JP2008007729A - Stain-resistant film and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an stain-resistant film that is provided with a water-repellent and oil-repellent treatment surface having excellent adhesivity to a substrate and has high stain resistance and its durability and to provide a method for producing the same. <P>SOLUTION: The stain-resistant film comprises a substrate and an organic-inorganic composite layer having a crosslinking structure formed by hydrolysis and condensation polymerization of an alkoxide of an element selected from Si, Ti, Zr and Al in a graft polymer layer composed of a graft polymer chain directly bonded to the surface of the substrate and is obtained by subjecting the surface of the organic-inorganic composite layer to water-repellent and oil-repellent treatment. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  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 hardly adheres and a method for producing the same.

  The “dirt” caused by the contaminants adhering to the surface of the material not only impairs the appearance but also reduces the function of the material surface due to the progress of the contamination. Thus, for “antifouling”, it is necessary to reduce the adhesion (interaction) of contaminants, and it is generally 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 has been used by wet coating (wet film formation) with a fluorine compound layer on the outermost surface (for example, (See Patent Document 1).
However, surface coating with an organic material has low surface hardness and durability, and it is necessary to improve them.
In order to solve these problems, the use of a silica layer having excellent water repellency and antifouling properties and low surface energy has been studied, and this silica layer is promising for improving the surface hardness and durability described above. Is being viewed.
However, when a silica layer having water repellency and antifouling properties is coated on a support to obtain a film having water repellency and antifouling properties, the surface energy of the silica layer is small, so There is a problem that the adhesion is reduced.

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, since the surface energy, water repellency, and antifouling properties vary greatly depending on the carbon content, there is a problem that the preparation thereof is difficult.
JP 2000-284102 A JP 2002-113805 A

  The object of the present invention in consideration of the above-mentioned problems of the prior art is to provide a water- and oil-repellent treated surface excellent in adhesion to a support, and have a high antifouling property and its durability. It is in providing the manufacturing method.

  As a result of diligent research on 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, It has been found that the above-mentioned problems can be solved by applying the organic-inorganic composite layer to an antifouling film, and the present invention has been completed.

That is, the antifouling film of the present invention is obtained by adding an alkoxide of an element selected from Si, Ti, Zr, and Al in a graft polymer layer comprising a support and a graft polymer chain directly bonded to the support surface. An organic-inorganic composite layer comprising a crosslinked structure formed by decomposition and condensation polymerization, and the surface of the organic-inorganic composite layer is subjected to a water / oil repellent treatment.
Such a graft polymer chain is preferably generated by a polymerization reaction starting from the starting species generated on the surface of the support.
The graft polymer chain preferably has an alkoxide group and / or an amide group of an element selected from Si, Ti, Zr, and Al in the chain.
Furthermore, the graft polymer chain is a co-polymer of a structural unit having a 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 a preferred embodiment that it is a coalescence.

  Further, the method for producing an antifouling film of the present invention comprises a step of forming a graft polymer chain directly bonded to the surface of a support to form a graft polymer layer comprising the graft polymer chain, and in the graft polymer layer. A step of forming an organic-inorganic composite layer by performing hydrolysis and condensation polymerization of an alkoxide of an element selected from Si, Ti, Zr, and Al, and a water / oil repellent treatment on the surface of the organic-inorganic composite layer And the step of applying.

Although the operation of the present invention is not clear, it is estimated as follows.
The organic-inorganic composite layer in the present invention is selected from Si, Ti, Zr, and Al in the graft polymer chain (organic component) formed by direct bonding to the support surface and the graft polymer layer comprising the graft polymer chain. And a crosslinked structure (inorganic component) formed by hydrolysis and condensation polymerization of the alkoxide of the element. Even if such an organic-inorganic composite layer is a thin layer, the wear resistance is increased and it has high durability.
In particular, when the graft polymer chain has a polar group, a polar interaction is formed with the crosslinked structure by the function of the polar group, and an organic-inorganic composite layer having excellent strength and durability can be obtained. Further, when the graft polymer chain has an alkoxide group of an element selected from Si, Ti, Zr, and Al in the chain, a covalent bond is formed between the graft polymer chain and the crosslinked structure, and organic -The strength and durability of the 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 Al. The reactive group and the water / oil repellent treatment By forming a covalent bond with the compound used in the above, a water / oil repellent treated surface having excellent adhesion to the support can be obtained.
As a result, it is presumed that an antifouling film having high antifouling properties and its durability can be obtained.

