, cyclohexane, petroleum essence, toluene, and xylene. The alcohol-based organic solvent is preferably methanol, ethanol, propanol, isopropanol, and the like.

The ketone-based organic solvent is preferably acetone, methyl ethyl ketone, methyl isobutyl ketone, or the like. As the ether-based organic solvent, diethyl ether, tetrahydrofuran, tetraethylene glycol dimethyl ether, etc. are preferred. As the ester-based organic solvent, ethyl acetate, butyl acetate, etc. are preferred.

Chlorine solvents include 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1, 2,2-tetrachloroethane, pentachloroethane, 1,1-dichloroethylene, (Z)-1,2-dichloroethylene, (E)-1,2-dichloroethylene, trichloroethylene, Tetrachloroethylene, chloroform, carbon tetrachloride, methylene chloride, etc. are suitable. From the viewpoint of the solubility of the second silane compound, the non-fluorine-based organic solvent is preferably a ketone-based organic solvent.

From the viewpoint of improving the solubility of the second silane compound, the second solvent is preferably selected from fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, compounds composed only of hydrogen atoms and carbon atoms, and only At least one organic solvent in the group consisting of compounds composed of hydrogen atoms, carbon atoms, and oxygen atoms. And it is particularly preferably a fluorine-based organic solvent selected from fluorinated alkanes, fluorinated aromatic compounds and fluoroalkyl ethers.

From the viewpoint of improving the solubility of the second silane compound, the second solvent preferably contains a total of 90% by mass or more of the organic solvent, and the organic solvent is selected from the group consisting of fluorinated alkane , Fluorinated aromatic compounds, fluoroalkyl ethers, and non-fluorinated organic solvents are at least one of the group consisting of compounds consisting only of hydrogen atoms, carbon atoms, and oxygen atoms.

The coating liquid should preferably contain 70 to 99.999 mass% of the second solvent relative to the total coating liquid, and more preferably 80 to 99.99 mass %. Specific examples of the second solvent include 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 Corporation), C ₄ F ₉ OC ₂ H ₅ (Novec-7200: product name, manufactured by 3M Corporation), C ₆ F ₁₃ OCH ₃ (Novec-7300 : Product name, manufactured by 3M Company), these can be used alone, or a mixture of these can be used. The mixture is named under the name of the product, and the following combinations can be mentioned.

Can be any combination of the following: AC-6000 and AE-3000 combination, AC-6000 and Novec-7100 combination, AC-6000 and Novec-7200 combination, AC-6000 and Novec-7300 combination, AE- 3000 and Novec-7100, AE-3000 and Novec-7200, AE-3000 and Novec-7300, AC-6000 and AE-3000 and Novec-7100, AC-6000 and AE-3000 and Novec-7200 combination, AC-6000 and AE-3000 and Novec-7300 combination, Novec-7100 and Novec-7200 combination, Novec-7100 and Novec-7300 combination, Novec-7200 and Novec-7300 combination, The combination of AE-3000 and isopropanol, the combination of AC-6000 and isopropanol, the combination of AE-3000 and isopropanol, etc.

When AC-6000 and AE-3000 are used in combination, the ratio of AE-3000 should be 5 to 20% by mass relative to the total of AC-6000 and AE-3000. When AC-6000, AE-3000 and Novec-7100 are used in combination, the ratio of AE-3000 should be 0.05~0.15% by mass relative to the total amount of AC-6000, AE-3000 and Novec-7100, and Novec-7100 The ratio 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 should be 0.05~0.15% by mass relative to the total amount of AC-6000, AE-3000 and Novec-7200, and Novec-7200 The ratio 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 should be 0.05~0.15% by mass relative to the total amount of AC-6000, AE-3000 and Novec-7300, and Novec-7300 The ratio is preferably 95 to 99.5% by mass.

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

The coating liquid may further contain other ingredients as required. Other components include well-known additives such as an acid catalyst or an alkaline catalyst that can promote the hydrolysis and condensation reaction of the hydrolyzable silicon group. Examples of the acid catalyst and the alkaline catalyst are the same compounds described in the composition for the undercoat layer. The content of other components in the coating liquid should preferably account for 10% by mass or less, and preferably 1% by mass or less.

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 with a convection dryer at 120°C for 4 hours.

