WO2013005368A1 - Protection film for wheel - Google Patents

Protection film for wheel Download PDF

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Publication number
WO2013005368A1
WO2013005368A1 PCT/JP2012/003367 JP2012003367W WO2013005368A1 WO 2013005368 A1 WO2013005368 A1 WO 2013005368A1 JP 2012003367 W JP2012003367 W JP 2012003367W WO 2013005368 A1 WO2013005368 A1 WO 2013005368A1
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WO
WIPO (PCT)
Prior art keywords
protective film
wheel
meth
pressure
sensitive adhesive
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PCT/JP2012/003367
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French (fr)
Japanese (ja)
Inventor
甲斐 誠
和彦 金原
加藤 直人
一康 花木
Original Assignee
日東電工株式会社
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Publication of WO2013005368A1 publication Critical patent/WO2013005368A1/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22Plastics; Metallised plastics
    • C09J7/24Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241Polyolefin, e.g.rubber
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • C09J7/381Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385Acrylic polymers

Definitions

  • the present invention relates to a wheel protective film.
  • the protective film used for automobile wheels must be kept in the state of being attached until the car is delivered. When the protective film is peeled off after delivery, it can be easily peeled off. In addition, it is required that no adhesive residue is generated on the wheel surface.
  • Patent Document 1 a protective film is attached to the outside of a disk surface of an automobile wheel, a pressure relief portion is formed on the protective film, and the wheel is caused by a pressure difference or negative pressure inside and outside the automobile wheel during transportation of the automobile.
  • a method for preventing the protective film affixed to the outer surface from peeling off is disclosed.
  • Patent Documents 2 to 9 disclose automobile brake disc antitrust films and the like that have weather resistance and are difficult to peel off from the wheel surface.
  • This invention is made
  • the place made into the objective is providing the protective film for wheels which can maintain the stable sticking state of the protective film to wheels, such as a vehicle. It is in.
  • the wheel protective film includes a base material layer and a pressure-sensitive adhesive layer provided on one surface of the base material layer.
  • the wheel protective film has one or more cut portions formed inward from the outer edge.
  • the protective film when the protective film is attached to the wheel, the generation of wrinkles due to the shape of the wheel can be suppressed.
  • a tear preventing portion connected to the cut portion may be formed at the inner end of the cut portion.
  • the tear preventing portion may be an opening section defined by a curve.
  • the wheel protective film may be circular, and a plurality of cut portions may be arranged at equal intervals.
  • This protective film for wheels has a base material layer and an adhesive layer provided on one surface of the base material layer.
  • the wheel protective film has one or more notches formed at the outer edge.
  • the protective film when the protective film is attached to the wheel, the generation of wrinkles due to the shape of the wheel can be suppressed.
  • the notch may have an R shape at the tip close to the center.
  • the wheel protective film may be circular, and a plurality of notches may be arranged at equal intervals.
  • a ventilation part through which air can pass from one surface to the other surface may be formed.
  • the ventilation part may be a slit.
  • the slit may be formed in an arc shape.
  • the present invention it is possible to maintain a stable application state of the protective film to a wheel of a vehicle or the like.
  • FIG. 2 is an AA cross-sectional view of the protective film shown in FIG. It is a front view of the protective film which concerns on 2nd Embodiment. It is a front view of the protective film which concerns on 3rd Embodiment. It is a front view of the protective film which concerns on 4th Embodiment. It is a front view of the protective film which concerns on 5th Embodiment. It is a front view of the protective film which concerns on 6th Embodiment.
  • the wheel protective film according to each embodiment described below includes a base material layer and a pressure-sensitive adhesive layer provided on one surface of the base material layer.
  • the protective film according to each embodiment has scratches on the wheel surface during the period until delivery, dirt adheres to it, and further, when the vehicle is transported on the sea for a long time, such as when exporting automobiles, It is possible to prevent rust from occurring on the disc brake on the inner surface side.
  • the protective film of a certain aspect which concerns on embodiment can improve the problem that a base material layer tears in the case of peeling.
  • the protective film according to the present embodiment is affixed to the front side (outside) of the disk part of the wheel of the wheel when the vehicle is transported over the sea for a long time, such as when the automobile is exported as described above.
  • the plurality of openings formed in the cylinder are temporarily blocked to prevent rust of a disc brake rotor (not shown) disposed inside the wheel.
  • FIG. 1 is a front view of the protective film according to the first embodiment.
  • FIG. 2 is a cross-sectional view of the protective film shown in FIG.
  • the separator for protecting the adhesive layer is affixed on the protective film shown in FIG.1 and FIG.2.
  • the thicknesses and diameters of the layers shown in FIG. 2 do not necessarily represent actual scale ratios, but are merely schematically shown for convenience of explanation.
  • the protective film 10 has a disk (circular) shape. Moreover, the protective film 10 has the base material layer 12 and the adhesive layer 14 provided in the one surface of the base material layer 12, as shown in FIG. A separator 16 is attached to the surface of the pressure-sensitive adhesive layer 14 on the side where the base material layer 12 is not formed. The separator 16 prevents the surface of the pressure-sensitive adhesive layer 14 from being contaminated between the production of the protective film 10 and the use of the protective film 10 to reduce the adhesive force.
  • the separator 16 is provided with a knob 20 on the outer periphery.
  • the knob 20 is for facilitating the separation of the separator 16 itself from the adhesive layer 14 when the protective film 10 is attached to the wheel.
  • the protective film 10 has a notch 18 formed from the outer edge toward the inner side (center).
  • a plurality (for example, 18 in FIG. 1) of the cutout portions 18 are arranged at equal intervals.
  • the cutout part should just be formed 1 (piece) or more in the outer edge part of a protective film.
  • a shape of a notch part it can be set as appropriate shapes, such as triangular shape and semicircle shape, for example.
  • the pressure-sensitive adhesive layer used in the protective film 10 according to the present embodiment is not particularly limited, but is preferably composed of, for example, a pressure-sensitive adhesive composition containing a (meth) acrylic polymer and a crosslinking agent. More preferably, the (meth) acrylic polymer comprises a (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms as a main component.
  • the main component (meth) acrylic monomer constituting the (meth) acrylic polymer is not particularly limited as long as it is a (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms.
  • the carbon number is 1-12, more preferably, the carbon number is 2-10.
  • the main component is a (meth) acrylic monomer having an alkyl group having 1 to 4 carbon atoms.
  • the above (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms contains 40 to 80% by mass of the (meth) acrylic monomer having an alkyl group having 1 to 4 carbon atoms. It is preferably 50 to 75% by mass.
  • Examples of the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl methacrylate, isoamyl (meth) Acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, cyclopentyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl
  • ethyl (meth) acrylate n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate and the like are preferably used.
  • the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms may be used alone or in combination of two or more.
  • the content of the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms based on the whole is preferably 40 to 90% by mass, and more preferably 50 to 80% by mass. If it exceeds 90% by mass, the cohesive force of the pressure-sensitive adhesive may be remarkably reduced. If it is less than 40% by mass, the initial adhesiveness is deteriorated, which is not preferable.
  • the (meth) acrylic polymer contains other monomer components as long as the performance of the protective film is not impaired.
  • a hydroxyl group-containing monomer can be used.
  • the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyhexyl (meth) acrylate, and 6-hydroxyhexyl.
  • the above hydroxyl group-containing monomer may be used alone or in combination of two or more, but the content of the above hydroxyl group-containing monomer with respect to the whole monomer is It is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and particularly preferably 3 to 10% by mass. If it exceeds 30% by mass, the initial adhesiveness may be deteriorated, and if it is less than 1% by mass, the cohesive force of the pressure-sensitive adhesive is significantly reduced, which is not preferable.
  • the above-mentioned (meth) acrylate having an alkyl group having 1 to 14 carbon atoms and a vinyl monomer copolymerizable with a hydroxyl group-containing monomer can also be contained.
  • sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, cyano group-containing monomers, vinyl ester monomers, aromatic vinyl monomers and other cohesive force / heat resistance improving components carboxyl group-containing monomers, acid anhydride group-containing monomers, Amide group-containing monomers, amino group-containing monomers, imide group-containing monomers, epoxy group-containing monomers, vinyl ether monomers and other components having functional groups that act as crosslinking points and other alkyl groups (meth) Acrylic monomers can be used as appropriate. These monomer compounds may be used alone or in admixture of two or more.
  • sulfonic acid group-containing monomer examples include styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, (meth) And acryloyloxynaphthalene sulfonic acid.
  • Examples of the phosphate group-containing monomer include 2-hydroxyethylacryloyl phosphate.
  • Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.
  • vinyl ester monomer examples include vinyl acetate, vinyl propionate, vinyl laurate, vinyl pyrrolidone, and the like.
  • aromatic vinyl monomer examples include styrene, chlorostyrene, chloromethylstyrene, ⁇ -methylstyrene, and benzyl (meth) acrylate.
  • carboxyl group-containing monomer examples include acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid.
  • acrylic acid and methacrylic acid are particularly preferably used.
  • Examples of the acid anhydride group-containing monomer include maleic anhydride and itaconic anhydride.
  • amide group-containing monomer examples include acrylamide, methacrylamide, diethyl (meth) acrylamide, N-vinylpyrrolidone, N-vinyl-2-pyrrolidone, N- (meth) acryloylpyrrolidone, N, N-dimethylacrylamide, N , N-dimethylmethacrylamide, N, N-diethylacrylamide, N, N-diethylmethacrylamide, N, N'-methylenebisacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethylaminopropylmethacrylamide, etc. Can be given.
  • amino group-containing monomer examples include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N- (meth) acryloylmorpholine, and (meth) acrylic acid aminoalkyl ester. Etc.
  • Examples of the imide group-containing monomer include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, and itaconimide.
  • epoxy group-containing monomer examples include glycidyl (meth) acrylate and allyl glycidyl ether.
  • vinyl ether monomer examples include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and the like.
  • the copolymerizable vinyl monomer may be used alone or in combination of two or more, but the total content is a (meth) acrylic polymer.
  • the total amount of the monomer components is preferably 10 to 50% by mass, more preferably 20 to 40% by mass. If it exceeds 50% by mass, the initial adhesiveness may be reduced, and if it is less than 10% by mass, the cohesive force of the pressure-sensitive adhesive may be remarkably reduced.
  • the glass transition temperature (Tg) of the (meth) acrylic polymer is 0 ° C. or lower (usually ⁇ 100 ° C. or higher), preferably ⁇ 10 ° C. or lower, and more preferably, because the adhesive performance is easily balanced. It is ⁇ 20 ° C. or lower.
  • the glass transition temperature (Tg) of a (meth) acrylic-type polymer can be adjusted in the said range by changing the monomer component and composition ratio to be used suitably.
  • the glass transition temperature (Tg) (° C.) may be a general value. For example, Polymer Handbook Fourth Edition (edited by J. Brandup et al., 1999 John Wiley & Sons, Inc), Chapter VI, 198-253. The numerical value etc. which are described in the term can be used.
  • the peak temperature of loss tangent (tan ⁇ ) in a viscoelasticity measurement method (shear method, measurement frequency: 1 Hz) may be adopted as the glass transition temperature (Tg).
  • the (meth) acrylic polymer For the production of the (meth) acrylic polymer, a known radical polymerization method such as solution polymerization, bulk polymerization, and emulsion polymerization can be appropriately selected. Further, the (meth) acrylic polymer obtained may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.
  • solution polymerization for example, methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, mesitylene, methanol, ethanol, n-propanol, isopropanol, water are used as polymerization solvents.
  • Various aqueous solutions are used.
  • the reaction is usually carried out at about 60 to 80 ° C. for about 4 to 10 hours under an inert gas stream such as nitrogen.
  • the polymerization initiator, chain transfer agent and the like used for radical polymerization are not particularly limited and can be appropriately selected and used.
  • polymerization initiator used in the present embodiment examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2 -(5-Methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-dimethylene) Isobutylamidine), 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (manufactured by Wako Pure Chemical Industries, Ltd., VA-057), azo initiators, potassium persulfate, Persulfates such as ammonium sulfate, di (2-ethylhexyl) peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate , Di-
  • the polymerization initiator may be used alone or in combination of two or more, but the total content is 0.005 to 1 part by mass with respect to 100 parts by mass of the monomer.
  • the amount is preferably 0.02 to 0.5 parts by mass.
  • a chain transfer agent may be used in the polymerization.
  • a chain transfer agent By using a chain transfer agent, the molecular weight of the acrylic polymer can be appropriately adjusted.
  • chain transfer agent examples include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol.
  • chain transfer agents may be used alone or in admixture of two or more kinds, but the total content is 0.01 to 0.00 with respect to 100 parts by mass of the monomer. About 1 part by mass.
  • the pressure-sensitive adhesive composition used in the present embodiment can be obtained by cross-linking the above (meth) acrylic polymer using a cross-linking agent, so that it is more excellent in weather resistance, heat resistance, etc. It is valid.
  • a cross-linking agent used in the present invention a compound having at least two functional groups capable of reacting (bonding) with the functional group of the above-mentioned functional group-containing (meth) acrylic monomer is used, and an isocyanate compound
  • An epoxy compound, an oxazoline compound, a melamine resin, an aziridine derivative, a metal chelate compound, and the like can be used.
  • examples of the isocyanate compound include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, aliphatic isocyanates such as hexamethylene diisocyanate, and emulsified isocyanates.
  • More specific isocyanate compounds include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate, and 2,4-tolylene diisocyanate.
  • lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate
  • alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate
  • 2,4-tolylene diisocyanate 2,4-tolylene diisocyanate.
  • Aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate and xylylene diisocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (trade name Coronate L, manufactured by Nippon Polyurethane Industry), trimethylolpropane / hexamethylene diisocyanate Trimer adduct (product name: Coronate HL, manufactured by Nippon Polyurethane Industry), isocyanurate of hexamethylene diisocyanate Door body (manufactured by Nippon Polyurethane Industry Co., trade name: Coronate HX) isocyanate adducts such as, self-emulsifying type polyisocyanate (Nippon Polyurethane Industry Co., Ltd., trade name AQUANATE 200), and the like. These isocyanate compounds may be used alone or in combination of two or more.
  • oxazoline compound examples include 2-oxazoline, 3-oxazoline, 4-oxazoline, 5-keto-3-oxazoline, and Epocros (manufactured by Nippon Shokubai). These compounds may be used alone or in combination.
  • Examples of the epoxy compound include N, N, N ′, N′-tetraglycidyl-m-xylenediamine (trade name: TETRAD-X, manufactured by Mitsubishi Gas Chemical) and 1,3-bis (N, N-diglycidylamino).
  • Methyl) cyclohexane (trade name: TETRAD-C, manufactured by Mitsubishi Gas Chemical Co., Inc.), polyglycidylamine compounds such as tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, diglycidylaniline, and diglycidyl-o-toluidine. . These compounds may be used alone or in combination.