  ADVANTAGE OF THE INVENTION According to this invention, the antifouling film which has the water- and oil-repellent treatment surface excellent in the adhesiveness with respect to a support body, has high antifouling property and its durability, and its manufacturing method can be provided.

Hereinafter, the present invention will be described in detail.
The antifouling film of the present invention comprises hydrolysis of an alkoxide of an element selected from Si, Ti, Zr and Al in a graft polymer layer comprising a support and a graft polymer chain directly bonded to the support surface. And an organic-inorganic composite layer comprising a crosslinked structure formed by condensation polymerization, and the surface of the organic-inorganic 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 by using Si alkoxide in view of reactivity and availability of the compound.
In the present invention, the above-described crosslinked structure formed by hydrolysis and condensation polymerization of the alkoxide is hereinafter referred to as “sol-gel crosslinked structure” as appropriate.

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, in the method for producing an antifouling film of the present invention, a step of forming a graft polymer chain directly bonded to the support surface and forming a graft polymer layer comprising the graft polymer chain [hereinafter referred to as “graft polymer” This is referred to as a “layer formation step”. And 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 [hereinafter, This is referred to as “organic-inorganic composite layer forming step”. And (3) a step of performing a water / oil repellent treatment on the surface of the organic-inorganic composite layer [hereinafter referred to as a “water / oil repellent treatment step” as appropriate. It is preferable that a method having the following is applied.
Hereinafter, the “graft polymer layer forming step”, “organic-inorganic composite layer forming step”, and “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 support surface is generated to form a graft polymer layer composed of the graft polymer chain.
As a method of generating a graft polymer chain directly bonded to the support surface, (1) a method of generating a graft polymer chain by surface-grafting a compound having a polymerizable double bond from the support as a base point, (2) There is a method of forming a graft polymer chain by chemically bonding a polymer having a functional group that reacts with a support and the surface of the support.
These two methods will be described below.

(1) A method in which a graft polymer chain is formed by surface graft polymerization of a compound having a polymerizable double bond from a support as a starting point. This method is generally referred to as surface graft polymerization. The surface graft polymerization method is a polymerizable double bond arranged so as to be in contact with the support from the active species by providing the active species on the support surface by plasma irradiation, light irradiation, heating or the like. This is a method of polymerizing a compound having the following. According to this method, the end of the resulting graft polymer chain is directly bonded and fixed to the support surface.

Any known method described in the literature can be used as the surface graft polymerization method for carrying out the present invention. For example, New Polymer Experiment 10, edited by Polymer Society, 1994, published by Kyoritsu Shuppan Co., Ltd., P135 describes a photograft polymerization method and a plasma irradiation graft polymerization method as surface graft polymerization methods. In addition, the adsorption technique handbook, NTS Co., Ltd., supervised by Takeuchi, 1999.2, p203, p695 describes radiation-induced graft polymerization methods such as γ rays and electron beams. As a specific method of the photograft polymerization method, the methods described in JP-A-63-92658, JP-A-10-296895, and JP-A-11-119413 can be used. In the plasma irradiation graft polymerization method and the radiation irradiation graft polymerization method, the literatures described above and Y.C. Ikada et al, Macromolecules vol. 19, page 1804 (1986), and the like can be applied.
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 2 A graft polymer chain can be generated by reacting a compound having a heavy bond (for example, a monomer).
In addition to the above-mentioned documents, photograft polymerization can be carried out as described in JP-A No. 53-17407 (Kansai Paint) and JP-A No. 2000-212313 (Dainippon Ink). It can also be carried out by applying a photopolymerizable composition to the surface, bringing a radical polymerization compound into contact with the surface and irradiating light.

A compound useful in producing a graft polymer chain by the 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, it is a compound having a polymerizable double bond and having a polar group. Is preferred. 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.
As a compound applied to this method, a polymer, an oligomer, a monomer, a monomer having a double bond in the molecule and, if necessary, a polar group and / or a specific element alkoxide group may be used. Any compound can be used.
One of the compounds useful in the present invention is a monomer having a polar group.