(IIa) Step Step (IIa) is a post-treatment step performed on the antifouling layer after forming the antifouling layer on the surface of the undercoat layer by the above-mentioned dry coating method or wet coating method. The post-treatment may be, for example, an operation to promote the reaction between the second silane compound and the undercoat layer to improve the durability against friction of the antifouling layer. Examples of this operation include heating, humidification, and light irradiation. For example, heating a substrate with an undercoat layer and an antifouling layer on the surface of an organic material in sequence in the atmosphere with moisture can promote the following reaction: The hydrolyzable silyl group of the second silane compound is hydrolyzed to a silanol group Hydrolysis reaction and condensation reaction between silanol groups on the surface of the undercoating layer and the silanol groups generated from the second silane compound and the condensation reaction of the silanol groups generated from the second silane compound to generate siloxane bonds, etc. .

In addition, after the anti-fouling layer is formed, compounds that are in the anti-fouling layer and that are not chemically bonded to other compounds or the undercoat layer can also be removed as needed. A specific method may be, for example, a method of rinsing the anti-fouling layer with a solvent such as a second solvent, or a method of wiping with a cloth soaked with a solvent such as the second solvent. Examples

In the examples, after preparing the composition for an undercoat layer and the composition for an antifouling layer for wet coating, the resulting composition was used to sequentially form an undercoat layer and an antifouling on the main surface of a plate-shaped metal substrate Layer and evaluate. In addition, Examples 1 to 3, 9, 10, 12, 14, 15, 17 are examples, and Examples 4 to 8, 11, 13, 16, 18 are comparative examples.

>Substrate> The metal substrates 1 to 5 for the test were prepared for the base material. The metal substrates shown in Table 2 were prepared and washed with the alkaline aqueous solution shown in Table 2 by the method shown in Table 2, followed by ion-exchanged water Wash. In addition, the metal substrate used for the test metal substrate 5 is a metal substrate (iron material, manufactured by SPCC) whose surface is plated with nickel and chromium plating (thickness 30 μm).

[Table 2]

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

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

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

(Composition for preparing base coat) For the above-mentioned first silane compound and the silane compound for comparative examples, isopropyl alcohol (IPA) was used as the dilution solvent as needed, and the components and the compositions for primer layer 1 to 7 shown in Table 3 were prepared. . The compositions 1 and 2 for the undercoat layer are commercial compositions directly using commercial products (concentration of silane compound: 2.0% by mass).

[table 3]

(Composition of anti-fouling layer composition) For the above-mentioned second silane compound and AC-6000 (product name, manufactured by Asahi Glass Co., Ltd.), a composition for a wet coating antifouling layer containing 0.1% by mass of the second silane compound relative to the total composition was prepared. Thing.

[Examples 1 to 8] (Activation treatment of test metal substrate) Corona treatment was performed to remove the contamination layer on the main surface of test metal substrate 1 and to impart wettability to the surface of the substrate. Corona treatment is a state where the metal substrate 1 for test is electrically floated between the two electrodes under the corona discharge with a discharge capacity of 80 W·min/m ² , with the distance between the electrode and the main surface of the metal substrate maintained at 1 to 2 mm, respectively Go through.

(Step of forming the undercoat layer) On the main surface of the test metal substrate 1 after the corona treatment, the above-mentioned prepared undercoat layer compositions 1 to 7 were applied by spin coating (coating conditions: 1000 rpm/ 30sec, adhesion amount of the first silane compound: 55 mg/m ² ), and heating on a 120°C hot plate for 10 minutes, drying to remove the solvent, and reacting the first silane compound to obtain an undercoat layer with a thickness of 5 nm.

(Step of forming antifouling layer) On the undercoat layer of the test metal substrate 1 on which the above undercoat layer is formed, the above prepared antifouling layer composition (the adhesion amount of the second silane compound: 64mg/m ² ), heated in a hot air circulation oven at 120°C for 10 minutes, dried to remove AC-6000, and reacted the second silane compound to form an antifouling layer with a thickness of 15 nm, and obtained antifouling articles of Examples 1-7 . In addition, in Example 8, an antifouling article was formed after forming an antifouling layer with a thickness of 15 nm on the main surface of the test metal substrate 1 after corona treatment without forming an undercoat layer in the same manner as above. .