  • melamine resin examples include hexamethylol melamine and water-soluble melamine resin.
  • aziridine derivative examples include a commercial name HDU (manufactured by Mutual Yakuko), a brand name TAZM (manufactured by Mutual Yakuko), a brand name TAZO (manufactured by Mutual Yakuko), and the like. These compounds may be used alone or in combination.
  • metal chelate compound examples include aluminum, iron, tin, titanium, and nickel as metal components, and acetylene, methyl acetoacetate, and ethyl lactate as chelate components. These compounds may be used alone or in combination.
  • the content of these crosslinking agents is appropriately selected as a protective film depending on the balance with the (meth) acrylic polymer to be crosslinked.
  • the content is more preferably 0.2 to 4 parts by mass, and particularly preferably 0.4 to 2 parts by mass.
  • a weather stabilizer can be contained in the pressure-sensitive adhesive layer.
  • the above-mentioned weather stabilizer refers to an ultraviolet absorber, a light stabilizer, or an antioxidant, and these compounds may be used alone as a weather stabilizer, or a mixture of two or more thereof. May be.
  • UV absorber examples include benzotriazole UV absorbers, triazine UV absorbers, benzophenone UV absorbers, salicylate UV absorbers, and cyanoacrylate UV absorbers.
  • the ultraviolet absorber include, for example, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetrabutyl) -6- (2H-benzotriazole)], 2- (4,6-diphenyl-1,3 5-Triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydride Examples thereof include roxybenzoate, 4-t-butylphenyl
  • a benzotriazole ultraviolet absorber it is preferable to use a benzotriazole ultraviolet absorber.
  • a benzotriazole-based ultraviolet absorber weather resistance can be further improved, so that it is possible to further prevent the adhesive force from being reduced by bleeding of the ultraviolet absorber.
  • the film can be peeled off from the wheel during traveling due to a decrease in the adhesive force even when stored for a long period of time. This can be sufficiently prevented.
  • the adhesive residue after long-term storage can be sufficiently prevented.
  • the content of the ultraviolet absorber is preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of the resin solid content of the acrylic pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer.
  • the amount is more preferably 0.1 to 1.5 parts by mass. If it is less than 0.05 parts by mass, the effect of improving weather resistance may not be obtained. If it exceeds 2 parts by mass, the UV absorber may bleed.
  • the light stabilizer conventionally known light stabilizers can be used.
  • known light stabilizers such as hindered amine light stabilizers and benzoate light stabilizers can be appropriately used.
  • HALS HindAmine Light Stabilizer
  • HALS HindAmine Light Stabilizer
  • the film can be peeled off from the wheel during traveling due to a decrease in the adhesive force even when stored for a long period of time. This can be sufficiently prevented.
  • the adhesive residue after long-term storage can be sufficiently prevented.
  • hindered amine light stabilizer examples include, for example, bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate, [dimethyl-1- (2-hydroxyethyl) -4-succinate].
  • Examples of the hindered amine light stabilizer described above include reactive types such as ADK STAB LA-82 and LA-87 manufactured by Asahi Denka Co., Ltd., Hostabin N-20 manufactured by Hoechst Japan, and Tomisorp 77 manufactured by Yoshitomi Fine Chemical Co., Ltd. And a monomer type such as Sanol LS-770 manufactured by Sankyo Lifetech Co., and an oligomer type such as Uvinal 5050H manufactured by BSF Japan.
  • reactive types such as ADK STAB LA-82 and LA-87 manufactured by Asahi Denka Co., Ltd., Hostabin N-20 manufactured by Hoechst Japan, and Tomisorp 77 manufactured by Yoshitomi Fine Chemical Co., Ltd.
  • a monomer type such as Sanol LS-770 manufactured by Sankyo Lifetech Co.
  • an oligomer type such as Uvinal 5050H manufactured by BSF Japan.
  • the content of the light stabilizer is preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of the resin solid content of the acrylic pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer.
  • the amount is more preferably 0.05 to 1.5 parts by mass. If it is less than 0.05 parts by mass, the effect of improving weather resistance may not be obtained. If it exceeds 2 parts by mass, the light stabilizer may bleed.
  • antioxidant for example, a known antioxidant such as a hindered phenol-based antioxidant, a phosphorus-based processing heat stabilizer, a lactone-based processing heat stabilizer, a sulfur-based heat stabilizer can be appropriately used. These antioxidants may be used alone or in combination of two or more.
  • the addition amount of the antioxidant is preferably 3 parts by mass or less, more preferably 1 part by mass or less, and still more preferably about 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the base polymer of each resin layer. It is.
  • a tackifier may be added to the pressure-sensitive adhesive composition.
  • the tackifier described above is not particularly limited, and those conventionally used for pressure-sensitive adhesives can be used.
  • a rosin resin, an aromatic petroleum resin, and a terpene phenol resin are preferable from the viewpoint of excellent adhesion to an automobile wheel such as an aluminum wheel. These may be used alone or in combination of two or more.
  • the content of the tackifier is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the resin solid content of the acrylic pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer.
  • the amount is preferably 5 to 50 parts by mass.
  • the pressure-sensitive adhesive composition may contain other known additives, such as powders such as colorants and pigments, dyes, surfactants, plasticizers, surface lubricants, leveling agents, Surfactants, softeners, antistatic agents, inorganic or organic fillers, metal powders, particles, foils, and the like can be added as appropriate according to the intended use.
  • area of the surface protection material can be used for the compounding quantity of these arbitrary components.
  • a method of forming an adhesive layer on a base material layer can be used.
  • a method of applying the pressure-sensitive adhesive composition to a peeled separator, drying and removing the polymerization solvent, and transferring the pressure-sensitive adhesive layer to the base material layer, or the pressure-sensitive adhesive composition on the base material layer It is produced by, for example, a method of forming a pressure-sensitive adhesive layer on a substrate layer by applying and removing a polymerization solvent by drying. Thereafter, curing (aging treatment) may be performed for the purpose of adjusting the component transfer of the pressure-sensitive adhesive layer or adjusting the crosslinking reaction.
  • one or more solvents (other than the polymerization solvent) in the pressure-sensitive adhesive composition can be applied uniformly on the base material layer ( (Solvent) may be newly added.
  • Examples of the solvent used in this embodiment include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, mesitylene, methanol, ethanol, n-propanol, isopropanol, water And various aqueous solutions. These solvents may be used alone or in combination of two or more.
  • a known method used for the production of a surface protective film is used. Specifically, for example, methods such as roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, extrusion coat method using a die coater, etc. Can be given.
  • the thickness of the above-mentioned pressure-sensitive adhesive layer is not particularly limited and is appropriately selected.
  • the thickness is preferably 3 to 50 ⁇ m, and more preferably 5 to 40 ⁇ m. Thereby, the adhesiveness and adhesive force of an adhesive layer and the wheel for motor vehicles can be improved. If the thickness is less than 3 ⁇ m, sufficient adhesion and adhesive strength may not be obtained. Even if it exceeds 50 ⁇ m, an improvement in the effect cannot be expected, which may be disadvantageous economically.
  • the surface of the pressure-sensitive adhesive layer may be subjected to a surface treatment such as a corona treatment, a plasma treatment, or an ultraviolet treatment.
  • the gel fraction of the pressure-sensitive adhesive layer measured based on the measurement method described later is preferably 60 to 95% by mass, more preferably 70 to 93% by mass, and particularly preferably 75. ⁇ 90% by mass. If the gel fraction is less than 60% by mass, the cohesive force is reduced, so that it may be inferior in impact resistance (durability) or the like, and if it exceeds 95% by mass, the adhesion may be inferior.
  • the gel fraction of the pressure-sensitive adhesive layer can be adjusted by the addition amount of the crosslinking agent, the crosslinking treatment conditions (heat treatment temperature, heating time, etc.) and the like.
  • the crosslinking treatment may be performed at the temperature during the drying step of the pressure-sensitive adhesive layer, or a separate crosslinking treatment step may be provided after the drying step.
  • the weight average molecular weight (Mw) of the sol content of the pressure-sensitive adhesive layer measured based on the measurement method described later is preferably 5000 to 300,000, more preferably 10,000 to 200,000. It is a range. In the case of being in the above-mentioned range, in addition to the balance between the adhesive property and cohesiveness of the pressure-sensitive adhesive composition, it is possible to prevent contamination of the adherend (automobile wheel) with a low molecular weight material, which is preferable. .
  • the degree of swelling of the pressure-sensitive adhesive layer measured based on the measurement method described later in the present embodiment is preferably 5 to 40 times, more preferably 10 to 30 times. When the degree of swelling is outside the above range, the effect of improving the adhesion to the adherend (automobile wheel) tends to be poor.
  • constituent materials of the separator include plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and Although suitable thin leaf bodies, such as these laminates, can be mentioned, paper is preferably used in terms of excellent surface smoothness.
  • the film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer, and for example, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer.
  • a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer examples thereof include a coalesced film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.
  • the thickness of the separator is usually about 5 to 200 ⁇ m, preferably about 5 to 100 ⁇ m.
  • release agent and antifouling treatment with silicone, fluorine, long chain alkyl or fatty acid amide release agent, silica powder, etc., coating type, kneading type, vapor deposition type It is also possible to carry out antistatic treatment such as.
  • the release property from the pressure-sensitive adhesive layer can be further improved by appropriately performing a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the separator.
  • the release-treated sheet (release sheet, separator, release liner) can be used as it is as a separator for the protective film, and the process can be simplified.
  • the automobile wheel protective film according to the present embodiment is formed by forming the pressure-sensitive adhesive layer having the above-described configuration on one side or both sides of the base material layer.
  • the film means a planar material, and usually includes what is called a tape or a sheet.
  • Base material layer As the base material layer according to the present embodiment, a polyethylene resin composed of a polyethylene resin from the viewpoint of weather resistance (water resistance, moisture resistance, heat resistance, etc.), impact resistance (tear strength, etc.) and transparency. It is preferable to use a layer.
  • polyethylene resin layer examples include ethylene polymers (low density, high density, linear low density polyethylene resin, etc.), olefin polymers such as ethylene / ⁇ -olefin copolymers, ethylene / vinyl acetate copolymers, ethylene
  • olefin polymers such as ethylene / ⁇ -olefin copolymers, ethylene / vinyl acetate copolymers
  • ethylene examples include resin layers composed of olefin-based polymers of ethylene and other monomers such as methyl methacrylate copolymer, ethylene / propylene copolymer, ethylene / propylene / ⁇ -olefin copolymer. More preferably. Use of these polyethylene layers is preferable in terms of weather resistance, impact resistance, and transparency.
  • the base material layer is particularly preferably a single layer made of only a low density polyethylene resin.
  • a base material layer formed by blending a plurality of different types of polyolefin resins such as polyethylene and polypropylene becomes brittle and may cause a problem of tearing when the aforementioned film (surface protective film) is peeled off. In addition, when peeling at a high speed, tearing of the base material layer occurs, which is not preferable.
  • the base material layer may be a resin stretched or non-stretched. Moreover, the said polyethylene-type resin layer may be used independently, and 2 or more types may be bonded together and used.
  • the thickness of the base material layer is not particularly limited, but is preferably 10 to 200 ⁇ m, for example, and more preferably 30 to 150 ⁇ m. If it is less than 10 ⁇ m, it is inferior in pasting workability.
  • the surface of the base material layer (or each resin layer) is subjected to surface treatment such as corona treatment, plasma treatment, or ultraviolet treatment. You may go. Moreover, you may perform a back surface process to a base material layer (resin layer).
  • the base material layer can also be appropriately treated with a weather stabilizer within a range that does not impair the transparency of the present invention.
  • the treatment using the above-mentioned weathering stabilizer can be carried out by coating or transferring treatment on the surface of the resin layer, kneading into the resin layer, or the like.
  • an optional additive such as a flame retardant, inert inorganic particles, organic particles, a lubricant, an antistatic agent, or a pigment can be blended in the base material layer as long as the effects of the present embodiment are not impaired.
  • the base material layer is a resin film having heat resistance and solvent resistance and flexibility.
  • the pressure-sensitive adhesive composition can be applied by a roll coater or the like, and can be wound into a roll.
  • the base material layer may include a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based mold release agent, mold release with silica powder, and antifouling treatment, acid treatment, alkali treatment, Antistatic treatment such as primer treatment, coating type, kneading type, and vapor deposition type can also be performed.
  • a surface coat layer for example, a hard coat layer or a soft coat layer can be appropriately provided on the base material layer as necessary.
  • a surface coating layer include a thermosetting type or a chemical reaction curing type such as a silicone type, a melamine type, a urethane type, a silane type, and an acrylate type. Thereby, it can be set as the surface protection film for motor vehicles more excellent in abrasion resistance, chemical resistance, a weather resistance, anti-fogging property, etc.
  • the protective film of the present embodiment has a function excellent in weather resistance, adhesion reliability, transparency, and impact resistance by using the pressure-sensitive adhesive layer and the base material layer. It is suitable for a protective film that has undergone a long-term storage and distribution process.
  • the protective film means a film that protects the wheel surface of an automobile or the like indoors / outdoors, such as a small automobile, a normal passenger car, a large automobile, a special vehicle, a heavy machine, or a motorcycle. These include those used for protecting the wheel surface used in various types of vehicles and exhibiting the rust prevention effect of the disc brake on the inner surface side of the wheel.
  • the material of the automobile wheel to which the protective film is attached is not particularly limited as long as it is used as a material for the wheel.
  • an aluminum wheel is preferred because it has a relatively large adhesive force after being stored for a long time in a pasted state and can sufficiently prevent adhesive residue.
  • the protective film 10 can maintain a stable attachment state to a wheel of a vehicle or the like.
  • the notch 18 has an R-shaped tip 18a (see FIG. 1) close to the center.
  • the front end portion close to the center portion into an R shape, for example, when the protective film 10 attached to the wheel is peeled off, the front end portion 18a of the cutout portion 18 is not easily torn.
  • the protective film obtained in this embodiment has a low-density polyethylene resin that is a base material layer and an adhesive layer provided on one surface of the base material layer. Since this pressure-sensitive adhesive layer is a water-dispersed pressure-sensitive adhesive composition containing a light stabilizer, even if the pressure-sensitive adhesive layer is left on the tire or wheel for a long time under sunlight. The performance degradation of the layer is suppressed.
  • the protective film obtained in the present embodiment is attached to a wheel having unevenness or a curved surface, wrinkles are folded by the notch portion 18, and thus generation of wrinkles due to the shape of the wheel is suppressed. As a result, the protective film 10 can maintain a stable state of being attached to a wheel of a vehicle or the like.