  Monomers having a polar group useful in the present invention include positively charged monomers such as ammonium and phosphonium, negatively charged or negatively charged monomers such as sulfonic acid groups, carboxyl groups, phosphoric acid groups, and phosphonic acid groups. Monomers having acidic groups that can be dissociated by charge are mentioned, but in addition, monomers having polar groups having nonionic groups such as hydroxyl groups, amide groups, sulfonamido groups, alkoxy groups, cyano groups, etc. 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 salt and amine salt, itaconic acid or its alkali metal salt and amine salt, allylamine or its hydrohalide salt, 3-vinylpropionic acid or its alkali metal salt and amine salt Vinyl sulfonic acid or its alkali metal salt and amine salt, styrene sulfonic acid or its alkali metal salt and amine salt, 2-sulfoethylene (meth) acrylate, 3-sulfopropylene (meth) acrylate or its alkali metal salt and amine salt 2-acrylamido-2-methylpropanesulfonic acid or its alkali metal salts and amine salts, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate or their salts, 2-dimethylaminoethyl (meth) ) Acrylate or its hydrohalide, 3-trimethylammoniumpropyl (meth) acrylate, 3-trimethylammoniumpropyl (meth) acrylamide, N, N, N-trimethyl-N- (2-hydroxy-3-methacryloyloxypropyl) ) Ammonium chloride, etc. can be used. In addition, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, N-vinylpyrrolidone, N-vinylacetamide, polyoxyethylene glycol mono (meth) ) Acrylate is also useful.

A macromer having a polar group useful in the present invention can be obtained by a synthesis method described in “New Polymer Experiment 2, Synthesis and Reaction of Polymer” edited by Polymer Society, Kyoritsu Shuppan Co., Ltd. 1995. It is also described in detail in Yamashita Yu et al., “Chemical Monomer Chemistry and Industry”, IPC, 1989.
Specifically, using a monomer having the polar group specifically described above, such as acrylic acid, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, N-vinylacetamide, etc. Macromers having groups can be synthesized.

Among the macromers having a polar group used in the present invention, those particularly useful are macromers derived from carboxyl group-containing monomers such as acrylic acid and methacrylic acid, 2-acrylamido-2-methylpropane sulfonic acid, and styrene sulfone. Sulphonic acid-based macromers derived from monomers of acids and salts thereof, amide-based macromers such as acrylamide and methacrylamide, and amide systems derived from N-vinylcarboxylic acid amide monomers such as N-vinylacetamide and N-vinylformamide Macromers derived from hydroxyl-containing monomers such as macromers, hydroxyethyl methacrylate, hydroxyethyl acrylate, glycerol monomethacrylate, methoxyethyl acrylate, methoxypolyethylene glycol acrylate, poly Macromers derived from alkoxy group or ethylene oxide group-containing monomers such as Chi glycol acrylate. A monomer having a polyethylene glycol chain or a polypropylene glycol chain can also be usefully used as the macromer of the present invention.
Among these, it is preferable to use a macromer having an amide group as a polar group from the viewpoint that the polar interaction with the sol-gel crosslinked structure formed in the organic-inorganic composite layer forming step described later is strongly formed.
Among these macromers, the useful molecular weight is in the range of 400 to 100,000, the preferred range is 1000 to 50,000, and the particularly preferred range is 1500 to 20,000.

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 Al (hereinafter, appropriately referred to as a specific element alkoxide group) in the chain. It is preferable to have. 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. Thus, a covalent bond can be formed between the sol-gel crosslinked structure formed in the below-mentioned organic-inorganic composite layer formation process and a graft polymer chain because a graft polymer chain has a specific element alkoxide group.
When the surface graft polymerization 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 silane coupling groups suitable for the present invention include functional groups as shown in the following general formula (I).

In the 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.
Examples of the hydrocarbon group in the case where 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, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group 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 ethyl group from the viewpoints of effects and availability.

  Examples of the monomer having a functional group represented by the general formula (I) include (3-acryloxypropyl) trimethoxysilane, (3-acryloxypropyl) dimethylmethoxysilane, and (3-acryloxypropyl) methyldimethoxysilane. , (Methacryloxymethyl) dimethylethoxysilane, (methacryloxymethyl) triethoxysilane, (methacryloxymethyl) trimethoxysilane, (methacryloxypropyl) dimethylethoxysilane, (methacryloxypropyl) dimethylmethoxysilane, (methacryloxypropyl) ) Methyldiethoxysilane, (methacryloxypropyl) triethoxysilane, (methacryloxypropyl) triisopropylsilane, methacryloxypropyl (trismethoxyethoxy) silane, and the like.

  In the present invention, when the 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, and surface graft polymerization is used. It is preferable to copolymerize to produce a graft polymer chain. Among these, it is more preferable to use a monomer or macromer having an amide group as a polar group.

