JP2008050419A - Water-dispersible antifouling resin composition and antifouling sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-dispersible antifouling resin composition that exhibits antifouling effects for long terms to maintain a display sheet in a clear state and permits a treatment of the display sheet for preventing it from getting visually unsightly or hurting its images, and an excellently convenient antifouling sheet that allows ready replacement of only an antifouling member if the circumstances require. <P>SOLUTION: The water-dispersible antifouling resin composition comprises an acrylic copolymer (A) having a glass transition temperature (Tg) of -40 to +20°C, colloidal silica (B) and an ionic liquid (C), where 10-1,000 pts.wt. of the colloidal silica (B) and 0.01-50 pts.wt. of the ionic liquid (C) are compounded with 100 pts.wt. of the acrylic copolymer (A). The antifouling sheet comprises a sheet-like substrate 2, and the water-dispersible antifouling resin composition with a surface having a contact angle to water of at most 45° applied on one surface thereof and an adhesive layer 11 formed on the other surface. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a water-dispersed antifouling resin composition and an antifouling sheet, and in particular, has an antifouling effect for a long period of time, can maintain a display sheet in a clear state, and is visually inconvenient. Suitable as a water-dispersed antifouling resin composition that can be processed so that it does not appear or damage the image, and signs such as signboards, posters, road signs or construction signs with less pollution Also, the present invention relates to an antifouling sheet excellent in convenience that can easily replace only the antifouling member as required.

  In recent years, display sheets such as signboards, posters, banners, banners, road signs, guide signs, construction signs, and display sheets such as display boards have been used, but such display sheets are always clean and clean. Need to be maintained. If dirt is attached, it may cause discomfort to the eyes, sometimes make it difficult to read the display items, and may damage the image of the product or the business.

  However, since display sheets are often attached outdoors, they are easily contaminated by dust or the like. Furthermore, since the materials of these display sheets are made of a plastic material, there is a problem in that the electrical insulation is high, static electricity is generated during friction and peeling, and dust, dust, etc. are attached and the surface is contaminated. Therefore, in order to prevent such problems and maintain a clear state, frequent cleaning and replacement are required.

  As a method for reducing the contamination of outdoor equipment, conventionally, a water-repellent synthetic resin, or an antifouling agent containing a fluorine-based material or a silicon-based material for improving water repellency has been applied. However, those utilizing water repellency have the problem that when rainwater or the like adheres, water droplets are formed, and when dried as they are, contaminants adhere to the dry marks and form dot-like stains.

In recent years, as a method for reducing contamination, it has been proposed to make the surface hydrophilic (Patent Documents 1, 2, and 3). This is because, when the surface is made hydrophilic, hydrophilic pollutants adhere, but they are easily removed by natural purification action such as rain, while lipophilic pollutants that are hard to be washed away are difficult to adhere. It is a thing.
JP-A-11-267585 JP 2004-142161 A JP 2003-55480 A

  However, Patent Documents 1, 2, and 3 do not propose to prevent contamination of the display sheet and maintain the display in a clear state for a long time.

  In addition, the method of applying the antifouling agent to make the surface of the display sheet hydrophilic has a problem that the display sheet itself needs to be replaced when the antifouling effect is lowered with time.

  For this reason, the display sheet excellent in the pollution prevention effect was obtained, and when the pollution prevention property fell, development of the pollution prevention technique which can be reproduced | regenerated was requested | required.

  Therefore, the object of the present invention is to prevent the contamination of the display sheet for a long period of time, maintain the display sheet in a clear state, and prevent it from being visually unsightly or damaging the image. The present invention provides a water-dispersible antifouling resin composition that can be used, and an excellent antifouling sheet capable of easily replacing only the antifouling member as required.

  Other problems of the present invention will become apparent from the following description.

  The above-described problems of the present invention are solved by the following inventions.

(Claim 1)
It contains an acrylic copolymer (A) having a glass transition point (Tg) of −40 to + 20 ° C., colloidal silica (B), and an ionic liquid (C), and the acrylic copolymer (A). The water-dispersed type prevention characterized by mix | blending the said colloidal silica (B) in the range of 10-1000 weight part and the said ionic liquid (C) in the range of 0.01-50 weight part with respect to 100 weight part. Dirty resin composition.

(Claim 2)
The aqueous dispersion according to claim 1, wherein the ionic liquid (C) is at least one selected from an imidazolium salt derivative, a pyridinium salt derivative, an alkylammonium salt derivative, a phosphonium salt derivative or a pyrazolium salt derivative. Mold antifouling resin composition.

(Claim 3)
The water-dispersed antifouling resin composition according to claim 1 or 2, wherein the acrylic copolymer (A) is an amphoteric acrylic copolymer obtained by emulsion copolymerization of the following monomers. object.
(A) (Meth) acrylic monomer 99.8% by weight or less (b) Anionic group-containing radical polymerizable monomer 0.1 to 10% by weight
(C) Cationic group-containing radical polymerizable monomer 0.1 to 10% by weight
(D) Comonomers other than the monomers (a) to (c) 75% by weight or less [However, the total of the monomers (a) to (d) is 100% by weight. ]

(Claim 4)
The water dispersion type according to any one of claims 1 to 3, wherein an average particle size of the copolymer particles in the aqueous dispersion of the acrylic copolymer (A) is 0.2 µm or less. Antifouling resin composition.