  • the protective film according to each embodiment below is the same as the protective film 10 according to the first embodiment in that the base material layer 12, the pressure-sensitive adhesive layer 14, and the separator 16 are laminated.
  • the material is the same as in the first embodiment.
  • FIG. 3 is a front view of the protective film according to the second embodiment.
  • the separator is omitted.
  • the protective film 22 according to the present embodiment has a circular shape.
  • the protective film 22 has a cut portion 24 formed inward from the outer edge.
  • a plurality for example, 18 in FIG. 3 of the cut portions 24 are arranged at equal intervals.
  • the cut portion may be formed by one (piece) or more from the outer edge of the protective film toward the inside.
  • a shape of a notch part it can be set as appropriate shapes, such as linear form and wavy line form, for example.
  • a tear preventing portion 26 connected to the cut portion 24 is formed at the inner end of the cut portion 24.
  • the tear preventing unit 26 is an opening sectioned by a curve. Therefore, for example, when the protective film 22 attached to the wheel is peeled off, the protective film 22 is not easily torn by the tear preventing portion 26 provided at the tip of the cut portion 24.
  • FIG. 4 is a front view of the protective film according to the third embodiment.
  • the protective film 28 according to the present embodiment is the same as the protective film 10 according to the first embodiment, except that a ventilation portion 30 through which air can pass from one surface to the other surface is formed.
  • the separator is omitted.
  • the ventilation part 30 is formed in the state in which the protective film 28 and the separator were integrated from the ease of manufacture. Therefore, although the ventilation part 30 is formed also in the separator, the ventilation part is not necessarily required for the separator.
  • a plurality of ventilation portions 30 according to the present embodiment are formed. Thereby, compared with the case where the ventilation part 30 is one, the pressure difference inside and outside of a wheel is relieve
  • FIG. 5 is a front view of the protective film according to the fourth embodiment.
  • the protective film 32 according to the present embodiment is the same as the protective film 22 according to the second embodiment except that a ventilation portion 30 through which air can pass from one surface to the other surface is formed.
  • the separator is omitted.
  • the function of the ventilation portion 30 in the protective film 32 according to the present embodiment is as described in the third embodiment.
  • FIG. 6 is a front view of the protective film according to the fifth embodiment.
  • the protective film 34 according to the present embodiment has a plurality of ventilation portions 36 formed in a ring at regular intervals.
  • the protective film 28 according to the third embodiment and the protective film 34 according to the fifth embodiment have the same configuration except that the shape of the ventilation portion is different.
  • the ventilation portion 36 according to the fifth embodiment is a slit formed in an arc shape. Therefore, when the wheel is stationary, it is difficult for water and contaminants to enter the inside of the wheel to which the protective film 34 is attached. Further, in the state where the wheel is rotating, the arc-shaped slit is deformed by the flow of air passing through the ventilation portion 36 and the like, and the air is more easily distributed.
  • the circular arc is formed toward the outside from the center of the protective film 34, the circular arc may be formed toward the center of the protective film 34.
  • FIG. 7 is a front view of the protective film according to the sixth embodiment.
  • the protective film 38 according to the present embodiment has a plurality of ventilation portions 36 formed annularly at equal intervals.
  • the protective film 32 according to the fourth embodiment and the protective film 38 according to the sixth embodiment have the same configuration except that the shape of the ventilation portion is different.
  • the ventilation part 36 according to the sixth embodiment is also a slit formed in an arc shape.
  • the function of the ventilation portion 36 in the protective film 38 according to the present embodiment is as described in the fifth embodiment.
  • protective film 10 protective film, 12 base material layer, 14 adhesive layer, 16 separator, 18 notch, 18a tip, 22 protective film, 24 cut, 26 tear prevention, 28 protective film.
  • the present invention can be used for a protective film attached to a wheel of a vehicle such as an automobile.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

A protection film (10) for wheels has a base material layer, and an adhesive layer that is provided on one surface of the base material layer. The protection film for wheels has one or more cut portions (18) at an outer end portion. Each of the cut portions (18) may have a rounded leading edge portion (18a) close to the center. The protection film for wheels may be formed in a circular shape. A plurality of cut portions may be disposed at equal intervals.

Description

ホイール用保護フィルムProtective film for wheel
 本発明は、ホイール用保護フィルムに関する。 The present invention relates to a wheel protective film.
 従来、アルミホイール等の自動車ホイールは、自動車の輸送段階において、例えば船舶による輸送の場合、船内の湿度の変化などにより、外部から自動車ホイールの内側に、水が浸入し、これによりホイールの内面側のディスクブレーキに錆が発生する等の問題が生じており、この錆の発生を防止するため、ホイール表面に保護フィルムが貼り付けられている。 Conventionally, when an automobile wheel such as an aluminum wheel is transported by a ship, for example, when transported by ship, water infiltrates from the outside into the inside of the automobile wheel due to a change in humidity inside the ship. There is a problem that rust is generated on the disc brake, and a protective film is attached to the wheel surface in order to prevent the rust.
 自動車ホイールに用いられる保護フィルムは、自動車の納車時まで貼り付けられた状態を維持する必要があり、納車後、保護フィルムを剥離する際には、容易に剥離することができ、剥離した際に、ホイール表面に糊残りが発生しないこと等が要求されている。 The protective film used for automobile wheels must be kept in the state of being attached until the car is delivered. When the protective film is peeled off after delivery, it can be easily peeled off. In addition, it is required that no adhesive residue is generated on the wheel surface.
 特許文献1には、自動車ホイールのディスク面の外側に保護フィルムを取り付け、保護フィルムに圧力逃がし部を形成して、自動車の搬送時に自動車ホイールの内外の圧力差や負圧に起因して、ホイールの外面に貼り付けた保護フィルムが剥離することを防止する方法が開示されている。 In Patent Document 1, a protective film is attached to the outside of a disk surface of an automobile wheel, a pressure relief portion is formed on the protective film, and the wheel is caused by a pressure difference or negative pressure inside and outside the automobile wheel during transportation of the automobile. A method for preventing the protective film affixed to the outer surface from peeling off is disclosed.
 特許文献2~9には、耐候性を有し、ホイール表面から剥がれにくい自動車ブレーキディスクアンチトラストフィルム等が開示されている。 Patent Documents 2 to 9 disclose automobile brake disc antitrust films and the like that have weather resistance and are difficult to peel off from the wheel surface.
特開2005-155758号公報JP 2005-155758 A 特開2006-35914号公報JP 2006-35914 A 国際公開第05/090453号パンフレットInternational Publication No. 05/090453 Pamphlet 国際公開第05/090098号パンフレットInternational Publication No. 05/090098 Pamphlet 国際公開第07/114450号パンフレットInternational Publication No. 07/114450 Pamphlet 国際公開第08/111663号パンフレットWO08 / 111663 pamphlet 特許第3879985号公報Japanese Patent No. 3879985 特開2008-137547号公報JP 2008-137547 A 特開2009-227746号公報JP 2009-227746 A
 ところで、前述のような保護フィルムをホイールに貼り付ける場合、ホイールの貼り付け面に凹凸があったり、貼り付け面自体が曲面であったりすると、保護フィルムの外縁部にシワが生じやすくなる。このようなシワが生じた状態で車両が走行すると、風圧によってシワを起点とした剥がれが生じる可能性がある。 By the way, when the protective film as described above is attached to the wheel, if the attaching surface of the wheel is uneven or the attaching surface itself is a curved surface, wrinkles are likely to occur at the outer edge of the protective film. When the vehicle travels in a state where such wrinkles are generated, there is a possibility that peeling will start from the wrinkles due to wind pressure.
 しかしながら、前述の各特許文献に開示されている保護フィルムでは、この点が考慮されておらず、更なる改善の余地がある。 However, the protective films disclosed in the above-mentioned patent documents do not consider this point, and there is room for further improvement.
 本発明はこうした状況に鑑みてなされたものであり、その目的とするところは、車両等のホイールへの保護フィルムの安定した貼り付け状態を維持することが可能なホイール用保護フィルムを提供することにある。 This invention is made | formed in view of such a condition, The place made into the objective is providing the protective film for wheels which can maintain the stable sticking state of the protective film to wheels, such as a vehicle. It is in.
 上記課題を解決するために、本発明のある態様のホイール用保護フィルムは、基材層と、基材層の一方の面に設けられた粘着剤層とを有する。ホイール用保護フィルムは、外縁から内側に向かって1以上の切り込み部が形成されている。 In order to solve the above problems, the wheel protective film according to an aspect of the present invention includes a base material layer and a pressure-sensitive adhesive layer provided on one surface of the base material layer. The wheel protective film has one or more cut portions formed inward from the outer edge.
 この態様によると、保護フィルムをホイールに貼り付ける際に、ホイールの形状によるシワの発生を抑制できる。 According to this aspect, when the protective film is attached to the wheel, the generation of wrinkles due to the shape of the wheel can be suppressed.
 切り込み部の内側の端部に、該切り込み部と連なる引き裂き防止部が形成されていてもよい。引き裂き防止部は、曲線で区画された開口部であってもよい。ホイール用保護フィルムは、円形であり、切り込み部は、等間隔に複数配列されていてもよい。 A tear preventing portion connected to the cut portion may be formed at the inner end of the cut portion. The tear preventing portion may be an opening section defined by a curve. The wheel protective film may be circular, and a plurality of cut portions may be arranged at equal intervals.
 本発明の別の態様もまた、ホイール用保護フィルムである。このホイール用保護フィルムは、基材層と、基材層の一方の面に設けられた粘着剤層とを有する。ホイール用保護フィルムは、外縁部に1以上の切り欠き部が形成されている。 Another aspect of the present invention is also a wheel protective film. This protective film for wheels has a base material layer and an adhesive layer provided on one surface of the base material layer. The wheel protective film has one or more notches formed at the outer edge.
 この態様によると、保護フィルムをホイールに貼り付ける際に、ホイールの形状によるシワの発生を抑制できる。 According to this aspect, when the protective film is attached to the wheel, the generation of wrinkles due to the shape of the wheel can be suppressed.
 切り欠き部は、中心に近い先端部がR形状であってもよい。ホイール用保護フィルムは、円形であり、切り欠き部は、等間隔に複数配列されていてもよい。 The notch may have an R shape at the tip close to the center. The wheel protective film may be circular, and a plurality of notches may be arranged at equal intervals.
 ホイール用保護フィルムは、一方の面から他方の面へ空気が通過できる通気部が形成されていてもよい。通気部は、スリットであってもよい。スリットは、円弧状に形成されていてもよい。 In the protective film for a wheel, a ventilation part through which air can pass from one surface to the other surface may be formed. The ventilation part may be a slit. The slit may be formed in an arc shape.
 本発明によれば、車両等のホイールへの保護フィルムの安定した貼り付け状態を維持することが可能となる。 According to the present invention, it is possible to maintain a stable application state of the protective film to a wheel of a vehicle or the like.
第1の実施の形態に係る保護フィルムの正面図である。It is a front view of the protective film which concerns on 1st Embodiment. 図1に示す保護フィルムのA-A断面図である。FIG. 2 is an AA cross-sectional view of the protective film shown in FIG. 第2の実施の形態に係る保護フィルムの正面図である。It is a front view of the protective film which concerns on 2nd Embodiment. 第3の実施の形態に係る保護フィルムの正面図である。It is a front view of the protective film which concerns on 3rd Embodiment. 第4の実施の形態に係る保護フィルムの正面図である。It is a front view of the protective film which concerns on 4th Embodiment. 第5の実施の形態に係る保護フィルムの正面図である。It is a front view of the protective film which concerns on 5th Embodiment. 第6の実施の形態に係る保護フィルムの正面図である。It is a front view of the protective film which concerns on 6th Embodiment.
 以下、図面を参照しながら、本発明を実施するための形態について詳細に説明する。なお、以下の各実施の形態では、保護フィルムの適用対象として自動車用のホイールを例に説明するが、保護フィルムの適用対象はこのようなホイールに限られない。以下に述べる各実施の形態に係るホイール用保護フィルム(以下、適宜「保護フィルム」という。)は、基材層と、基材層の一方の面に設けられた粘着剤層とを有する。 Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings. In the following embodiments, an automobile wheel will be described as an example of an application target of the protective film, but the application target of the protective film is not limited to such a wheel. The wheel protective film according to each embodiment described below (hereinafter, appropriately referred to as “protective film”) includes a base material layer and a pressure-sensitive adhesive layer provided on one surface of the base material layer.
 また、各実施の形態に係る保護フィルムは、納車までの期間にホイール表面に傷が付くこと、汚れが付着すること、さらには、自動車の輸出時等に長時間海上を輸送する際にホイールの内面側のディスクブレーキに錆が発生することを防止することができる。また、実施の形態に係るある態様の保護フィルムは、剥離の際に基材層が裂ける問題を改善できる。 In addition, the protective film according to each embodiment has scratches on the wheel surface during the period until delivery, dirt adheres to it, and further, when the vehicle is transported on the sea for a long time, such as when exporting automobiles, It is possible to prevent rust from occurring on the disc brake on the inner surface side. Moreover, the protective film of a certain aspect which concerns on embodiment can improve the problem that a base material layer tears in the case of peeling.
 [第1の実施の形態]
 (保護フィルム)
 本実施の形態に係る保護フィルムは、前述の如く自動車の輸出時等に長時間海上を輸送するような場合に、その車輪のホイールのディスク部の表側(外側)に貼り付けるもので、ディスク部に形成された複数の開口部を一時的に閉塞してホイールの内側に配設されたディスクブレーキのロータ(不図示)の錆を抑制するものである。
[First Embodiment]
(Protective film)
The protective film according to the present embodiment is affixed to the front side (outside) of the disk part of the wheel of the wheel when the vehicle is transported over the sea for a long time, such as when the automobile is exported as described above. The plurality of openings formed in the cylinder are temporarily blocked to prevent rust of a disc brake rotor (not shown) disposed inside the wheel.
 図1は、第1の実施の形態に係る保護フィルムの正面図である。図2は、図1に示す保護フィルムのA-A断面図である。なお、図1及び図2に示す保護フィルムは、粘着剤層を保護するためのセパレータが貼り付けられている。また、図2に示す各層の厚みや直径は、必ずしも実際の縮尺比を表したものではなく、あくまでも説明の便宜上、模式的に示したものである。 FIG. 1 is a front view of the protective film according to the first embodiment. FIG. 2 is a cross-sectional view of the protective film shown in FIG. In addition, the separator for protecting the adhesive layer is affixed on the protective film shown in FIG.1 and FIG.2. Further, the thicknesses and diameters of the layers shown in FIG. 2 do not necessarily represent actual scale ratios, but are merely schematically shown for convenience of explanation.
