JP4287761B2 - Antifouling surface material and method for producing the same - Google Patents

Description

  The present invention relates to an antifouling surface material and a method for producing the same, and more particularly to a surface material such as a hard coat film having excellent antifouling properties and durability and a simple production method thereof.

In recent years, plastic products have been replaced with glass products in terms of processability and weight reduction. However, since the surface of these plastic products is easily damaged, a hard coat layer is provided for the purpose of imparting scratch resistance or a hard coat layer. In many cases, a film provided with an adhesive is used. In addition, with regard to conventional glass products, plastic films are increasingly being bonded for the purpose of preventing scattering in the event of breakage, and in order to enhance the surface hardness of these films, a hard coat layer is formed on the surface. Is widely practiced.
However, when using hard coat layers for surface protection, dirt such as human fingerprints (sebum), sweat, and cosmetics is likely to adhere, and once attached dirt is difficult to remove, it is transparent. In this case, there is a problem that the visibility and the reflectivity are deteriorated, resulting in poor visibility.

  For the purpose of making it difficult for dirt to adhere to the surface of the hard coat layer, or to easily remove the attached dirt, the hard coat layer surface is coated with a fluorine-based polymer, or the hard coat layer is made of fluorine or silicon. In general, a method of containing the polymer is used. For example, a polymer having a perfluoroalkylpolyether side chain is used for the purpose of improving the stain resistance of an antireflection film in which a hard coat layer, a high refractive index layer and a low refractive index layer are provided in this order on a transparent support. Application on a refractive index layer is disclosed (for example, see Patent Document 1). This method utilizes the excellent slipperiness of the perfluoroalkyl polyether compound, protects the surface side layer of the antireflection film from dirt, and improves scratch resistance. However, since the perfluoroalkyl polyether compound is merely coated and formed on the surface, there is a problem that it is easily peeled off by repeated rubbing and has poor antifouling durability.

  Also proposed is a technology to form a hard coat film with excellent antifouling properties by adding a fluorine monomer to a hard coat layer photocurable composition containing an acrylate and a polymerization initiator, and then exposing, heating and curing. (For example, see Patent Document 2). This method immobilizes the fluorine compound showing antifouling property in the hard coat layer by a covalent bond, and although the ease of peeling by repeated rubbing has been improved, there is a problem that the antifouling property is low. . Moreover, when the addition amount of the fluorine monomer is increased for improving the antifouling property, the hardness of the hard coat layer tends to decrease, and it is generally difficult to achieve both the antifouling property and the hard coat hardness.

Further, as another means for preventing the peeling of the fluoropolymer on the surface of the hard coat layer, it is bonded to the first layer made of a polymer having a photopolymerization initiating group in the molecule via the photopolymerization initiating group. A technique for forming a second layer made of a fluorine-containing polymer formed from a fluorine-containing monomer has been proposed (see, for example, Patent Document 3). Here, the polymer having a photopolymerization initiating group contained in the first layer has low adhesion to the substrate, and the adhesion between the first layer and the fluorine-containing layer on the surface is good, but the first It was found that the expected durability could not be obtained because each layer was easily peeled off. Furthermore, there is also a problem that high energy is required to bind the fluorine-containing monomer starting from the initiating group.
JP 2000-284102 A JP 2003-335984 A Japanese Patent Laid-Open No. 10-279834

The object of the present invention in consideration of the above problems is to provide an antifouling surface material with excellent durability, which has excellent antifouling properties on the surface, little deterioration of antifouling properties due to rubbing, etc., and excellent surface hardness. It is to provide.
Another object of the present invention is to provide a simple method for producing the antifouling surface material having excellent antifouling properties and durability.

The present inventors have studies a result, polymerization, a fluorine-containing monomer is applied on the intermediate layer formed by curing by graft polymerizing a fluoromonomer by the surface grafting method on the intermediate layer formed by curing, The inventors have found that the above-mentioned problems can be solved by irradiating active energy rays to provide a fluoropolymer film that is directly chemically bonded to the cured intermediate layer, thereby completing the present invention.
That antifouling surface material of the present invention, to form an intermediate layer containing a photopolymerization initiator and an acrylate and / or methacrylate on the surface of the base material, irradiated with light is cured, fluorinated to the cured intermediate layer It is characterized in that a fluorine-containing polymer-containing coating film is provided which is coated with a monomer and irradiated with active energy rays and directly bonded to the intermediate layer.
The cured intermediate layer preferably has a high hardness. Specifically, the hardness of the pencil according to the pencil hardness evaluation method specified by JIS-K-5400, which will be described in detail later, is preferably 2H or more. More preferably, it is the above.
Moreover, it is preferable that the intermediate layer further contains a cationic polymerizable compound, and it is a more preferable embodiment that the intermediate layer contains a cationic polymerizable compound and fine particles.

In the method for producing an antifouling surface material according to claim 4 of the present invention, an intermediate layer containing a photopolymerization initiator and acrylate and / or methacrylate is formed on the substrate surface, and the intermediate layer is irradiated with light and cured. And at least one fluorine-containing monomer selected from the group consisting of general formulas (I), (II), (III), (IV) and (V) described in detail below on the surface of the cured intermediate layer The fluorine-containing monomer is polymerized to the residual acrylate polymerization terminal contained in the cured intermediate layer by a surface graft method by applying active energy rays and directly bonded to the surface of the cured intermediate layer. A fluorine-containing polymer coating is provided.
In addition, in this specification, when showing any one or both of an acrylate and a methacrylate, it may describe with (meth) acrylate. Further, the contents described below for “acrylate” are the same when part or all of them are replaced with “methacrylate” unless otherwise specified.

The working mechanism of the present invention is not clear, but is considered as follows. First, in forming the intermediate layer, after applying an intermediate layer containing a photopolymerization initiator and (meth) acrylate having an unsaturated double bond, the double bond is polymerized and crosslinked structure by light irradiation. Therefore, a hard layer having excellent strength is formed. If the reaction at this time is described by taking acrylate as an example, not all acrylates participate in the reaction in the process of forming the intermediate layer, and unreacted acrylate remains. Then, by applying a fluorine-containing monomer and irradiating actinic rays, the fluorine-containing monomer is graft polymerized by a surface graft method to obtain a fluorine polymer layer directly covalently bonded to the initiator in the intermediate layer. Become. In this case, the fluoropolymer is produced by reacting with the remaining acrylate polymerization terminal in the intermediate layer. The acrylate in the intermediate layer is a polyfunctional acrylate, and a part of the acrylate is polymerized and crosslinked with other acrylates to form the intermediate layer. Therefore, it can be said that the fluoropolymer produced by reacting with the residual acrylate polymerization terminal in the intermediate layer is directly covalently bonded to the hard coat crosslinked film. For this reason, the fluoropolymer film is not worn by rubbing, and the deterioration of the antifouling property is suppressed.
In the present invention, the fluoropolymer film is formed by graft polymerization starting from the unsaturated double bond of the intermediate layer, and is bonded to the surface of the intermediate layer only at one end of the polymer, but the other end is free. It exists in, and the molecule is easy to move and has high mobility. For this reason, it is presumed that the antifouling property inherent to the fluorine graft polymer is effectively exhibited.