(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. In this method, a functional group that reacts with the support at the main chain end or side chain. A graft polymer chain can be generated by chemically reacting the functional group with a functional group on the surface of the support. 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, a hydroxyl group, Examples thereof include a carboxyl group, a sulfonic acid group, a phosphoric acid group, an epoxy group, an allyl group, a methacryloyl group, and an acryloyl group.
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, and a carboxyl group at the polymer end. A polymer having an epoxy group at the polymer terminal and a polymer having an isocyanate group at the polymer terminal.
The polymer used at this time preferably further has a polar group. Specific examples of the polymer having a polar group include polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, poly-2-acrylamide- Examples thereof include 2-methylpropanesulfonic acid and salts thereof, polyacrylamide, and polyvinyl acetamide.
In addition to these, the polymer of the monomer which has a polar group used by the method of above-mentioned (1), or the copolymer containing the monomer which has a polar group can also be used.
In addition, it is preferable to use the polymer which has an amide group as a polar group from the point that the polar interaction with the sol gel crosslinked structure formed in the organic-inorganic composite layer formation process mentioned later is formed strongly.

On the other hand, the polymer having a functional group that reacts with the support at the terminal or side chain of the main chain preferably further has an alkoxide group (specific element alkoxide group) of an element selected from Si, Ti, Zr, and Al. By using this polymer, a specific element alkoxide group can be introduced into the resulting graft polymer chain. Thus, a covalent bond can be formed between the sol-gel crosslinked structure formed in the below-mentioned organic-inorganic composite layer formation process and a graft polymer chain because a graft polymer chain has a specific element alkoxide group.
In the present invention, it is particularly preferable that the polymer having a functional group that reacts with the support at the main chain terminal or side chain has both an amide group and a specific element alkoxide group as polar groups.

In the present invention, amide groups and / or specific element alkoxide groups are contained in the graft polymer chain produced by the above method from the viewpoint of the formation of polar interaction with the sol-gel crosslinked structure and the formation of covalent bonds. It is preferable to have.
The preferable introduction amount of the amide group in the graft polymer chain in the present invention is in the range of 10 mol% to 90 mol%, and the introduction amount of the specific element alkoxide group is preferably in the range of 10 mol% to 90 mol%.

  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 or a polymerizable group is introduced, By using these groups, a crosslinked structure may be formed between the graft polymer chains.

[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 preferred. used.
Specific examples of the film used as the support include polyester films such as polyethylene terephthalate film, polyethylene terephthalate copolymer polyester film, and polyethylene naphthalate film; nylon 66 film, nylon 6 film, and metaxylidenediamine copolymer. Polyamide film such as polyamide film; Polyolefin film such as polypropylene film, polyethylene film, ethylene-propylene copolymer film; Polyimide film; Polyamideimide film; Polyvinyl alcohol film; Ethylene-vinyl alcohol copolymer film; Polyphenylene film; Film; polyphenylene sulfide film; and the like. Among these, polyester films such as polyethylene terephthalate film and polyolefin films such as polyethylene film and polypropylene film are preferable from the viewpoint of cost performance and transparency. These films may be either stretched or unstretched, and may be used alone or may be used by laminating films having different properties.

  Moreover, unless the effect of this invention is impaired, the film used as a support body may contain various additives and stabilizers, or may be applied. Examples of the additive that can be used include an antioxidant, an antistatic agent, an ultraviolet ray inhibitor, a plasticizer, a lubricant, and a heat stabilizer. Further, surface treatment such as corona treatment, plasma treatment, glow discharge treatment, ion bombardment treatment, chemical treatment, solvent treatment, and roughening treatment may be performed.

  The thickness of the support is not particularly limited because it can be appropriately set in consideration of suitability for the purpose of use, such as packaging material, but is in the range of 3 μm to 1 mm from a general practical viewpoint. From the viewpoint of flexibility and workability, it is more preferably in the range of 10 to 300 μm.

Such a support may be used as it is as long as it can generate active species by energy application, but for the purpose of more efficiently generating the starting species that form the graft polymer chain, You may have the surface layer which has a polymerization initiating ability on the support body surface.
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 polymerization initiation layer obtained by immobilizing a polymerization initiator by a crosslinking reaction is preferable, and a polymer having a functional group having a polymerization initiating ability and a crosslinkable group is crosslinked in a side chain. A polymerization initiating layer that is fixed by a reaction is more preferable.
Regarding the polymerization initiating layer formed by immobilizing a polymer having a functional group having a polymerization initiating ability in the side chain and a polymer having a crosslinkable group by a crosslinking reaction, paragraphs [0011] to [0169] of JP-A No. 2004-161995 This polymerization initiating layer can be applied to the present invention.