(Claim 5)
The water-dispersed antifouling resin composition according to any one of claims 1 to 4 is applied to one side of a sheet-like substrate, and the contact angle of water on the surface is 45 degrees or less, and the other side An antifouling sheet characterized in that an adhesive layer is formed on the antifouling sheet.

  According to the present invention, there is an effect of preventing contamination over a long period of time, the display sheet can be maintained in a clear state, and can be processed so as not to be visually unsightly or to damage the image. A water-dispersible antifouling resin composition that can be produced and an antifouling sheet excellent in convenience capable of easily replacing only the antifouling member as required can be obtained.

  The water-dispersed antifouling resin composition of the present invention comprises an acrylic copolymer (A), colloidal silica (B) having a glass transition point (hereinafter abbreviated as “Tg” if necessary) of −40 to + 20 ° C., And an ionic liquid (C).

  Examples of the acrylic copolymer (A) having a Tg of −40 to + 20 ° C. include a (meth) acrylic monomer (a), an anionic group-containing radical polymerizable monomer (b), and a cationic group-containing radical. A copolymerized monomer (c) and a comonomer (d) other than the above monomers (a) to (c) are suitable for further improving the effects of the present invention. used.

  As the (meth) acrylic monomer (a), acrylate or methacrylate can be used, and these are linear or branched alkyl groups having 1 to 18 carbon atoms, linear or branched atoms having 12 to 18 carbon atoms. Those having an alkenyl group, a cycloalkyl group having 6 to 8 carbon atoms or an aralkyl group having 7 to 12 carbon atoms are preferred. Specifically, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, n-nonyl acrylate, isononyl acrylate, lauryl acrylate, stearyl acrylate, Lauryl methacrylate, stearyl methacrylate and the like can be used, and these can be used alone or in combination of two or more.

  The amount of the (meth) acrylic monomer (a) used is 99.8% by weight or less, and the total of the monomers (a) to (d) is 100% by weight. It is the remaining amount of b) to (d).

  Examples of the anionic group-containing radical polymerizable monomer (b) include α, β-unsaturated mono- or di-carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride or fumaric acid. In addition, a monomer having a functional group other than a carboxyl group can also be used. For example, phosphoric acid-2- (meth) acryloyloxyalkyl ester, vinyl sulfonic acid, t-butylacrylamide sulfonic acid, 2 -Sulfoethyl (meth) acrylate, styrene sulfonic acid, etc. are mentioned. These can be used alone or in combination of two or more.

  Preferable as the anionic group-containing radical polymerizable monomer (b) is acrylic acid or methacrylic acid.

  The amount of the anionic group-containing radical polymerizable monomer (b) used is preferably in the range of 0.1 to 10% by weight, more preferably 100% by weight in total of the monomers (a) to (d). Is in the range of 0.5 to 5% by weight, particularly preferably in the range of 1 to 4% by weight. When the usage-amount of a monomer (b) exceeds an upper limit amount, the water resistance of the antifouling agent layer formed may fall and it is not preferable. On the other hand, if the amount used is 0.1% by weight or more, the mechanical stability of the obtained water-dispersed antifouling resin composition and the adhesive strength of the obtained antifouling agent layer are moderate and excellent in cohesive strength. Therefore, it is better to select and use within the above range.

  Examples of the cationic group-containing radical polymerizable monomer (c) include aminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and dimethyl Examples include N-aminoalkyl (meth) acrylamides such as aminopropyl (meth) acrylamide and dimethylaminoethyl (meth) acrylamide. Of these, diethylaminoethyl (meth) acrylate is preferable.

  The content of the anionic group-containing radically polymerizable monomer (b) and the cationic group-containing radically polymerizable monomer (c) is balanced between anionic and cationic so as to be amphoteric in the aqueous dispersion. Need to take.

  The amount of the cationic group-containing radical polymerizable monomer (c) used is preferably in the range of 0.1 to 10% by weight, more preferably 100% by weight in total of the monomers (a) to (d). Is in the range of 0.5 to 5% by weight, particularly preferably in the range of 1 to 4% by weight. Below this lower limit, polymerization stability is impaired during copolymerization, and above the upper limit, adhesion of the resulting antifouling agent layer when wet is difficult to obtain.

  Examples of the comonomer (d) other than the monomers (a) to (c) include, for example, vinyl formate, vinyl acetate, vinyl persate, vinyl pivalate, acrylonitrile, methacrylonitrile, vinyl propionate, styrene, Vinyl monomers such as vinyltoluene and ethylvinylbenzene, or vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltris (2- Silicon-containing monomers such as (methoxyethoxy) silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyldimethylethoxysilane, and 3-acryloxypropyldimethylmethoxysilane can be used.

  In particular, the comonomer (d) used in the present invention is represented by the following formula (1) from the viewpoint of good dispersibility between the resulting acrylic copolymer (A) and colloidal silica (B). Preferred are silicon-containing monomers.

