JP2007146009A - Oil-repellent and water-repellent material and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a simple method for producing a water-repellent or oil-repellent material excellent in surface stainproofness, slight in the decline of stainproofness by rubbing or the like, exhibiting high surface hardness, thus useful as a stainproof facing material with high stainproofness and high transparency, and to provide the water-repellent or oil-repellent material having high surface water repellency or oil repellency and useful as a stainproof facing material, obtained by the above method. <P>SOLUTION: The method for producing the water-repellent and oil-repellent material comprises the step of contacting, on a substrate capable of generating radicals on exposure to light, a mixture of a low-molecular compound having polymerizable unsaturated group and a high-molecular compound having oil-repellent and water-repellent functional group and polymerizable unsaturated double bond on the side chain, and the step of exposing the substrate to light to form a graft polymer layer made from the low-molecular compound and the high-molecular compound on the substrate. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an oil and water repellent material having surface oil and water repellency and a method for producing the same. Specifically, the present invention relates to a surface oil and water repellent material useful as an antifouling surface material such as a hard coat film imparted with antifouling property, durability and transparency, and a method for producing the same.

In recent years, plastic substrates are being replaced with glass substrates in terms of processability and weight reduction. Since the surface of these plastic substrates is easily scratched, a hard coat layer is often provided for the purpose of imparting scratch resistance, or a film provided with a hard coat layer is often used by bonding. 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 such a hard coat layer for surface protection, dirt such as human fingerprints (sebum), sweat, and cosmetics is likely to adhere. In addition, since it is difficult to remove the dirt once adhered, there is a problem that transparency and reflectivity are impaired and visibility is deteriorated.

  Therefore, in order to make it difficult for dirt to adhere to the surface of the hard coat layer and 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-based or silicon. A method of incorporating a polymer of a system is generally performed. For example, it has a perfluoroalkyl polyether side chain 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 substrate that is a transparent support. It is disclosed that a polymer is applied on a low refractive index layer (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 applied and formed on the surface, the perfluoroalkyl polyether compound is easily peeled off by repeated rubbing, resulting in a problem of poor antifouling properties.

  In order to solve this problem, a technique for forming a hard coat film by adding a fluorine monomer to a hard coat layer photocurable composition containing an acrylate and a polymerization initiator, and exposing, heating and curing is proposed. (For example, refer to Patent Document 2). This method immobilizes a fluorine compound exhibiting antifouling property in the hard coat layer by a covalent bond, and although it is difficult to peel off even after repeated rubbing, there is a problem that the antifouling property is low. Moreover, when the addition amount of the fluorine monomer was increased for improving the antifouling property, the hardness of the hard coat layer tended to decrease. Therefore, it is generally difficult to achieve both antifouling properties and scratch resistance.

  Apart from this, as a means for preventing the peeling of the fluoropolymer on the surface of the hard coat layer, a first layer made of a polymer having a photopolymerization initiating group in the molecule is provided on the substrate, and photopolymerization is started thereon. A technique for forming a second layer made of a fluorine-containing polymer formed from a fluorine-containing monomer bonded through a group has been proposed (see, for example, Patent Document 3). However, the polymer having a photopolymerization initiating group contained in the first layer improves the adhesion between the first layer and the second layer made of a fluorine-containing polymer on the surface, but the first layer It was found that the expected durability could not be obtained due to easy peeling from the substrate. Further, there is a problem that high energy is required to bind the fluorine-containing monomer starting from the photopolymerization initiating group.

  Furthermore, when using antifouling films with fluoropolymers on the surface of these hard coat layers as optical materials such as flat panel displays, they are not only durable but also transparent to maintain visibility. Is also required.

JP 2000-284102 A JP 2003-335984 A Japanese Patent Laid-Open No. 10-279834

  An object of the present invention in consideration of the above problems is to provide a highly transparent oil-repellent and water-repellent material having excellent antifouling property on the surface of the substrate, less deterioration of the antifouling property due to rubbing and the like, and high transparency. . Another object of the present invention is to provide an oil repellent and water repellent material excellent in antifouling property and durability and further transparency obtained by the production method of the present invention.

As a result of intensive studies, the present inventors have found that the above problem can be solved by forming a graft polymer layer having oil and water repellent functional groups using a base material capable of generating a polymerization initiation active site by exposure, The present invention has been completed.
That is, in the method for producing an oil-repellent and water-repellent substrate according to claim 1 of the present invention, (1) an oil-repellent and water-repellent functional group and polymerizable unsaturated are formed on the substrate surface capable of generating radicals upon exposure. A step of mixing a high molecular compound having a double bond in a side chain with a low molecular compound having a polymerizable unsaturated group and bringing it into contact with the substrate; and (2) exposing the substrate to the low molecule. Forming a graft polymer layer comprising the compound and the polymer compound on the substrate.

Although the operation of the present invention is not clear, it is estimated as follows.
In the present invention, when a graft polymer is formed, a low molecular compound having a polymerizable unsaturated group is mixed in a polymer compound solution having an oil and water repellent functional group and a polymerizable unsaturated double bond in the side chain. The substrate is brought into contact with a substrate having a polymerization initiating ability. Since this low molecular weight compound is involved in the polymerization together with the high molecular weight compound, a graft polymer having a functional group that is difficult to peel off from the substrate and has an excellent antifouling property is uniformly formed on the surface of the substrate, and has a uniform and excellent durability. Antifouling property can be imparted to the substrate surface. Further, it is considered that the uniformity of the polymerization is improved in this way, thereby suppressing the light scattering by suppressing the roughness of the film surface and forming a highly transparent graft polymer film.