<Organic-inorganic composite layer forming step>
In this step, in the graft polymer layer obtained in the above-mentioned graft polymer layer forming step, an organic-inorganic composite is subjected to a crosslinking reaction by hydrolysis and condensation polymerization of an alkoxide of an element selected from Si, Ti, Zr, and Al. Form a layer.
That is, the organic-inorganic composite layer in the present invention is formed by performing 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 Al. It is a layer in which an inorganic component having a crosslinked structure (sol-gel crosslinked structure) is mixed.

First, in this step, a compound capable of forming a crosslinked structure formed by performing a crosslinking reaction by hydrolysis and condensation polymerization of an alkoxide of an element selected from Si, Ti, Zr, and Al (hereinafter simply referred to as “crosslinking”). It is preferable to form the sol-gel cross-linked structure in the present invention using the “agent”.
As the crosslinking agent in the present invention, for example, a compound represented by the following general formula (II) is used.
When the graft polymer chain has a specific element alkoxide group, the compound represented by the following general formula (II) is hydrolyzed and polycondensed with the specific element alkoxide group, so that the graft polymer chain and the sol-gel crosslinked structure are A covalent bond can be formed. Thereby, a strong organic-inorganic composite layer can be formed.

In the general formula (II), 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.
When R ⁶ and R ⁷ represent an alkyl group, the carbon number 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.

Although the specific example of a compound represented by general formula (II) below is given, this invention is not limited to this.
In the case where X is Si, that is, those containing silicon in the hydrolyzable compound include, for example, trimethoxysilane, triethoxysilane, tripropoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxy Silane, ethyltriethoxysilane, propyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, γ-chloropropyltriethoxysilane, γ-mercaptopropyltri Methoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, diph Alkenyl dimethoxysilane, mention may be made of diphenyl diethoxy silane.
Among these, tetramethoxysilane, tetraethoxysilane, methyltolumethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxy are particularly preferable. Examples include silane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like.

In addition, when X is Al, that is, examples of the hydrolyzable compound containing aluminum include, for example, trimethoxy aluminate, triethoxy aluminate, tripropoxy aluminate, tetraethoxy aluminate and the like. it can.
When X is Ti, i.e., those containing titanium include, for example, trimethoxy titanate, tetramethoxy titanate, triethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, chlorotrimethoxy titanate, chlorotriethoxy titanate, ethyl triethoxy titanate. Examples thereof include methoxy titanate, methyl triethoxy titanate, ethyl triethoxy titanate, diethyl diethoxy titanate, phenyl trimethoxy titanate, and phenyl triethoxy titanate.
In the case where X is Zr, that is, those containing zirconium include, for example, zirconates corresponding to the compounds exemplified as those containing titanium.

In order to form a sol-gel crosslinked structure in the graft polymer layer using such a crosslinking agent, after dissolving the crosslinking agent in a solvent such as ethanol, a catalyst is added as necessary to prepare a coating solution composition. Then, a method of applying this onto the graft polymer layer, heating and drying can be used. 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. or less from the viewpoint of production suitability and the like. The heating time (crosslinking time) is preferably within 1 hour.

  The content of the crosslinking agent in the coating liquid composition may be determined according to the amount of the sol-gel crosslinked structure to be formed. From the viewpoint of the surface hardness of the formed organic-inorganic composite layer and the adhesion to the support. In general, it is preferably in the range of 5 to 50 mass%, more preferably in the range of 10 to 40 mass%.

When the graft polymer chain has a specific element alkoxide group in the chain, the content of the crosslinking agent in the coating liquid composition is such that the crosslinkable group in the crosslinking agent is 5 mol% or more with respect to the specific element alkoxide group. Furthermore, it is preferable that the amount is adjusted to 10 mol% or more.
At this time, the upper limit of the content of the crosslinking agent is not particularly limited as long as it is within a range that can be sufficiently crosslinked with the specific element alkoxide group, but when added in a large excess, the organic material formed by the crosslinking agent not involved in crosslinking. -It may cause problems such as stickiness of the inorganic composite layer.