The antifouling surface material of the present invention is excellent in antifouling properties on the surface, shows little deterioration in antifouling properties due to rubbing, etc., and exhibits excellent surface hardness, not only in strength but also in antifouling durability. The effect is excellent.
Moreover, according to the method for producing an antifouling surface material of the present invention, an antifouling surface material excellent in antifouling property and durability can be obtained by a simple method.
Since the antifouling surface material of the present invention is excellent in surface hardness, antifouling property and durability, it is suitably used for an image display device, a touch panel, a plastic plate, a glass plate and the like, and its application range is wide.

The antifouling surface material of the present invention forms an intermediate layer containing a photopolymerization initiator and (meth) acrylate on the surface of a substrate, and is cured by irradiation with light. A fluorine-containing monomer is formed on the intermediate layer. In the present invention, the intermediate layer is cured and the fluorine-containing graft is subsequently formed on the intermediate layer. It is important to contain a sufficient photopolymerization initiator and a (meth) acrylate-based compound having an unsaturated double bond in the molecule. As this (meth) acrylate, it is preferable to use polyfunctional (meth) acrylate from the viewpoint of the curability of the intermediate layer, the formation of the graft origin, and the like.
Here, the photopolymerization initiator remaining in the intermediate layer formed into a hard coat film by light irradiation and the remaining (meth) acrylate are polymerized by energy application, and a polymerization end of (meth) acrylate is generated. Next, this polymerization terminal and the fluorine monomer present on the surface react with each other to cause a surface graft reaction to form a film made of a graft polymer containing fluorine.

Hereinafter, the antifouling surface material of the present invention will be described in detail together with its production method.
In the antifouling surface material of the present invention, the fluorine-containing polymer coating is formed by irradiating a polyfunctional acrylate and a photopolymerization initiator on a substrate to form a cured intermediate layer, and a fluorine-containing single amount on the layer. It is obtained by coating the body and irradiating active energy rays to cause photograft polymerization on the surface of the intermediate layer .

That is, when an active energy ray such as UV exposure is applied to an intermediate layer which is irradiated with light and cured with a polyfunctional acrylate and a photopolymerization initiator and then hardened, polymerization is started from the initiator remaining in the intermediate layer. Initiating and polymerization ends occur in the polyfunctional acrylate. A fluorine-containing monomer is graft-polymerized from the polymerization terminal, whereby a layer containing a fluorine polymer is formed on a strong intermediate layer having a crosslinked structure. Therefore, the resulting fluorine-containing polymer coating has a two-layer structure in which a fluorine polymer layer composed of a graft polymer chain made from a fluorine-containing monomer bonded to the intermediate layer surface via a polyfunctional acrylate as a raw material is formed. Have.
In this two-layer structure, the intermediate layer formed on the surface of the base material is in close contact with the base material as a hard coat layer having a crosslinked structure, and the intermediate layer itself is high in hardness. The antifouling surface material of the present invention is excellent in hardness and adhesion, and the high antifouling property due to the fluoropolymer lasts for a long time because it is fixed by chemical bonding with the material constituting the layer. Become.

[Middle layer]
The intermediate layer of the present invention contains acrylate and / or methacrylate, preferably polyfunctional acrylate, and a photopolymerization initiator.
(Acrylate and / or methacrylate)
The acrylate compound [(meth) acrylate] that can be used in the present invention is not particularly limited as long as it has an acryloyl group that is an ethylenically unsaturated group in the molecule, but is curable and the hardness of the formed intermediate layer. From the viewpoint of improving the strength, a polyfunctional monomer is preferable.
The polyfunctional monomer that can be suitably used in the present invention is preferably an ester of a polyhydric alcohol and acrylic acid or methacrylic acid. Examples of polyhydric alcohols include ethylene glycol, 1,4-cyclohexanol, pentaerythritol, trimethylolpropane, trimethylolethane, dipentaerythritol, 1,2,4-cyclohexanol, polyurethane polyol and polyester polyol. . Of these, trimethylolpropane, pentaerythritol, dipentaerythritol and polyurethane polyol are preferable. The intermediate layer may contain two or more types of polyfunctional monomers.
The polyfunctional monomer is one containing at least two ethylenically unsaturated groups in the molecule, and more preferably containing three or more. Specific examples include polyfunctional acrylate monomers having 3 to 6 acrylate groups in the molecule, and several acrylic acids in the molecule called urethane acrylate, polyester acrylate, and epoxy acrylate. An oligomer having an ester group and having a molecular weight of several hundred to several thousand can be preferably used as a component of the intermediate layer of the present invention.

  Specific examples of acrylates having three or more acrylic groups in the molecule include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol. Examples thereof include polyol polyacrylates such as hexaacrylate, and urethane acrylates obtained by reaction of polyisocyanates with hydroxyl group-containing acrylates such as hydroxyethyl acrylate.

  In the present invention, a compound containing a repeating unit represented by the following general formula (1) can also be preferably used as an acrylate having three or more ethylenically unsaturated groups in the same molecule. Hereinafter, the polymerizable compound containing the repeating unit represented by the general formula (1) will be described in detail.

In the general formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group.
P ¹ represents a monovalent ethylenically unsaturated group or a monovalent substituent having an ethylenically unsaturated group.
L ¹ represents a single bond or a divalent or higher valent linking group, preferably a single bond or a divalent linking group listed below. Divalent linking groups: —O—, alkylene group, arylene group, * —COO—, * —CONH—, * —OCO—, * —NHCO—, etc., are given here. Represents a divalent group linked to the main chain on the * side.
Preferred P ^1, an acryloyl group, a methacryloyl group, and a monovalent substituent containing either styryl group, or a mixture, and most preferably is a monovalent substituent containing it or acryloyl group.
Although the preferable specific example [(A-1)-(A-44)] of the repeating unit represented by General formula (1) below is shown, this invention is not limited to these.