The molecular weight of the low molecular weight compound having a polymerizable unsaturated group used in this production method is preferably less than 1000.
Further, the low molecular weight compound having a polymerizable unsaturated group is more preferably at least one selected from the group consisting of (meth) acrylic acid ester monomers and acrylamide monomers, and more preferably Is an alkyl (meth) acrylic acid ester having an alkyl group having 1 to 6 carbon atoms.
Further, the oil and water repellent material according to claim 5 is produced by the method for producing an oil and water repellent material of the present invention.
In this specification, “oil repellency and water repellency” means “oil repellency and water repellency”. Hereinafter, this may be referred to as “oil / water repellency”.

  ADVANTAGE OF THE INVENTION According to this invention, it can provide the manufacturing method of oil-repellent and water-repellent material which is excellent in antifouling property of the base-material surface, there is little fall of antifouling property by rubbing etc., and is highly transparent. In addition, the oil and water repellent material obtained by the production method of the present invention has an effect of being excellent in antifouling property and durability and having high transparency.

The method for producing an oil repellent and water repellent substrate of the present invention comprises: (1) a low molecular weight compound having a polymerizable unsaturated group and an oil repellent and water repellent functional group on a substrate surface capable of generating radicals upon exposure; A step of mixing a polymer compound having a polymerizable unsaturated double bond in a side chain and bringing it into contact with the substrate; and (2) exposing the substrate to the low molecular compound and the polymer compound. Forming a graft polymer layer comprising: a base material on a base material, and a method for producing an oil and water repellent material.

-(1) Process-
Hereinafter, the details of the method for producing the oil- and water-repellent material of the present invention will be described in the order of steps.
First, (1) a low molecular weight compound having a polymerizable unsaturated group, an oil-repellent and water-repellent functional group, and a polymerizable unsaturated double bond in a side chain on a substrate surface capable of generating radicals upon exposure. The process of mixing and contacting the polymer compound will be described. In the method of the present invention, first, using a “base material capable of generating radicals upon exposure”, a low molecular compound having a polymerizable unsaturated group on the surface of the base material, and an oil-repellent and water-repellent functional group, A step of mixing and contacting a polymer compound having a polymerizable unsaturated double bond in the side chain (hereinafter referred to as a specific oil-repellent polymer as appropriate) is performed.

<Base material capable of generating radicals upon exposure>
The “base material capable of generating radicals upon exposure” includes (a) a base material containing a radical generator, (b) a base material containing a polymer compound having a radical generating site in the side chain, (c) Examples include a base material in which a coating liquid containing a crosslinking agent and a polymer compound having a radical generating site in the side chain is applied to the surface of the support and dried to form a crosslinked structure in the coating. Among these, representative examples include (a) a base material containing a radical generator, and (b) a base material containing a polymer compound having a radical generating site in the side chain.
Regardless of which base material is used, a graft polymer is generated by starting and advancing radical polymerization by bringing a specific oil-repellent polymer into contact with the surface of the base material, starting from the active point generated by exposure. The base material is selected so that it can generate a starting species such as a radical with high sensitivity upon exposure.

The “a compound capable of generating radicals upon exposure (hereinafter, appropriately referred to as a radical generator”) to be contained in the substrate (a) may be a low molecular compound or a high molecular compound, and generally known compounds are used. .
Examples of the low molecular radical generator include known radical generators such as acetophenones, benzophenones, Michler's ketone, benzoylbenzoate, benzoins, α-acyloxime ester, tetramethylthiuram monosulfide, trichloromethyltriazine and thioxanthone. Can be used. In addition, since sulfonium salts and iodonium salts used as photoacid generators usually act as radical generators upon irradiation with light, they may be used in the present invention.
As the polymer radical generator, active carbonyl groups described in paragraphs [0012] to [0030] of JP-A-9-77891 and paragraphs [0020] to [0073] of JP-A-10-45927 are included in the side chain. A high molecular compound etc. can be used. Among such polymer radical generators, those containing a polymer compound having a radical generating site in the side chain correspond to the (b) substrate.

In the base material, a sensitizer can be contained in addition to the radical generator for the purpose of increasing sensitivity. Examples of such sensitizers include n-butylamine, triethylamine, tri-n-butylphosphine, and thioxanthone derivatives.
The sensitizer is preferably contained in an amount of about 50 to 200% by weight with respect to the radical generator.

Each base material used in the present invention may contain other components depending on the purpose in addition to the radical generator and the sensitizer used in combination.
When the oil repellent and water repellent material obtained by the present invention is used as an antifouling surface material requiring antifouling durability especially in repeated rubbing, the radical generator (photopolymerization initiator) is contained inside the substrate. In addition to ()), it is important to contain 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 polyfunctional (meth) acrylate used 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.

  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. By containing this compound, the surface hardness of the intermediate layer is increased, and an intermediate layer having excellent scratch resistance is formed. The intermediate layer formed in this way has a small volume shrinkage and curling after curing, 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 compounds having a ring structure in which ring-opening polymerization proceeds by the action of a cation, anion, radical, etc., but in the present invention, volume shrinkage after polymerization is small. 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 ether, etc.), cycloaliphatic epoxies [(commercially available products: Celoxide 2021P, Celoxide 2081, Epolide GT-301, Epolide GT-401; above, Daicel Chemical Industries, Ltd., EHPE; Daicel Chemical Industries, Ltd.) ), Phenol novolak resin polycyclohexyl epoxy methyl ether, etc.], oxetanes (commercially available products: OX-SQ, PNOX-1009; above, manufactured by Toagosei Co., Ltd.) and the like. It is not limited to.