  The solvent used in preparing the coating solution composition is not particularly limited as long as it can uniformly dissolve and disperse the crosslinking agent and other components. For example, methanol, ethanol, water, etc. Aqueous solvents are preferred.

In addition, in order to promote the hydrolysis and polycondensation reaction of the crosslinking agent, it is preferable to use an acidic catalyst or a basic catalyst in the coating solution composition, and when it is intended to obtain a practically preferable reaction efficiency. The catalyst is essential.
As this catalyst, an acid or a basic compound can be used as they are, or those dissolved in a solvent such as water or alcohol (hereinafter referred to as an acidic catalyst and a 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. , The polycondensation rate tends to increase. However, if a basic catalyst with a high concentration is used, a precipitate may be generated in the coating liquid composition. Therefore, when a basic catalyst is used, the concentration may be 1 N or less in terms of concentration in an aqueous solution. desirable.

The type of the acidic catalyst or the basic catalyst is not particularly limited. However, when it is necessary to use a catalyst having a high concentration, a catalyst composed of an element that hardly remains in the coating film after drying is preferable.
Specifically, the acid catalyst is represented by hydrogen halide such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acid such as formic acid or acetic acid, and its RCOOH. Examples of the basic catalyst include ammoniacal bases such as aqueous ammonia, amines such as ethylamine and aniline, and the like. Etc.

  Moreover, various additives can be used for this coating liquid composition according to the objective, 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, applied to a support on which radicals as active species are generated by treating it with plasma or electron beam, and heated and dried.
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 generated, and a graft polymer layer is formed. Further, when the coating composition is heated and dried, hydrolysis and condensation polymerization reaction of the crosslinking agent occurs, and a crosslinked structure can be formed in the graft polymer layer.
That is, according to such a method, a graft polymer layer and an organic-inorganic composite layer can be formed at a time by a series of steps of preparing a coating liquid composition, coating, heating, and drying. .

  In preparing the coating solution composition, a hydrophilic polymer may be separately included. 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, and when the content is less than 10% by mass, the film characteristics are decreased, and the possibility of cracks in the film increases. Absent.

  As described above, the formation of the organic-inorganic composite layer in the present invention utilizes the sol-gel method. Regarding the sol-gel method, Sakuo Sakuo, “Science of Sol-Gel Method”, Agne Jofusha (published) (1988), Satoshi Hirashima, “Technology Center for Functional Thin Films Using the Latest Sol-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.

  The film thickness of the organic-inorganic composite layer can be selected depending on the use of the antifouling film, but generally it is preferably in the range of 0.1 μm to 10 μm, more preferably in the range of 0.5 μm to 10 μm. 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 and bending resistance are less likely to occur.

<Water / oil repellent treatment process>
In this step, the surface of the organic-inorganic composite layer obtained by the organic-inorganic composite layer forming step is subjected to water / oil repellent treatment.
Although there is no special restriction | limiting in the compound (water-repellent agent) used for the water / oil repellent treatment in this invention, and a processing method, It is preferable that a fluorine and an alkyl group are provided to the organic-inorganic composite layer surface. For the water / oil repellent treatment, for example, an organometallic compound such as a silylating agent, a titanate coupling agent, or an alkylaluminum is preferably used.
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.

The silylating agent is a compound in which an alkyl group, an aryl group, a fluoroalkyl group containing fluorine, 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.

In addition, the critical inclination angle of the water- and oil-repellent treated surface (that is, the inclination angle of the plate on which a certain amount of water droplets placed on the surface of the antifouling film placed horizontally) is reduced, and the water droplets easily fall. Therefore, a polydimethylsiloxane compound may be used as a water repellent.
The water repellent is hydrolyzed as necessary and then used for coating the water repellent layer.

The surface treatment with the water repellent as described above is performed by coating by a spray method, a flow coating method, a spin coating method, a dip pulling method, or the like, or by surface adsorption by a liquid phase adsorption method or the like.
The support treated with the water repellent is dried and then heat-treated at a temperature of 300 ° C. or lower, preferably 100 ° C. to 250 ° C. for 10 minutes to 1 hour.
If the water-repellent agent forms a monomolecular layer on the surface of the organic-inorganic composite layer, it exhibits water-repellent performance, and even if the thickness of the water-repellent agent exceeds 10 nm, the effect does not increase any more. The preferred thickness of the oil repellent layer is 1 to 10 nm.

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, and as a result. The water / oil repellent treated surface has excellent adhesion to the support.
Therefore, the antifouling film of the present invention is excellent in antifouling property and excellent in its sustainability.