Such an acrylate is preferably contained in the intermediate layer in a solid content concentration of 5 to 100% by mass, more preferably in the range of 20 to 90% by mass.
In addition to the acrylate, the intermediate layer may contain other polymerizable compound, for example, a polymerizable compound (monomer or oligomer) containing one or two ethylenically unsaturated groups as long as the effects of the present invention are not impaired. You may use together.

As the polymerizable compound other than the polyfunctional acrylate suitably used in the present invention, a compound having a ring-opening polymerizable group is preferably contained. This increases the surface hardness of the intermediate layer and forms an intermediate layer with excellent scratch resistance. By using such a compound, the volume shrinkage rate is stabilized, curling after curing is reduced, and cracks during handling are less likely to occur. Furthermore, by making the film thickness of the intermediate layer constant, the above effect becomes more remarkable.
Examples of the polymerizable compound containing a ring-opening polymerizable group include a compound having a ring structure in which ring-opening polymerization proceeds by the action of a cation, anion, radical, etc., but in the present invention, there is little deposition shrinkage after polymerization. Therefore, from the viewpoint that the formed film has high strength and no cracks are generated, a cationically polymerizable compound is preferable, and a heterocyclic group-containing compound is particularly preferable. Examples of such polymerizable compounds include cyclic imino ethers such as epoxy derivatives, oxetane derivatives, tetrahydrofuran derivatives, cyclic lactone derivatives, cyclic carbonate derivatives, and oxazoline derivatives, and epoxy derivatives, oxetane derivatives, and oxazoline derivatives are particularly preferable.

  In the present invention, the polymerizable compound having a ring-opening polymerizable group preferably has two or more ring-opening polymerizable groups in the same molecule, but more preferably has three or more. Two or more polymerizable compounds having a ring-opening polymerizable group may be used in combination. In this case, a polymerizable compound having one ring-opening polymerizable group in the same molecule may be combined with a polymerizable compound having two or more ring-opening polymerizable groups in the same molecule, or may be opened in the same molecule. Only two or more polymerizable compounds having two or more ring polymerizable groups may be combined.

  The polymerizable compound having a ring-opening polymerizable group referred to in the present invention is not particularly limited as long as it is a polymerizable compound having a cyclic structure as described above. Preferred examples of such polymerizable compounds include monofunctional glycidyl ethers, monofunctional alicyclic epoxies, difunctional alicyclic epoxies, diglycidyl ethers (for example, ethylene glycol diglycidyl ether as glycidyl ethers). Bisphenol A diglycidyl ether), trifunctional or higher glycidyl ethers (trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, tris (glycidyloxyethyl) isocyanurate, etc.) Glycidyl ethers (sorbitol tetraglycidyl ether, pentaerythritol tetraglycyl ether, polyglycidyl ether of cresol novolac resin, phenol novolac tree Polyglycidyl ethers, etc.), cycloaliphatic epoxies (Celoxide 2021P, Celoxide 2081, Epolide GT-301, Epolide GT-401 (above, manufactured by Daicel Chemical Industries, Ltd.)), EHPE (produced by Daicel Chemical Industries, Ltd.) ), Phenol novolak resin polycyclohexyl epoxy methyl ether, etc.), oxetanes (OX-SQ, PNOX-1009 (above, manufactured by Toagosei Co., Ltd.), etc.), etc., but the present invention is limited to these. It is not a thing.

In the present invention, it is particularly preferable that the polymerizable compound having a ring-opening polymerizable group contains a crosslinkable polymer containing a repeating unit represented by the general formula (2). These crosslinkable polymers are described in detail below.
In general formula (2), R ² has the same meaning as R ¹ in general formula (1), and L ² has the same meaning as L ^1, and preferred examples are also the same.
P ² is a monovalent ring-opening polymerizable group or a monovalent group having a ring-opening polymerizable group. Preferred examples of P ² include an epoxy ring, an oxetane ring, a tetrahydrofuran ring, a lactone ring, a carbonate ring, and an oxazoline ring. And monovalent groups having an iminoether ring, and the like. Among these, a monovalent group having an epoxy ring, an oxetane ring or an oxazoline ring is particularly preferred.

In the present invention, the crosslinkable polymer containing the repeating unit represented by the general formula (2) is preferably synthesized by polymerizing a corresponding monomer. In this case, radical polymerization is the simplest and preferable as the polymerization reaction.
Although the preferable specific example [(E-1)-(E-26)] of the repeating unit represented by General formula (2) below is shown, this invention is not limited to these.

  In the present invention, the polymerizable compound containing the repeating unit represented by the general formula (2) may be a copolymer composed of different repeating units, or other than the one represented by the general formula (2). A copolymer containing a repeating unit (for example, a repeating unit not containing a ring-opening polymerizable group) may be used. Particularly suitable is a method of controlling the Tg or hydrophilicity / hydrophobicity of the crosslinkable polymer or a copolymer containing a repeating unit other than the general formula (2) for the purpose of controlling the content of the ring-opening polymerizable group of the crosslinkable polymer. It is. As a method for introducing the repeating unit other than the general formula (2), a method of introducing the corresponding monomer by copolymerization is preferable.

  When the repeating unit other than the general formula (2) is introduced by polymerizing the corresponding vinyl monomer, the monomer preferably used is derived from acrylic acid or α-alkylacrylic acid (for example, methacrylic acid). Esters (eg, methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, n-propyl acrylate, i-propyl acrylate, 2-hydroxypropyl acrylate, 2-methyl-2-nitropropyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, t-pentyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-methoxymethoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate 2,2-dimethylbutyl acrylate, 3-methoxybutyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, n-pentyl acrylate, 3-pentyl acrylate, octafluoropentyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, cyclopentyl Acrylate, cetyl acrylate, benzyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, 4-methyl-2-propylpentyl acrylate, heptadecafluorodecyl acrylate, n-octadecyl acrylate, methyl methacrylate, 2, 2, 2-trifluoro Ethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, Droxyethyl methacrylate, 2-hydroxypropyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, sec-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, benzyl methacrylate , Heptadecafluorodecyl methacrylate, n-octadecyl methacrylate, 2-isobornyl methacrylate, 2-norbornylmethyl methacrylate, 5-norbornen-2-ylmethyl methacrylate, 3-methyl-2-norbornylmethyl methacrylate, dimethyl Aminoethyl methacrylate),

Amides derived from acrylic acid or α-alkylacrylic acid (such as methacrylic acid) (for example, Ni-propylacrylamide, Nn-butylacrylamide, Nt-butylacrylamide, N, N-dimethyl) Acrylamide, N-methylmethacrylamide, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, acrylamidopropyltrimethylammonium chloride, methacrylamide, diacetone acrylamide, acryloylmorpholine, N-methylolacrylamide, N-methylolmethacrylamide), acrylic S derived from acids or α-alkyl acrylic acids (acrylic acid, methacrylic acid, itaconic acid, etc.), vinyl esters (eg vinyl acetate), maleic acid or fumaric acid Tellurium (dimethyl maleate, dibutyl maleate, diethyl fumarate, etc.), maleimide (N-phenylmaleimide, etc.), maleic acid, fumaric acid, sodium salt of p-styrenesulfonic acid, acrylonitrile, methacrylonitrile, dienes (For example, butadiene, cyclopentadiene, isoprene), aromatic vinyl compounds (for example, styrene, p-chlorostyrene, t-butylstyrene, α-methylstyrene, sodium styrenesulfonate), N-vinylpyrrolidone, N-vinyloxazolidone, N -Vinyl succinimide, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, 1-vinylimidazole, 4-vinylpyridine, vinylsulfonic acid, vinyl Sodium sulfonic acid, sodium allyl sulfonate, sodium methallyl sulfonate, vinylidene chloride, vinyl alkyl ethers (e.g. methyl vinyl ether), ethylene, propylene, 1-butene, isobutene and the like.

  When such a cationically polymerizable compound is used in combination, the content in the intermediate layer is preferably 5 to 95% by mass, more preferably 10 to 80% by mass. Moreover, it is preferable that it is the range of 5-2000 mass% with respect to (meth) acrylate.

(Fine particles)
In the intermediate layer of the present invention, it is preferable to add inorganic fine particles or organic fine particles as a filler for the purpose of improving the hardness and suppressing the curing shrinkage of the polyfunctional monomer.
Examples of the inorganic fine particles include silicon dioxide particles, titanium dioxide particles, aluminum oxide particles, tin oxide particles, calcium carbonate particles, barium sulfate particles, talc, kaolin and calcium sulfate particles.
As organic fine particles, methacrylic acid-methyl acrylate copolymer powder, silicon resin powder, polystyrene powder, polycarbonate powder, acrylic acid-styrene copolymer powder, benzoguanamine resin powder, melamine resin powder, polyolefin powder, polyester powder, polyamide powder, polyimide powder and Examples thereof include polyfluorinated ethylene powder.
The average particle size of the fine particles used as the filler is preferably 0.01 to 2 μm, and more preferably 0.02 to 0.5 μm. Further, the addition amount is preferably 1 to 10% by mass from the viewpoints of effects and layer uniformity.

  Various additives can be used in combination with the intermediate layer or the coating solution depending on the purpose as long as the effects of the present invention are not impaired. Examples of additives include colorants (pigments, dyes), antifoaming agents, thickeners, leveling agents, flame retardants, ultraviolet absorbers, antioxidants, and modifying resins.

(Polymerization initiator)
In this invention, after forming an intermediate | middle layer, an intermediate | middle layer is hardened by irradiating light, For this reason, it is required for an intermediate | middle layer to contain a polymerization initiator. In addition, since the polymerization initiator contributes to the graft polymerization performed subsequent to the curing of the intermediate layer, it is preferable to select the polymerization initiator in consideration of both.
For example, the intermediate layer containing a polymerizable compound is preferably cured by irradiation with active energy rays, so that the crosslinking reaction often proceeds at a low temperature. Further, light irradiation with other wavelengths may be used for curing the intermediate layer, and ultraviolet irradiation may be used when graft polymerization is performed.
In the present invention, radiation, gamma rays, alpha rays, electron beams, ultraviolet rays, and the like can be used as active energy rays for causing and advancing these polymerizations or effect reactions. Among them, a method of adding a polymerization initiator that generates radicals or cations using ultraviolet rays and curing with ultraviolet rays is particularly preferable. Further, there may be a case where curing can be further advanced by heating after irradiation with ultraviolet rays, and this method can be preferably used. The preferable heating temperature in this case is 140 ° C. or less, and more preferably in the range of 30 to 120 ° C.

In the present invention, when a curing reaction is caused by ultraviolet irradiation, a polymerization initiator that generates radicals by ultraviolet irradiation as a polymerization initiator, such as acetophenones, benzophenones, Michler's ketone, benzoylbenzoate, benzoins, α- Known radical generators such as acyloxime ester, tetramethylthiuram monosulfide and thioxanthone can be used. In general, sulfonium salts and iodonium salts used as photoacid generators also act as radical generators upon irradiation with ultraviolet rays, and these may be used alone in the present invention.
In addition to the radical polymerization initiator, a sensitizer may be used for the purpose of increasing sensitivity. Examples of the sensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, and thioxanthone derivatives.

When a cationically polymerizable compound having a ring-opening polymerizable group is used in combination in the intermediate layer of the present invention, a photoacid generator can be used as a polymerization initiator. Examples of photoacid generators that generate cations by ultraviolet irradiation include ionic polymerizable compounds such as triarylsulfonium salts and diaryliodonium salts, and nonionic polymerizable compounds such as nitrobenzyl esters of sulfonic acids, Various known photoacid generators such as polymerizable compounds described in “Organic Materials for Imaging”, published by “Organic Materials for Imaging” (published in 1997), etc. can be used. Among these, a sulfonium salt or an iodonium salt is particularly preferable, and PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , B (C ₆ F ₅ ) ₄ ^{− and the} like are preferable as a counter ion.

As described above, the polymerization initiator may be used in appropriate combination according to the polymerizable compound contained in the intermediate layer as described above, or in the case of a polymerizable compound that generates both radicals and cations alone. It can be used alone.
The addition amount of the polymerization initiator is 0.1 to 15 with respect to the total mass of the ethylenically unsaturated group-containing acrylate compound and the ring-opening polymerizable group-containing polymerizable compound contained in the polymerizable compound constituting the intermediate layer. It is preferable to use in the range of mass%, and it is more preferable to use in the range of 1 to 10 mass%.

  In order to form the intermediate layer of the present invention, the intermediate layer coating solution containing each of the above components is prepared by dissolving it in an appropriate solvent, for example, an organic solvent such as a ketone, alcohol, or ester, which will be described later. What is necessary is just to apply | coat on a base material. Furthermore, when adding the fine particles, it is preferable from the viewpoint of uniformity that a fine particle counting liquid such as a surface-modified hard inorganic fine particle dispersion or soft fine particle dispersion is prepared in advance and then added to the intermediate layer coating liquid.

For the application of the intermediate layer, for example, a known thin film forming method such as a dipping method, a spinner method, a spray method, a roll coater method, a gravure method, a wire bar method, a slot extrusion coater method (single layer, multi-layer), a slide coater method, etc. Can be performed. The intermediate layer can be prepared by applying and drying the intermediate layer coating solution on a substrate and then irradiating with an active energy ray to cure.
Drying is preferably performed under conditions where the organic solvent concentration in the applied liquid film is 5% by mass or less after drying, more preferably 2% by mass or less, and even more preferably 1% by mass or less. The drying conditions are affected by the thermal strength of the substrate, the conveyance speed, the length of the drying process, and the like, but the one having as low an organic solvent content as possible is preferable in terms of increasing the polymerization rate.
The thickness of the intermediate layer after formation is preferably 1 to 15 μm.

(Substrate: Support)
The substrate on which the intermediate layer is provided may be transparent or opaque, and can be selected according to the purpose, but is transparent for applying the antifouling surface material of the present invention to optical applications. It is preferable to use a simple support substrate.
Examples of the transparent support that can be used as a substrate in the present invention include glass and plastic film, but a plastic film is generally used from the viewpoint of the degree of freedom of the application site.
Examples of plastic film materials constituting the substrate include cellulose esters (eg, triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate). , Polyethylene naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene), Polyolefin (eg, polypropylene, polyethylene, polymethylpentene), polysulfone, polyethersulfone, polyarylate, polyetherimide, Examples thereof include polymethyl methacrylate and polyether ketone. Among them, triacetyl cellulose, polycarbonate, polyethylene terephthalate, and the like are preferable from the viewpoint of optical properties (transparency) and strength.
The light transmittance of the transparent support referred to in the present invention is preferably 80% or more, and more preferably 86% or more. The haze of the transparent support is preferably 2.0% or less, and more preferably 1.0% or less. The refractive index of the transparent support is preferably 1.4 to 1.7.

  Examples of the opaque support include colored plastic films in which carbon black and pigments are dispersed, metal supports such as aluminum, iron, and copper.

For the purpose of improving the adhesion between the base material and the intermediate layer, one or both surfaces of the base material can be subjected to a surface treatment by an oxidation method, an unevenness method, or the like as desired. Examples of the oxidation method include corona discharge treatment, glow discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like.
Further, one or more undercoat layers can be provided on the substrate surface. Examples of the material for the undercoat layer include copolymers such as vinyl chloride, vinylidene chloride, butadiene, (meth) acrylic acid ester, and vinyl ester, or water-soluble polymers such as latex, low molecular weight polyester, and gelatin.
This undercoat layer can contain a metal oxide such as tin oxide, tin oxide / antimony oxide composite oxide, tin oxide / indium oxide composite oxide, or an antistatic agent such as a quaternary ammonium salt.

[Fluorine-containing polymer coating layer]
After providing the cured intermediate layer on the substrate surface as described above, a fluorine-containing polymer coating layer is formed.
(Fluorine-containing monomer)
The fluorine-containing polymer coating provided on the intermediate layer is at least one fluorine-containing monomer selected from the group consisting of the following general formulas (I), (II), (III), (IV) and (V) It is formed from the body.
CH ₂ = CR ¹ COOR ₂ R _f (I)
[Wherein, R ¹ is a hydrogen atom or a methyl group, R ² is —C _p H _2p —, —C (C _p H _{2p + 1} ) H—, —CH ₂ C (C _p H _{2p + 1} ) H— or -CH ₂ CH ₂ O-, the _{R f -C n F 2n + 1} , - (CF 2) n H, -C n F 2n + 1 -CF 3, - (CF 2) p OC n H 2n C _{i F 2i + 1, - (} CF 2) p OC m H 2m C i F 2i H, -N (C p H 2p + 1) COC n F 2n + 1, -N (C p H 2p + 1) SO ₂ C _n F _{2n + 1} . However, p is 1-10, n is 1-16, m is 0-10, i is an integer of 0-16. ]

CF ₂ = CFOR _g (II)
(In the formula, R _g represents a fluoroalkyl group having 1 to 20 carbon atoms.)
CH ₂ = CHR _g (III)
(In the formula, R ^g represents a fluoroalkyl group having 1 to 20 carbon atoms.)
CH ₂ = CR ³ COOR ⁵ R _j R ⁶ OCOCR ⁴ = CH ₂ (IV)
[Wherein R ³ and R ⁴ are hydrogen atoms or methyl groups, R ⁵ and R ⁶ are —C _q H _2q −, —C (C _q H _{2q + 1} ) H—, —CH ₂ C (C _q H _2q + 1) H- or -CH ₂ CH ₂ O-, R _j is -C _t F _2t. However, q is an integer of 1 to 10, and t is an integer of 1 to 16. ]
CH ₂ = CHR ⁷ COOCH ₂ (CH ₂ R _k ) CHOCOCR ⁸ = CH ₂ (V)
(Wherein R ⁷ and R ⁸ are a hydrogen atom or a methyl group, R _k is —C _y F _{2y + 1} , where y is an integer of ₁ to 16)

Hereinafter, although the specific example of a fluorine-containing monomer is given, this invention is not restrict | limited to this.
Examples of the monomer represented by the general formula (I) include CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCH═CH ₂ , CF ₃ CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₄ CH ₂ CH _{2 OCOC (CH 3) = CH} 2, C 7 F 15 CON (C 2 H 5) CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 3) CH 2 CH 2 OCOCH = CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCH═CH ₂ , C ₂ F ₅ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOC (CH _{3) = CH 2, (CF} 3) 2 CF (CF 2) 6 (CH 2) 3 OCOCH = CH 2, (CF 3) 2 CF (CF 2) 10 (CH 2) 3 OCOC (CH 3) = CH _{2, CF 3 (CF 2)} 4 CH (CH 3) OCOC (CH 3) = CH 2,

CF ₃ CH ₂ OCH ₂ CH ₂ OCOCH═CH ₂ , C ₂ F ₅ (CH ₂ CH ₂ O) ₂ CH ₂ OCOCH═CH ₂ , (CF ₃ ) ₂ CFO (CH ₂ ) ₅ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₄ OCH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , C ₂ F ₅ CON (C ₂ H ₅ ) CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₂ CON (CH ₃ ) CH (CH ₃ ) CH ₂ OCOCH═CH ₂ , H (CF ₂ ) ₆ C (C ₂ H ₅ ) OCOC (CH ₃ ) ═CH ₂ , H (CF ₂ ) ₈ CH ₂ OCOCH═CH ₂ , H (CF ₂ ) ₄ CH ₂ OCOCH═CH ₂ , H (CF ₂ ) CH ₂ OCOC (CH ₃ ) ═CH ₂ ,

, CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₁₀ OCOCH═CH ₂ , C ₂ F ₅ SO ₂ N (C ₂ H ₅ ) CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₄ OCOCH═CH ₂ , C ₂ F ₅ SO ₂ N (C ₂ H ₅ ) C (C ₂ H ₅ ) HCH ₂ OCOCH═CH _{2 and the} like.