[Examples 9-11] The antifouling articles of Examples 9 and 10 were produced in the same manner except that the test metal substrate 1 was replaced with the test metal substrate 2 in Examples 1 and 2. In addition, the test metal substrate 2 was corona-treated in the same manner as in Example 9, and no undercoat layer was formed. That is, a thickness was formed on one main surface of the test metal substrate 2 after the corona treatment in the same manner as above The antifouling layer of 15 nm was used as the antifouling article of Example 11.

[Example 12, 13] The antifouling article of Example 12 was produced in the same manner except that the test metal substrate 1 was replaced with the test metal substrate 3 in Example 2. In addition, the test metal substrate 3 was corona-treated in the same manner as in Example 12, and no undercoat layer was formed. That is, a thickness was formed on one main surface of the test metal substrate 3 after the corona treatment in the same manner as above The antifouling layer of 15 nm was used as the antifouling article of Example 13.

[Examples 14-16] The antifouling articles of Examples 14 and 15 were prepared in the same manner except that the test metal substrate 1 was replaced with the test metal substrate 4 in Examples 1 and 2. In addition, the test metal substrate 4 was subjected to corona treatment in the same manner as in Example 14, and no undercoat layer was formed, that is, a thickness was formed on one main surface of the test metal substrate 4 after the corona treatment in the same manner as above The antifouling layer of 15 nm was used as the antifouling article of Example 16.

[Example 17, 18] The antifouling article of Example 17 was prepared in the same manner except that the test metal substrate 1 was replaced with the test metal substrate 5 in Example 2. In addition, the test metal substrate 5 was corona-treated in the same manner as in Example 17, and no undercoat layer was formed. That is, a thickness was formed on one main surface of the test metal substrate 5 after the corona treatment in the same manner as above The antifouling layer of 15 nm was used as the antifouling article of Example 18.

(Evaluation) >Measurement method of water contact angle> For the antifouling articles of Examples 1 to 18 obtained above, a contact angle measuring device DM-500 (manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the contact angle of approximately 2 μL of distilled water placed on the surface of the antifouling layer. Measure at 5 different places on the surface of the antifouling layer and calculate the average value. The 2θ method is used to calculate the contact angle. If the water contact angle is above 100°, it can be said to have sufficient antifouling properties in actual use.

(Evaluation of abrasion resistance) According to JIS L 0849:2013 (ISO 105-X12:2001), a reciprocating plane abrasion tester (PA-300A manufactured by Daiei Seiki Co., Ltd.) was used, under load: 1 kg/cm ² , speed 60 rpm 1. Under a 40mm amplitude, rub a thin white cloth (canequim) (No. 30) back and forth, and measure the water contact angle after every predetermined number of times. The test was terminated when the water contact angle became 100° or less.

Regarding the results, Examples 1 to 8 are listed in Table 4, and Examples 9 to 18 are listed in Table 5. In Examples 4 and 5 using the undercoating compositions 4 and 5, respectively, when applying the antifouling layer composition on the undercoating layer, the antifouling layer composition was removed and the antifouling layer could not be formed . In Tables 4 and 5, "-" indicates that the water contact angle has not been measured, and the oblique line indicates that the wear resistance test has not been conducted.

[Table 4]

[table 5]

Industrial availability The anti-fouling article of the present invention can be used in a wide range of fields, such as housings for smartphones, home appliances, faucets, plumbing and other washing accessories, and elevator walls. In addition, the entire contents of the specification, patent application scope, drawings, and abstract of Japanese Patent Application No. 2018-112799, which was filed on June 13, 2018, are hereby incorporated and disclosed as the specification of the present invention.

Claims (15)