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

[Example 1]
<Preparation of substrate A>
A biaxially stretched polyethylene terephthalate film (A4100, manufactured by Toyobo Co., Ltd.) with a film thickness of 188 μm was used, and a lithographic magnetron sputtering apparatus (CFS-10-EP70 manufactured by Shibaura Eletech Co., Ltd.) was used as a glow processing apparatus. Glow treatment was performed to obtain a PET support.

-Oxygen glow treatment conditions-
Initial vacuum: 1.2 × 10 ⁻³ Pa
Oxygen pressure: 0.9 Pa
RF glow: 1.5 kW
Processing time: 60 sec

<Formation of graft polymer layer 1>
Next, N, N-dimethylacrylamide, methacryloxypropyltriethoxysilane, ethanol mixed solution (N, N-dimethylacrylamide: methacryloxypropyltriethoxysilane = 1: 1 (molar ratio), concentration: 50% by mass) Nitrogen was bubbled. 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 a graft polymer layer in which a graft polymer chain having a silane coupling group and an amide group which are specific element alkoxide groups in the structure is directly bonded to the support surface is formed. Formed. The PET support having this graft polymer layer was designated as support A.

<Formation 1 of organic-inorganic composite layer>
A coating solution composition 1 containing ethanol, water, tetraethoxysilane, and phosphoric acid in the following amounts was stirred for 24 hours at room temperature, and dried by heating at 100 ° C. for 10 minutes. Thus, an organic-inorganic hybrid film A was obtained by forming an organic-inorganic composite layer.

-Coating liquid composition 1-
・ Tetraethoxysilane [Crosslinking agent] 0.9g
-Ethanol 3.7g
・ 8.7g of water
・ Phosphoric acid aqueous solution (0.85% aqueous solution) 1.3 g

<Water and oil repellent treatment>
The obtained organic-inorganic hybrid film A was immersed in 0.1% by mass of 1H, 1H, 2H, 2H perfluorodecyltrichlorosilane / hexane solution for 10 minutes, pulled up, and then dried by heating (100 ° C., 30 min. ) To obtain an antifouling film A.
The total thickness of the formed water / oil repellent treatment layer and organic-inorganic composite layer was 500 nm.

[Example 2]
In <Formation 1 of organic-inorganic composite layer> in Example 1, 0.9 g of tetraethoxysilane contained in the coating liquid composition 1 used for forming the organic-inorganic composite layer was replaced with 1.0 g of tetramethoxytitanate. Except for the above, an antifouling film B was obtained in the same manner as in Example 1.

[Example 3]
In <Formation 1 of organic-inorganic composite layer 1> in Example 1, 0.9 g of tetraethoxysilane contained in the 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.

[Example 4]
In <Formation 1 of organic-inorganic composite layer 1> in Example 1, 0.9 g of tetraethoxysilane contained in the coating liquid composition 1 used for forming the organic-inorganic composite layer was changed to 0.7 g of trimethoxyaluminate. An antifouling film D was obtained in the same manner as in Example 1 except that it was replaced.

[Example 5]
In Example 1, <Formation 1 of graft polymer layer> was changed to <Formation 2 of graft polymer layer 2> below to prepare support B, and the support used in <Formation 1 of organic-inorganic composite layer> An antifouling film E was obtained in the same manner as in Example 1 except that the organic-inorganic hybrid film B was produced by changing the body A to the support B.

<Formation of graft polymer layer 2>
An aqueous acrylamide solution (concentration: 50% by mass) was bubbled with nitrogen. 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. A PET support having this graft polymer layer was designated as Support B.

[Example 6]
<Formation of graft polymer layer 3>
A methacryloxypropyltriethoxysilane / ethanol solution (concentration: 50% by mass) was bubbled with nitrogen. The PET support used in Example 1 was immersed in this 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 a silane coupling group as a specific element alkoxide group in the structure was directly bonded to the support surface. . The PET support having this graft polymer layer was designated as Support C.

<Formation of organic-inorganic composite layer 2>
A coating solution composition 2 containing 2-propanol, water, tetraethoxysilane, and phosphoric acid in the following amounts was stirred for 5 hours at room temperature, and heated at 100 ° C. for 10 minutes. An organic-inorganic hybrid film C was obtained by drying to form an organic-inorganic composite layer.