Examples of the fluoroalkylated olefin represented by the general formulas (II) and (III) include C ₃ F ₇ CH═CH ₂ , C ₄ F ₉ CH═CH ₂ , C ₁₀ F ₂₁ CH═CH ₂ , C such as _{3 F 7 OCF = CF 2,} C 7 F 15 OCF = CF 2 and C ₈ F ₁₇ OCF = CF ₂ and the like.

Formula (IV) and a monomer represented by (V) for _{example, CH 2 = CHCOOCH 2 (CF} 2) 3 CH 2 OCOCH = CH 2, CH 2 = CHCOOCH 2 CH (CH 2 C 8 F 17) OCOCH = CH _{2 and the} like can be mentioned.

As a monomer for forming the fluorine-containing polymer film, in addition to the fluorine-containing monomer, a monomer having no fluorine can be used in combination as long as the effects of the present invention are not impaired. Such monomers are not particularly limited as long as they can be radically polymerized, and specifically, unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, and alkyls thereof. Alternatively, glycidyl esters, styrene, vinyl esters of alkyl acids, silicon-containing monomers, and the like can be given.
When used in combination, the blending amount is preferably 50% by weight or less based on the fluorine-containing monomer.

(Formation of fluorine-containing polymer film)
Next, a method for forming a fluorine-containing polymer film will be described. In order to form a coating layer by this graft polymerization, a fluorine-containing monomer is disposed on the surface of the intermediate layer, and activation energy is applied. At this time, it may be carried out in the so-called solvent-free state in which the fluorine-containing monomer is provided alone, but may be applied as a composition containing other solvents and additives.
In the former case, the concentration of the fluorine-containing monomer in the composition containing the fluorine-containing monomer applied to the intermediate layer surface is 100%. Further, from the viewpoint of handling properties, it may be diluted with a solvent in which the fluorine-containing monomer is dissolved. Although there is no restriction | limiting in particular in the solvent used here, Methanol, acetone, methyl ethyl ketone, ethanol, hexane, heptane, benzene, toluene etc. are preferable. At this time, in addition to the fluorine-containing monomer, other monofunctional and polyfunctional monomers, and additives such as surfactants and thickeners may be added to the composition.

  When the fluorine-containing monomer-containing composition is applied to the intermediate layer surface, the intermediate layer is insufficiently cured, or contains a compound such as a solvent that easily dissolves the intermediate layer in the composition. In such a case, the surface of the intermediate layer may be dissolved, the appearance may be deteriorated due to whitening or the like, and the fluorine-containing polymer-containing coating layer may become non-uniform so that the antifouling property may be deteriorated. For this reason, it is preferable to select a fluorine-containing monomer or a solvent or other compound contained in the composition containing the monomer that has physical properties that do not dissolve the surface of the intermediate layer. In addition, when the intermediate layer is sufficiently photocured, it is preferable that the intermediate layer is sufficiently photocured because the solubility resistance to fluorine monomers and the like is improved.

  As a method of applying the fluorine-containing monomer on the intermediate layer, a method of applying a fluorine-containing monomer or a composition containing the same on the intermediate layer, a substrate formed by forming the intermediate layer on the surface contains fluorine. Examples thereof include a method of immersing in a monomer or a composition containing the monomer. In addition, in order to prevent polymerization inhibition by oxygen, the application of these compositions and the graft polymerization reaction are performed in an inert gas atmosphere such as nitrogen, or the surface to which a fluorine-containing monomer is applied is caused to cause the graft polymerization reaction. For example, the active energy ray may be covered with a material such as glass, quartz, or a transparent plastic plate or film.

  This fluorine-containing monomer is at least one fluorine-containing monomer selected from the group consisting of the compounds represented by the general formulas (I) to (V) as described above. Specifically, the fluorine-containing monomer mentioned above is mentioned, Among these monomers, the 1 type is used individually or in mixture of 2 or more types as appropriate.

  The active energy ray for causing the graft polymerization reaction in the fluorine-containing monomer is not particularly limited as long as the photopolymerization initiator remaining in the intermediate layer can absorb and generate an initiating species. Specifically, ultraviolet rays and visible rays having a wavelength of 200 to 800 nm, preferably 300 to 600 nm are desirable. Examples of the light source include a high-pressure mercury lamp, a low-pressure mercury lamp, a halogen lamp, a xenon lamp, an excimer laser, a dye laser, a YAG laser, and sunlight.

From the starting point generated on the surface of the intermediate layer by irradiation of active energy , that is, from the residual acrylate polymerization terminal contained in the cured intermediate layer , the fluorine-containing monomer is polymerized by the surface graft method, and one end is formed in the intermediate layer. A surface graft polymer layer that is chemically bonded, has a high degree of freedom at the other end, and has a plurality of fluorine-containing functional groups is formed. In this case, one end of the fluorine-containing polymer is generated by reacting with the remaining acrylate polymerization terminal in the intermediate layer, and is thus chemically bonded and fixed to the intermediate layer. The acrylate in the intermediate layer is preferably a polyfunctional acrylate, part of which is polymerized and cross-linked with another acrylate to form an intermediate layer having a strong cross-linked structure.

  If the thickness of the fluorine-containing polymer film formed as described above is too thin, the surface performance due to fluorine cannot be exhibited, and if it is too thick, the appearance as a film is impaired, so the range of 0.01 to 100 μm desirable. The thickness of the coating can be controlled by adjusting the exposure amount.

  After forming the fluorine-containing polymer film, that is, when unreacted fluorine-containing monomer or a homopolymer of the fluorine-containing monomer remains after irradiation with active energy rays, they may be converted to petroleum ether as necessary. It is preferable to wash and remove by, for example.

The antifouling surface material obtained as described above is covalently bonded to the acrylate terminal having a cross-linked structure in which the fluorine-containing polymer terminal of the fluorine-containing polymer coating existing on the outermost surface is contained in the intermediate layer. Therefore, it has excellent adhesion to the base material, and can exhibit excellent functions such as water and oil repellency and antifouling properties inherent in the fluorine compound, and the effect is sustained.
In addition, since the fluorine-containing polymer film has good uniformity, it can exhibit performance in a thin layer, has excellent transparency, is difficult to swell, has no fear of being scratched, and peeled off. Has film strength.
In addition, according to the production method of the present invention, an intermediate layer containing a photopolymerization initiator and (meth) acrylate is formed on the surface of the substrate, and after applying a fluorine-containing monomer thereon, active energy rays are applied. A simple method of irradiating can efficiently produce a fluorine-containing polymer film on the surface of the substrate, and by using a polyfunctional monomer as the fluorine-containing monomer, the crosslink density is improved and high strength is achieved. It also has the advantage that a fluorine-containing polymer film is obtained.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
(Example 1: polyfunctional acrylate monomer + initiator / fluorine graft)
(Preparation of intermediate layer)
439 g of industrial use, 125 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.) 125 g and urethane acrylate oligomer (UV-6300B, Nippon Synthetic Chemical Industry Co., Ltd.) Dissolved in denatured ethanol. A solution obtained by dissolving 7.5 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and 5.0 g of a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) in 49 g of methyl ethyl ketone was added to the obtained solution. added. After the mixture was stirred, it was filtered through a polypropylene filter having a pore size of 1 μm to prepare an intermediate layer coating solution.

  An 80 μm thick triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) was used as a substrate, and a gelatin subbing layer was provided on the surface. The intermediate layer coating solution is applied onto the gelatin subbing layer using a bar coater, dried at 120 ° C., and then irradiated with a high-pressure mercury lamp for 30 seconds to cure the coating layer to a thickness of 15 μm. An intermediate layer was formed. The high pressure mercury lamp used was UVX-02516S1LP01 manufactured by Ushio Corporation.

(Formation of fluorine-containing polymer film)
0.5 g of 2- (perfluorobutyl) ethyl acrylate (manufactured by Amax Co., Ltd.) and 0.5 g of 1-methoxy-2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.) which are fluorine-containing monomers Mix to make a homogeneous solution.
The base material (TAC) having a cured intermediate layer obtained as described above is cut into 4 cm × 5 cm, about 0.5 ml of the above solution is dropped on the intermediate layer, and a quartz plate is covered from above to be as uniform as possible. A liquid film was formed. This was exposed for 5 minutes with a UV exposure apparatus (UVX-02516S1LP01, high-pressure mercury lamp, manufactured by USHIO). After the exposure, the quartz plate was removed, and the resulting fluorine-based graft film was washed with acetone to remove impurities such as unreacted fluorine-containing monomer, whereby the antifouling surface material of Example 1 was obtained.
The contact angle of the water droplet was measured and found to be 107.8 degrees, indicating that it had excellent water repellency.

(Example 2)
Implemented except that CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCH═CH ₂ (Dainippon Ink) was used in place of the fluorine-containing monomer used in Example 1. The antifouling surface material of Example 2 was obtained in the same manner as Example 1.
(Example 3)
Instead of the fluorine-containing monomer used in Example _{1 CH 2 = CHCOOCH 2 CH 2} R f [wherein R _f is _{-C n F 2n + 1 -CF 3} , n = 6,8,10,12 ] An antifouling surface material of Example 2 was obtained in the same manner as Example 1 except that Cheminox (FAAC-M, manufactured by Nippon Mektron Co., Ltd.) was used.

(Example 4)
Example except that 2- (perfluorooctyl) ethyl acrylate ethanol solution (20 wt%) was applied to the intermediate layer surface so that the dry film thickness was 1 μm instead of the fluorine-containing monomer used in Example 1. In the same manner as in Example 1, an antifouling surface material of Example 4 was obtained.
(Example 5)
In Example 4, the antifouling surface of Example 5 was applied in the same manner as in Example 4 except that the step of irradiating ultraviolet rays was performed in a nitrogen atmosphere after the fluorine-containing monomer solution was applied on the intermediate layer. Obtained material.

(Example 6: polyfunctional acrylate monomer + initiator + cationic polymerization system / fluorine graft)
(Preparation of intermediate layer)
(Preparation of intermediate layer coating solution (h-1))
Glycidyl methacrylate is dissolved in methyl ethyl ketone (MEK) and reacted at 80 ° C. for 2 hours while adding a thermal polymerization initiator (V-65 (manufactured by Wako Pure Chemical Industries, Ltd.)), and the resulting reaction solution is dissolved in hexane. The polyglycidyl methacrylate obtained by dripping and drying the precipitate under reduced pressure (polystyrene equivalent molecular weight: 12,000) was dissolved in methyl ethyl ketone at a concentration of 50% by mass to 100 parts by mass of trimethylolpropane triacrylate (biscoat). # 295; 150 parts by mass of Osaka Organic Chemical Co., Ltd.), 6 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Geigy) and 6 parts by mass of a cationic photopolymerization initiator (Lordsil 2074, manufactured by Rhodia) What was dissolved in 30 parts by mass of methyl isobutyl ketone was mixed with stirring, Layer coating solution (h-1) was prepared.

(Formation of intermediate layer)
Latex made of styrene-butadiene copolymer with a refractive index of 1.55 and a glass transition temperature of 37 ° C. on the surface on which the intermediate layer is placed on both sides of PET (biaxially stretched polyethylene terephthalate film) with a thickness of 175 μm (LX407C5, Japan) Zeon Co., Ltd.) and tin oxide / antimony oxide composite oxide (FS-10D, manufactured by Ishihara Sangyo Co., Ltd.) are mixed at a mass ratio of 5: 5, and the coating thickness is 200 nm after drying. After forming an undercoat layer with an antistatic layer, the intermediate layer coating solution (h-1) is applied by an extrusion method, dried, and irradiated with ultraviolet rays (700 mJ / cm ² ) to dry the intermediate layer. A hard coat film having a thickness of 20 μm was prepared.
(Formation of fluorine-containing polymer film)
A fluorine-containing polymer film was formed on the hard coat film surface in the same manner as in Example 1 except that 2- (perfluorooctyl) ethyl methacrylate was used as the fluorine monomer. Got.

(Example 7: polyfunctional acrylate monomer + initiator + cationic polymerization system + fine particles / fluorine graft)
The intermediate layer coating solution was prepared in the same manner as in Example 6 except that 10 parts by mass of titanium dioxide (manufactured by Taki Chemical Co., Ltd.) was added as fine particles to the intermediate layer coating solution. The antifouling surface material of Example 7 was obtained in the same manner as Example 6.