An anti-fouling article characterized by: Base material, at least part of its surface is made of metal; An undercoat layer provided on the aforementioned surface; and Antifouling layer, which is arranged on the primer layer; The aforementioned undercoat layer is a layer formed using a first silane compound, which is a silane compound having a weight average molecular weight of 500 to 200,000, has a hydrolyzable group bonded to a silicon atom, and does not have a fluorine atom, and Containing the hydrolyzable group at a ratio of 30% by mass or more relative to the entire silane compound; The aforementioned antifouling layer is a layer formed using a second silane compound having a perfluoropolyether group and a hydrolyzable silicon group. The antifouling article according to claim 1, wherein the first silane compound is a silane compound whose main chain is formed by a siloxane bond. The antifouling article according to claim 1 or 2, wherein the second silane compound has a poly(oxyperfluoroalkylene) chain and is connected through at least one end of the poly(oxyperfluoroalkylene) chain The silane compound having a hydrolyzable silicon group, and the poly(oxyperfluoroalkylene) chain system is represented by -(C _a F _2a O) _b- (where a is an integer of 1 to 6, b is 2 The above integer, -(C _a F _2a O) _b -unit may be linear or branched, and may have two or more kinds of carbon numbers different from each other -(C _a F _2a O) _b -unit). The antifouling article of claim 3, wherein the second silane compound is represented by the following formula (S3); [AO-(C _a F _2a O) _b -]Q[-SiL _m R _3-m ] _p … (S3) The symbols in the formula (S3) are as follows: A is a perfluoroalkyl group having 1 to 6 carbon atoms or -Q ¹⁰ -SiL _m R _3-m ; in (C _a F _2a O) _b , a is 1 Integer of ~6, b is an integer of 2 or more, -(C _a F _2a O) _b -unit may be linear or branched, and may have two or more different carbon numbers -(C _a F _2a O) _b -unit; Q is a (1+p) valent linking group; Q ¹⁰ is a divalent linking group; p is an integer from 1 to 10; L is a hydrolyzable group; R is a hydrogen atom or a monovalent hydrocarbon group; m is An integer from 1 to 3. The antifouling article according to any one of claims 1 to 4, wherein the thickness of the aforementioned primer layer is 3 to 200 nm. The antifouling article according to any one of claims 1 to 5, wherein the thickness of the foregoing antifouling layer is 10 to 100 nm. A method for manufacturing an anti-fouling article is a method for manufacturing the following anti-fouling article. The anti-fouling article has: Base material, at least part of its surface is made of metal; An undercoat layer provided on the aforementioned surface; and Antifouling layer, which is provided on the aforementioned primer layer; The aforementioned manufacturing method is characterized by including the following steps: Applying a composition for an undercoat layer containing a first silane compound and a first solvent to the surface and reacting the first silane compound to obtain an undercoat layer, the first silane compound is a silane compound having a weight average molecular weight of 500 to 200,000 , A hydrolyzable silicon group having a hydrolyzable group bonded to a silicon atom and no fluorine atom, and containing the aforementioned hydrolyzable group at a ratio of 30% by mass or more relative to the entire silane compound; and A composition for antifouling layer containing a second silane compound is attached to the undercoat layer and the second silane compound is reacted to obtain an antifouling layer. The second silane compound has a perfluoropolyether group and a hydrolyzable silicon group . The manufacturing method according to claim 7, wherein the first silane compound is a silane compound whose main chain is formed by a siloxane bond. The manufacturing method according to claim 7 or 8, wherein the first solvent includes a non-fluorine-based organic solvent or a non-fluorine-based organic solvent and water. The manufacturing method according to any one of claims 7 to 9, wherein the undercoat layer composition is applied so that the adhesion amount of the first silane compound is 50 to 1000 mg/m ² . The manufacturing method according to any one of claims 7 to 10, wherein the composition for an undercoat layer contains the first silane compound in a ratio of 0.1 to 3.0% by mass relative to the total amount of the composition. The manufacturing method according to any one of claims 7 to 11, wherein the second silane compound is a poly(oxyperfluoroalkylene) chain having at least one end of the poly(oxyperfluoroalkylene) chain Silane compound having a hydrolyzable silicon group through a linking group, and the poly(oxyperfluoroalkylene) chain system is represented by -(C _a F _2a O) _b- (where a is an integer of 1 to 6, b It is an integer of 2 or more, -(C _a F _2a O) _b -unit may be linear or branched, and may have two or more different carbon numbers -(C _a F _2a O) _b -unit) . The manufacturing method according to any one of claims 7 to 12, which adheres the composition for an antifouling layer such that the adhesion amount of the second silane compound is 30 to 80 mg/m ² . The manufacturing 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 attaching to the undercoat layer is coating. The manufacturing method according to claim 14, which contains the second silane compound in a ratio of 0.1 to 0.5% by mass relative to the total amount of the antifouling layer composition.