[Wherein R ² is hydrogen or a methyl group; X is a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, COOZ ¹ or CONHZ ² , and Z ¹ and Z ² are each independently carbon A linear or branched alkylene group having 2 to 6 carbon atoms; R ³ is a linear or branched alkyl group having 1 to 6 carbon atoms; Y may be the same or different, and may be halogen, OR ⁴ or OZ ³ OR ^5. R ⁴ is hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms or an acyl group having 1 to 6 carbon atoms, Z ³ is a linear or branched alkylene group having 2 to 6 carbon atoms, R ⁵ Is a straight or branched alkyl group having 1 to 6 carbon atoms in which hydrogen or a part of hydrogen atoms may be substituted with a hydroxyl group; n represents an integer of 0 to 2]

Examples of such silicon-containing monomers include those in which X is a single bond, such as vinyltrichlorosilane, vinyltribromosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, and vinyltri-i-. Propoxysilane, vinyltri-n-butoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltris (2-hydroxymethoxyethoxy) silane, vinyltriacetoxysilane, vinyldiethoxysilanol, vinylethoxysiladiol, vinylmethyldiethoxysilane, Vinyldimethylethoxysilane, vinylmethyldiacetoxysilane, etc .; X is a linear or branched alkylene group having 1 to 12 carbon atoms, such as allyltrimethoxysilane, allyltriethoxysilane, etc .; X is COOZ ¹ or CONHZ ² , wherein Z ¹ and Z ² are linear or branched alkylene groups having 2 to 6 carbon atoms, such as 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3 -Methacryloxypropyltris (2-methoxyethoxy) silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyldimethylethoxysilane, 3-acryloxypropyldimethylmethoxysilane, 2-acrylamidoethyltriethoxysilane, etc .; Can be mentioned.

  In general, the content of the comonomer (d) is preferably 75% by weight or less with respect to the total of 100% by weight of the monomers (a) to (d) because it is difficult to obtain sufficient adhesive strength when the content is increased. More preferably, it is in the range of 0 to 50% by weight, and still more preferably in the range of 5 to 50% by weight.

  The amount of the comonomer (d) used varies depending on the type of the monomer (d) and cannot be determined uniquely. However, the balance between the adhesive force and the flexibility and the balance between these and the cohesive force are adjusted as desired. Therefore, it can be appropriately selected in an amount within the above range to meet such purpose.

  The acrylic copolymer (A) used in the present invention is obtained by copolymerizing the monomers (a) to (d), and its Tg needs to be in the range of −40 to + 20 ° C. Preferably, it is the range of -30 to +10 degreeC. When the Tg exceeds the upper limit temperature and is high, the resulting antifouling agent layer tends to be insufficient in flexibility. On the other hand, when the Tg is lower than the lower limit temperature, the antifouling performance as an antifouling sheet and the prevention of dust adhesion The function cannot be obtained. In the present invention, Tg of the acrylic copolymer (A) refers to a value measured by a DSC method.

  As a suitable method for producing an aqueous dispersion of the acrylic copolymer (A) used in the present invention, for example, the monomers (a) to (d) are used for polymerization with an appropriate surfactant. The emulsification copolymerization in an aqueous medium can be mentioned as an emulsifier.

  The surfactant used in the present invention is preferably a so-called “reactive emulsifier” having a radical polymerizable unsaturated group in the molecule from the viewpoint of the water resistance of the resulting antifouling agent layer. As such reactive emulsifiers, for example, “Eleminol JS-2”, “Eleminol RS-30” [manufactured by Sanyo Chemical Industries, Ltd.], “Aqualon KH-05”, “Aquaron KH-10” [ “Daiichi Kogyo Seiyaku Co., Ltd.”, “Adekaria Soap SE, SR Series” [Asahi Denka Kogyo Co., Ltd.], “Latemuru S-180”, “Latemuru S-180A” [above, Kao Corporation Anionic reactive emulsifiers such as “ADEKA rear soap NE, ER series” (manufactured by Asahi Denka Kogyo Co., Ltd.), “Latemul PD-420”, “Latemul PD-430”, “Latemul PD-” 450 ”(manufactured by Kao Corporation) and the like; and the like.

  The use amount of the reactive emulsifier is preferably in the range of 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the total of the monomers (a) to (d). The amount of degree can be illustrated. If the amount used is not less than the lower limit, the resulting water-dispersed antifouling resin composition is preferably good in mechanical stability, while if not more than the upper limit, the antifouling agent layer to be formed is preferred. Cohesive force and water resistance are improved.

  In the emulsion copolymerization, various surfactants such as known nonionic surfactants and anionic surfactants can be used together with reactive emulsifiers as polymerization emulsifiers. Nonionic surfactants For example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether; for example, polyoxyethylene alkyl phenol ethers such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether; Sorbitan higher fatty acid esters such as laurate, sorbitan monostearate and sorbitan trioleate; for example, polyoxyethylene sorbitan higher such as polyoxyethylene sorbitan monolaurate Fatty acid esters; for example, polyoxyethylene higher fatty acid esters such as polyoxyethylene monolaurate and polyoxyethylene monostearate; for example, glycerine higher fatty acid esters such as oleic acid monoglyceride and stearic acid monoglyceride; Examples thereof include oxyethylene / polyoxypropylene / block copolymer;

  Examples of the anionic surfactants include higher fatty acid salts such as sodium oleate; alkyl aryl sulfonates such as sodium dodecylbenzene sulfonate; alkyl sulfate esters such as sodium lauryl sulfate; Polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate; for example, polyoxyethylene alkyl aryl ether sulfates such as polyoxyethylene nonylphenol ether sodium sulfate; sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate , Alkylsulfosuccinic acid ester salts such as sodium polyoxyethylene lauryl sulfosuccinate and derivatives thereof; .