-Coating liquid composition 2-
・ 8g 2-propanol
・ Tetraethoxysilane [Crosslinking agent] 1.0g
・ Water 1.0g
・ Phosphoric acid aqueous solution (0.85% aqueous solution) 1.0 g

<Water and oil repellent treatment>
The obtained organic-inorganic hybrid film C was subjected to the same treatment as the <water / oil repellent treatment> of Example 1 to obtain an antifouling film F.
The total thickness of the formed water / oil repellent treatment layer and organic-inorganic composite layer was 1.2 μm.

[Comparative Example 1]
A mixture of 0.5 g of 2- (perfluorobutyl) ethyl acrylate (manufactured by Azmax Co., Ltd.) and 0.5 g of 1-methoxy-2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.) was mixed uniformly. It was set as the solution. The PET support used in Example 1 was immersed in this solution at 70 ° C. for 7 hours. The immersed PET support was thoroughly washed with ethanol to obtain an antifouling film G having a graft polymer chain (hydrophobic graft polymer chain) containing fluorine atoms in its structure directly bonded to the support surface. .

[Comparative Example 2]
An 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.

[Performance evaluation of antifouling film]
About Examples 1-6 and antifouling film AH of comparative examples 1 and 2, performance evaluation was performed as follows. The results are shown in Table 1 below.

1. Evaluation of water repellency Kyowa Interface Science Co., Ltd. on the surface of the antifouling films A to H treated with water and oil repellency (in the antifouling film G, the surface in which graft polymer chains containing fluorine atoms are directly bonded). Using CA-Z, the angle 20 seconds after the addition of pure water was measured. A water droplet contact angle of 150 ° or more was evaluated as “◯”. The results are shown in Table 1.

2. Evaluation of adhesion In accordance with JIS K5400, the water and oil repellent treated surfaces of the antifouling films A to H (the surface formed by direct bonding of graft polymer chains containing fluorine atoms in the antifouling film G), A 100 mm square grid of 1 mm square was attached with a rotary cutter, and cello tape (manufactured by Nichiban Co., Ltd., registered trademark) was pressure-bonded, and then a 90 ° peel test was performed three 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.

3. 3. Evaluation of antifouling property 3.1 Evaluation of initial antifouling property Water- and oil-repellent treated surface of antifouling films A to H (surface in which antifouling film G is directly bonded with graft polymer chains containing fluorine atoms) On the other hand, characters were written using a quick-drying oil-based ink (Zebra, “Mackey” (registered trademark)). Next, the number of times until the character was wiped clean was measured using “Bem Cotton” (registered trademark) manufactured by Asahi Kasei Corporation. The results are shown in Table 1.

3.12 Evaluation of Repeated Antifouling Property Using “Bem Cotton” (registered trademark) manufactured by Asahi Kasei Co., Ltd., a water- and oil-repellent treated surface of the antifouling films A to H (in the antifouling film G, a graft containing fluorine atoms) After rubbing the surface of the polymer chain directly 500 times strongly, write on the surface with quick-drying oil-based ink (Zebra, “Mackey” (registered trademark)), and count the number of times until it can be wiped off. Indicated. The results are shown in Table 1.

From the results of Table 1, it can be seen that the antifouling films A to F of Examples having an organic-inorganic composite layer have good water repellency and adhesion between the support and the water / oil repellent treatment layer. Moreover, antifouling film AF of an Example is excellent in initial antifouling property and repeated antifouling property.
From these, it can be seen that the antifouling film of the present invention is excellent in antifouling property and its durability.

  The antifouling film of the present invention can be suitably applied to a display such as a CRT, LCD, PDP, FED, touch panel, glass, table, decorative plywood, and a surface protective film in a recording medium such as a CD or DVD.

Claims (4)

  A crosslinked structure formed by hydrolysis and polycondensation of an alkoxide of an element selected from Si, Ti, Zr, and Al in a graft polymer layer composed of a support and a graft polymer chain directly bonded to the surface of the support. And an organic-inorganic composite layer, and the surface of the organic-inorganic composite layer is subjected to a water / oil repellent treatment.   The antifouling film according to claim 1, wherein the graft polymer chain has an alkoxide group of an element selected from Si, Ti, Zr, and Al in the chain.   The antifouling film according to claim 1 or 2, wherein the graft polymer chain has an amide group in the chain. Forming a graft polymer chain directly bonded to the support surface to form a graft polymer layer comprising the graft polymer chain;
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 water / oil repellent treatment to the surface of the organic-inorganic composite layer;
A method for producing an antifouling film, comprising: