WO2008001665A1 - Antifouling film and method for producing the same - Google Patents

Abstract

Disclosed is an antifouling film comprising a supporting body and an organic-inorganic composite layer wherein a crosslinked structure formed by hydrolysis and condensation polymerization of an alkoxide of an element selected from Si, Ti, Zr and Al is contained in a graft polymer layer composed of a graft polymer chain directly bonded to the surface of the supporting body. In this antifouling film, the surface of the organic-inorganic composite layer is subjected to a water/oil repellent treatment. Also disclosed is a method for producing such an antifouling film.

Description

 Specification

 Antifouling film and method for producing the same

 Technical field

 TECHNICAL FIELD [0001] The present invention relates to an antifouling film and a method for producing the same, and more particularly to an antifouling film having an antifouling surface to which oily dirt or the like is difficult to adhere and a method for producing the same.

 Background art

 [0002] "Dirty" caused by the adhesion of contaminants to the material surface not only impairs the aesthetics but also reduces the functions of the material surface as the contamination progresses. Therefore, it is necessary to reduce the adhesion (interaction) of pollutants for “antifouling”. In general, the decrease in the adhesion of pollutants is achieved by making the material surface hydrophilic or oil repellent.

 Conventionally, as a film having water repellency and antifouling property, a film having a water repellency and antifouling property by wet coating (wet film formation) with a fluorine compound layer on the outermost surface thereof has been used. (For example, see Patent Document 1). However, surface coating with organic materials required improvements to reduce surface hardness and durability.

 [0004] In order to solve these problems, it has been studied to use a silica layer having excellent water repellency and antifouling properties and low surface energy. This silica layer has the above-mentioned surface hardness and durability. Promising for improvement. However, when a silica layer having water repellency and antifouling properties is coated on the support to obtain a film having water repellency and antifouling properties, the surface energy of the silica force layer is small, which When the adhesion between the body and the body is reduced, there is a problem.

[0005] In order to improve the adhesion between the support and the surface silica layer, it is proposed to provide an adhesion silica layer having a carbon content of less than 20 atomic% as an intermediate layer between the support and the surface silica layer. (For example, see Patent Document 2). In this method, an adhesion silica layer having a large surface energy is provided between the surface silica layer and the support to improve the adhesion between the support and the surface silica layer. However, this adhesion is sufficient. Furthermore, the surface energy, water repellency, and antifouling properties vary greatly depending on the carbon content, making it difficult to prepare. There was a point.

 Patent Document 1: Japanese Patent Laid-Open No. 2000-284102

 Patent Document 2: Japanese Patent Laid-Open No. 2002-113805

 Disclosure of the invention

 Problems to be solved by the invention

[0006] Therefore, there is a need for an antifouling film having a water and oil repellent surface having excellent adhesion to a support, having high antifouling properties and its durability, and a method for producing the same. Means for solving the problem

[0007] The present inventors have developed an organic-inorganic composite layer including a graft polymer chain directly bonded on a support and a crosslinked structure formed by hydrolysis and polycondensation reaction of a metal alkoxide. The present invention was completed by intensive research and applying the organic-inorganic composite layer to an antifouling film.

 [0008] The first aspect of the present invention is that the antifouling film of the present invention comprises Si, Ti, Zr, and the like in a graft polymer layer comprising a support and a graft polymer chain directly bonded to the surface of the support. An organic-inorganic composite layer comprising a crosslinked structure formed by hydrolysis and condensation polymerization of an alkoxide of an element selected from Al, and the surface of the organic-inorganic composite layer is subjected to a water / oil repellent treatment. Provide antifouling film.

 [0009] The graft polymer chain is preferably formed by a polymerization reaction starting from an initiation species generated on the surface of the support. Further, the graft polymer chain strength preferably includes an alkoxide group and / or an amide group of an element selected from Si, Ti, Zr, and Al in the chain. And a structural unit having a graft polymer chain strength polar group, preferably an amide group, and a structural unit having an alkoxide group of an element selected from Si, Ti, Zr, and Al, such as a silane coupling group, It is preferable to be a copolymer of the above.

[0010] According to a second aspect of the present invention, in the method for producing an antifouling film of the present invention, a graft polymer chain directly bonded to the surface of a support is generated, and a graft polymer layer comprising the graft polymer chain is formed. A step of forming an organic-inorganic composite layer by performing a crosslinking reaction by hydrolysis and condensation polymerization of an alkoxide of an element selected from Si, Ti, Zr, and Al in the graft polymer layer; Applying a water / oil repellent treatment to the surface of one inorganic composite layer; A method for producing an antifouling film is provided.

 The invention's effect

 [0011] The present invention can provide an antifouling film having a water and oil repellent treatment surface excellent in adhesion to a support, having high antifouling properties and its durability, and a method for producing the same.

 BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described in detail. In the present specification, “to” indicates a range including numerical values described before and after the minimum and maximum values, respectively.

 [0013] The antifouling film of the present invention comprises an alkoxide of an element selected from Si, Ti, Zr, and A1 in a graft polymer layer comprising a support and a graft polymer chain directly bonded to the surface of the support. And an organic monoinorganic composite layer comprising a cross-linked structure formed by hydrolysis and condensation polymerization of the organic monoinorganic composite layer, and the surface of the organic monoinorganic composite layer is subjected to a water / oil repellent treatment.

 As the antifouling film of the present invention, it is preferable that a crosslinked structure is formed using Si alkoxide because of its reactivity and availability of the compound.

 [0014] In the present invention, the above-mentioned crosslinked structure formed by hydrolysis and polycondensation of an alkoxide is hereinafter referred to as "sol-gel crosslinked structure" as appropriate.

 [0015] Such an antifouling film of the present invention is produced by the following method for producing an antifouling film of the present invention. That is, the method for producing an antifouling film of the present invention comprises a step of forming a graft polymer chain formed of a graft polymer chain by directly forming a graft polymer chain bonded directly to the surface of the support [hereinafter referred to as “graft” as appropriate. This is referred to as “polymer layer forming step”. And a step of forming an organic-inorganic composite layer by carrying out a crosslinking reaction by hydrolysis and polycondensation of an alkoxide of an element whose Si, Ti, Zr, and A1 forces are also selected in the graft polymer layer [hereinafter referred to as “organic This is referred to as “inorganic composite layer forming step”. And (3) a step of subjecting the surface of the organic / inorganic composite layer to a water / oil repellent treatment [hereinafter referred to as a “water / oil repellent treatment step” as appropriate. ] And that the method that has the power S is preferred.