  The thickness of the substrate is selected according to the purpose of use and is not particularly limited, but is generally about 10 μm to 10 cm.

  The content of the radical generator can be appropriately selected in consideration of the type of base material, the amount of desired graft polymer produced, etc., but generally 0.1 to 40% by weight in the case of a low molecular radical generator. In the case of a polymer radical generator, it is preferably in the range of 1.0 to 50% by weight.

In the step (1) of the present invention, a specific high molecular compound and a low molecular compound are mixed and brought into contact with the above-described base material surface. Each compound which is a material of the graft polymer used here will be described.
<Polymer compound having oil- and water-repellent functional groups and polymerizable unsaturated double bond in side chain>
The molecular weight of the specific oil-repellent polymer is in the range of 1,000 to 1,000,000, and particularly preferably in the range of 5,000 to 100,000. By using a specific oil-repellent polymer in this molecular weight range, excellent water and oil repellency is realized, and the solvent is excellent in solubility when being brought into contact with the substrate surface, and the handleability is also good.
The present inventor uses a polymer compound having an oil repellent and water repellent functional group and a polymerizable unsaturated double bond in the side chain when forming the graft polymer layer in the step (2) described in detail below. Then, the surface water-repellent effect of the obtained water- and oil-repellent material is enhanced rather than using a low-molecular compound having an oil-repellent and water-repellent functional group. The present inventors have found that the uniformity of polymerization is further improved by coexisting with a compound, thereby completing the present invention. This polymer compound is a radically polymerizable polymer compound having a water / oil repellency functional group in the molecule which gives water / oil repellency characteristics to the surface of the substrate.

Such a radically polymerizable group-containing specific oil-repellent polymer can be synthesized as follows.
(I) a method of copolymerizing a water / oil repellent monomer such as a fluorine monomer and a monomer having an ethylene addition polymerizable unsaturated group; (ii) a monomer having a water / oil repellent monomer and a double bond precursor; Next, a method of introducing a double bond by treatment with a base or the like, (iii) a water- and oil-repellent polymer having a functional group such as carboxylic acid, and a compound having an ethylene addition polymerizable unsaturated group And the like. Among these, the method (iii) is particularly preferable from the viewpoint of synthesis suitability.

When the radically polymerizable group-containing oil-repellent polymer is synthesized by the method (i), examples of the monomer having an ethylene addition polymerizable unsaturated group that is copolymerized with the oil-repellent monomer include an allyl group-containing monomer. Examples include allyl (meth) acrylate and 2-allyloxyethyl methacrylate.
In addition, when synthesizing the radically polymerizable group-containing oil-repellent polymer by the method (ii), a monomer having a double bond precursor that is copolymerized with the oil-repellent monomer includes 2- (3-chloro-1-oxopropoxy ) Ethyl methacrylate.
Furthermore, when synthesizing a radical polymerizable group-containing oil-repellent polymer by the method (iii), a reaction between a carboxyl group, an amino group or a salt thereof in the oil-repellent polymer and a functional group such as a hydroxyl group and an epoxy group is performed. Monomers having an addition-polymerizable unsaturated group used for introducing unsaturated groups using (meth) acrylic acid, glycidyl (meth) acrylate, allyl glycidyl ether, 2-isocyanatoethyl (meth) acrylate Etc.

  Here, examples of the monomer having an oil repellent and water repellent functional group used for synthesizing a specific oil repellent polymer include a fluorine monomer and a silicon-based (silicon-based) monomer.

(Fluorine-containing monomer)
The fluorine-containing monomer used as a raw material for the specific oil-repellent polymer used for the formation of the graft polymer layer is selected from the group consisting of the following general formulas (I), (II), (III), (IV) and (V). And at least one selected fluorine-containing monomer.
_{^{CH 2 = CR 1 COOR 2 R}} f ··· general formula (I)
Wherein, ^{R 1} represents 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 -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: general formula (II)
(Wherein R ^g represents a fluoroalkyl group having 1 to 20 carbon atoms.)
CH ₂ = CHR ^g: general formula (III)
(Wherein 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 ··· formula (IV)
^Wherein, 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-, ^{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 ··· formula (V)
^(Wherein, R 7, ^{R 8} represents a hydrogen atom or a methyl group, the ^{R k} is _-C y _{F 2y + 1.} However, y is 1 to 16 integer.)

Hereinafter, although the specific example of the fluorine-containing monomer which can be used for this invention 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, C _{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.

The monomer represented by the general formula (IV) and (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 that can be used for the synthesis of the specific oil-repellent polymer used for the formation of the graft polymer layer, in addition to the above-mentioned 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 alkyl or glycidyl thereof. Examples include esters, styrene, vinyl esters of alkyl acids, and silicon-containing monomers.
The blending amount when used in combination is preferably 50% by weight or less based on the fluorine-containing monomer.

(Silicon monomer)
Examples of the silicon-based monomer that can be used as a raw material for the specific oil-repellent polymer in the present invention include silicon-based monomers having a —Si—CH ₃ group or a —O—Si—CH ₃ group. Specifically, a silicon acrylate or silicone methacrylate, the general formula _{(CH 3 O) n Si (} CH 3) 3-n -R 3 -O-CO-CR 4 = are those represented by CH _2, R ³ is a linking group, and R ⁴ is methyl or hydrogen. In addition, for example, a silicon-based monomer described in paragraph No. [0025] of JP-A-2003-335984 can also be mentioned as a preferable example.