  The average particle diameter of the copolymer particles in the aqueous dispersion of the obtained acrylic copolymer (A) is preferably 0.2 μm or less, more preferably 0.1 μm or less. If the average particle diameter exceeds the upper limit, the water resistance tends to be insufficient. In addition, the average particle diameter as used in the field of this invention is measured by the dynamic light scattering method.

  As the colloidal silica (B) used in the water-dispersed antifouling resin composition of the present invention, an aqueous dispersion in which silica particles having a particle diameter of 1 to 100 nm are colloidally dispersed in water can be used. For example, Snowtex XS, OXS, S, OS, 20, 30, 40, O, C, AK, 50, O-40, CM, 20L, OL, XL, ZL, UP, OUP, PS-S, PS-M, 45, MP-2040, MP-4540M [Nissan Chemical Industry Co., Ltd.], Cataloid-S series [Catalyst Kasei Kogyo Co., Ltd.], Adelite AT series [Asahi Denka Kogyo Co., Ltd.], etc. You can use what you have.

  The compounding quantity of colloidal silica (B) is the range of 10-1000 weight part with respect to 100 weight part of acrylic copolymers (A), More preferably, it is the range of 20-500 weight part, Especially preferably, it is 25-25. The range is 400 parts by weight.

  As the ionic liquid (C), organic nitrogen-based, organic phosphorus-based, and organic sulfur-based ones can be used. For example, imidazolium salt derivatives [the following formulas (2) to (4)], pyridinium salt derivatives [the following formulas (5)], alkylammonium salt derivatives [following formula (6)], phosphonium salt derivatives [following formula (7)], pyrazolium salt derivatives [following formula (8)] and the like.

  Examples of the ionic liquid (C) include 1,3-dimethylimidazolium methyl sulfate, 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, 1-ethyl-3-methylimidazolium. Bis (pentafluoroethylsulfonyl) imide, 1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium nitrate, 1-ethyl-3-methyl Imidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium tosylate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3 -Methylimidazolium Xafluorophosphate, 1-butyl-3-methylimidazolium-2- (2-methoxyethoxy) ethyl sulfate, 1-butyl-3-methylimidazolium methyl sulfate, 1-butyl-3-methylimidazolium octyl sulfate 1-butyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium tetrafluoroborate 1-methyl-3-octylimidazolium chloride, 1-methyl-3-octylimidazolium tetrafluoroborate, 1,2-dimethyl-3-propylimidazolium bis (trifluoromethylsulfonyl) imide, 1,2-dimethyl Ru-3-propylimidazolium bis (trifluoromethylsulfonyl) methide, 1-butyl-2,3-dimethylimidazolium chloride, 1-butyl-2,3-dimethylimidazolium hexafluorophosphate, 1-butyl-2, 3-dimethylimidazolium tetrafluoroborate, 1-methyl-3- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) imidazolium hexa Fluorophosphate, 1-butyl-3- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) imidazolium hexafluorophosphate n, 1- Imidazolium salt derivatives such as propyl-3-methylpyridinium bis (trifluoromethylsulfonyl) imide; 1-butyl-3 -Methylpyridinium bis (trifluoromethylsulfonyl) imide, 1-butyl-4-methylpyridinium bromide, 1-butyl-4-methylpyridinium chloride, 1-butyl-4-methylpyridinium hexafluorophosphate, 1-butyl-4- Pyridinium salt derivatives such as methylpyridinium tetrafluoroborate; tetrabutylammonium heptadecafluorooctanesulfonate, tetrabutylammonium nonafluorobutanesulfonate, tetrapentylammonium methanesulfonate, tetrapentylammonium thiocyanate, methyl-tri-n-butylammonium methylsulfate, diethyl Methyl (2-methoxyethyl) ammonium tetrafluoroborate, diethylmethyl (2-methoxyethyl) Alkyl ammonium salt derivatives such as ammonium bis ((trifluoromethylsulfonyl) imide; tetrabutylphosphonium methylsulfate, tetrabutylphosphonium nitrate, tetrabutylphosphonium-p-toluenesulfonate, trihexyltetradecylphosphonium bis (trifluoromethylsulfonyl) ) Imido, trihexyltetradecylphosphonium bis (2,2,4-trimethylpentyl) hypophosphite, trihexyltetradecylphosphonium bromide, trihexyltetradecylphosphonium chloride, trihexyltetradecylphosphonium decanoate, trihexyl Tetradecylphosphonium dicyanamide, trihexyltetradecylphosphonium hexafluorophosphate, trihexyltetradec Phosphonium salt derivatives such as ruphosphonium tetrafluoroborate; 1-ethyl-2,3,5, -trimethylpyrazolium bistrifluoromethanesulfonylimide, 1-propyl-2,3,5, -trimethylpyrazolium bistrifluoromethane Pyrazolium salt derivatives such as sulfonylimide, 1-butyl-2,3,5, -trimethylpyrazolium bistrifluoromethanesulfonylimide, 1-methyl-2,3,5, -trimethylpyrazolium bistrifluoromethanesulfonylimide, etc. Can be mentioned.

  The blending amount of the ionic liquid (C) is generally in the range of 0.01 to 50 parts by weight, more preferably 0.025 to 40 parts by weight with respect to 100 parts by weight of the acrylic copolymer (A). In particular, the range is 0.05 to 20 parts by weight. If it is less than 0.01 part by weight, sufficient dust adhesion preventing property cannot be obtained, and if it exceeds 50 parts by weight, the adhesion strength of the film layer made of thermoplastic resin is lowered, which is not preferable.

  As shown in FIG. 1, the obtained water-dispersed antifouling resin composition was applied on the surface of a sheet-like substrate 2 and dried or cured to form an antifouling agent layer 3. The antifouling sheet 1 is formed by forming the pressure sensitive adhesive 11 with the pressure sensitive adhesive and attached to the display sheet or the like to prevent contamination of the member to be antifouled. The curing conditions are not particularly limited, but are usually performed at a temperature of 60 to 150 ° C. for 1 to 20 minutes. The thickness of the antifouling agent layer 3 is usually 0.1 to 15 μm, preferably 0.5 to 10 μm.

  The antifouling sheet 1 is usually prepared so that the water contact angle on the surface is 45 degrees or less, preferably 40 degrees or less at the initial stage of use (within one month immediately after construction). If the water contact angle on the surface of the antifouling sheet 1 is 45 ° or less, the antifouling property can be effectively enhanced and a clean state can be maintained over a long period of time.

  The material of the sheet-like substrate 2 is not particularly limited, but a flexible material is desirable for the purpose of the invention, and cellophane, celluloid, or a thermoplastic resin can be used.

  Examples of the thermoplastic resin include high-pressure low-density polyethylene, high-density polyethylene, linear low-density polyethylene, ethylene-based polymers such as ethylene / vinyl acetate copolymer, or propylene / α-propylene mainly composed of polypropylene and propylene. A propylene polymer such as an olefin copolymer, or a thermoplastic resin such as polyester, polyamide, or acrylic resin can be used. Among them, a thermoplastic resin excellent in weather resistance and heat resistance such as an acrylic polymer or a polyester polymer is desirable.

  The sheet-like base material 2 made of thermoplastic resin can be formed by T-die extrusion molding, cast molding, calendar molding, or inflation molding. Further, biaxial stretching of the obtained sheet is also a desirable method for improving waist, tensile strength and the like.

  In the present invention, the sheet is generally referred to as a flat sheet regardless of the thickness, and the sheet-like substrate 2 is generally referred to as a film, sheet, plate-like body, or cloth-like body. Those having a thickness of 5 to 300 μm, preferably 15 to 200 μm are preferable.

  Further, the sheet-like substrate 2 can be a laminated sheet in which two or more kinds of materials are laminated. As shown in FIG. 2, a surface layer having excellent coating properties on the surface of the base layer 4 having excellent strength. A laminated sheet obtained by laminating 5 can be used as the substrate 2.

  In addition, when used in applications requiring strength such as transverse membranes, partition sheets, etc., as shown in FIG. 3, the striated filaments 6a and 6b obtained by uniaxially stretching a thermoplastic resin are woven as warp yarns. As shown in FIG. 4, the stretched linear bodies 6a, 6b are arranged in parallel so as to intersect vertically and horizontally, and the intersections are obtained from the cross-bonded cloth (SOF) obtained by heat fusion. A cloth-like body 7 can be used.

  As the drawn filament 6, a thermoplastic resin can be used, and a thermoplastic resin having excellent mechanical strength is desirable. Specifically, high-density polyethylene, linear low-density polyethylene, and ethylene / vinyl acetate are used. Use ethylene-based polymers such as polymers, polypropylene produced using polypropylene, metallocene catalysts, propylene-based polymers such as propylene / α-olefin copolymers mainly composed of propylene, polyesters, polyamides, etc. be able to. Of these, polyolefins such as ethylene polymers or propylene polymers are desirable.

  A tape-like body, monofilament, long fiber, short fiber, or the like can be used as the stretched linear body 6 forming the cloth-like body 7, and twisted as necessary.

  The obtained cloth-like body 7 can be used alone as the sheet-like substrate 2 as the cloth-like body 7, but is desirably a laminated resin film laminated with a film-like body 10 of a thermoplastic resin.

  As the thermoplastic resin for forming the film-like body 10, an ethylene polymer such as a high pressure method low density polyethylene, a high density polyethylene, a linear low density polyethylene, an ethylene / vinyl acetate copolymer, or a polypropylene or metallocene catalyst may be used. Propylene-based polymers such as polypropylene, propylene-based α-olefin copolymers mainly composed of propylene, polyesters, polyamides, and the like can be used. Among these, polyolefins such as ethylene polymers or propylene polymers are desirable, and ethylene polymers or propylene polymers produced using a metallocene catalyst are particularly preferable.

  The method of laminating the film-like body 10 of the thermoplastic resin can be performed by means known per se. For example, the cloth-like body 7 formed of the drawn filament 6 is supplied to a laminator, and the cloth-like body is obtained. 7 and the melted film-like body 10 can be stacked, and the cloth-like body 7 and the melted thermoplastic resin-like film body 10 can be laminated by pressing with an elastic roll and a metal roll. Also, as shown in FIG. 5, it is possible to have a sandwich structure in which the cloth-like body 7 is used as a core material and the thermoplastic resin film-like bodies 10 and 10 are laminated on both sides. When the film-like body 10 is laminated, the film-like body 10 of a thermoplastic resin melted on the other surface can be laminated by the same method.

  In addition, various additives can be appropriately blended in the thermoplastic resin constituting the sheet-like base material 2 within a range not impairing the effects of the invention. Specifically, phenol-based, organic phosphite , Antioxidants such as organic phosphorus such as phosnite and thioethers; light stabilizers such as hindered amines; UV absorbers such as benzophenones, benzotriazoles, and benzoates; nonionics, cationics, anions, etc. Antistatic agent; Dispersing agent such as bisamide, wax, organometallic salt; Chlorine scavenger such as carboxylate of alkaline earth metal salt; Amide, wax, organometallic salt, ester Lubricants; metal deactivators such as hydrazine and amine acid; antibacterial agents and the like.

  A pressure sensitive adhesive is applied to the other surface of the sheet-like substrate 2 to form the pressure-sensitive adhesive layer 11. In addition, in order to raise the adhesive force with an adhesive to the surface which applies the adhesive layer 11 of the sheet-like base material 2, the surface is subjected to physical treatment such as sandblasting, flame treatment, corona treatment or plasma treatment. It is preferable to apply a physicochemical treatment such as a primer treatment or the like.

  The pressure-sensitive adhesive is usually dissolved in an appropriate organic solvent or made into an emulsion, coated on the sheet-like substrate 2 and then dried, or coated on a process paper that has been subjected to a release treatment. What was dried after the work is transferred onto the support to form the antifouling sheet 1 in which the sheet-like base material 2 and the pressure-sensitive adhesive layer 11 are laminated. There is no restriction | limiting in a coating means and a drying method, A well-known thing is employable.

  The pressure-sensitive adhesive used in the present invention may be those generally used as pressure-sensitive adhesives for pressure-sensitive adhesive tapes, such as acrylic resin-based pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives such as natural rubber and synthetic rubber, and styrene-butadiene- Styrene block copolymer, styrene-isoprene-styrene block copolymer, block copolymer adhesive such as hydrogenated products, ethylene-vinyl acetate copolymer adhesive, polyvinyl ether resin adhesive, silicone resin Among them, an acrylic resin-based pressure-sensitive adhesive that is excellent in durability and weather resistance and has little dirt during handling is preferably used. These pressure-sensitive adhesives may be used alone or in combination of two or more.

  The form of these pressure-sensitive adhesives is not particularly limited, and for example, any form such as a solution-type pressure-sensitive adhesive, an emulsion-type pressure-sensitive adhesive, a reactive pressure-sensitive adhesive, a photopolymerizable monomer-type pressure-sensitive adhesive, etc. Good.

  In addition, these pressure-sensitive adhesives may include cross-linking agents such as polyisocyanate compounds, aziridine compounds, metal chelate compounds, tackifiers, couplings, etc., as long as the object of the present invention is not impaired. Agent, filler, softener, plasticizer, surfactant, antioxidant (anti-aging agent), heat stabilizer, light stabilizer, ultraviolet absorber, colorant, antifoaming agent, flame retardant, antistatic agent, etc. One or two or more of these various additives may be added.

  Moreover, although the adhesive layer 11 formed on the sheet-like base material 2 is not specifically limited, It is preferable that the thickness is 10 micrometers-0.5 mm. When the thickness of the pressure-sensitive adhesive layer 11 is less than 10 μm, the adhesion to the rough surface of the antifouling sheet 1 and the unevenness followability may be insufficient, and conversely the thickness of the pressure-sensitive adhesive layer 11 is 0.5 mm. Above this, the tackiness and adhesion are no longer improved, but the cost increases.

  The acrylic resin-based adhesive will be described in more detail. As the acrylic resin-based adhesive, an acrylic polymer obtained by polymerizing a carboxyl group-containing monomer and a (meth) acrylic acid alkyl ester monomer is used. The number of carbon atoms of the alkyl group of the (meth) acrylic acid alkyl ester monomer is preferably about 4 to 12, and specifically, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-octyl (meth) acrylate. , Isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, and the like, and n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferable. Examples of the carboxyl group-containing monomer include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and itaconic acid; dicarboxylic acids such as fumaric acid and maleic acid, and monoesters thereof. Of these carboxyl group-containing radical polymerizable monomers, acrylic acid and methacrylic acid are preferably used. The carboxyl group-containing polymerizable monomer is preferably about 1 to 20% by weight of the whole monomer.

  In the acrylic resin-based pressure-sensitive adhesive used in the present invention, a small amount of a modifying component monomer may be copolymerized for the purpose of adjusting the glass transition temperature, polarity and the like. Examples of such monomers include methyl (meth) acrylate, ethyl (meth) acrylate, acrylamide, vinyl acetate, styrene, acrylonitrile, vinyl pyrrolidone and the like.

  The acrylic polymer is blended with a polyfunctional compound having two or more functional groups that react with a carboxyl group in the molecule, or a polyfunctional compound and a monofunctional compound having one functional group in the molecule. Can be crosslinked. Examples of this type of functional group-containing compound include an isocyanate group-containing compound, an epoxy group (or glycidyl group) -containing compound, an aziridinyl group-containing compound, a metal complex, and a melamine compound.

  Moreover, it is preferable to mix | blend a small amount of plasticizers in an adhesive composition. The kind of the plasticizer to be blended is not limited. For example, a low molecular plasticizer such as an ester of an aliphatic polyvalent carboxylic acid, an ester of an aromatic polyvalent carboxylic acid, a phosphate ester or a high molecular weight such as a polyester. Molecular plasticizers can be exemplified, but aliphatic dibasic acid esters are particularly effective, and adipic acid diester is most preferred. The blending amount is preferably 0.05 to 4% by weight.

  On the pressure-sensitive adhesive layer 11, as shown in FIG. 5, in order to lighten the peeling force (also referred to as a developing force) when rewinding, it is common to apply a release paper 12 that has been subjected to a release treatment. is there. Examples of the release treatment include application of a silicon release agent accompanied by a curing reaction, a fluorine release agent, and a long-chain alkyl graft polymer release agent, if necessary.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by this Example.

<Preparation of aqueous dispersion of acrylic copolymer>
Preparation Example 1
In a flask equipped with a reflux condenser, a thermometer, a stirrer, and a sequential dropping device, 70 parts by weight of ion-exchanged water and “AQUALON KH-10” (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.15 as an initial added emulsifier Part by weight, 0.04 part by weight of ammonium persulfate (APS) as a polymerization initiator and 0.04 part by weight of sodium metabisulfite (SMBS) as a reducing agent were charged, and the internal temperature was raised to 70 ° C. On the other hand, 20 parts by weight of ion-exchanged water, 3 parts by weight of “Latemul PD-430” (manufactured by Kao Corporation) and 5 parts by weight of “Latemul PD-450” (manufactured by Kao Corporation) are charged in a separate container. This was dissolved by stirring, and then 87 parts by weight of ethyl acrylate (EA), 9 parts by weight of butyl acrylate (BA), 2 parts by weight of acrylic acid (AA), 2 parts by weight of diethylaminoethyl methacrylate (DE), and “KBM- 503 "[3-methacryloxypropyltrimethoxysilane; manufactured by Shin-Etsu Chemical Co., Ltd.] A monomer mixture consisting of 0.01 parts by weight was added and stirred to obtain a monomer premix.

  While stirring the contents of the reactor under a nitrogen stream and maintaining the temperature of the contents at 70 ° C., the above monomer premix and 4 wt% APS aqueous solution were sequentially added to initiate polymerization, and the polymerization reaction was continued for about 4 hours. Went. After completion of the polymerization reaction, stirring was continued for about 1 hour at the same temperature, followed by cooling and adjusting the pH using aqueous ammonia to obtain an aqueous dispersion of an acrylic copolymer.

  Table 1 shows the copolymer composition, viscosity, solid content, average particle size, and Tg of the acrylic copolymer.

Preparation Examples 2-3, Comparative Preparation Example 1
An aqueous dispersion of an acrylic copolymer was obtained in the same manner as in Preparation Example 1, except that the proportion of BA used in Preparation Example 1 was changed or methyl methacrylate (MMA) was used instead of BA.

  Table 1 shows the copolymer composition, viscosity, solid content, average particle size, and Tg of the acrylic copolymer.

Preparation Example 4
In Preparation Example 1, an acrylic copolymer aqueous dispersion was obtained in the same manner as Preparation Example 1 except that the initial added emulsifier was not used.

  Table 1 shows the copolymer composition, viscosity, solid content, average particle size, and Tg of the acrylic copolymer.

Example 1
(Preparation of water-dispersed antifouling resin composition)
With respect to 100 parts by weight (solid content: about 50 parts by weight) of the acrylic copolymer (A) obtained in Preparation Example 1, 850 parts by weight of ion-exchanged water, colloidal silica (B) “Snowtex 30” [Nissan Chemical Industry Co., Ltd.] 50 parts by weight and 1 part by weight of ionic liquid (C) 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIB) are mixed and stirred to obtain a water-dispersed antifouling resin. A composition was prepared.

(Preparation of test antifouling sheet)
A water-dispersed antifouling resin composition obtained by the method of Example 1 was applied to a transparent acrylic film “Sanduren 014NST” (trade name, manufactured by Kaneka Corporation) with a thickness of 50 μm using a gravure coating machine. This was applied to a thickness of 0.5 μm and dried and cured at 100 ° C. for 1 minute to form an antifouling agent layer.

Thereafter, an acrylic pressure-sensitive adhesive composition “Nissetsu PE-121 / CK-401 = 100 parts by weight / 1.5 parts by weight of a mixture” [trade name, manufactured by Nippon Carbide Industries Co., Ltd.] solution on the mold release agent. It was applied so that the thickness of the pressure-sensitive adhesive layer at the time of drying was about 25 g / m ^2, and the pressure-sensitive adhesive dried with a hot air circulation dryer at 100 ° C. for 1 minute was bonded together, and the conditions were 23 ° C. and 65% RH. The antifouling sheet was obtained by crosslinking for 7 days.

(Evaluation methods)
Using the test antifouling sheet obtained by the above preparation, evaluation was performed by the following test method. The results are shown in Table 2.

(Test method)
a. Contact angle:
One drop of distilled water was dropped on the surface of the antifouling agent layer of the test antifouling sheet, and the contact angle after 1 minute was measured.

  If the water contact angle on the surface is 45 degrees or less, it is possible to effectively improve the stain resistance and maintain a clean state for a long period of time.

b. water resistant:
A test antifouling sheet was attached to the vapor-deposited surface of a 50 μm aluminum vapor-deposited polyethylene terephthalate film so that its adhesion area was 50 × 50 mm ² . After this was immersed in warm water of 60 ° C. for 48 hours, the state of whitening of the test antifouling sheet was observed and evaluated according to the following criteria.

○: No whitening △: Whitening only at the periphery ×: Whitening of the entire surface

c. Antifouling performance:
The difference in whiteness L ^* value was measured in accordance with a type I test for promoting antifouling materials for civil engineering (using a 5% by weight tap water dispersion of carbon black).

d. Adhesive strength:
It measured based on JIS-Z0237.

e. Dust adhesion prevention performance The state of adhesion of dust floating in the air was visually compared according to the following criteria.

○: Good with no deposit ×: With deposit

Examples 2-3 and Comparative Examples 1-2
In Example 1, a water-dispersed antifouling resin composition was prepared in the same manner as in Example 1 except that the use ratio of the colloidal silica (B) “Snowtex 30” was changed or the Snowtex 30 was not used. Also, a test antifouling sheet was prepared and evaluated in the same manner. The results are shown in Table 2.

Example 4
In Example 1, an aqueous dispersion was used in the same manner as in Example 1 except that the aqueous acrylic copolymer dispersion of Preparation Example 2 was used instead of the aqueous acrylic copolymer dispersion of Preparation Example 1. A mold antifouling resin composition was prepared and a test antifouling sheet was prepared and evaluated in the same manner. The results are shown in Table 2.

Example 5
In Example 1, an aqueous dispersion was used in the same manner as in Example 1 except that the aqueous acrylic copolymer dispersion of Preparation Example 3 was used instead of the aqueous acrylic copolymer dispersion of Preparation Example 1. A mold antifouling resin composition was prepared and a test antifouling sheet was prepared and evaluated in the same manner. The results are shown in Table 2.

Comparative Example 3
In Example 1, water was used in the same manner as in Example 1 except that the aqueous acrylic copolymer dispersion of Comparative Preparation Example 1 was used instead of the aqueous acrylic copolymer dispersion of Preparation Example 1. A dispersion-type antifouling resin composition was prepared, and a test antifouling sheet was prepared and evaluated in the same manner. The results are shown in Table 2.

Example 6
In Example 1, water dispersion was carried out in the same manner as in Example 1, except that the aqueous acrylic copolymer dispersion of Preparation Example 4 was used instead of the aqueous acrylic copolymer dispersion of Preparation Example 1. A mold antifouling resin composition was prepared and a test antifouling sheet was prepared and evaluated in the same manner. The results are shown in Table 2.

Examples 7-8
In Example 1, water dispersion was carried out in the same manner as in Example 1 except that instead of using colloidal silica (B) Snowtex 30, Snowtex PS-S or Snowtex OUT [manufactured by Nissan Chemical Industries, Ltd.] was used. A mold antifouling resin composition was prepared and a test antifouling sheet was prepared and evaluated in the same manner. The results are shown in Table 2.

Example 9, Comparative Example 4
In Example 1, instead of using 1 part by weight of the ionic liquid (C) “EMIB”, 0.5 part by weight of diethylmethyl (2-methoxyethyl) ammonium tetrafluoroborate (EMEAB) is used, or EMIB is not used. A water-dispersed antifouling resin composition was prepared in the same manner as in Example 1, and a test antifouling sheet was prepared and evaluated in the same manner. The results are shown in Table 2.

The longitudinal cross-sectional view which shows an example of the antifouling sheet | seat which concerns on this invention Longitudinal sectional view showing another example of the antifouling sheet according to the present invention It is a figure which shows the other example of the antifouling sheet | seat which concerns on this invention, (A) is a top view, (B) is a longitudinal cross-sectional view Longitudinal sectional view showing another example of the antifouling sheet according to the present invention Longitudinal sectional view showing another example of the antifouling sheet according to the present invention

Explanation of symbols

1: Antifouling sheet 2: Base material 3: Antifouling agent layer 4: Base layer 5: Surface layer 6: Uniaxially stretched striate body 7: Cloth body 10: Film body 11: Adhesive layer 12: Release paper

Claims (5)

  It contains an acrylic copolymer (A) having a glass transition point (Tg) of −40 to + 20 ° C., colloidal silica (B), and an ionic liquid (C), and the acrylic copolymer (A). The water-dispersed type prevention characterized by mix | blending the said colloidal silica (B) in the range of 10-1000 weight part and the said ionic liquid (C) in the range of 0.01-50 weight part with respect to 100 weight part. Dirty resin composition.   The aqueous dispersion according to claim 1, wherein the ionic liquid (C) is at least one selected from an imidazolium salt derivative, a pyridinium salt derivative, an alkylammonium salt derivative, a phosphonium salt derivative or a pyrazolium salt derivative. Mold antifouling resin composition. The water-dispersed antifouling resin composition according to claim 1 or 2, wherein the acrylic copolymer (A) is an amphoteric acrylic copolymer obtained by emulsion copolymerization of the following monomers. object.
(A) (Meth) acrylic monomer 99.8% by weight or less (b) Anionic group-containing radical polymerizable monomer 0.1 to 10% by weight
(C) Cationic group-containing radical polymerizable monomer 0.1 to 10% by weight
(D) Comonomers other than the monomers (a) to (c) 75% by weight or less [However, the total of the monomers (a) to (d) is 100% by weight. ]   The water dispersion type according to any one of claims 1 to 3, wherein an average particle size of the copolymer particles in the aqueous dispersion of the acrylic copolymer (A) is 0.2 µm or less. Antifouling resin composition.   The water-dispersed antifouling resin composition according to any one of claims 1 to 4 is applied to one side of a sheet-like substrate, and the contact angle of water on the surface is 45 degrees or less, and the other side An antifouling sheet characterized in that an adhesive layer is formed on the antifouling sheet.

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