 [0016] The effect of the present invention is not clear, but is estimated as follows.

The organic / inorganic composite layer in the present invention is selected from Si, Ti, Zr, and A1 in a graft polymer chain (organic component) formed by direct bonding to the support surface and a graft polymer layer comprising the graft polymer chain. Formed by hydrolysis and condensation polymerization of alkoxides And a crosslinked structure (inorganic component). Even if such an organic-inorganic composite layer is a thin layer, the wear resistance is increased and the durability is high.

 [0017] Particularly, when the graft polymer chain has a polar group, a polar interaction is formed with the cross-linked structure by the function of the polar group, and the organic-inorganic composite layer having excellent strength and durability is obtained. be able to. Furthermore, when the graft polymer chain strength has an alkoxide group of an element selected from Si, Ti, Zr, and A1 in the chain, a covalent bond is formed between the graft polymer chain and the crosslinked structure, and organic The strength and durability of one inorganic composite layer are improved. Furthermore, the crosslinked structure in the organic-inorganic composite layer has a reactive group derived from an alkoxide of an element selected from Si, Ti, Zr, and A1, and this reactive group and the water / oil repellent treatment By forming a covalent bond with the compound used for the substrate, it is possible to obtain a water / oil repellent treated surface having excellent adhesion to the support. As a result, it is presumed that an antifouling film having high antifouling properties and durability can be obtained.

 [0018] Hereinafter, the "graft polymer layer forming step", the "organic / inorganic composite layer forming step", and the "water / oil repellent treatment step" will be described in order.

 <Graft polymer layer forming step>

 In this step, a graft polymer chain directly bonded to the surface of the support is generated to form a graft polymer layer composed of the graph polymer chain.

 [0020] As a method for producing a graft polymer chain directly bonded to the surface of the support, (1) a compound having a polymerizable double bond is surface graft polymerized from the support as a base point to form a graft polymer chain. (2) A method of forming a graft polymer chain by chemically bonding a polymer having a functional group that reacts with the support and the surface of the support (hereinafter referred to as “method 1” as appropriate) Hereinafter, this is referred to as “Method 2” as appropriate.

 These two methods are described below.

 [0021] (1) A method of producing a graft polymer chain by surface graft polymerization of a compound having a polymerizable double bond from a support as a starting point (Method 1)

Method 1 is a method generally called surface graft polymerization. The surface graft polymerization method is a polymerizable double layer disposed so as to be in contact with the support by giving an active species on the surface of the support by a method such as plasma irradiation, light irradiation, or heating, and using the active species as a base point. Have a bond This is a method of polymerizing a compound. According to this method, the end of the resulting graft polymer chain is directly bonded and fixed to the support surface.

 [0022] As the surface graft polymerization method for carrying out the present invention, any known method described in literatures can be used. For example, New Polymer Experiment 10, edited by Society of Polymer Science, 1994, published by Kyoritsu Shuppan Co., Ltd., P135 describes photograft polymerization and plasma irradiation graft polymerization as surface graft polymerization methods. Also, the adsorption technique manual, NTS Co., Ltd., supervised by Takeuchi, published in February 1999, p203, p695, describes the radiation-induced graft polymerization method such as γ-rays and electron beams. As specific methods of the photograft polymerization method, methods described in JP-A-63-92658, JP-A-10-296895, and JP-A-11-119413 can be used. For the plasma irradiation graft polymerization method and the radiation irradiation graft polymerization method, the methods described in the above-mentioned literature and Y. Ikada et al, Macromolecules vol. 19, page 1804 (1986) can be applied. it can.

 [0023] Specifically, a polymer surface such as PET is treated with plasma or electron beam to generate radicals as active species on the surface, and then polymerized with a support surface having the active species. A graft polymer chain can be formed by reacting with a compound having a possible double bond (eg, a monomer).

 [0024] In addition to the above-mentioned documents, photograft polymerization is described in JP-A-53-17407 (Kansai Vint) and JP-A-2000-212313 (Dainippon Ink). It can also be carried out by applying a photopolymerizable composition to the surface of the film support, bringing the radical polymerization compound into contact with the film, and irradiating with light.

 [0025] A compound useful in producing a graft polymer chain by Method 1 needs to have a polymerizable double bond. In addition, in consideration of the formation of polar interaction with the sol-gel crosslinked structure formed in the organic-inorganic composite layer forming step described later, a double bond that can be combined and a polar group is added. It is preferable that it is a compound which has. Furthermore, in consideration of forming a covalent bond with the sol-gel crosslinked structure formed in the organic-inorganic composite layer forming step described later, it has a polymerizable double bond and a specific element alkoxide group. A compound is preferred.

[0026] The compound applied to Method 1 has a double bond in the molecule, and if necessary polar As long as it has a group and / or a specific element alkoxide group, either a polymer, an oligomer or a monomer can be used. One of the compounds useful in the present invention is a monomer having a polar group.

 [0027] Monomers having a polar group useful in the present invention include positively charged monomers such as ammonium and phosphonium, and negative charges such as sulfonic acid groups, carboxyl groups, phosphoric acid groups, and phosphonic acid groups. In addition, there is a force that includes a monomer having an acidic group that can be dissociated into a negative charge. In addition, for example, it has a nonionic group such as a hydroxyl group, an amide group, a sulfonamide group, an alkoxy group, or a cyano group. Monomers having polar groups can also be used

In the present invention, specific examples of the monomer having a particularly useful polar group include the following monomers. For example, (meth) acrylic acid or its alkali metal salts and ammine salts, itaconic acid or its alkali metal salts and amine salts, arylamine or its hydrohalides, 3-bipropionic acid or its alkali metals Salts and amine salts, vinyl sulfonic acid or alkali metal salts and amine salts thereof, styrene sulfonic acid or alkali metal salts and amine salts thereof, 2-sulfoethylene (meth) acrylate, 3-sulfopropylene (meth) acrylate or the salt thereof Alkali metal salts and amine salts, 2-acrylamide 2-methylpropanesulfonic acid or its alkali metal salts and amin salts, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate or their salts, 2-dimethylaminoethyl (Meta Atalylate or its hydrohalide salt, 3-trimethylammonium propyl (meth) atalylate, 3-trimethylammonium propyl (meth) acrylamide, N, N, N trimethyl N— (2 hydroxy-l-methacryloyloxy Propyl) ammonium chloride, etc. can be used. In addition, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N monomethylol nore (meth) acrylamide, N dimethylol (meth) acrylamide, N bulpyrrolidone, N bulacetoamide, polyoxyethylene glycol mono (meta) ) Atarirate is also useful.