 本実施の形態に係る保護フィルム10は、円盤(円形)状の形態である。また、保護フィルム10は、図2に示すように、基材層12と、基材層12の一方の面に設けられた粘着剤層14とを有する。粘着剤層14の基材層12が形成されていない側の表面には、セパレータ16が貼り付けられている。セパレータ16は、保護フィルム10を製造してから使用するまでの間に粘着剤層14の表面が汚染され、粘着力が低下すること防止する。 The protective film 10 according to the present embodiment has a disk (circular) shape. Moreover, the protective film 10 has the base material layer 12 and the adhesive layer 14 provided in the one surface of the base material layer 12, as shown in FIG. A separator 16 is attached to the surface of the pressure-sensitive adhesive layer 14 on the side where the base material layer 12 is not formed. The separator 16 prevents the surface of the pressure-sensitive adhesive layer 14 from being contaminated between the production of the protective film 10 and the use of the protective film 10 to reduce the adhesive force.
 セパレータ16は、外周部につまみ20が設けられている。つまみ20は、保護フィルム10をホイールに貼り付ける際に、セパレータ16自体を粘着剤層14からはく離しやすくするためのものである。保護フィルム10は、外縁から内側(中心)に向かって切り欠き部18が形成されている。本実施の形態に係る保護フィルム10において、切り欠き部18は、等間隔に複数(例えば、図1においては18個)配列されている。切り欠き部は、保護フィルムの外縁部に1(個)以上形成されていればよい。また、切り欠き部の形状としては、例えば、三角形状、半円状等の適宜の形状とすることができる。 The separator 16 is provided with a knob 20 on the outer periphery. The knob 20 is for facilitating the separation of the separator 16 itself from the adhesive layer 14 when the protective film 10 is attached to the wheel. The protective film 10 has a notch 18 formed from the outer edge toward the inner side (center). In the protective film 10 according to the present embodiment, a plurality (for example, 18 in FIG. 1) of the cutout portions 18 are arranged at equal intervals. The cutout part should just be formed 1 (piece) or more in the outer edge part of a protective film. Moreover, as a shape of a notch part, it can be set as appropriate shapes, such as triangular shape and semicircle shape, for example.
 (粘着剤層)
 本実施の形態に係る保護フィルム10に用いられる粘着剤層は、特に限定するものではないが、例えば、(メタ)アクリル系ポリマー及び架橋剤を含有する粘着剤組成物からなることが好ましく、前述の(メタ)アクリル系ポリマーが、炭素数1~14であるアルキル基を有する(メタ)アクリル系モノマーを主成分とすることがより好ましい。前述の(メタ)アクリル系ポリマーを構成する主成分の(メタ)アクリル系モノマーは、前述の炭素数1~14のアルキル基を有する(メタ)アクリル系モノマーであれば、特に制限はないが、好ましくは、炭素数が1~12であり、より好ましくは、炭素数が2~10である。炭素数が前述の範囲内にあるものを使用することにより、初期の接着性、冬場など低温雰囲気下での接着性を確保できることとなり、自動車ホイール保護用途に適している。また、炭素数1~4のアルキル基を有する(メタ)アクリル系モノマーを主成分とすることが、特に好ましい態様である。なお、前述の炭素数1~14のアルキル基を有する(メタ)アクリル系モノマー全量中において、前述の炭素数1~4のアルキル基を有する(メタ)アクリル系モノマーを40~80質量%含有することが好ましく、より好ましくは50~75質量%である。前述の炭素数1~4のアルキル基を有する(メタ)アクリル系モノマーを上記範囲で用いることにより、粘着剤の凝集力が向上し、使用後に剥離する際に糊残りを防止することができ、有効である。
(Adhesive layer)
The pressure-sensitive adhesive layer used in the protective film 10 according to the present embodiment is not particularly limited, but is preferably composed of, for example, a pressure-sensitive adhesive composition containing a (meth) acrylic polymer and a crosslinking agent. More preferably, the (meth) acrylic polymer comprises a (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms as a main component. The main component (meth) acrylic monomer constituting the (meth) acrylic polymer is not particularly limited as long as it is a (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms. Preferably, the carbon number is 1-12, more preferably, the carbon number is 2-10. By using the carbon number within the above-mentioned range, it is possible to secure the initial adhesiveness and the adhesiveness in a low temperature atmosphere such as winter, which is suitable for automobile wheel protection applications. In addition, it is a particularly preferable embodiment that the main component is a (meth) acrylic monomer having an alkyl group having 1 to 4 carbon atoms. The above (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms contains 40 to 80% by mass of the (meth) acrylic monomer having an alkyl group having 1 to 4 carbon atoms. It is preferably 50 to 75% by mass. By using the above-mentioned (meth) acrylic monomer having an alkyl group having 1 to 4 carbon atoms in the above range, the cohesive strength of the pressure-sensitive adhesive is improved, and adhesive residue can be prevented when peeling after use. It is valid.
 前述の炭素数1~14のアルキル基を有する(メタ)アクリル系モノマーとして、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、sec-ブチル(メタ)アクリレート、t-ブチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、t-ブチルシクロヘキシル(メタ)アクリレート、2-エチルヘキシルメタクリレート、イソアミル(メタ)アクリレート、n-ペンチル(メタ)アクリレート、イソペンチル(メタ)アクリレート、シクロペンチル(メタ)アクリレート、n-オクチル(メタ)アクリレート、イソオクチル(メタ)アクリレート、シクロオクチル(メタ)アクリレート、n-ノニル(メタ)アクリレート、イソノニル(メタ)アクリレート、n-デシル(メタ)アクリレート、イソデシル(メタ)アクリレート、n-ドデシル(メタ)アクリレート、イソミリスチル(メタ)アクリレート、n-トリデシル(メタ)アクリレート、n-テトラデシル(メタ)アクリレートなどがあげられる。中でも、エチル(メタ)アクリレート、n-ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、sec-ブチル(メタ)アクリレート、t-ブチル(メタ)アクリレートなどが好適に用いられる。 Examples of the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl methacrylate, isoamyl (meth) Acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, cyclopentyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, cyclooctyl (Meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, isomyristyl (meth) acrylate, n-tridecyl (Meth) acrylate, n-tetradecyl (meth) acrylate and the like. Of these, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate and the like are preferably used.
 本実施の形態において、前述の炭素数1~14のアルキル基を有する(メタ)アクリル系モノマーは、単独で使用してもよく、また2種以上を混合して使用してもよいが、モノマー全体に対する前述の炭素数1~14のアルキル基を有する(メタ)アクリル系モノマーの含有量は、40~90質量%が好ましく、50~80質量%であることがより好ましい。90質量%を超えると、粘着剤の凝集力が著しく低下する場合があり、40質量%未満であると、初期接着性が低下する原因となり好ましくない。 In the present embodiment, the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms may be used alone or in combination of two or more. The content of the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms based on the whole is preferably 40 to 90% by mass, and more preferably 50 to 80% by mass. If it exceeds 90% by mass, the cohesive force of the pressure-sensitive adhesive may be remarkably reduced. If it is less than 40% by mass, the initial adhesiveness is deteriorated, which is not preferable.
 また、前述の(メタ)アクリル系ポリマーが、前述の炭素数1~14のアルキル基を有する(メタ)アクリル系モノマー以外に、保護フィルムの性能を損なわない範囲で、他のモノマー成分を含有してもよく、例えば、ヒドロキシル基含有モノマーが用いることができる。前述のヒドロキシル基含有モノマーを使用することにより、架橋剤との架橋性が高くなり、糊残りを防止することができ、有効である。前述のヒドロキシル基含有モノマーとして、例えば、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、2-ヒドロキシヘキシル(メタ)アクリレート、6-ヒドロキシヘキシル(メタ)アクリレート、8-ヒドロキシオクチル(メタ)アクリレート、10-ヒドロキシデシル(メタ)アクリレート、12-ヒドロキシラウリル(メタ)アクリレート、(4-ヒドロキシメチルシクロへキシル)メチルアクリレート、N-メチロール(メタ)アクリルアミド、N-ヒドロキシ(メタ)アクリルアミド、ビニルアルコール、アリルアルコール、2-ヒドロキシエチルビニルエーテル、4-ヒドロキシブチルビニルエーテル、ジエチレングリコールモノビニルエーテルなどがあげられる。中でも、2-ヒドロキシエチル(メタ)アクリレートや、2-ヒドロキシヘキシル(メタ)アクリレートなどが好適に用いられる。 In addition to the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms, the (meth) acrylic polymer contains other monomer components as long as the performance of the protective film is not impaired. For example, a hydroxyl group-containing monomer can be used. By using the above-mentioned hydroxyl group-containing monomer, the crosslinkability with the cross-linking agent is increased, and adhesive residue can be prevented, which is effective. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyhexyl (meth) acrylate, and 6-hydroxyhexyl. (Meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl acrylate, N-methylol (meth) Acrylamide, N-hydroxy (meth) acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monobi Such as ether, and the like. Of these, 2-hydroxyethyl (meth) acrylate and 2-hydroxyhexyl (meth) acrylate are preferably used.
 本実施の形態において、前述のヒドロキシル基含有モノマーは、単独で使用してもよく、また2種以上を混合して使用してもよいが、モノマー全体に対する前述のヒドロキシル基含有モノマーの含有量は、1~30質量%が好ましく、2~20質量%であることがより好ましく、3~10質量%が特に好ましい。30質量%を超えると、初期接着性が低下する場合があり、1質量%未満であると、粘着剤の凝集力が著しく低下する原因となり、好ましくない。 In the present embodiment, the above hydroxyl group-containing monomer may be used alone or in combination of two or more, but the content of the above hydroxyl group-containing monomer with respect to the whole monomer is It is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and particularly preferably 3 to 10% by mass. If it exceeds 30% by mass, the initial adhesiveness may be deteriorated, and if it is less than 1% by mass, the cohesive force of the pressure-sensitive adhesive is significantly reduced, which is not preferable.
 さらに、上記炭素数1~14のアルキル基を有する(メタ)アクリレートや、ヒドロキシル基含有モノマーと共重合可能なビニル系モノマーを含有することもできる。例えば、スルホン酸基含有モノマー、リン酸基含有モノマー、シアノ基含有モノマー、ビニルエステルモノマー、芳香族ビニルモノマーなどの凝集力・耐熱性向上成分や、カルボキシル基含有モノマー、酸無水物基含有モノマー、アミド基含有モノマー、アミノ基含有モノマー、イミド基含有モノマー、エポキシ基含有モノマー、ビニルエーテルモノマーなどの接着力向上や架橋化基点として働く官能基を有する成分、並びに、その他のアルキル基を有する(メタ)アクリル系モノマーなどを適宜用いることができる。これらのモノマー化合物は単独で使用してもよく、また2種以上を混合して使用してもよい。 Furthermore, the above-mentioned (meth) acrylate having an alkyl group having 1 to 14 carbon atoms and a vinyl monomer copolymerizable with a hydroxyl group-containing monomer can also be contained. For example, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, cyano group-containing monomers, vinyl ester monomers, aromatic vinyl monomers and other cohesive force / heat resistance improving components, carboxyl group-containing monomers, acid anhydride group-containing monomers, Amide group-containing monomers, amino group-containing monomers, imide group-containing monomers, epoxy group-containing monomers, vinyl ether monomers and other components having functional groups that act as crosslinking points and other alkyl groups (meth) Acrylic monomers can be used as appropriate. These monomer compounds may be used alone or in admixture of two or more.
 上記スルホン酸基含有モノマーとしては、例えば、スチレンスルホン酸、アリルスルホン酸、2-(メタ)アクリルアミド-2-メチルプロパンスルホン酸、(メタ)アクリルアミドプロパンスルホン酸、スルホプロピル(メタ)アクリレート、(メタ)アクリロイルオキシナフタレンスルホン酸などがあげられる。 Examples of the sulfonic acid group-containing monomer include styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, (meth) And acryloyloxynaphthalene sulfonic acid.
 上記リン酸基含有モノマーとしては、例えば、2-ヒドロキシエチルアクリロイルホスフェートがあげられる。 Examples of the phosphate group-containing monomer include 2-hydroxyethylacryloyl phosphate.
 上記シアノ基含有モノマーとしては、例えば、アクリロニトリル、メタクリロニトリルなどがあげられる。 Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.
 上記ビニルエステルモノマーとしては、例えば、酢酸ビニル、プロピオン酸ビニル、ラウリン酸ビニル、ビニルピロリドンなどがあげられる。 Examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, vinyl laurate, vinyl pyrrolidone, and the like.
 上記芳香族ビニルモノマーとしては、例えば、スチレン、クロロスチレン、クロロメチルスチレン、α-メチルスチレン、ベンジル(メタ)アクリレートなどがあげられる。 Examples of the aromatic vinyl monomer include styrene, chlorostyrene, chloromethylstyrene, α-methylstyrene, and benzyl (meth) acrylate.
 上記カルボキシル基含有モノマーとしては、例えば、アクリル酸、メタクリル酸、カルボキシエチル(メタ)アクリレート、カルボキシペンチル(メタ)アクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸などがあげられる。中でも、特にアクリル酸、およびメタクリル酸が好ましく用いられる。 Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Among these, acrylic acid and methacrylic acid are particularly preferably used.
 上記酸無水物基含有モノマーとしては、例えば、無水マレイン酸、無水イタコン酸などがあげられる。 Examples of the acid anhydride group-containing monomer include maleic anhydride and itaconic anhydride.
 上記アミド基含有モノマーとしては、例えば、アクリルアミド、メタクリルアミド、ジエチル(メタ)アクリルアミド、N-ビニルピロリドン、N-ビニル-2-ピロリドン、N-(メタ)アクリロイルピロリドン、N,N-ジメチルアクリルアミド、N,N-ジメチルメタクリルアミド、N,N-ジエチルアクリルアミド、N,N-ジエチルメタクリルアミド、N,N’-メチレンビスアクリルアミド、N,N-ジメチルアミノプロピルアクリルアミド、N,N-ジメチルアミノプロピルメタクリルアミドなどがあげられる。 Examples of the amide group-containing monomer include acrylamide, methacrylamide, diethyl (meth) acrylamide, N-vinylpyrrolidone, N-vinyl-2-pyrrolidone, N- (meth) acryloylpyrrolidone, N, N-dimethylacrylamide, N , N-dimethylmethacrylamide, N, N-diethylacrylamide, N, N-diethylmethacrylamide, N, N'-methylenebisacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethylaminopropylmethacrylamide, etc. Can be given.
 上記アミノ基含有モノマーとしては、例えば、N,N-ジメチルアミノエチル(メタ)アクリレート、N,N-ジメチルアミノプロピル(メタ)アクリレート、N-(メタ)アクリロイルモルホリン、(メタ)アクリル酸アミノアルキルエステルなどがあげられる。 Examples of the amino group-containing monomer include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N- (meth) acryloylmorpholine, and (meth) acrylic acid aminoalkyl ester. Etc.
 上記イミド基含有モノマーとしては、例えば、シクロヘキシルマレイミド、イソプロピルマレイミド、N-シクロヘキシルマレイミド、イタコンイミドなどがあげられる。 Examples of the imide group-containing monomer include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, and itaconimide.
 上記エポキシ基含有モノマーとしては、例えば、グリシジル(メタ)アクリレート、アリルグリシジルエーテルなどがあげられる。 Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate and allyl glycidyl ether.
 上記ビニルエーテルモノマーとしては、例えば、メチルビニルエーテル、エチルビニルエーテル、イソブチルビニルエーテルなどがあげられる。 Examples of the vinyl ether monomer include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and the like.
 本実施の形態において、共重合可能なビニル系モノマーは、単独で使用してもよく、また2種以上を混合して使用してもよいが、全体としての含有量は(メタ)アクリル系ポリマーのモノマー成分全体において、10~50質量%が好ましく、20~40質量%であることがより好ましい。50質量%を超えると、初期接着性が低下する場合があり、10質量%未満であると、粘着剤の凝集力が著しく低下する場合があり好ましくない。 In the present embodiment, the copolymerizable vinyl monomer may be used alone or in combination of two or more, but the total content is a (meth) acrylic polymer. The total amount of the monomer components is preferably 10 to 50% by mass, more preferably 20 to 40% by mass. If it exceeds 50% by mass, the initial adhesiveness may be reduced, and if it is less than 10% by mass, the cohesive force of the pressure-sensitive adhesive may be remarkably reduced.
 また、粘着性能のバランスが取りやすい理由から、上記(メタ)アクリル系ポリマーのガラス転移温度(Tg)が0℃以下(通常-100℃以上)、好ましくは-10℃以下であり、より好ましくは-20℃以下である。ガラス転移温度が0℃より高い場合、ポリマーが流動しにくく被着体への濡れが不十分となり、自動車ホイールと保護フィルムの粘着剤層との間に発生するフクレの原因となる傾向がある。なお、(メタ)アクリル系ポリマーのガラス転移温度(Tg)は、用いるモノマー成分や組成比を適宜変えることにより上記範囲内に調整することができる。なお、ガラス転移温度(Tg)(℃)は、一般的な値を採用してよく、例えば、Polymer Handbook Fourth Edition(J.Brandupら編、1999 John Wiley & Sons,Inc)VI章198項から253項に記載されている数値等を用いることができる。また、新規ポリマーの場合には、粘弾性測定法(剪断法、測定周波数:1Hz)における損失正接(tanδ)のピーク温度をガラス転移温度(Tg)として採用すればよい。 In addition, the glass transition temperature (Tg) of the (meth) acrylic polymer is 0 ° C. or lower (usually −100 ° C. or higher), preferably −10 ° C. or lower, and more preferably, because the adhesive performance is easily balanced. It is −20 ° C. or lower. When the glass transition temperature is higher than 0 ° C., the polymer is difficult to flow and the adherence to the adherend is insufficient, which tends to cause blisters generated between the automobile wheel and the adhesive layer of the protective film. In addition, the glass transition temperature (Tg) of a (meth) acrylic-type polymer can be adjusted in the said range by changing the monomer component and composition ratio to be used suitably. The glass transition temperature (Tg) (° C.) may be a general value. For example, Polymer Handbook Fourth Edition (edited by J. Brandup et al., 1999 John Wiley & Sons, Inc), Chapter VI, 198-253. The numerical value etc. which are described in the term can be used. In the case of a novel polymer, the peak temperature of loss tangent (tan δ) in a viscoelasticity measurement method (shear method, measurement frequency: 1 Hz) may be adopted as the glass transition temperature (Tg).
 このような上記(メタ)アクリル系ポリマーの製造は、溶液重合、塊状重合、乳化重合などの公知のラジカル重合法を適宜選択できる。また、得られる(メタ)アクリル系ポリマーは、ランダム共重合体、ブロック共重合体、グラフト共重合体などいずれでもよい。 For the production of the (meth) acrylic polymer, a known radical polymerization method such as solution polymerization, bulk polymerization, and emulsion polymerization can be appropriately selected. Further, the (meth) acrylic polymer obtained may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.
 なお、溶液重合においては、重合溶媒として、例えば、メチルエチルケトン、アセトン、酢酸エチル、テトラヒドロフラン、ジオキサン、シクロへキサノン、n-へキサン、トルエン、キシレン、メシチレン、メタノール、エタノール、n-プロパノール、イソプロパノール、水、各種水溶液などが用いられる。反応は窒素などの不活性ガス気流下で、通常、60~80℃程度で、4~10時間程度行われる。 In solution polymerization, for example, methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, mesitylene, methanol, ethanol, n-propanol, isopropanol, water are used as polymerization solvents. Various aqueous solutions are used. The reaction is usually carried out at about 60 to 80 ° C. for about 4 to 10 hours under an inert gas stream such as nitrogen.
 ラジカル重合に用いられる重合開始剤、連鎖移動剤などは特に限定されず適宜選択して使用することができる。 The polymerization initiator, chain transfer agent and the like used for radical polymerization are not particularly limited and can be appropriately selected and used.
 本実施の形態に用いられる重合開始剤としては、例えば、2,2’-アゾビスイソブチロニトリル、2,2’-アゾビス(2-アミジノプロパン)ジヒドロクロライド、2,2’-アゾビス[2-(5-メチル-2-イミダゾリン-2-イル)プロパン]ジヒドロクロライド、2,2’-アゾビス(2-メチルプロピオンアミジン)二硫酸塩、2,2’-アゾビス(N,N’-ジメチレンイソブチルアミジン)、2,2’-アゾビス[N-(2-カルボキシエチル)-2-メチルプロピオンアミジン]ハイドレート(和光純薬製、VA-057)などのアゾ系開始剤、過硫酸カリウム、過硫酸アンモニウムなどの過硫酸塩、ジ(2-エチルヘキシル)パーオキシジカーボネート、ジ(4-t-ブチルシクロヘキシル)パーオキシジカーボネート、ジ-sec-ブチルパーオキシジカーボネート、t-ブチルパーオキシネオデカノエート、t-ヘキシルパーオキシピバレート、t-ブチルパーオキシピバレート、ジラウロイルパーオキシド、ジ-n-オクタノイルパーオキシド、1,1,3,3-テトラメチルブチルパーオキシ-2-エチルヘキサノエート、ジ(4-メチルベンゾイル)パーオキシド、ジベンゾイルパーオキシド、t-ブチルパーオキシイソブチレート、1,1-ジ(t-ヘキシルパーオキシ)シクロヘキサン、t-ブチルハイドロパーオキシド、過酸化水素などの過酸化物系開始剤、過硫酸塩と亜硫酸水素ナトリウムの組合せ、過酸化物とアスコルビン酸ナトリウムの組合せなどの過酸化物と還元剤とを組み合わせたレドックス系開始剤などをあげることができるが、これらに限定されるものではない。 Examples of the polymerization initiator used in the present embodiment include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2 -(5-Methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-dimethylene) Isobutylamidine), 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (manufactured by Wako Pure Chemical Industries, Ltd., VA-057), azo initiators, potassium persulfate, Persulfates such as ammonium sulfate, di (2-ethylhexyl) peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate , Di-sec-butylperoxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, di-n-octanoylper Oxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1- Peroxide initiators such as di (t-hexylperoxy) cyclohexane, t-butyl hydroperoxide, hydrogen peroxide, combinations of persulfate and sodium bisulfite, combinations of peroxide and sodium ascorbate, etc. And redox initiators that combine peroxides and reducing agents. But it is not limited thereto.
 上記重合開始剤は、単独で使用してもよく、また2種以上を混合して使用してもよいが、全体としての含有量はモノマー100質量部に対して、0.005~1質量部であることが好ましく、0.02~0.5質量部であることがより好ましい。 The polymerization initiator may be used alone or in combination of two or more, but the total content is 0.005 to 1 part by mass with respect to 100 parts by mass of the monomer. The amount is preferably 0.02 to 0.5 parts by mass.
 また、本実施の形態においては、重合において連鎖移動剤を用いてもよい。連鎖移動剤を用いることにより、アクリル系ポリマーの分子量を適宜調整することができる。 In this embodiment, a chain transfer agent may be used in the polymerization. By using a chain transfer agent, the molecular weight of the acrylic polymer can be appropriately adjusted.
 連鎖移動剤としては、例えば、ラウリルメルカプタン、グリシジルメルカプタン、メルカプト酢酸、2-メルカプトエタノール、チオグリコール酸、チオグルコール酸2-エチルヘキシル、2,3-ジメルカプト-1-プロパノールなどがあげられる。 Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol.
 これらの連鎖移動剤は、単独で使用してもよく、また2種以上を混合して使用してもよいが、全体としての含有量はモノマー100質量部に対して、0.01~0.1質量部程度である。 These chain transfer agents may be used alone or in admixture of two or more kinds, but the total content is 0.01 to 0.00 with respect to 100 parts by mass of the monomer. About 1 part by mass.
 本実施の形態において用いられる粘着剤組成物は、上記の(メタ)アクリル系ポリマーを、架橋剤を用いて架橋することにより、より耐候性・耐熱性などに優れたものを得ることができ、有効である。本発明に用いられる架橋剤としては、上記の官能基含有(メタ)アクリル系モノマーの官能基と反応(結合形成)可能な官能基を少なくとも2つ以上分子内に有する化合物が用いられ、イソシアネート化合物、エポキシ化合物、オキサゾリン化合物、メラミン系樹脂、アジリジン誘導体、および金属キレート化合物などが用いることができる。 The pressure-sensitive adhesive composition used in the present embodiment can be obtained by cross-linking the above (meth) acrylic polymer using a cross-linking agent, so that it is more excellent in weather resistance, heat resistance, etc. It is valid. As the cross-linking agent used in the present invention, a compound having at least two functional groups capable of reacting (bonding) with the functional group of the above-mentioned functional group-containing (meth) acrylic monomer is used, and an isocyanate compound An epoxy compound, an oxazoline compound, a melamine resin, an aziridine derivative, a metal chelate compound, and the like can be used.
 このうち、イソシアネート化合物としては、トリレンジイソシアネート、キシレンジイソシアネートなどの芳香族イソシアネート、イソホロンジイソシアネートなどの脂環族イソシアネート、ヘキサメチレンジイソシアネートなどの脂肪族イソシアネート、乳化型イソシアネートなどがあげられる。 Of these, examples of the isocyanate compound include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, aliphatic isocyanates such as hexamethylene diisocyanate, and emulsified isocyanates.
 より具体的なイソシアネート化合物としては、ブチレンジイソシアネート、ヘキサメチレンジイソシアネートなどの低級脂肪族ポリイソシアネート類、シクロペンチレンジイソシアネート、シクロヘキシレンジイソシアネート、イソホロンジイソシアネートなどの脂環族イソシアネート類、2,4-トリレンジイソシアネート、4,4’-ジフェニルメタンジイソシアネート、キシリレンジイソシアネートなどの芳香族ジイソシアネート類、トリメチロールプロパン/トリレンジイソシアネート3量体付加物(日本ポリウレタン工業製、商品名コロネートL)、トリメチロールプロパン/ヘキサメチレンジイソシアネート3量体付加物(日本ポリウレタン工業製、商品名コロネートHL)、ヘキサメチレンジイソシアネートのイソシアヌレート体(日本ポリウレタン工業製、商品名コロネートHX)などのイソシアネート付加物、自己乳化型ポリイソシアネート(日本ポリウレタン工業製、商品名アクアネート200)などがあげられる。これらのイソシアネート化合物は単独で使用してもよく、また2種以上を混合して使用してもよい。 More specific isocyanate compounds include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate, and 2,4-tolylene diisocyanate. Aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate and xylylene diisocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (trade name Coronate L, manufactured by Nippon Polyurethane Industry), trimethylolpropane / hexamethylene diisocyanate Trimer adduct (product name: Coronate HL, manufactured by Nippon Polyurethane Industry), isocyanurate of hexamethylene diisocyanate Door body (manufactured by Nippon Polyurethane Industry Co., trade name: Coronate HX) isocyanate adducts such as, self-emulsifying type polyisocyanate (Nippon Polyurethane Industry Co., Ltd., trade name AQUANATE 200), and the like. These isocyanate compounds may be used alone or in combination of two or more.
 オキサゾリン化合物としては、例えば、2-オキサゾリン、3-オキサゾリン、4-オキサゾリン、5-ケト-3-オキサゾリン、エポクロス(日本触媒製)などがあげられる。これらの化合物は単独で用いてもよいし、組み合わせて用いてもよい。 Examples of the oxazoline compound include 2-oxazoline, 3-oxazoline, 4-oxazoline, 5-keto-3-oxazoline, and Epocros (manufactured by Nippon Shokubai). These compounds may be used alone or in combination.
 エポキシ化合物としては、例えば、N,N,N’,N’-テトラグリシジル-m-キシレンジアミン(商品名TETRAD-X、三菱瓦斯化学製)や1,3-ビス(N,N-ジグリシジルアミノメチル)シクロへキサン(商品名TETRAD-C、三菱瓦斯化学製)、テトラグリシジルジアミノジフェニルメタン、トリグリシジル-p-アミノフェノール、ジグリシジルアニリン、ジグリシジル-o-トルイジンなどのポリグリシジルアミン化合物などがあげられる。これらの化合物は単独で用いてもよいし、組み合わせて用いてもよい。 Examples of the epoxy compound include N, N, N ′, N′-tetraglycidyl-m-xylenediamine (trade name: TETRAD-X, manufactured by Mitsubishi Gas Chemical) and 1,3-bis (N, N-diglycidylamino). Methyl) cyclohexane (trade name: TETRAD-C, manufactured by Mitsubishi Gas Chemical Co., Inc.), polyglycidylamine compounds such as tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, diglycidylaniline, and diglycidyl-o-toluidine. . These compounds may be used alone or in combination.
 メラミン系樹脂としてはヘキサメチロールメラミン、水溶性メラミン系樹脂などがあげられる。 Examples of the melamine resin include hexamethylol melamine and water-soluble melamine resin.
 アジリジン誘導体としては、例えば、市販品としての商品名HDU(相互薬工製)、商品名TAZM(相互薬工製)、商品名TAZO(相互薬工製)などがあげられる。これらの化合物は単独で用いてもよいし、組み合わせて用いてもよい。 Examples of the aziridine derivative include a commercial name HDU (manufactured by Mutual Yakuko), a brand name TAZM (manufactured by Mutual Yakuko), a brand name TAZO (manufactured by Mutual Yakuko), and the like. These compounds may be used alone or in combination.
 金属キレート化合物としては、金属成分としてアルミニウム、鉄、スズ、チタン、ニッケルなど、キレート成分としてアセチレン、アセト酢酸メチル、乳酸エチルなどがあげられる。これらの化合物は単独で用いてもよいし、組み合わせて用いてもよい。 Examples of the metal chelate compound include aluminum, iron, tin, titanium, and nickel as metal components, and acetylene, methyl acetoacetate, and ethyl lactate as chelate components. These compounds may be used alone or in combination.
 これらの架橋剤の含有量は、架橋すべき(メタ)アクリル系ポリマーとのバランスにより、さらには、保護フィルムとして、適宜選択される。(メタ)アクリル系ポリマーの凝集力により充分な耐候性、耐熱性を得るためには、上記(メタ)アクリル系ポリマー100質量部に対して、0.1~6質量部含有することが好ましく、0.2~4質量部含有されていることがより好ましく、0.4~2質量部含有されていることが特に好ましい。架橋剤の含有量が0.1質量部よりも少ない場合、架橋剤による架橋形成が不十分となり、溶剤不溶分率が低下する傾向があり、また、粘着剤層の凝集力が小さくなり、糊残りの原因となる傾向がある。一方、含有量が6質量部を超える場合、粘着剤層の初期接着力が不足し、また、ポリマーの凝集力が大きく、流動性が低下し、被着体への濡れが不十分となって、剥がれの原因となる傾向がある。 The content of these crosslinking agents is appropriately selected as a protective film depending on the balance with the (meth) acrylic polymer to be crosslinked. In order to obtain sufficient weather resistance and heat resistance due to the cohesive strength of the (meth) acrylic polymer, it is preferable to contain 0.1 to 6 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer. The content is more preferably 0.2 to 4 parts by mass, and particularly preferably 0.4 to 2 parts by mass. When the content of the cross-linking agent is less than 0.1 parts by mass, the cross-linking by the cross-linking agent is insufficient, the solvent insoluble content tends to decrease, and the cohesive force of the pressure-sensitive adhesive layer is reduced. There is a tendency to cause the rest. On the other hand, when the content exceeds 6 parts by mass, the initial adhesive force of the pressure-sensitive adhesive layer is insufficient, the cohesive force of the polymer is large, the fluidity is lowered, and the wetness to the adherend becomes insufficient. , Tend to cause peeling.
 本実施の形態の保護フィルムに耐候性を付与するため、粘着剤層に耐候安定剤を含有することができる。前述の耐候安定剤とは、紫外線吸収剤、光安定剤、または酸化防止剤をいい、これらの化合物は耐候安定剤として、単独で使用してもよく、また2種以上を混合して使用してもよい。前述の耐侯安定剤を使用することにより、本実施の形態の保護フィルムをホイールに貼り付けた状態での長期間保管後において、フィルムの剥がれ、糊残りを防止することができる。 In order to provide weather resistance to the protective film of the present embodiment, a weather stabilizer can be contained in the pressure-sensitive adhesive layer. The above-mentioned weather stabilizer refers to an ultraviolet absorber, a light stabilizer, or an antioxidant, and these compounds may be used alone as a weather stabilizer, or a mixture of two or more thereof. May be. By using the above-mentioned anti-wrinkle stabilizer, the film can be prevented from being peeled off and adhesive residue can be prevented after long-term storage with the protective film of the present embodiment attached to the wheel.
 上記紫外線吸収剤としては、例えば、ベンゾトリアゾール系紫外線吸収剤、トリアジン系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、サリチレート系紫外線吸収剤、シアノアクリレート系紫外線吸収剤等をあげることができる。 Examples of the UV absorber include benzotriazole UV absorbers, triazine UV absorbers, benzophenone UV absorbers, salicylate UV absorbers, and cyanoacrylate UV absorbers.
 上記紫外線吸収剤の具体例としては、例えば、2-ヒドロキシ-4-メトキシベンゾフェノン、2-ヒドロキシ-4-n-オクチルオキシベンゾフェノン、2-(2′-ヒドロキシ-5′-メチルフェニル)ベンゾトリアゾール、2-(2′-ヒドロキシ-3′-t-ブチル-5′-メチルフェニル)-5-クロロベンゾトリアゾール、2-[2-ヒドロキシ-3,5-ビス(α,α-ジメチルベンジル)フェニル]-2H-ベンゾトリアゾール、2,2′-メチレンビス[4-(1,1,3,3-テトラブチル)-6-(2H-ベンゾトリアゾール)]、2-(4,6-ジフェニル-1,3,5-トリアジン-2-イル)-5-[(ヘキシル)オキシ]-フェノール、2,4-ジ-t-ブチルフェニル-3,5-ジ-t-ブチル-4-ヒドロキシベンゾエート、4-t-ブチルフェニルサリチレート、エチル-2-シアノ-3,3-ジフェニルアクリレート等をあげることができる。これらの紫外線吸収剤は、単独で用いてもよく、2種以上を併用してもよい。 Specific examples of the ultraviolet absorber include, for example, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetrabutyl) -6- (2H-benzotriazole)], 2- (4,6-diphenyl-1,3 5-Triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydride Examples thereof include roxybenzoate, 4-t-butylphenyl salicylate, and ethyl-2-cyano-3,3-diphenyl acrylate. These ultraviolet absorbers may be used alone or in combination of two or more.
 上記紫外線吸収剤の中でも、ベンゾトリアゾール系紫外線吸収剤を使用することが好ましい。ベンゾトリアゾール系紫外線吸収剤を用いる場合には、耐侯性をより向上させることができるため、紫外線吸収剤のブリードによって、粘着力が低下してしまうことをより防止することができる。そして、その結果、保護フィルムをホイールに貼り付けた後、長期間保管した場合であっても、粘着力を充分に保持することができるため、粘着力の低下によって走行中にホイールからフィルムが剥がれることを充分に防止することができる。また、長期間保管後の糊残りを充分に防止することができる。 Among the above ultraviolet absorbers, it is preferable to use a benzotriazole ultraviolet absorber. In the case of using a benzotriazole-based ultraviolet absorber, weather resistance can be further improved, so that it is possible to further prevent the adhesive force from being reduced by bleeding of the ultraviolet absorber. As a result, even after the protective film is attached to the wheel, the film can be peeled off from the wheel during traveling due to a decrease in the adhesive force even when stored for a long period of time. This can be sufficiently prevented. Moreover, the adhesive residue after long-term storage can be sufficiently prevented.
 上記粘着剤層において、紫外線吸収剤の含有量は、上記粘着剤層中に含まれるアクリル系粘着剤の樹脂固形分100質量部に対して、0.05~2質量部であることが好ましく、0.1~1.5質量部であることがより好ましい。0.05質量部未満であると、耐侯性を向上させる効果を得ることができないおそれがある。2質量部を超えると、紫外線吸収剤がブリードするおそれがある。 In the pressure-sensitive adhesive layer, the content of the ultraviolet absorber is preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of the resin solid content of the acrylic pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer. The amount is more preferably 0.1 to 1.5 parts by mass. If it is less than 0.05 parts by mass, the effect of improving weather resistance may not be obtained. If it exceeds 2 parts by mass, the UV absorber may bleed.
 上記光安定剤としては、従来公知のものを使用することができるが、例えば、ヒンダードアミン系光安定剤やベンゾエート系光安定剤など公知の光安定剤を適宜使用することができる。中でも特に、ヒンダードアミン系光安定剤(HALS:HinderdAmine Light Stabilizer)を使用する場合には、耐侯性をより向上させることができるため、光安定剤のブリードによって、粘着力が低下してしまうことをより防止することができる。そして、その結果、保護フィルムをホイールに貼り付けた後、長期間保管した場合であっても、粘着力を充分に保持することができるため、粘着力の低下によって走行中にホイールからフィルムが剥がれることを充分に防止することができる。また、長期間保管後の糊残りを充分に防止することができる。 As the light stabilizer, conventionally known light stabilizers can be used. For example, known light stabilizers such as hindered amine light stabilizers and benzoate light stabilizers can be appropriately used. In particular, when using a hindered amine light stabilizer (HALS: HindAmine Light Stabilizer), it is possible to further improve the weather resistance, so that the adhesive strength decreases due to bleeding of the light stabilizer. Can be prevented. As a result, even after the protective film is attached to the wheel, the film can be peeled off from the wheel during traveling due to a decrease in the adhesive force even when stored for a long period of time. This can be sufficiently prevented. Moreover, the adhesive residue after long-term storage can be sufficiently prevented.
 前述のヒンダードアミン系光安定剤としては、例えば、例えば、ビス-(2,2,6,6-テトラメチル-4-ピペリジル)セバケート、[コハク酸ジメチル-1-(2-ヒドロキシエチル)-4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン]縮合物、1,2,2,6,6-ペンタメチル-4-ピペリジル-トリデシル-1,2,3,4-ブタンテトラカルボキシレート、1,2,2,6,6-ペンタメチル-4-ピペリジノール及び3,9-ビス(2-ヒドロキシ-1,1-ジメチルエチル)-2,4,8,10-テトラスピロ[5,5]ウンデカンとブタンテトラカルボン酸とのエステル等をあげることができる。これらの光安定剤は、単独で用いてもよく、2種以上を併用してもよい。 Examples of the above-mentioned hindered amine light stabilizer include, for example, bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate, [dimethyl-1- (2-hydroxyethyl) -4-succinate]. Hydroxy-2,2,6,6-tetramethylpiperidine] condensate, 1,2,2,6,6-pentamethyl-4-piperidyl-tridecyl-1,2,3,4-butanetetracarboxylate, 1, 2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraspiro [5,5] undecane and butanetetra Examples include esters with carboxylic acids. These light stabilizers may be used alone or in combination of two or more.
 また、前述のヒンダードアミン系光安定剤としては、例えば、旭電化社製のアデカスタブLA-82、LA-87などの反応型、ヘキスト・ジャパン社製のホスタビンN-20、吉富ファインケミカル社製のトミソープ77や、三共ライフテック社製のサノールLS-770などのモノマータイプ、ビーエーエスエフ・ジャパン社製のUvinal5050Hなどのオリゴマータイプのものがあげられる。 Examples of the hindered amine light stabilizer described above include reactive types such as ADK STAB LA-82 and LA-87 manufactured by Asahi Denka Co., Ltd., Hostabin N-20 manufactured by Hoechst Japan, and Tomisorp 77 manufactured by Yoshitomi Fine Chemical Co., Ltd. And a monomer type such as Sanol LS-770 manufactured by Sankyo Lifetech Co., and an oligomer type such as Uvinal 5050H manufactured by BSF Japan.
 上記粘着剤層において、上記光安定剤の含有量は、粘着剤層中に含まれるアクリル系粘着剤の樹脂固形分100質量部に対して、0.05~2質量部であることが好ましく、0.05~1.5質量部であることがより好ましい。0.05質量部未満であると、耐侯性を向上させる効果を得ることができないおそれがある。2質量部を超えると、光安定剤がブリードするおそれがある。 In the pressure-sensitive adhesive layer, the content of the light stabilizer is preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of the resin solid content of the acrylic pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer. The amount is more preferably 0.05 to 1.5 parts by mass. If it is less than 0.05 parts by mass, the effect of improving weather resistance may not be obtained. If it exceeds 2 parts by mass, the light stabilizer may bleed.
 酸化防止剤としては、例えば、ヒンダードフェノール系酸化防止剤、リン系加工熱安定剤、ラクトン系加工熱安定剤、イオウ系耐熱安定剤など公知の酸化防止剤を適宜使用することができる。これらの酸化防止剤は単独で使用してもよく、また2種以上を混合して使用してもよい。 As the antioxidant, for example, a known antioxidant such as a hindered phenol-based antioxidant, a phosphorus-based processing heat stabilizer, a lactone-based processing heat stabilizer, a sulfur-based heat stabilizer can be appropriately used. These antioxidants may be used alone or in combination of two or more.
 上記酸化防止剤の添加量は、各樹脂層のベースポリマー100質量部に対して、3質量部以下が好ましく、より好ましくは1質量部以下、さらに好ましくは0.01~0.5質量部程度である。 The addition amount of the antioxidant is preferably 3 parts by mass or less, more preferably 1 part by mass or less, and still more preferably about 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the base polymer of each resin layer. It is.
 また、更に上記粘着剤組成物には、粘着付与剤を添加してもかまわない。前述の粘着付与剤としては特に限定されず、従来、粘着剤に用いられているものを使用することができ、例えば、キシレン樹脂、ロジンや重合ロジン、水添ロジン、ロジンエステル等の変性ロジン系樹脂;テルペン樹脂、テルペンフェノール樹脂、ロジンフェノール樹脂等のテルペン系樹脂;脂肪族系、芳香族系及び脂環式系石油樹脂;クマロン樹脂、スチレン系樹脂、アルキルフェノール樹脂等をあげることができる。中でも、アルミホイール等の自動車ホイールとの接着性に優れる点から、ロジン系樹脂、芳香族石油樹脂、テルペンフェノール樹脂が好ましい。これらは、単独で用いてもよく、2種以上を併用してもよい。 Furthermore, a tackifier may be added to the pressure-sensitive adhesive composition. The tackifier described above is not particularly limited, and those conventionally used for pressure-sensitive adhesives can be used. For example, xylene resin, rosin, polymerized rosin, hydrogenated rosin, modified rosin such as rosin ester Resins; terpene resins such as terpene resins, terpene phenol resins, and rosin phenol resins; aliphatic, aromatic, and alicyclic petroleum resins; coumarone resins, styrene resins, alkylphenol resins, and the like. Among these, a rosin resin, an aromatic petroleum resin, and a terpene phenol resin are preferable from the viewpoint of excellent adhesion to an automobile wheel such as an aluminum wheel. These may be used alone or in combination of two or more.
 上記粘着剤層において、上記粘着付与剤の含有量は、上記粘着剤層中に含まれるアクリル系粘着剤の樹脂固形分100質量部に対して、1~100質量部であることが好ましく、より好ましくは5~50質量部である。1質量部未満であると、粘着剤層の接着力が不十分となるおそれがある。100質量部を超えると、自動車ホイールから保護フィルムを剥がす際に、ホイールからフィルムをきれいに剥離させることができず、ホイール上に糊が残ってしまうおそれがある。 In the pressure-sensitive adhesive layer, the content of the tackifier is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the resin solid content of the acrylic pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer. The amount is preferably 5 to 50 parts by mass. There exists a possibility that the adhesive force of an adhesive layer may become inadequate that it is less than 1 mass part. When the amount exceeds 100 parts by mass, when the protective film is peeled off from the automobile wheel, the film cannot be peeled cleanly from the wheel, and there is a possibility that glue remains on the wheel.
 更に上記粘着剤組成物には、その他の公知の添加剤を含有していてもよく、例えば、着色剤、顔料などの粉体、染料、界面活性剤、可塑剤、表面潤滑剤、レベリング剤、界面活性剤、軟化剤、帯電防止剤、無機または有機の充填剤、金属粉、粒子状、箔状物などを使用する用途に応じて適宜添加することができる。また、これらの任意成分の配合量は、表面保護材の分野で通常用いられている使用量を用いることができる。 Furthermore, the pressure-sensitive adhesive composition may contain other known additives, such as powders such as colorants and pigments, dyes, surfactants, plasticizers, surface lubricants, leveling agents, Surfactants, softeners, antistatic agents, inorganic or organic fillers, metal powders, particles, foils, and the like can be added as appropriate according to the intended use. Moreover, the usage-amount normally used in the field | area of the surface protection material can be used for the compounding quantity of these arbitrary components.
 本実施の形態の保護フィルムの製造方法としては、基材層上に粘着剤層を形成する方法が使用できる。例えば、上記粘着剤組成物を剥離処理したセパレータなどに塗布し、重合溶剤などを乾燥除去して粘着剤層を基材層に転写形成する方法、または基材層上に上記粘着剤組成物を塗布し、重合溶剤などを乾燥除去して粘着剤層を基材層に形成する方法などにより作製される。その後、粘着剤層の成分移行の調整や架橋反応の調整などを目的として養生(エージング処理)を行ってもよい。また、粘着剤組成物を基材層上に塗布して保護フィルムを作製する際には、基材層上に均一に塗布できるよう、粘着剤組成物中に重合溶剤以外の一種以上の溶媒(溶剤)を新たに加えてもよい。 As a method for producing the protective film of the present embodiment, a method of forming an adhesive layer on a base material layer can be used. For example, a method of applying the pressure-sensitive adhesive composition to a peeled separator, drying and removing the polymerization solvent, and transferring the pressure-sensitive adhesive layer to the base material layer, or the pressure-sensitive adhesive composition on the base material layer It is produced by, for example, a method of forming a pressure-sensitive adhesive layer on a substrate layer by applying and removing a polymerization solvent by drying. Thereafter, curing (aging treatment) may be performed for the purpose of adjusting the component transfer of the pressure-sensitive adhesive layer or adjusting the crosslinking reaction. Moreover, when producing a protective film by applying the pressure-sensitive adhesive composition on the base material layer, one or more solvents (other than the polymerization solvent) in the pressure-sensitive adhesive composition can be applied uniformly on the base material layer ( (Solvent) may be newly added.
 本実施の形態において用いられる溶媒としては、例えば、メチルエチルケトン、アセトン、酢酸エチル、テトラヒドロフラン、ジオキサン、シクロへキサノン、n-へキサン、トルエン、キシレン、メシチレン、メタノール、エタノール、n-プロパノール、イソプロパノール、水、各種水溶液などがあげられる。これらの溶剤は単独で使用してもよく、また2種以上を混合して使用してもよい。 Examples of the solvent used in this embodiment include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, mesitylene, methanol, ethanol, n-propanol, isopropanol, water And various aqueous solutions. These solvents may be used alone or in combination of two or more.
 また、本実施の形態の粘着剤層の形成方法としては、表面保護フィルムの製造に用いられる公知の方法が用いられる。具体的には、例えば、ロールコート、キスロールコート、グラビアコート、リバースコート、ロールブラッシュ、スプレーコート、ディップロールコート、バーコート、ナイフコート、エアーナイフコート、ダイコーター等による押し出しコート法などの方法があげられる。 Also, as a method for forming the pressure-sensitive adhesive layer of the present embodiment, a known method used for the production of a surface protective film is used. Specifically, for example, methods such as roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, extrusion coat method using a die coater, etc. Can be given.
 前述の粘着剤層の厚さは、特に制限されず、適宜選択されるが、例えば、3~50μmであることが好ましく、より好ましくは、5~40μmである。これにより、粘着剤層と自動車用ホイールとの密着性及び接着力を向上させることができる。3μm未満であると、充分な密着性及び接着力を得ることができないおそれがある。50μmを超えても、効果の向上は望めず、経済的に不利となるおそれがある。 The thickness of the above-mentioned pressure-sensitive adhesive layer is not particularly limited and is appropriately selected. For example, the thickness is preferably 3 to 50 μm, and more preferably 5 to 40 μm. Thereby, the adhesiveness and adhesive force of an adhesive layer and the wheel for motor vehicles can be improved. If the thickness is less than 3 μm, sufficient adhesion and adhesive strength may not be obtained. Even if it exceeds 50 μm, an improvement in the effect cannot be expected, which may be disadvantageous economically.
 また、上記粘着剤層の表面にはコロナ処理、プラズマ処理、紫外線処理などの表面処理を行ってもよい。 The surface of the pressure-sensitive adhesive layer may be subjected to a surface treatment such as a corona treatment, a plasma treatment, or an ultraviolet treatment.
 本実施の形態においては、後述の測定方法に基づき測定される粘着剤層のゲル分率が60~95質量%であることが好ましく、より好ましくは70~93質量%であり、特に好ましくは75~90質量%である。ゲル分率が60質量%より小さくなると、凝集力が低下するため耐衝撃性(耐久性)等に劣る場合があり、95質量%を超えると、接着性に劣る場合がある。 In the present embodiment, the gel fraction of the pressure-sensitive adhesive layer measured based on the measurement method described later is preferably 60 to 95% by mass, more preferably 70 to 93% by mass, and particularly preferably 75. ~ 90% by mass. If the gel fraction is less than 60% by mass, the cohesive force is reduced, so that it may be inferior in impact resistance (durability) or the like, and if it exceeds 95% by mass, the adhesion may be inferior.
 粘着剤層のゲル分率は、架橋剤の添加量や、架橋処理条件(加熱処理温度、加熱時間など)等で調整することができる。なお、架橋処理は、粘着剤層の乾燥工程時の温度で行ってもよいし、乾燥工程後に別途架橋処理工程を設けてもよい。 The gel fraction of the pressure-sensitive adhesive layer can be adjusted by the addition amount of the crosslinking agent, the crosslinking treatment conditions (heat treatment temperature, heating time, etc.) and the like. The crosslinking treatment may be performed at the temperature during the drying step of the pressure-sensitive adhesive layer, or a separate crosslinking treatment step may be provided after the drying step.
 本実施の形態においては、後述の測定方法に基づき測定される粘着剤層のゾル分の重量平均分子量(Mw)は、好ましくは、5000~30万であり、より好ましくは1万~20万の範囲である。前述の範囲内にある場合には、粘着剤組成物の接着性と凝集性のバランスの他、低分子量物による被着体(自動車ホイール)に対して、汚染防止などを図ることができ、好ましい。 In the present embodiment, the weight average molecular weight (Mw) of the sol content of the pressure-sensitive adhesive layer measured based on the measurement method described later is preferably 5000 to 300,000, more preferably 10,000 to 200,000. It is a range. In the case of being in the above-mentioned range, in addition to the balance between the adhesive property and cohesiveness of the pressure-sensitive adhesive composition, it is possible to prevent contamination of the adherend (automobile wheel) with a low molecular weight material, which is preferable. .
 本実施の形態における後述の測定方法に基づき測定される粘着剤層の膨潤度としては、5~40倍が好ましく、より好ましくは、10~30倍である。膨潤度が上記範囲外となると、被着体(自動車ホイール)に対する密着性の向上効果が乏しくなる傾向となる。 The degree of swelling of the pressure-sensitive adhesive layer measured based on the measurement method described later in the present embodiment is preferably 5 to 40 times, more preferably 10 to 30 times. When the degree of swelling is outside the above range, the effect of improving the adhesion to the adherend (automobile wheel) tends to be poor.
 本実施の形態の保護フィルムに用いられる粘着剤層表面が、露出する場合には、実用に供されるまで剥離処理したシート(剥離シート、セパレータ、剥離ライナー)で粘着剤層を保護してもよい。 When the surface of the pressure-sensitive adhesive layer used in the protective film of the present embodiment is exposed, even if the pressure-sensitive adhesive layer is protected with a sheet (release sheet, separator, release liner) subjected to release treatment until it is put to practical use. Good.
 セパレータ(剥離シート、剥離ライナー)の構成材料としては、例えば、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリエステルフィルムなどのプラスチックフィルム、紙、布、不織布などの多孔質材料、ネット、発泡シート、金属箔、およびこれらのラミネート体などの適宜な薄葉体などをあげることができるが、表面平滑性に優れる点から紙が好適に用いられる。 Examples of constituent materials of the separator (release sheet, release liner) include plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and Although suitable thin leaf bodies, such as these laminates, can be mentioned, paper is preferably used in terms of excellent surface smoothness.
 そのフィルムとしては、上記粘着剤層を保護し得るフィルムであれば特に限定されず、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリウレタンフィルム、エチレン-酢酸ビニル共重合体フィルムなどがあげられる。 The film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer, and for example, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer. Examples thereof include a coalesced film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.
 上記セパレータの厚みは、通常5~200μm、好ましくは5~100μm程度である。 The thickness of the separator is usually about 5 to 200 μm, preferably about 5 to 100 μm.
 上記セパレータには、必要に応じて、シリコーン系、フッ素系、長鎖アルキル系若しくは脂肪酸アミド系の離型剤、シリカ粉等による離型および防汚処理や、塗布型、練り込み型、蒸着型などの帯電防止処理もすることもできる。特に、上記セパレータの表面にシリコーン処理、長鎖アルキル処理、フッ素処理などの剥離処理を適宜行うことにより、上記粘着剤層からの剥離性をより高めることができる。 For the separator, if necessary, release agent and antifouling treatment with silicone, fluorine, long chain alkyl or fatty acid amide release agent, silica powder, etc., coating type, kneading type, vapor deposition type It is also possible to carry out antistatic treatment such as. In particular, the release property from the pressure-sensitive adhesive layer can be further improved by appropriately performing a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the separator.
 なお、上記の製造方法において、剥離処理したシート(剥離シート、セパレータ、剥離ライナー)は、そのまま保護フィルムのセパレータとして用いることができ、工程面における簡略化ができる。 In the above manufacturing method, the release-treated sheet (release sheet, separator, release liner) can be used as it is as a separator for the protective film, and the process can be simplified.
 また、本実施の形態に係る自動車ホイール用保護フィルムは、上記の構成を有する粘着剤層を基材層の片面または両面に形成してなるものである。 Further, the automobile wheel protective film according to the present embodiment is formed by forming the pressure-sensitive adhesive layer having the above-described configuration on one side or both sides of the base material layer.
 なお、本実施の形態において、フィルムとは、平面状の材料を意味し、通常、テープ、シートとよばれるものを含む。 In the present embodiment, the film means a planar material, and usually includes what is called a tape or a sheet.
 (基材層)
 本実施の形態に係る基材層としては、耐候性(耐水性、耐湿性、耐熱性など)、耐衝撃性(引裂強度など)及び、透明性の観点から、ポリエチレン系樹脂からなるポリエチレン系樹脂層を用いることが好ましい。ポリエチレン系樹脂層としては、例えば、エチレン系ポリマー(低密度、高密度、リニア低密度ポリエチレン樹脂等)、エチレン・αオレフィン共重合体などのオレフィン系ポリマー、エチレン・酢酸ビニル共重合体、エチレン・メタクリル酸メチル共重合体、エチレン・プロピレン共重合体、エチレン・プロピレン・αオレフィン共重合体などのエチレンと他モノマーとのオレフィン系ポリマーなどからなる樹脂層があげられ、特に、低密度ポリエチレン樹脂からなることがより好ましい。これらのポリエチレン層を用いることにより、耐候性、耐衝撃性、及び、透明性の観点において好ましいものとなる。
(Base material layer)
As the base material layer according to the present embodiment, a polyethylene resin composed of a polyethylene resin from the viewpoint of weather resistance (water resistance, moisture resistance, heat resistance, etc.), impact resistance (tear strength, etc.) and transparency. It is preferable to use a layer. Examples of the polyethylene resin layer include ethylene polymers (low density, high density, linear low density polyethylene resin, etc.), olefin polymers such as ethylene / α-olefin copolymers, ethylene / vinyl acetate copolymers, ethylene Examples include resin layers composed of olefin-based polymers of ethylene and other monomers such as methyl methacrylate copolymer, ethylene / propylene copolymer, ethylene / propylene / α-olefin copolymer. More preferably. Use of these polyethylene layers is preferable in terms of weather resistance, impact resistance, and transparency.
 また、上記基材層としては、特に、低密度ポリエチレン樹脂のみからなり、単一層であることがより好ましい態様である。ポリエチレンとポリプロピレンなどの異種複数種のポリオレフィン樹脂を配合して形成された基材層は、脆くなり、前述のフィルム(表面保護フィルム)を剥離する際に、裂けるという問題が生じるおそれがある。また、高速での剥離の際に、特に基材層の裂けが発生するため、好ましくない。 Further, the base material layer is particularly preferably a single layer made of only a low density polyethylene resin. A base material layer formed by blending a plurality of different types of polyolefin resins such as polyethylene and polypropylene becomes brittle and may cause a problem of tearing when the aforementioned film (surface protective film) is peeled off. In addition, when peeling at a high speed, tearing of the base material layer occurs, which is not preferable.
 また、上記基材層は樹脂を延伸したものであっても、無延伸のものでもよい。また、上記ポリエチレン系樹脂層は単独で使用してもよく、また2種以上を貼り合わせて使用してもよい。 The base material layer may be a resin stretched or non-stretched. Moreover, the said polyethylene-type resin layer may be used independently, and 2 or more types may be bonded together and used.
 上記基材層の厚さは、特に限定されないが、例えば、10~200μmが好ましく、30~150μmであることがより好ましい。10μm未満では貼り付け作業性に劣り、200μmを超えると曲面への追従性に劣る傾向にある。 The thickness of the base material layer is not particularly limited, but is preferably 10 to 200 μm, for example, and more preferably 30 to 150 μm. If it is less than 10 μm, it is inferior in pasting workability.
 また、他の樹脂層、粘着剤層、下塗り剤等との密着性を向上させるため、基材層(または各樹脂層)の表面には、コロナ処理、プラズマ処理、紫外線処理などの表面処理を行ってもよい。また、基材層(樹脂層)には背面処理を行ってもよい。 In addition, in order to improve adhesion to other resin layers, pressure-sensitive adhesive layers, undercoats, etc., the surface of the base material layer (or each resin layer) is subjected to surface treatment such as corona treatment, plasma treatment, or ultraviolet treatment. You may go. Moreover, you may perform a back surface process to a base material layer (resin layer).
 また、耐候性の観点より、本発明の透明性等を損なわない範囲内で、上記基材層にも、耐候安定剤を用いた処理を適宜行うことができる。 Further, from the viewpoint of weather resistance, the base material layer can also be appropriately treated with a weather stabilizer within a range that does not impair the transparency of the present invention.