(Other monomers)
The polymer compound having an oil-repellent and water-repellent functional group and a polymerizable unsaturated double bond in the side chain of the present invention includes, in addition to the oil-repellent and water-repellent group, and the polymerizable unsaturated double bond group as constituent elements. In addition, other monomers may be copolymerized. These monomers are used to increase the solvent solubility of the polymer compound of the present invention. Although it does not specifically limit as a monomer used for such a purpose, Acrylic acid ester, such as (meth) acrylic acid methyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid methoxyethyl ester, is used. be able to.
Examples of polymer compounds having the oil- and water-repellent functional groups and polymerizable unsaturated double bonds in the side chain [Exemplary compounds (1) to (11)] used in the present invention are the structural units. And the molar ratio of each structural unit. However, the present invention is not limited to these.

Next, the “low molecular compound having a polymerizable unsaturated group” used for forming the graft polymer layer together with the polymer compound will be described.
<Low molecular compound having a polymerizable unsaturated group>
The low molecular weight compound having a polymerizable unsaturated group used in the present invention is preferably a low molecular weight compound having a molecular weight of 1000 or less and having a polymerizable unsaturated group, and the molecular weight is more preferably in the range of 100 to 600. .
Any known compound can be used as long as it has such a low molecular weight and has a polymerizable unsaturated group. Specifically, a (meth) acrylic acid ester monomer, an acrylamide monomer, a (meth) acrylic acid ester monomer having a perfluoro group, and the silicon (meth) acrylate are preferable. Among these, specific examples of (meth) acrylic acid ester monomers include those having 1 carbon number such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isopropyl (meth) acrylate and the like. Ammonium salt structures such as alkyl (meth) acrylates having up to 12 alkyl groups, 2-dimethylammoniumethyl (meth) acrylate, 2-trimethylammoniumethyl (meth) acrylate, 2-isopropylammoniumethyl (meth) acrylate, etc. Examples include substituted alkyl (meth) acrylate esters, cyclohexyl esters, phenyl-substituted (meth) acrylate esters such as t-butyl ester benzyl (meth) acrylate, and the like. In particular, an alkyl (meth) acrylate having an alkyl group having 1 to 6 carbon atoms is more preferable from the viewpoint that the obtained oil / water repellent material has high transparency.
Specific examples of acrylamide monomers include N, N-dimethylacrylamide, N- (3-dimethylaminopropyl) (meth) acrylamide and the like, such as acrylamide substituted with alkyl at the N position, and acroylmorpholine. Examples thereof include acrylamide having a heterocyclic ring. Among these, N, N-dimethylacrylamide is particularly preferable.

  In the step (1), as a method of mixing the specific oil-repellent polymer with the low molecular compound having a polymerizable unsaturated group and bringing them into contact with the substrate surface, these two kinds of polymers and low molecular compounds are mixed. For example, a method of applying the dissolved solution or the dispersed dispersion on the surface of the substrate, a method of immersing the substrate in the solution or the dispersion, and the like are included.

  At this time, the concentration of the specific oil-repellent polymer in the coating liquid / dispersion is preferably 1 to 50% by mass, and the concentration of the low molecular compound to be added is preferably 20 to 50% by mass with respect to the specific oil-repellent polymer.

  Examples of the solvent / dispersion medium used in the coating liquid / dispersion liquid include ketone solvents such as acetone, ester solvents such as ethyl acetate, and alcohol solvents such as 1-methoxy-2-propanol. A fluorine-based solvent such as hexafluoropropanol can also be used.

-(2) Process-
Next, (2) the substrate is exposed, a specific oil-repellent polymer and a low molecular weight compound having a polymerizable unsaturated group are mixed from the radical generated on the substrate surface by the exposure, and the substrate is mixed. A process for producing a graft polymer having oil-repellent and water-repellent functional groups directly bonded to the substrate by contacting them will be described.

As described above, a solution containing a specific oil-repellent polymer and a low molecular weight compound having a polymerizable unsaturated group is brought into contact with the surface of a substrate capable of generating radicals upon exposure by coating or dipping. In that state, by irradiating the base material with light, the mixture of the specific oil-repellent polymer and the low molecular weight compound having a polymerizable unsaturated group from the starting point generated on the base material is graft-polymerized to the base material. Join directly. By producing in the above process, a water- and oil-repellent film having excellent durability and high transparency is formed.
In particular, when trying to obtain a durable antifouling surface material, a coating solution containing a polyfunctional acrylate and a photopolymerization initiator is applied onto a substrate capable of generating radicals upon exposure, An intermediate layer cured by light irradiation is formed, and the specific oil-repellent polymer and a low molecular compound having a polymerizable unsaturated group are mixed on the intermediate layer and contacted by a method such as coating. Thereafter, it is preferable to carry out step (2), that is, a step of irradiating active energy rays to cause photograft polymerization on the substrate surface.
In other words, when an application liquid containing a polyfunctional acrylate and a photopolymerization initiator is applied, and irradiated with light and cured to form a hard coat, the intermediate layer is irradiated with active energy rays such as UV exposure. Polymerization starts from the remaining initiator, and a polymerization terminal is generated in the polyfunctional acrylate. Based on the polymerization terminal, a specific oil-repellent polymer and a low-molecular compound having a polymerizable unsaturated group are mixed and fixed by graft polymerization, so that the oil-repellent property is formed on a strong intermediate layer having a crosslinked structure. A layer containing the polymer is formed. Therefore, the obtained water- and oil-repellent functional group-containing polymer film such as fluorine is graft polymerized from a water- and oil-repellent functional group-containing monomer that is further bonded to the intermediate layer surface via a polyfunctional acrylate. It has a two-layer structure in which a water- and oil-repellent functional group-containing polymer layer composed of chains is formed.