[0029] A macromer having a polar group useful in the present invention can be obtained by a synthesis method described in "New Polymer Experiments 2, Polymer Synthesis and Reaction" edited by Polymer Society of Japan, Kyoritsu Publishing Co., Ltd. 1995. Can do. It is also described in detail in Yu Yamashita et al., “Macromonomer Chemistry and Industry” IPC, 1989. Specifically, using a monomer having the polar group specifically described above, such as acrylic acid, attalinoleamide, 2-atalinoleamide-2 methylpropane sulfonic acid, N vinylacetamide, etc. According to the method, a macromer having a polar group can be synthesized.

 [0030] Among the macromers having a polar group used in the present invention, particularly useful macromers having a carboxyl group-containing monomer such as acrylic acid and methacrylic acid, 2_ acrylamide _ 2_ methylpropane sulfonic acid, Sulphonic acid-based macromers derived from monomers of styrene sulfonic acid and its salts, amide-based macromers such as acrylamide and methacrylamide, N-bulu amides such as N-buluacetoamide and N-buluformamide Monomer power derived from amide macromers derived from hydroxyl group-containing monomers such as hydroxyethyl methacrylate, hydroxyethyl acrylate, glycerol monomethacrylate, methoxyethyl acrylate, methoxypolyethylene Dali Call Atarirate, It is a macromer derived from an alkoxy group or ethylenoxide group-containing monomer such as polyethylene glycol acrylate. In addition, a monomer having a polyethylene glycol chain or a polypropylene glycol chain can be usefully used as the macromer of the present invention.

 [0031] Among these macromers, it is preferable to use a macromer having an amide group as a polar group from the viewpoint that a strong polar interaction with the sol-gel crosslinked structure formed in the organic-inorganic composite layer forming step described later is formed. .

 [0032] Among these macromers, the useful molecular weight is in the range of 400 to 100,000, the preferred range is 1,000 to 50,000, and the particularly preferred range is 1500 to 20,000.

[0033] In addition, as described above, the graft polymer chain in the present invention includes an alkoxide group of an element selected from Si, Ti, Zr, and A1 (hereinafter appropriately referred to as a specific element alkoxide group and Preferably). This specific element alkoxide group is a substituent capable of forming a covalent bond through hydrolysis and polycondensation reaction with a crosslinking agent (metal alkoxide) described later. In this way, the graft polymer chain has a specific element alkoxide group, so that the sol-gel crosslinked structure formed in the organic-inorganic composite layer forming step described later and the graft polymer are formed. A covalent bond can be formed with the remer chain.

 [0034] When the surface graft polymerization method of Method 1 is used, it is preferable to use a monomer or macromer having a specific element alkoxide group. The specific element alkoxide group will be specifically described by taking a typical silane coupling group as an example. Examples of the silane coupling group suitable for the present invention include functional groups represented by the following general formula (I).

 [0035] [Chemical 1]

Formula (I)

_{^{(R 1) m (OR 2}} ) 3. M -Si-

In general formula (I), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms, and m represents an integer of 0 to 2.

[0037] Examples of the hydrocarbon group when R ¹ and R ² represent a hydrocarbon group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 8 or less carbon atoms is preferable. Specifically, methylol group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, sbutyl group, tbutyl group, isopentyl group, neopentyl group, Examples include 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.

R ¹ and R ² are preferably a hydrogen atom, a methyl group or an ethynole group from the viewpoints of effects and availability.

[0038] Monomers having a functional group as shown in the general formula (I) include (3-Atalyloxypropylene) trimethoxysilane, (3-Ataryloxypropyl) dimethylmethoxysilane, (3-Atarioxypropyl) Methyldimethoxysilane, (methacryloxymethyl) dimethylethoxysilane, (methacryloxymethyl) triethoxysilane, (methacryloxymethyl) trimethoxysilane, (methacryloxypropyl) dimethylethoxysilane, (methacryloxypropyl) dimethylmethoxysilane, (Methacryloxypropyl) methyl jetoxysilane, (methacryloxypropyl) triethoxysilane, (methacryloxypropyl) triisopropyl silane, methacryloxypropi Nore (trismethoxyethoxy) silane and the like.

 [0039] In the present invention, when Method 1 is used, a monomer or macromer having a polar group and a monomer or macromer having a specific element alkoxide group such as a silane coupling group are used in combination with a surface graft weight. It is preferable to copolymerize by a combined method to form a graft polymer chain. Among them, it is more preferable to use a monomer or macromer having an amide group as a polar group.

 [0040] (2) Method of producing a graph polymer chain by chemically bonding a polymer having a functional group that reacts with the support and the surface of the support (Method 2)

 In Method 2, a polymer having a functional group that reacts with the support at the main chain end or side chain is used, and the functional group on the surface of the support is chemically reacted to generate a graft polymer chain. be able to. The functional group that reacts with the support is not particularly limited as long as it can react with the functional group on the support surface. For example, a silane coupling group such as alkoxysilane, an isocyanate group, an amino group, and a hydroxyl group. , A carboxynole group, a sulfonic acid group, a phosphoric acid group, an epoxy group, an aryl group, a methacryloylole group, an attalyloyl group, and the like.

 [0041] Particularly useful as a polymer having a functional group that reacts with the support at the main chain end or side chain is a polymer having a trialkoxysilyl group at the polymer end, a polymer having an amino group at the polymer end, a carboxylate A polymer having a group at the polymer terminal, a polymer having an epoxy group at the polymer terminal, and a polymer having an isocyanate group at the polymer terminal.

 [0042] In addition, the polymer used at this time preferably has a polar group. Specific examples of the polymer having a polar group include polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, Examples include 2_acrylamide_2_methylpropanesulfonic acid and salts thereof, polyacrylamide, polybuluacetamide, and the like. In addition to these, a polymer of a monomer having a polar group used in the above-described method (1) or a copolymer containing a monomer having a polar group can also be used.

[0043] A polymer having an amide group as a polar group from the viewpoint that a strong polar interaction with the sol-gel crosslinked structure formed in the organic-inorganic composite layer forming step described later is formed. Is preferably used.

 On the other hand, the polymer having a functional group that reacts with the support at the main chain end or side chain further has an alkoxide group (specific element alkoxide group) of an element selected from Si, Ti, Zr, and A1. Is preferred. By using this polymer, a specific element alkoxide group can be introduced into the resulting graft polymer chain. Thus, when the graft polymer chain has a specific element alkoxide group, a covalent bond can be formed between the zonore gel cross-linked structure formed in the organic-inorganic composite layer forming step described later and the graft polymer chain.

 In the present invention, it is particularly preferable to have both an amide group and a specific element alkoxide group as a polymer-polar group having a functional group that reacts with the support at the terminal or side chain of the main chain.

 [0045] In the present invention, in the graft polymer chain produced by the above method, an amide group and an amide group are present in view of the formation of polar interaction with the zonoregel cross-linked structure and the formation of a covalent bond.

It is preferable to have a specific element alkoxide group.

[0046] A preferable introduction amount of the amide group in the graft polymer chain in the present invention is 10 mol% to 9

The range of Omol%, and the amount of alkoxide group introduced is 10mol% ~

The range is preferably 90 mol%.

[0047] The graft polymer chain in the present invention preferably has a polar group or a specific element alkoxide group as described above in the chain, but in addition to these groups, a crosslinkable group, a polymerizable group, etc. May be introduced and a cross-linked structure may be formed between the graft polymer chains by using these groups.

[0048] (Support)

 As the support in the present invention, any support having mechanical strength and dimensional stability can be used. However, when the antifouling film requires transparency, a transparent film is used. Preferably used.

[0049] Specific examples of the film used as the support include polyester films such as polyethylene terephthalate phenol, polyethylene terephthalate copolymer polyester film, and polyethylene naphthalate film; nylon 66 film, nylon 6 film Polyamide film such as polypropylene film, polyethylene film, ethylene propylene copolymer film; Polyimide film; Polyamide imide film; Polybutyl alcohol phenolic; Examples include vinylenoreconole copolymer Finorem; Polyphenylene Finolem; Polysulfone film; Polyphenylene sulfide film; and the like. Of these, polyester films such as polyethylene terephthalate film and polyolefin films such as polyethylene film and polypropylene film are preferred from the viewpoint of cost performance and transparency. These films may be stretched or unstretched, or may be used alone or may be used by laminating films having different properties.

 [0050] The film used as the support may contain various additives and stabilizers or may be coated as long as the effects of the present invention are not impaired. Examples of additives that can be used include an antioxidant, an antistatic agent, an ultraviolet ray inhibitor, a plasticizer, a lubricant, and a heat stabilizer. The film may be subjected to surface treatment such as corona treatment, plasma treatment, glow discharge treatment, ion bombardment treatment, chemical treatment, solvent treatment, or roughening treatment.

 [0051] The thickness of the support is not particularly limited because it can be set as appropriate in consideration of the suitability for the purpose of use, such as packaging material. From the viewpoint of general practical use, From the viewpoint of flexibility and workability that is preferably in the range of m to lmm, it is more preferably in the range of 10 μΐη to 300 μΐη.

 [0052] The support itself may be used as long as it can generate active species upon application of energy. However, the purpose of the generation of the starting species for forming the graft polymer chain is more efficient. In addition, a surface layer having a polymerization initiating ability may be provided on the support surface.

 [0053] The surface layer having a polymerization initiating ability is preferably a layer containing a low-molecular or high-molecular polymerization initiator. Among these, from the viewpoint of stability and durability, a polymer having a functional group having a polymerization initiating ability in a side chain and a polymer having a crosslinkable group are preferably used as a polymerization initiating layer in which a polymerization initiator is immobilized by a crosslinking reaction. A polymerization initiation layer formed by immobilization by a crosslinking reaction is more preferable.

[0054] For the polymerization initiating layer formed by immobilizing a polymer having a functional group having a polymerization initiating ability and a crosslinkable group in the side chain by a cross-linking reaction, paragraph number of JP 2004-161995 A [0011] to [0169] are described in detail, and this polymerization initiation layer can be applied to the present invention.

[0055] <Organic / inorganic composite layer forming step>

 In this step, in the graft polymer layer obtained in the aforementioned graft polymer layer forming step

An organic-inorganic composite layer is formed by carrying out a bridge reaction by hydrolysis and condensation polymerization of an alkoxide of an element selected from Si, Ti, Zr, and A1.

That is, the organic-inorganic composite layer in the present invention is a crosslinking reaction by hydrolysis and condensation polymerization of an organic component composed of a graft polymer chain and an alkoxide of an element selected from Si, Ti, Zr, and A1. It is a layer in which an inorganic component having a cross-linked structure (sol-gel cross-linked structure) formed by performing is mixed.

[0057] First, in this step, a compound capable of forming a crosslinked structure formed by hydrolysis and condensation polymerization of an alkoxide of an element whose Si, Ti, Zr, and A1 forces are also selected.

It is preferable to form the sol-gel bridge structure in the present invention using (hereinafter, sometimes simply referred to as “crosslinking agent”).

[0058] As the crosslinking agent in the present invention, for example, a compound represented by the following general formula (II) is used.

 [0059] When the graft polymer chain has a specific element alkoxide group, the compound represented by the following general formula (Π) is hydrolyzed and polycondensed with the specific element alkoxide group, whereby the graft polymer chain and the sol-gel crosslinked A covalent bond can be formed with the structure. Thereby, a strong organic-inorganic composite layer can be formed.

 [0060] [Chemical Formula 2] General Formula (I I)

(R ⁶ ) _m -X- (OR ⁷ ) ₄ .m

[0061] In the general formula ( ⁶ ), R ⁶ represents a hydrogen atom, an alkyl group, or an aryl group, R ⁷ represents an alkyl group or an aryl group, X represents Si, Al, Ti, or Zr, m represents an integer of 0-2. [0062] When R ⁶ and R ⁷ represent an alkyl group, the carbon number thereof is preferably 1 to 4. The alkyl group or aryl group may have a substituent, and examples of the substituent that can be introduced include a halogen atom, an amino group, and a mercapto group.

 This compound is a low molecular compound and preferably has a molecular weight of 1000 or less.

 [0063] Specific examples of the compound represented by the general formula (II) are shown below, but the present invention is not limited thereto.

When X is Si, i.e., the hydrolyzable compound contains silicon, for example, trimethoxysilane, triethoxysilane, tripropoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane , Methyltrimethoxysilane, ethyltriethoxysilane, _{propyltrimethoxysilane,} methyltriethoxysilane, ethyltriethoxysilane, _{propyltriethoxysilane} , dimethyldimethoxysilane, _{jetyljetoxysilane} , _Ί

—Black opening propyl triethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxy Examples thereof include silane, diphenylenomethoxymethoxy and diphenyloxysilane.

 Among these, particularly preferred are tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, dimethinolegetoxysilane, and phenolinotrimethoxysilane. , Phenoletriethoxysilane, diphenyldimethoxysilane, diphenyljetoxysilane, and the like.

 [0064] Further, when X is A1, that is, as the hydrolyzable compound containing aluminum, for example, trimethoxy aluminate, triethoxy aluminate, tripropoxy aluminate, tetraethoxy aluminate, etc. Can be mentioned.

When X is Ti, i.e., titanium includes, for example, trimethoxy titanate, tetramethoxy titanate, triethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, chlorotrimethoxy titanate, chlorotriethoxy titanate, ethinoretrimethoxy Titanate, methyl triethoxy titanate, etyl triethoxy titanate, dimethyl jetoxy titanate, phenyl trimethoxy titanate, phenyl triethoxy titanate Can be listed.

 When X is Zr, that is, those containing zirconium, for example, zirconates corresponding to the compounds exemplified as those containing titanium can be mentioned.

[0065] In order to form a sol-gel crosslinked structure in the graft polymer layer using such a crosslinking agent, the crosslinking agent is dissolved in a solvent such as ethanol, and then a catalyst or the like is added as necessary. A method can be used in which a composition is prepared, applied onto the graft polymer layer, heated and dried. By this method, a sol-gel crosslinked structure is formed by hydrolysis and polycondensation of the crosslinking agent.

 Here, the heating temperature and the heating time are not particularly limited as long as the solvent in the coating solution is removed and a strong film can be formed, but the heating temperature is 200 ° C from the viewpoint of production suitability and the like. The heating time (crosslinking time) preferably below is preferably within 1 hour.

 [0066] The content of the cross-linking agent in the coating liquid composition may be determined according to the amount of the sol-gel cross-linking structure to be formed, but the surface hardness of the formed organic-inorganic composite layer and the adhesion to the support. From the viewpoint of sex, in general, it is preferable to be in the range of 5-50% by mass, more preferably in the range of 10-40% by mass.

 [0067] When the graft polymer chain has a specific element alkoxide group in the chain, the content of the crosslinking agent in the coating solution composition is such that the crosslinking group in the crosslinking agent is relative to the specific element alkoxide group. Is preferably adjusted to an amount of 5 mol% or more, more preferably 10 mol% or more. In this case, the upper limit of the content of the cross-linking agent is not particularly limited as long as it is within a range that can sufficiently cross-link with the specific element alkoxide group, but when added in a large excess, the organic agent formed by the cross-linking agent not involved in the cross-linking. Problems such as stickiness of the inorganic composite layer may occur.

 [0068] The solvent used in preparing the coating liquid composition is not particularly limited as long as it can uniformly dissolve and disperse the crosslinking agent and other components. For example, methanol, ethanol, An aqueous solvent such as water is preferred.

[0069] In addition, in order to promote the hydrolysis and polycondensation reaction of the crosslinking agent in the coating liquid composition, it is preferable to use an acidic catalyst or a basic catalyst in combination. A catalyst is essential when trying to obtain As this catalyst, an acid or a basic compound can be used as it is, or it can be dissolved in a solvent such as water or alcohol. (Hereinafter referred to as acidic catalyst and basic catalyst, respectively) can be used. The concentration at which the catalyst is dissolved in the solvent is not particularly limited, and may be appropriately selected according to the characteristics of the acid or basic compound used, the desired content of the catalyst, etc. Hydrolysis and polycondensation rates tend to increase. However, if a basic catalyst with a high concentration is used, precipitates may be generated in the coating liquid composition. Therefore, when a basic catalyst is used, the concentration should be 1 N or less in terms of concentration in an aqueous solution. Is desirable.

 [0070] The type of the acidic catalyst or basic catalyst is not particularly limited, but if it is necessary to use a highly concentrated catalyst, the catalyst is composed of an element that hardly remains in the coating film after drying. Is good. Specifically, the acid catalyst includes hydrogen halides such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, formic acid, acetic acid and other rubonic acids, and their RCOOH. Examples thereof include substituted carboxylic acids obtained by substituting R in the structural formula with other elements or substituents, sulfonic acids such as benzenesulfonic acid, and the like, and basic catalysts include ammoniacal bases such as aqueous ammonia, ethylamine Amines such as diphosphorus are listed.

 [0071] In addition, various additives can be used in this coating solution composition depending on the purpose as long as the effects of the present invention are not impaired. For example, a surfactant or the like can be added to improve the uniformity of the coating solution.

 In the present invention, the graft polymer layer and the organic-inorganic composite layer may be formed by the following method. That is, for example, in addition to the polar group and the specific element alkoxide group as described above, a coating liquid composition containing a polymer having a functional group that reacts with the support at the main chain terminal or side chain, a crosslinking agent, and a catalyst. There is a method in which a product is prepared, treated with plasma, electron beam or the like, coated on a support on which radicals as active species are generated on the surface, heated and dried.

[0073] In this method, the functional group that reacts with the support of the polymer reacts with the support, whereby a graft polymer directly bonded to the support is formed, and a graft polymer layer is formed. Further, when the coating liquid composition is heated and dried, hydrolysis and polycondensation reaction of the crosslinking agent occurs, and a crosslinked structure can be formed in the graft polymer layer. In other words, according to such a method, when a coating liquid composition is prepared and applied, heated and dried, Through a series of steps, the graft polymer layer and the organic-inorganic composite layer can be formed at a time.

 [0074] In preparing this coating solution composition, a hydrophilic polymer may be included separately. The hydrophilic polymer can be obtained by polymerizing a monomer having a polar group useful for forming the graft polymer chain mentioned above. The content of the hydrophilic polymer is preferably 10% by mass or more and less than 50% by mass in terms of solid content. When the content is 50% by mass or more, the film strength tends to decrease. When the content is less than 10% by mass, the film characteristics are decreased, and the possibility of cracks in the film increases. Absent.

 [0075] As described above, the formation of the organic-inorganic composite layer in the present invention uses the sol-gel method. Regarding the Zonoregel method, Sakuo Sakuo "Sol-Gel Science", Agne Jofusha (published) (1988), Satoshi Hirashima "Functional Thin Film Making Technology Using the Latest Zonole-Gel Method" General Technology Center (Published) (1992) and the like, and the methods described therein can be applied to the formation of the organic-inorganic composite layer in the present invention.

 [0076] The film thickness of the organic-inorganic composite layer can be selected depending on the application of the antifouling film, but generally the range of 0.1 / 1 111 to 10/1 111 is preferred 0.5. The range of / 1 111 to 10/1 111 is even better. Within this film thickness range, an antifouling film excellent in adhesion and flexibility to the support is obtained, and curling is not likely to occur, and flexibility is less likely to cause a decrease in bending resistance. Good.

 [0077] <Water / oil repellent treatment process>

 In this step, the surface of the organic / inorganic composite layer obtained in the organic / inorganic composite layer forming step is subjected to water / oil repellent treatment.

 [0078] There are no particular limitations on the compound (water repellent) and the treatment method used in the water / oil repellent treatment in the present invention, but it is preferable that a fluorine or alkyl group is imparted to the surface of the organic-inorganic composite layer. Masle. For the water / oil repellent treatment, for example, an organometallic compound such as a silylating agent, a titanate coupling agent, or alkylaluminum is preferably used.

[0079] Since these compounds can form a covalent bond with the crosslinked structure in the present invention, the water- and oil-repellent treated surface is excellent in adhesion to the support. [0080] The silylating agent is a compound in which an alkyl group, aryl group, fluorine-containing fluoroalkyl group, or the like is bonded to a hydrolyzable silyl group having affinity or reactivity for the sol-gel crosslinked structure in the present invention. Examples of the hydrolyzable group bonded to silicon include an alkoxy group, a halogen atom, an acetoxy group, and a silazane. Specifically, it is preferable to use a perfluoroalkylsilane compound or an alkylsilane compound.

 [0081] Further, in order to reduce the critical inclination angle of the water- and oil-repellent treated surface so that water droplets can easily fall down, a polydimethylsiloxane compound may be used as a water-repellent agent. . The critical inclination angle of the water / oil repellent treatment surface is the inclination angle of the plate where a certain amount of water drops placed on the surface of the antifouling film start rolling. The water repellent is hydrolyzed as necessary before being used for coating the water repellent layer.

 [0082] The surface treatment with the water repellent as described above is performed by spraying, flow coating, spin coating, dipping and lifting, or surface adsorption by liquid phase adsorption.

[0083] The surface treated with the water repellent is dried and then at a temperature of 300 ° C or lower, preferably 100 ° C to 250 ° C.

Heat at ° C for 10 minutes to 1 hour.

[0084] If the water-repellent agent forms a monomolecular layer on the surface of the organic-inorganic composite layer, it exhibits water-repellent performance.

Even if the thickness of the water repellent exceeds 10 nm, the effect does not increase any more. Therefore, the preferred thickness of the water / oil repellent treated layer after the heat treatment is lnm˜:! Onm.

As described above, the antifouling film of the present invention is excellent in the adhesion between the water / oil repellent treated surface and the organic / inorganic composite layer, and the adhesion between the organic / inorganic composite layer and the support, As a result, the water and oil repellent surface is excellent in adhesion to the support. Therefore, the antifouling film of the present invention is excellent in antifouling property and excellent in its sustainability.

 Example

 [0086] The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

[0087] [Example 1]

 <Preparation of base material A>

Biaxially stretched polyethylene terephthalate film with a film thickness of 188 / im (A4100, Toyobo Co., Ltd.) Using a lithographic magnetron sputtering device (CFS-10-EP70, manufactured by Shibaura ELECTRIC CO., LTD.) As a glow treatment device, an oxygen glow treatment was performed under the following conditions to obtain a PET support.

 [0088] One oxygen glow-One treatment condition

Initial vacuum: 1. 2 X 10— ³ Pa

 Oxygen pressure: 0.9 Pa

 RF Glow: 1.5kW

 Processing time: 60sec

 [0089] <Formation of graft polymer layer 1>

 Next, N, N-dimethylacrylamide 1 ethoxysilane and ethanol mixed solution (N, N-dimethylacrylamide: metathari J ethoxysilane = 1: 1 (molar ratio), concentration: 50 mass%) were nitrogen-published. The PET support was immersed in this mixed solution at 70 ° C for 7 hours. After the immersion, the PET support is thoroughly washed with ethanol, and the graft polymer layer is formed by directly bonding the graft polymer chain having the silane coupling group and amide group, which are specific element alkoxide groups, in the structure to the support surface. Formed. The PET support having this graft polymer layer was designated as support A.

 [0090] <Formation of organic-inorganic composite layer 1>

 A coating solution composition 1 containing ethanol, water, tetraethoxysilane, and phosphoric acid in the following amounts was stirred on a support for 24 hours at room temperature, and heated at 100 ° C for 10 minutes. An organic / inorganic hybrid film A was obtained by drying to form an organic / inorganic composite layer.

 [0091] One coating composition 1

 'Tetraethoxysilane (crosslinking agent) 0.9 g

 'Ethanor 3.7 g

 'Water 8.7 g

 • Phosphoric acid aqueous solution (0.85% aqueous solution) 1.3 g

 [0092] <Water / oil repellent treatment>

The obtained organic-inorganic hybrid film A was mixed with 0.1% by mass of 1H, 1H, 2H, 2H An antifouling film A was obtained by dipping in a solution of monofluorodecyltrichlorosilane / hexane for 10 minutes, pulling up, and drying by heating (100 ° C., 30 min). The total thickness of the formed water / oil repellent layer and organic / inorganic composite layer was 500 nm.

[0093] [Example 2]

 In <Formation of organic one-inorganic composite layer 1> in Example 1, 0.9 g of tetraethoxysilane contained in the coating liquid composition 1 used for forming the organic one-inorganic composite layer was changed to tetramethoxytitanate 1. Og. An antifouling film B was obtained in the same manner as in Example 1 except that it was replaced.

[0094] [Example 3]

 In <Formation of organic-inorganic composite layer 1> in Example 1, 0.9 g of tetraethoxysilane contained in coating liquid composition 1 used for forming the organic-inorganic composite layer was changed to 1.6 g of tetramethoxyzirconate. An antifouling film C was obtained in the same manner as in Example 1 except that it was replaced.

[0095] [Example 4]

 In <Formation of organic-inorganic composite layer 1> in Example 1, 0.9 g of tetraethoxysilane contained in coating liquid composition 1 used for forming the organic-inorganic composite layer was replaced with 0.7 g of trimethoxyaluminate. Except for the above, an antifouling film D was obtained in the same manner as in Example 1.

[0096] [Example 5]

 In Example 1, <Formation of graft polymer layer 1> was changed to <Formation of graft polymer layer 2> below to prepare support B, and further used in <Formation of organic-inorganic composite layer 1> An antifouling film E was obtained in the same manner as in Example 1 except that the support A was changed to the support B to produce an organic-inorganic hybrid film B.

 [0097] <Formation of graft polymer layer 2>

 An aqueous acrylamide solution (concentration: 50% by mass) was subjected to nitrogen publishing. The PET support used in Example 1 was immersed in this aqueous solution at 70 ° C for 7 hours. The immersed PET support was thoroughly washed with distilled water to form a graft polymer layer in which a graft polymer chain having an amide group in the structure was directly bonded to the support surface. The PET support having this graft polymer layer was designated as support B.

 [Example 6]

<Formation of graft polymer layer 3> Methacryloxypropyl triethoxysilane ethanol solution (concentration: 50 mass _^0/0) were nitrogen Paburingu. The PET support used in Example 1 was immersed in this solution at 70 ° C. for 7 hours. After the immersion, the PET support is thoroughly washed with distilled water, and a graft polymer layer having a structure in which a graft polymer chain having a silane coupling group which is a specific element alkoxide group is directly bonded to the support surface is formed. Formed. The PET support having this graft polymer layer was designated as support C.

 [0099] Formation of organic-inorganic composite layer 2>

 On the obtained support C, a coating solution composition 2 containing 2_propanol, water, tetraethoxysilane, and phosphoric acid in the following amounts was stirred at room temperature for 5 hours, and then coated at 100 ° C., 10 Organic-inorganic hybrid film C was obtained by heating and drying for a minute to form an organic-inorganic hybrid layer.

 [0100] One coating composition 2—

 • 2 Propanore 8g

 .Tetraethoxysilane [Crosslinking agent] 1 · Og

 'Water 1. Og

 • Phosphoric acid aqueous solution (0.85% aqueous solution) 1. Og

 [0101] <Water and oil repellent treatment>

 The obtained organic / inorganic hybrid film C was treated in the same manner as the water / oil repellent treatment> in Example 1 to obtain an antifouling film F.

 The total thickness of the formed water / oil repellent layer and the organic / inorganic composite layer was 1.2 μm.

[0102] [Comparative Example 1]

 2_ (perfluorobutyl) ethyl acrylate (manufactured by Azmax Co., Ltd.) 0.5 g, 1-methoxy-2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.) 0.5 g, Mix to make a homogeneous solution. The PET support used in Example 1 was immersed in this solution at 70 ° C. for 7 hours. After the immersion, the PET support is thoroughly washed with ethanol to obtain an antifouling finalem G in which the graft polymer chain (hydrophobic graft polymer chain) containing fluorine atoms in the structure is directly bonded to the support surface. It was.

[0103] [Comparative Example 2] The antifouling film H was obtained in the same manner as in Example 1 except that the support (PET support having a graft polymer layer) A used in Example 1 was replaced with polyethylene terephthalate. It was.

 [0104] [Performance evaluation of antifouling film]

 Examples:! To 6, and antifouling films A to H of Comparative Examples 1 and 2 were evaluated for performance as follows. The results are shown in Table 1 below.

 [0105] 1. Evaluation of water repellency

 Anti-fouling film A to H water- and oil-repellent treated surfaces (in the antifouling film G, the surface where the graft polymer chains containing fluorine atoms are directly bonded), manufactured by Kyowa Interface Science Co., Ltd., CA- After using Z, and dropping pure water, the angle after 20 seconds was measured. A with a water droplet contact angle of 150 ° or more was designated as A. The results are shown in Table 1.

 [0106] 2. Evaluation of adhesion

 In accordance with JIS K5400, the surface of the antifouling film A to H is a rotary cutter against the water and oil repellent treated surface (in the antifouling film G, the surface where the graft polymer chains containing fluorine atoms are directly bonded). After attaching 100 square grids of lmm squares and crimping the cello tape (manufactured by Nichiban Co., Ltd., registered trademark), a 90 ° peel test was performed 3 times at a speed of 30000 mm / min. The evaluation was performed by measuring the number of cells remaining after the peel test. The results are shown in Table 1.

 [0107] 3. Evaluation of antifouling property

 3.1 Evaluation of initial antifouling property

 Anti-fouling film A to H water- and oil-repellent treated surfaces (in the anti-fouling film G, the surface where the graft polymer chains containing fluorine atoms are directly bonded) "(Registered trademark)). Next, the number of times until the characters were wiped clean using “Bemcoton” (registered trademark) manufactured by Asahi Kasei Corporation was measured. The results are shown in Table 1.

 [0108] 3.12 Repeated antifouling evaluation

Using “Bem Cotton” (registered trademark) manufactured by Asahi Kasei Co., Ltd., the water- and oil-repellent treated surfaces of the antifouling films A to H (in the antifouling film G, the graft polymer chains containing fluorine atoms are directly bonded. After the surface was rubbed strongly 500 times, letters were written on the surface with quick-drying oil-based ink (Zebra, “Mackey” (registered trademark)), and the number of times until it was wiped off was shown. The results are shown in Table 1.

 [table 1]

[0110] From the results in Table 1, the antifouling films A to F of the examples having an organic-inorganic composite layer have good water repellency and good adhesion between the support and the water / oil repellent treatment layer. I understand. Further, the antifouling films A to F of the examples are excellent in initial antifouling property and repeated antifouling property. From these facts, it can be seen that the antifouling film of the present invention is excellent in antifouling property and its sustainability.

 Industrial applicability

[0111] The antifouling film of the present invention is suitable for a display such as CRT, LCD, PDP, and FED, touch panel, glass, table, decorative plywood, and the like, as well as a surface protective film for recording media such as CD and DVD. Can adapt.

[0112] The disclosure of Japanese application 2006—182291 is hereby incorporated by reference in its entirety. All documents, patent applications, and technical standards mentioned in this specification are

, Patent applications, and technical standards are incorporated herein by reference to the same extent as if specifically and individually stated to be incorporated by reference.

Claims

The scope of the claims

 [1] It is formed by hydrolysis and condensation of an alkoxide of an element selected from Si, Ti, Zr, and A1 in a graft polymer layer composed of a support and a graft polymer chain directly bonded to the support surface. And an organic-inorganic composite layer comprising a crosslinked structure, and the surface of the organic-inorganic composite layer is subjected to a water / oil repellent treatment.

 [2] The antifouling film according to claim 1, wherein the chain strength of the graft polymer has an alkoxide group of an element selected from Si, Ti, Zr, and A1 in the chain.

 [3] The method for producing a photocatalytic film according to claim 2, wherein the alkoxide group is a group represented by the following general formula (I). .

 [Chemical 1]

General formula (I)

In general formula (I), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms, and m represents an integer of 0 to 2.

[4] The antifouling finem according to claim 1, wherein the graft polymer chain has an amide group in the chain.

 [5] The antifouling film according to claim 4, wherein the introduction amount of amide groups in the graft polymer chain is in the range of 10 mol% to 90 mol%.

6. The graft polymer chain strength is a copolymer having a structural unit having an amide group and a structural unit having an alkoxide group of an element selected from the group force consisting of Si, Ti, Zr, and A1. The antifouling film described in 1.

7. The method for producing a photocatalytic film according to claim 6, wherein the alkoxide group is a group represented by the following general formula (I). . [Chemical 2]

Formula (I)

(R ¹ ) _m (OR ² ) ₃ _ _m —Si—

In general formula (I), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms, and m represents an integer of 0 to 2.

8. The antifouling film according to claim 1, wherein the water / oil repellent treatment is a surface treatment using a compound used for the water / oil repellent treatment.

9. The antifouling film according to claim 8, wherein the compound used for the water / oil repellent treatment is a silylating agent, a titanate coupling agent, or an alkylaluminum.

[10] generating a graft polymer chain directly bonded to the surface of the support to form a graft polymer layer having the graft polymer chain force;

 A step of forming an organic-inorganic composite layer by performing a crosslinking reaction by hydrolysis and condensation polymerization of an alkoxide of an element selected from Si, Ti, Zr, and A1 in the graft polymer layer; and the surface of the organic-inorganic composite layer Applying water and oil repellent treatment to the

 A method for producing an antifouling film having

[11] The antifouling agent according to claim 10, wherein the graft polymer chain force is a graft polymer chain formed using a monomer or a macromer having an alkoxide group of an element selected from the group consisting of Si, Ti, Zr, and A1. For producing a conductive film.

12. The method for producing an antifouling film according to claim 11, wherein the alkoxide group is a group represented by the following general formula (I). .

[Chemical 3] Formula (I)

(R ¹ ) _m (OR ² ) ₃ _ _m —Si—

In general formula (I), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms, and m represents an integer of 0 to 2.

13. The method for producing an antifouling film according to claim 10, wherein the graft polymer chain strength is a graft polymer chain formed by using a monomer or a macromer having an amide group.

14. The method for producing an antifouling film according to claim 13, wherein the introduction amount of amide groups in the graft polymer chain is in the range of 10 mol% to 90 mol%.

[15] The copolymer produced by using the monomer having a graft polymer chain strength amide group and a monomer having an alkoxide group of an element selected from the group force consisting of Si, Ti, Zr, and A1. 14. A method for producing an antifouling film according to 14.

16. The method for producing an antifouling film according to claim 15, wherein the alkoxide group is a group represented by the following general formula (I).

 [Chemical 4]

Formula (I)

(R ¹ ) _m (OR ² ) ₃ _ _m — Si—

In general formula (I), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms, and m represents an integer of 0 to 2.

[17] The cross-linking reaction is a cross-linking reaction by hydrolysis and condensation polymerization of an alkoxide of an element selected from Si, Ti, Zr, and A1 included in the graft polymer layer and a cross-linking agent. The manufacturing method of the antifouling film of description.

 18. The method for producing an antifouling film according to claim 17, wherein the crosslinking agent is a compound represented by the following general formula (II).

 [Chemical 5]

(General formula Ι Ι)

(R ⁶ ) _m -X- (OR ⁷ ) _{4. m}

In general formula (Π), R ⁶ represents a hydrogen atom, an alkyl group, or an aryl group, R ⁷ represents an alkyl group or an aryl group, X represents Si, Al, Ti, or Zr, and m represents 0. Represents an integer of ~ 2.

 19. The method for producing an antifouling film according to claim 10, wherein the water / oil repellent treatment is a surface treatment using a compound used for the water / oil repellent treatment.

 20. The method for producing an antifouling film according to claim 19, wherein the compound used for the water / oil repellent treatment is a silylating agent, a titanate coupling agent, or an alkylaluminum.