(Comparative Example 1)
Using a substrate having a cured intermediate layer similar to that obtained in Example 1, a hexafluoroisopropanol solution of poly (2- (perfluorooctyl) ethyl acrylate) (molecular weight 130,000) (10 wt. %) Was applied so that the dry film thickness was 1 micron, and the antifouling surface material of Comparative Example 1 was obtained.
(Comparative Example 2)
It used for the evaluation test as it was, without providing a fluorine-containing polymer film on the surface of the base material having the same cured intermediate layer as that obtained in Example 1.
(Comparative Example 3)
A PET film that does not form an intermediate layer was used as it was, and a fluorine-containing monomer was dropped on the surface in the same manner as in Example 1 and irradiated in the same manner, but the surface did not change, and a polymer coating layer could be formed. There wasn't.

(Comparative Example 4)
In Example 1, a fluoropolymer film was formed by the same method as Example 1 except that no light was irradiated when the intermediate layer was formed. Since the uncured intermediate layer and the fluorine monomer were mixed, the fluoropolymer film was not localized on the surface, the antifouling property was low, and the surface hardness was low.
(Comparative Example 5)
An intermediate layer was formed in the same manner as in Example 6 except that the polyfunctional acrylate and the polymerization initiator (Irgacure 184) were omitted. Next, an attempt was made to form a fluorine-containing polymer film by the same method, but the graft reaction did not proceed at all, and no film was formed. The contact angle (water droplets in the air) was also 70 degrees, which was the same value as before the treatment with the fluorine-containing monomer.

[Evaluation of antifouling surface materials]
Each evaluation method was performed by the following method, and the performance of the antifouling surface material was evaluated. The results are shown in Table 1 below.
(Contact angle)
The antifouling surface material was cut to 2 × 2 cm ² and the contact angle of water droplets was measured in the air using a Contact-Angle meter (manufactured by Kyowa Interface Chemical Co., Ltd. 10927). The unit is degrees.
(Initial antifouling property)
A character was written on the surface of the fluorine-containing polymer coating of the antifouling surface material 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.

(Repeated antifouling property)
After rubbing the surface of the antifouling hard coat film 100 times using “Bem Cotton” (registered trademark) manufactured by Asahi Kasei Co., Ltd., the film surface was quickly dried with oil-based ink (Zebra, “Mackey” (registered trademark)). I wrote the letter and showed how many times it took to wipe it off.
(Pencil hardness test)
The hardness of the pencil scratch test is as follows. After the prepared antifouling surface material is conditioned at a temperature of 25 ° C. and a relative humidity of 60% for 2 hours, the test pencil specified in JIS-S-6006 is used. According to the pencil hardness evaluation method specified by K-5400, the hardness of a pencil with no scratches observed under a load of 9.8 N was determined.

  From the results shown in Table 1, it was found that all of the antifouling surface materials of Examples 1 to 7 of the present invention have high surface water repellency and antifouling properties and excellent antifouling properties. In Examples 6 to 7 to which a cationic polymerizable compound was added, in addition to these excellent antifouling properties, the surface hardness was also high, and the antifouling properties and surface hardness that could not be achieved with conventional techniques were at a high level. It shows that it has been realized.

Since the antifouling surface material of the present invention has a high hardness intermediate layer that functions as a hard coat layer and a fluorine-containing polymer film that is firmly bonded to the intermediate layer by chemical bonding, the antifouling property, It is a surface material that has excellent scratch resistance and anti-stain properties, and can be applied in various fields. By using a transparent substrate, it is transparent with excellent anti-stain properties and scratch resistance. A base material (hard coat film) can be obtained, and it is suitable for a surface protection film on a recording medium such as a display such as CRT, LCD, PDP, FED, touch panel, glass, table, decorative plywood, and CD, DVD, etc. Applicable.

Claims (4)

An intermediate layer containing a photopolymerization initiator and acrylate and / or methacrylate is formed on the substrate surface, cured by light irradiation, a fluorine-containing monomer is applied on the cured intermediate layer, and active energy rays are applied. An antifouling surface material provided with a fluorine-containing polymer-containing coating that is directly bonded to the cured intermediate layer by irradiation and surface grafting .   The antifouling surface material according to claim 1, further comprising a cationically polymerizable compound in the intermediate layer.   The antifouling surface material according to claim 1 or 2, wherein the intermediate layer further contains fine particles. An intermediate layer containing a photopolymerization initiator and acrylate and / or methacrylate is formed on the surface of the substrate, and the intermediate layer is irradiated with light and cured, and the following general formulas (I) and (II) are formed on the cured intermediate layer surface: At least one fluorine-containing monomer selected from the group consisting of (III), (IV) and (V) is applied , and the cured intermediate layer is applied to the cured intermediate layer by irradiation with active energy rays and surface grafting. A method for producing an antifouling surface material, characterized in that a fluorine-containing polymer film directly bonded to the surface of the cured intermediate layer is provided by polymerizing the fluorine-containing monomer at a residual acrylate polymerization terminal contained.
CH ₂ = CR ¹ COOR ₂ R _f (I)
[In formula (I), R ¹ is a hydrogen atom or a methyl group, R ² is _{-C p H 2p -, - C} (C p H 2p + 1) H -, - CH 2 C (C p H 2p + 1 ) H- or -CH ₂ CH ₂ O-, the _{R f -C n F 2n + 1} , - (CF 2) n H, -C n F 2n + 1 -CF 3, - (CF 2) p OC n _{H 2n C i F 2i + 1} , - (CF 2) p OC m H 2m C i F 2i H, -N (C p H 2p + 1) COC n F 2n + 1, -N (C p H 2p + ₁ ) SO ₂ C _n F _{2n + 1} . However, p is 1-10, n is 1-16, m is 0-10, i is an integer of 0-16. ]
CF ₂ = CFOR _g (II)
(In formula (II), R _g represents a fluoroalkyl group having 1 to 20 carbon atoms.)
CH ₂ = CHR _g (III)
(In formula (III), R ^g represents a fluoroalkyl group having 1 to 20 carbon atoms.)
CH ₂ = CR ³ COOR ⁵ R _j R ⁶ OCOCR ⁴ = CH ₂ (IV)
Wherein ^{(IV), R 3, R} 4 is a hydrogen atom or a methyl group, R ^5, R ⁶ is _{-C q H 2q -, - C} (C q H 2q + 1) H -, - CH 2 C ( C _q H _2q + 1) H- or -CH ₂ CH ₂ O-, the R _j is -C _t F _2t. However, q is an integer of 1 to 10, and t is an integer of 1 to 16. ]
CH ₂ = CHR ⁷ COOCH ₂ (CH ₂ R _k ) CHOCOCR ⁸ = CH ₂ (V)
(In the formula (V), R ⁷ and R ⁸ are a hydrogen atom or a methyl group, R _k is —C _y F _{2y + 1} , where y is an integer of ₁ to 16.)