  In this two-layer structure, the intermediate layer formed on the substrate surface capable of generating radicals upon exposure adheres closely to the substrate as a hard coat layer having a crosslinked structure, and the intermediate layer itself has high hardness, The film formed by mixing a specific oil-repellent polymer and a low molecular weight compound having a polymerizable unsaturated group, that is, a graft polymer layer having a water / oil-repellent functional group is chemically bonded to the material constituting the intermediate layer. Therefore, when the water / oil repellent material obtained by the method of the present invention is used as an antifouling surface material, it is excellent in hardness, adhesion, and transparency, and has a specific oil repellency such as a fluoropolymer. The high antifouling property due to the polymer will last for a long time.

In the step (2), the active energy ray used for the exposure for causing the graft polymerization reaction is such that the photopolymerization initiation site remaining on the surface of the substrate can absorb the energy and generate an active site. Although there is no particular limitation, specifically, ultraviolet rays and visible rays having a wavelength of 200 to 800 nm, preferably 300 to 600 nm are desirable.
Examples of the exposure 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. The exposure energy is preferably about 10 mJ / cm ^{2 to} 10000 J / cm ² .

〔Base material〕
As described above, the base material on which the graft polymer is formed by the method of the present invention is a base material capable of generating radicals upon exposure. The base material having such characteristics is a support as a structural material. It is formed by imparting a property capable of generating radicals upon exposure. Here, the material that can be used as the substrate support is not particularly limited, and may be an organic material, an inorganic material, or a hybrid material of organic and inorganic materials. It is appropriately selected according to the purpose.
Examples of the organic material constituting the substrate support include acrylic resins such as polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4. Polyester resins such as 4′-dicarboxylate and polybutylene terephthalate, and epoxy resins represented by commercial products such as Epicoat (trade name: manufactured by Yuka Shell Epoxy Co., Ltd.), polycarbonate resins, polyimide resins, and novolaks Resins, phenol resins, and the like can be used as appropriate.

  Other organic materials include cellulose esters (eg, triacetylcellulose, diacetylcellulose, propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose), polyamides, polystyrene (eg, syndiotactic polystyrene), polyolefins ( Examples include polypropylene, polyethylene, polymethylpentene), polysulfone, polyethersulfone, polyarylate, polyetherimide, and polyetherketone.

Thus, the substrate on which the surface graft polymer is formed by the method of the present invention is subjected to a treatment such as solvent immersion after the exposure, and the specific oil-repellent polymer remaining without being subjected to the graft polymerization, and the polymerizable property The low molecular weight compound having an unsaturated group is removed and purified. Specifically, washing with water or acetone, drying, and the like can be given.
From the standpoint of residual polymer removability, it is preferable to adopt means such as ultrasonic waves during washing. The polymer after the purification is completely removed of the polymer remaining on the surface, and only the oil-repellent graft polymer firmly bonded to the substrate exists.

  According to the method for producing an oil and water repellent material of the present invention, a surface water and oil repellent material having high oil and water repellency, high durability and transparency can be obtained. The water / oil repellent material obtained by the method of the present invention can be widely used as an antifouling and water repellent substrate.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these.
<Specific oil repellent polymer synthesis>
-Synthesis example 1. Synthesis of specific oil-repellent polymer P-1
The specific oil repellent polymer P-1 is synthesized through the following two steps.
<Step 1: Synthesis of 2- (perfluorooctyl) -ethyl methacrylate (FAMAC) and methacrylic acid 2-hydroxyethyl ester (HEMA) (FAMAC / HEMA = 33/67)>
Under a nitrogen atmosphere, 30 g of N, N-dimethylacetamide (DMAc, Wako Pure Chemical Industries) was placed in a 300 ml three-necked flask equipped with a condenser and heated to 65 ° C. in a water bath. Here, 30 g of DMAc, 5.0 g (0.038 mol) of methacrylic acid 2-hydroxyethyl ester (HEMA, Tokyo Chemical Industry) and 2- (perfluorooctyl) -ethyl methacrylate (FAMAC, manufactured by Daikin Fine Chemical Laboratories) 10. A homogeneous solution prepared by dissolving 0 g (0.019 mol) and 2.2'-azobis (isobutyric acid) (V601, Wako Pure Chemical Industries, Ltd.) 0.66 g (0.0029 mol) with a plunger pump was 0.54 ml / The solution was dropped at a rate of min. After completion of the dropwise addition, the reaction was stopped by stirring for 5 hours.
IR (KBr) (measured using Excalibur FTIR-8300 (SHIMADZU))
3471 (b), 2953 (b), 1732 (s), 1456 (s) cm ^-1

<Step 2: Introduction of double bond to copolymer>
3.0 g of the copolymer obtained in Step 1 and 0.0325 g of hydroquinone (Wako Pure Chemical Industries, Ltd.) were placed in a 300 ml three-necked flask installed in a cooling tube, and 40 g of DMAc was added and stirred at room temperature to obtain a uniform solution.
While stirring the solution, 1.53 g (0.00983 mol) of 2-methacryloyloxyethyl isocyanate (Karenz MOI, Showa Denko) was added dropwise. Subsequently, 1 drop of dilauric acid di-n-butyltin (Tokyo Kasei Kogyo) was added and heated in a 65 ° C. water bath with stirring. After 5 hours, the reaction was stopped and the mixture was naturally cooled to room temperature. The reaction solution was reprecipitated with 1500 ml of methanol, and the precipitated solid was collected by suction filtration to obtain a specific oil-repellent polymer P-1. (Yield 2.5g, Yield 55%)
IR (KBr) (measured using Excalibur FTIR-8300 (SHIMADZU))
3390 (b), 2961 (b), 1732 (s), 1639 (s) cm ^-1
The weight average molecular weight (GPC, THF, polystyrene conversion: Mw) was 30500.

-Synthesis example 2. Synthesis of specific oil-repellent polymer P-2
The specific oil-repellent polymer P-2 is synthesized through the following two steps.
<Step 1: Copolymerization of 2- (perfluorooctyl) -ethyl methacrylate (FAMAC), butyl methacrylate (BMA) and 2-hydroxyethyl methacrylate (HEMA) (FAMAC / BMA / HEMA = 30/30/40) Synthesis>
Under a nitrogen atmosphere, 31.88 g of N, N-dimethylacetamide (DMAc, Wako Pure Chemical Industries) was placed in a 300 ml three-necked flask equipped with a condenser and heated to 65 ° C. in a water bath. Here, 31.88 g of DMAc, 2.67 g (0.0188 mol) of butyl methacrylate (BMA, Tokyo Chemical Industry), 3.27 g (0.0251 mol) of 2-hydroxyethyl methacrylate (HEMA, Tokyo Chemical Industry) and 2- ( Perfluorooctyl) -ethyl methacrylate (FAMAC, manufactured by Daikin Fine Chemical Laboratories) 10.0 g (0.0188 mol) and 2.2′-azobis (isobutyric acid) (V601, Wako Pure Chemical Industries) 0.714 g (0. 0031 mol) was dissolved dropwise with a plunger pump at a rate of 0.37 ml / min. After completion of the dropwise addition, the reaction was stopped by stirring for 5 hours. The reaction solution was milky white.

<Step 2: Introduction of double bond to copolymer>
The reaction solution obtained in Step 1 was transferred to a 500 ml three-necked flask, to which 79.7 g of N, N-dimethylacetamide (DMAc, Wako Pure Chemical Industries) was added to dilute to 10 wt (%). Hydroquinone (Wako Pure Chemical Industries) 0.081g was added here, and it stirred at room temperature, and was set as the uniform solution. While stirring the solution, 3.79 g (0.024 mol) of 2-methacryloyloxyethyl isocyanate (Karenz MOI, Showa Denko) was added dropwise. Subsequently, 1 drop of dilauric acid di-n-butyltin (Tokyo Kasei Kogyo Co., Ltd.) was added, a condenser tube was installed, and the mixture was heated in a 65 ° C. water bath. After 5 hours, the reaction was stopped and the mixture was naturally cooled to room temperature. The reaction solution was light pink.
The molecular weight (GPC, THF, polystyrene conversion: Mw) was 30500.
¹ H NMR (ppm, CDCl 3, 300 Mz, manufactured by Brucker)
δ 0.80-1.80 (b, 18H), 1.40 (b, 2H), 1.60 (b, 2H), 1.85 (bs, 2H), 1.90 (b, 1H), 2.42 (b, 2H), 3.50 (mb, 2H), 3.82 (bs, 2H.), 4.12 (bs, 3H), 4.30 (b, 6H), 5.60 ( bs, 1H), 6.25 (bs, 1H)

-Synthesis example 3: Synthesis of compound A having a photopolymerization initiation site-
Synthesis of Compound A having a photopolymerization initiation site is performed by the following two steps.
<Step 1 Synthesis of Compound a>
24.5 g (0.12 mol) of 1-hydroxycyclohexyl phenyl ketone was dissolved in a mixed solvent of DMAc 50 g and THF 50 g, and 7.2 g (0.18 mol) of NaH (60% in oil) was gradually added in an ice bath. Thereto, 44.2 g (0.18 mol) of 11-bromo-1-undecene (95%) was added dropwise and reacted at room temperature. The reaction was completed in 1 hour. The reaction solution was poured into ice water and extracted with ethyl acetate to obtain a mixture containing Compound 2a as a yellow solution. 37 g of this mixture was dissolved in 370 ml of acetonitrile, and 7.4 g of water was added. 1.85 g of p-toluenesulfonic acid monohydrate was added and stirred at room temperature for 20 minutes. The organic phase was extracted with ethyl acetate and the solvent was distilled off. Compound a was isolated by column chromatography (filler: Wakogel C-200, developing solvent: ethyl acetate / hexane = 1/80).

<Step 2: Synthesis of Compound A by Hydrosilylation of Compound a>
Compound 5.0 g of (0.014 mol) in _{Speier catalyst (H 2 PtCl 6 ·} 6H 2 O / 2-PrOH, 0.1mol / l) and 2 drops of an ice bath trichlorosilane 2.8 g (0.021 mol ) Was added dropwise and stirred. After 1 hour, 1.6 g (0.012 mol) of trichlorosilane was added dropwise, and the temperature was returned to room temperature. The reaction was complete after 3 hours. After completion of the reaction, unreacted trichlorosilane was distilled off under reduced pressure to obtain Compound A.

[Example 1]
-Production of intermediate layer 1-
125 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) and 125 g of urethane acrylate oligomer (UV-6300B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) Dissolved in industrial modified 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. The mixture was stirred and then filtered through a polypropylene filter having a pore size of 1 μm to prepare an intermediate layer coating solution (1).

  An 80 μm thick triacetylcellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) was used as a support, and a gelatin subbing layer was provided on the surface. On the gelatin undercoat layer, the intermediate layer coating solution (1) is applied 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. A cured intermediate layer 1 having a thickness of 15 μm was formed, and a substrate capable of generating radicals upon exposure was obtained. The high pressure mercury lamp used was UVX-02516S1LP01 manufactured by Ushio Corporation.

-Contact between the specific oil-repellent polymer P-1 and butyl methacrylate on the substrate-
8. 0.5 g of the specific oil repellent polymer P-1 containing fluorine obtained in Synthesis Example 1 above, 0.15 g of butyl methacrylate, and 1-methoxy-2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.) 5 g was mixed to make a uniform solution.
The substrate (TAC) having a cured intermediate layer obtained as described above is cut into 4 cm × 5 cm, and using a spinner, the uniform solution is applied at 300 revolutions and dried at 100 ° C. for 1 minute, Both were made to contact by forming the film containing specific oil-repellent polymer P-1 and butylmethacrylate on the base-material surface which has an intermediate | middle layer.

-Formation of graft polymer by exposure to substrate-
A film containing the specific oil-repellent polymer P-1 was formed on the surface and brought into contact with each other, and then exposed for 5 minutes with a UV exposure device (UVX-02516S1LP01, high pressure mercury lamp, manufactured by USHIO) from the film forming side. After the exposure, the quartz plate was removed, and the resulting fluorine-based graft film was washed with acetone to remove impurities such as the unreacted specific oil-repellent polymer P-1 to obtain the water / oil-repellent material of Example 1. .
When the contact angle of water droplets on the surface of the obtained water / oil repellent material was measured, it was found to be 120 °, indicating excellent water repellency.

[Example 2]
A water- and oil-repellent material of Example 2 was obtained in the same manner as in Example 1 except that 0.15 g of methyl methacrylate was used instead of butyl methacrylate used in Example 1 and the drying temperature was 80 ° C.
Example 3
A water and oil repellent material of Example 3 was obtained in the same manner as in Example 1 except that 0.15 g of N, N-dimethylacrylamide was used in place of the butyl methacrylate used in Example 1.
Example 4
The water and water repellency of Example 4 was the same as Example 1 except that the specific oil repellent polymer P-2 obtained in Synthesis Example 2 was used instead of the specific oil repellent polymer P-1 used in Example 1. An oily material was obtained.
Example 5
A water- and oil-repellent material of Example 5 was obtained in the same manner as in Example 4 except that methyl methacrylate was used instead of butyl methacrylate used in Example 4.
Example 6
A water / oil repellent material of Example 6 was obtained in the same manner as in Example 4 except that N, N-dimethylacrylamide was used in place of the butyl methacrylate used in Example 4.

Example 7
-Production of intermediate layer 2-
<Preparation of intermediate layer coating solution (2)>
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 (2) was prepared.

-Formation of the intermediate layer 2-
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 the undercoat layer with an antistatic layer, the intermediate layer coating solution (2) is applied by an extrusion method, dried, and irradiated with ultraviolet rays (700 mJ / cm ² ) to dry the intermediate layer 2 after drying. A hard coat film having a thickness of 20 μm, that is, a base material capable of generating radicals upon exposure was prepared.

(Formation of a film of a mixture of the specific oil-repellent polymer P-1 and butyl methacrylate)
0.5 g of the specific oil-repellent polymer P-1 synthesized as described above, 0.15 g of butyl methacrylate, and 9.5 g of 1-methoxy-2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.) are mixed. A homogeneous solution. A fluorine-containing polymer film was formed in the same manner as in Example 1, and then exposed and purified in the same manner to obtain the water / oil repellent material of Example 7.

[Comparative Example 1]
Using a base material having a cured intermediate layer similar to that obtained in Example 1, poly (2- (perfluorooctyl) ethyl acrylate) (molecular weight 130,000) as a comparative fluoropolymer was formed on the intermediate layer surface. A water repellent / oil repellent material of Comparative Example 1 was obtained in the same manner as in Example 1 except that a solution (10 wt%) mixed with hexafluoroisopropanol and butyl methacrylate was applied so that the dry film thickness was 1 micron. It was.
[Comparative Example 2]
A water / oil repellent material of Comparative Example 2 was obtained in the same manner as in Example 1 except that butyl methacrylate was not added in the step of Example 1.

Example 8
By using a glass substrate instead of the TAC substrate used in Examples 1 to 7 and carrying out the following (1. Photoradical generator binding step) and (2. Graft polymer production step), oil and water repellency is achieved. A graft polymer layer having an aqueous function was formed on a glass substrate.
<1. Photoradical generator binding step>
A glass substrate (Matsunami Glass) 10 × 10 cm was rinsed with acetone, washed, and then exposed to a UV, O ₃ cleaner (NL-UV253 manufactured by Nippon Laser Electronics Co., Ltd.) for 5 minutes to introduce hydroxyl groups on the substrate surface. On this substrate, the photoradical generator (compound A) synthesized by the method described in [Synthesis Example 3] was bonded by the following two methods.
(1) This substrate was placed in a separable flask substituted with nitrogen, and immersed in a dehydrated toluene solution of 0.5% by mass of Compound A at 130 ° C. for 1 hour. After taking out, it wash | cleaned in order of toluene, acetone, and a pure water.
(2) A 1% by weight compound A dehydrated toluene solution was applied onto the substrate using a spinner and dried at 100 ° C. for 1 minute. Then, it wash | cleaned in order of toluene, acetone, and pure water.

<2. Graft polymer manufacturing process>
As a polymer compound having an oil-repellent / water-repellent functional group and a polymerizable unsaturated double bond in the side chain on the photoradical generator-bonded glass substrate prepared by the method of (1) or (2) above, 1.0 g of the specific oil-repellent polymer P-1 obtained in [Synthesis Example 1], 9.0 g of ethyl acetate (Tokyo Chemical Industry) and 0.3 g of butyl methacrylate (BMA, Tokyo Chemical Industry) are mixed to form a uniform solution. After coating with a 300-rotation spinner, the coating film was obtained by drying at 100 ° C. for 1 minute.
Thereafter, the film was exposed for 5 minutes with a UV exposure apparatus UVX-02516S1LP01 (high pressure mercury lamp, manufactured by USHIO), immersed in acetone for 1 hour, rinsed with acetone and washed to remove the polymer remaining on the surface.

Example 9
A water- and oil-repellent material of Example 9 was obtained in the same manner as in Example 8 except that 0.3 g of methyl methacrylate was used instead of butyl methacrylate used in Example 8.
Example 10
A water- and oil-repellent material of Example 10 was obtained in the same manner as in Example 8 except that 0.3 g of N, N-dimethylacrylamide was used instead of butyl methacrylate used in Example 8.
[Comparative Example 3]
A water / oil repellent material of Comparative Example 3 was obtained in the same manner as in Example 8 except that butyl methacrylate was not added in the step of Example 8.

[Evaluation of water and oil repellent materials]
Each evaluation method was performed by the following method, and the performance of the water / oil repellent material obtained by the method of the present invention was evaluated. The results are shown in Table 1 below.
1. Contact angle The water / oil repellent material was cut to 2 × 2 cm ² and the contact angle of water droplets was measured in the air using Contact-Angle meter (10927 manufactured by Kyowa Interface Chemical Co., Ltd.). (The unit is degrees.) The larger the value, the better the water repellency.
2. Initial antifouling property A character was written on the surface of the water / oil repellent 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. It is evaluated that the smaller the number of times, the lower the affinity for oil-based inks and the better the oil repellency (antifouling property against oily stains).

3. Oil Repellency / Durability / Transparency After the surface of the antifouling hard coat film was strongly rubbed 100 times with “Bem Cotton” (registered trademark) manufactured by Asahi Kasei Co., Ltd. Similar to the initial antifouling property evaluation, letters were written on the film surface with a quick-drying oil-based ink (manufactured by Zebra, “Mackey” (registered trademark)), and the number of times until it was wiped off was measured. The smaller the number of times, the higher the surface oil repellency after mechanical wear and the better the oil repellency durability. The transparency was evaluated visually.

  From the results in Table 1, the water / oil repellent materials of Examples 1 to 7 obtained by the method of the present invention are all excellent in transparency, surface water repellency and antifouling property (oil repellency), It was found to be excellent in soiling (oil repellency) durability. Further, in contrast with Example 1 and Example 7, the water / oil repellent material of Example 7 in which the hard coat-like intermediate layer 2 is formed is realized at a high level of oil repellency / durability. Is shown.

  From the results in Table 2, even when the TAC substrate is replaced with a glass substrate, the water and oil repellency material obtained by the production method of the present invention has surface water repellency, antifouling property (oil repellency), antifouling property ( It can be seen that the (oil repellency) durability is high and high transparency is realized.

  The water / oil repellent material obtained by the method of the present invention is useful as an antifouling surface material. In particular, when having a high hardness intermediate layer that functions as a hard coat layer, which is a preferred embodiment of the present invention, a high hardness intermediate layer having excellent adhesion to the substrate, and the intermediate layer is firmly bonded by chemical bonding It has a combined water / oil repellency graft polymer layer and is excellent in antifouling properties (water / oil repellency), scratch resistance, and transparency, and is a surface material that has long-lasting antifouling properties. These water- and oil-repellent materials can be applied in various fields, and by using a transparent substrate, it is possible to obtain a transparent substrate (hard coat film) having excellent antifouling properties and scratch resistance. It can be suitably applied to a display such as CRT, LCD, PDP, FED, touch panel, glass, table, decorative plywood, etc., as well as a surface protective film, antireflection film, etc. in a recording medium such as CD, DVD. Furthermore, the application possibility in the optical material field | area which was difficult to apply with the conventional raw material is anticipated.

Claims (5)

(1) A polymer compound having an oil and water repellant functional group and a polymerizable unsaturated double bond in the side chain on a substrate surface capable of generating radicals upon exposure, and a low molecule having a polymerizable unsaturated group Mixing the compound and bringing it into contact with the substrate; and (2) exposing the substrate to form a graft polymer layer comprising the low molecular weight compound and the polymer compound on the substrate. A method for producing an oil-repellent and water-repellent material.   The method for producing an oil repellent and water repellent material according to claim 1, wherein the molecular weight of the low molecular weight compound is less than 1000.   3. The oil and water repellent material according to claim 1 or 2, wherein the low molecular weight compound is at least one selected from the group consisting of (meth) acrylic acid ester monomers and acrylamide monomers. Manufacturing method.   The method for producing an oil and water repellent material according to any one of claims 1 to 3, wherein the low molecular weight compound is an alkyl (meth) acrylate having an alkyl group having 1 to 6 carbon atoms.   An oil repellent and water repellent material produced by the method for producing an oil repellent and water repellent material according to any one of claims 1 to 4.