 上記耐候安定剤(紫外線吸収剤、光安定剤、酸化防止剤)を用いた処理は、上記樹脂層表面に塗布処理、または転写処理、上記樹脂層への練り込み等によって行うことができる。 The treatment using the above-mentioned weathering stabilizer (ultraviolet absorber, light stabilizer, antioxidant) can be carried out by coating or transferring treatment on the surface of the resin layer, kneading into the resin layer, or the like.
 また、本実施の形態の効果を損なわない範囲内で、上記基材層に難燃剤、不活性無機粒子、有機粒子、滑剤、帯電防止剤、顔料など任意の添加剤も配合することができる。 In addition, an optional additive such as a flame retardant, inert inorganic particles, organic particles, a lubricant, an antistatic agent, or a pigment can be blended in the base material layer as long as the effects of the present embodiment are not impaired.
 また、本実施の形態は、自動車ホイール用の表面保護フィルムに用いるため、基材層として耐熱性および耐溶剤性を有するとともに可撓性を有する樹脂フィルムであることが好ましい。基材層が可撓性を有することにより、ロールコーターなどによって粘着剤組成物を塗布することができ、ロール状に巻き取ることができる。 Moreover, since this embodiment is used for a surface protective film for automobile wheels, it is preferable that the base material layer is a resin film having heat resistance and solvent resistance and flexibility. When the base material layer has flexibility, the pressure-sensitive adhesive composition can be applied by a roll coater or the like, and can be wound into a roll.
 また、上記基材層には、必要に応じて、シリコーン系、フッ素系、長鎖アルキル系若しくは脂肪酸アミド系の離型剤、シリカ粉等による離型および防汚処理や酸処理、アルカリ処理、プライマー処理、塗布型、練り込み型、蒸着型などの静電防止処理をすることもできる。 In addition, the base material layer may include a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based mold release agent, mold release with silica powder, and antifouling treatment, acid treatment, alkali treatment, Antistatic treatment such as primer treatment, coating type, kneading type, and vapor deposition type can also be performed.
 また、上記基材層には、必要に応じて、表面コート層、例えば、ハードコート層やソフトコート層を適宜設けることもできる。そのような例としては、シリコーン系、メラミン系、ウレタン系、シラン系、アクリレート系などの熱硬化型若しくは化学反応硬化型の表面コート層をあげることができる。これにより、耐擦傷性、耐薬品性、耐候性、防曇性などにおいて、より優れた自動車ホイール用の表面保護フィルムとすることができる。 In addition, a surface coat layer, for example, a hard coat layer or a soft coat layer can be appropriately provided on the base material layer as necessary. Examples of such a surface coating layer include a thermosetting type or a chemical reaction curing type such as a silicone type, a melamine type, a urethane type, a silane type, and an acrylate type. Thereby, it can be set as the surface protection film for motor vehicles more excellent in abrasion resistance, chemical resistance, a weather resistance, anti-fogging property, etc.
 また、本実施の形態の保護フィルムは、上記粘着剤層や基材層を使用することにより、耐候性、接着信頼性、透明性、および耐衝撃性に優れた機能を有するため、屋外等での長期保管、流通過程を経る保護フィルムに適したものとなる。 In addition, the protective film of the present embodiment has a function excellent in weather resistance, adhesion reliability, transparency, and impact resistance by using the pressure-sensitive adhesive layer and the base material layer. It is suitable for a protective film that has undergone a long-term storage and distribution process.
 なお、本実施の形態において、保護フィルムとは、屋内・屋外にて自動車等のホイール表面を保護するフィルムを意味し、例えば、小型自動車、普通乗用車、大型自動車、特殊車両、重機、またはオートバイなどの各種車両に使用されるホイール表面の保護、及び、ホイールの内面側のディスクブレーキの防錆効果を発揮するために用いられるものを含むものである。 In the present embodiment, the protective film means a film that protects the wheel surface of an automobile or the like indoors / outdoors, such as a small automobile, a normal passenger car, a large automobile, a special vehicle, a heavy machine, or a motorcycle. These include those used for protecting the wheel surface used in various types of vehicles and exhibiting the rust prevention effect of the disc brake on the inner surface side of the wheel.
 上記保護フィルムを貼り付ける自動車ホイールの素材としては、ホイールの素材として用いられているものであれば特に限定されず使用することができる。中でも、貼り付けた状態で長期間保管した後において、粘着力が比較的大きく、糊残りを充分に防止することができる点から、アルミホイールであることが好ましい。 The material of the automobile wheel to which the protective film is attached is not particularly limited as long as it is used as a material for the wheel. Among these, an aluminum wheel is preferred because it has a relatively large adhesive force after being stored for a long time in a pasted state and can sufficiently prevent adhesive residue.
 このような保護フィルムを自動車ホイールに貼り付けた場合、前述のように外周端部にシワが発生することがある。そのため、自動車走行時の風圧によって、そのシワを起点として、保護フィルムがホイールから剥がれる不具合が生じる可能性がある。そこで、本実施の形態に係る保護フィルム10は、切り欠き部18が形成されている。これにより、凹凸や曲面のあるホイールへ保護フィルムを貼り付ける際に、切り欠き部18によってシワが折り込まれるため、ホイールの形状によるシワの発生が抑制される。そして、シワの発生が抑制されることで、自動車走行時に発生する風圧によって、保護フィルムがホイールから剥がれる可能性が低下する。つまり、保護フィルム10は、車両等のホイールへへの安定した貼り付け状態を維持することが可能となる。 When such a protective film is affixed to an automobile wheel, wrinkles may occur at the outer peripheral edge as described above. Therefore, the wind pressure at the time of driving | running | working a vehicle may produce the malfunction which a protective film peels off from a wheel starting from the wrinkle. Therefore, the cutout portion 18 is formed in the protective film 10 according to the present embodiment. Thereby, when sticking a protective film on a wheel with an unevenness | corrugation or a curved surface, since a wrinkle is folded by the notch part 18, generation | occurrence | production of the wrinkle by the shape of a wheel is suppressed. And since generation | occurrence | production of a wrinkle is suppressed, possibility that a protective film will peel from a wheel by the wind pressure which generate | occur | produces at the time of a motor vehicle drive falls. That is, the protective film 10 can maintain a stable attachment state to a wheel of a vehicle or the like.
 また、切り欠き部18は、中心に近い先端部18a(図1参照)がR形状であることが好ましい。中心部に近い先端部をR形状とすることで、例えば、ホイールに貼り付けられた保護フィルム10を剥がす際に、切り欠き部18の先端部18aから裂けにくくなる。 Moreover, it is preferable that the notch 18 has an R-shaped tip 18a (see FIG. 1) close to the center. By making the front end portion close to the center portion into an R shape, for example, when the protective film 10 attached to the wheel is peeled off, the front end portion 18a of the cutout portion 18 is not easily torn.
 次に、本実施の形態に係る保護フィルムの好適な作製方法について以下に説明するが、製造方法や材質はこれらに限定されるものではない。 Next, although the suitable production method of the protective film which concerns on this Embodiment is demonstrated below, a manufacturing method and material are not limited to these.
 (水分散型アクリル系ポリマーの調整)
 冷却管、窒素導入管、温度計および撹拌装置を備えた反応容器に、ブチルアクリレート58部、ブチルメタクリレート40部、アクリル酸2.0部、重合開始剤として2,2´-アゾビス(2-アミジノプロパン)ジヒドロクロライド0.03部、ポリオキシエチレンアルキルフェニルエーテルリン酸2.4部、乳化剤としてポリオキシエチレンノニルフエニルエーテル硫酸アンモニウム0.8部および水150部を投入して、乳化重合し、10質量%アンモニア水によりpH8に調整して、水分散型アクリル系ポリマー(アクリル系ポリマーエマルジョン)を得た。
(Adjustment of water-dispersed acrylic polymer)
In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, 58 parts of butyl acrylate, 40 parts of butyl methacrylate, 2.0 parts of acrylic acid, and 2,2′-azobis (2-amidino as a polymerization initiator) Propane) dihydrochloride 0.03 part, polyoxyethylene alkylphenyl ether phosphoric acid 2.4 part, polyoxyethylene nonyl phenyl ether ammonium sulfate 0.8 part and water 150 part as an emulsifier, emulsion polymerization, 10 The aqueous dispersion type acrylic polymer (acrylic polymer emulsion) was obtained by adjusting the pH to 8 with mass% ammonia water.
 (粘着剤溶液の調整)
 前述の水分散型アクリル系ポリマーに、その固形分(水分散系共重合体)100部あたり、オキサゾリン基を含有する水溶性架橋剤として日本触媒(株)の商品名「エポクロスWS-500」(オキサゾリン基当量:220g・solid/eq.)2.0部、光安定剤としてチバ・ジャパン(株)の商品名「TINUVIN 765」2.0部を混合して、水分散型粘着剤組成物Aとした。
(Adjustment of adhesive solution)
As a water-soluble crosslinking agent containing an oxazoline group per 100 parts of its solid content (water-dispersed copolymer) in the water-dispersed acrylic polymer, the product name “Epocross WS-500” of Nippon Shokubai Co., Ltd. ( Oxazoline group equivalent: 220 g · solid / eq.) 2.0 parts, 2.0 parts of the trade name “TINUVIN 765” of Ciba Japan Co., Ltd. as a light stabilizer are mixed, and water-dispersed pressure-sensitive adhesive composition A It was.
 (ホイール用保護フィルムの作製)
 低密度ポリエチレン樹脂(ペトロセン180、密度:0.922g/cm、東ソー株式会社製)を用い、インフレーション法で160℃に加熱したダイスから押し出し、75μmのポリエチレンフィルムを成膜し、更に前記ポリエチレンフィルムの片面にコロナ処理を施した。このコロナ処理面に、前述の水分散型粘着剤Aを塗布し、80℃で1分間加熱して、厚さ10μmの粘着剤層を形成し、ホイール用保護フィルムを作製した。得られたホイール用保護フィルムについて、その外縁部に図1に記載の如く三角形状の切り欠き部を等間隔で18個形成し、第1の実施の形態に係るホイール用保護フィルムを作製した。
(Preparation of wheel protection film)
Using a low-density polyethylene resin (Petrocene 180, density: 0.922 g / cm 3 , manufactured by Tosoh Corporation), the film was extruded from a die heated to 160 ° C. by an inflation method to form a 75 μm polyethylene film. A corona treatment was applied to one side of the. The above-mentioned water-dispersed pressure-sensitive adhesive A was applied to this corona-treated surface and heated at 80 ° C. for 1 minute to form a pressure-sensitive adhesive layer having a thickness of 10 μm, thereby producing a wheel protective film. About the obtained wheel protective film, 18 triangular notch parts were formed in the outer edge part as shown in FIG. 1 at equal intervals, and the wheel protective film which concerns on 1st Embodiment was produced.
 本実施の形態で得られた保護フィルムは、基材層である低密度ポリエチレン樹脂と、基材層の一方の面に設けられた粘着剤層とを有する。この粘着剤層は、光安定剤を含む水分散型粘着剤組成物であるため、タイヤやホイールに貼り付けられた状態で太陽光の下、長期間放置された場合であっても、粘着剤層の性能低下が抑制される。 The protective film obtained in this embodiment has a low-density polyethylene resin that is a base material layer and an adhesive layer provided on one surface of the base material layer. Since this pressure-sensitive adhesive layer is a water-dispersed pressure-sensitive adhesive composition containing a light stabilizer, even if the pressure-sensitive adhesive layer is left on the tire or wheel for a long time under sunlight. The performance degradation of the layer is suppressed.
 また、本実施の形態で得られた保護フィルムは、凹凸や曲面のあるホイールへ貼り付ける際に、切り欠き部18によってシワが折り込まれるため、ホイールの形状によるシワの発生が抑制される。その結果、保護フィルム10は、車両等のホイールへの安定した貼り付け状態を維持することが可能となる。 Further, when the protective film obtained in the present embodiment is attached to a wheel having unevenness or a curved surface, wrinkles are folded by the notch portion 18, and thus generation of wrinkles due to the shape of the wheel is suppressed. As a result, the protective film 10 can maintain a stable state of being attached to a wheel of a vehicle or the like.
 [第2の実施の形態]
 以下の各実施の形態に係る保護フィルムは、基材層12、粘着剤層14、セパレータ16が積層されている点で、第1の実施の形態に係る保護フィルム10と同様であり、各層の材質についても第1の実施の形態と同様である。
[Second Embodiment]
The protective film according to each embodiment below is the same as the protective film 10 according to the first embodiment in that the base material layer 12, the pressure-sensitive adhesive layer 14, and the separator 16 are laminated. The material is the same as in the first embodiment.
 図3は、第2の実施の形態に係る保護フィルムの正面図である。なお、図3において、セパレータは省略されている。本実施の形態に係る保護フィルム22は、円形状である。保護フィルム22は、外縁から内側に向かって切り込み部24が形成されている。本実施の形態に係る保護フィルム22において、切り込み部24は、等間隔に複数(例えば、図3においては18個)配列されている。 FIG. 3 is a front view of the protective film according to the second embodiment. In FIG. 3, the separator is omitted. The protective film 22 according to the present embodiment has a circular shape. The protective film 22 has a cut portion 24 formed inward from the outer edge. In the protective film 22 according to the present embodiment, a plurality (for example, 18 in FIG. 3) of the cut portions 24 are arranged at equal intervals.
 切り込み部は、保護フィルムの外縁から内側に向かって1(個)以上形成すればよい。また、切り込み部の形状としては、例えば直線状、波線状等の適宜の形状とすることができる。 The cut portion may be formed by one (piece) or more from the outer edge of the protective film toward the inside. Moreover, as a shape of a notch part, it can be set as appropriate shapes, such as linear form and wavy line form, for example.
 これにより、凹凸や曲面のあるホイールへ保護フィルムを貼り付ける際に、切り込み部24によってシワが折り込まれるため、ホイールの形状によるシワの発生が抑制される。そして、シワの発生が抑制されることで、自動車走行時に発生する風圧によって、保護フィルムがホイールから剥がれる可能性が低下する。つまり、保護フィルム22は、車両等のホイールへの安定した貼り付け状態を維持することが可能となる。 Thus, when a protective film is applied to a wheel having irregularities or a curved surface, wrinkles are folded by the cut portion 24, so that generation of wrinkles due to the shape of the wheel is suppressed. And since generation | occurrence | production of a wrinkle is suppressed, possibility that a protective film will peel from a wheel by the wind pressure which generate | occur | produces at the time of a motor vehicle drive falls. That is, the protective film 22 can maintain a stable attachment state to a wheel of a vehicle or the like.
 保護フィルム22は、切り込み部24の内側の端部に、切り込み部24と連なる引き裂き防止部26が形成されている。引き裂き防止部26は、曲線で区画された開口部である。そのため、例えば、ホイールに貼り付けられた保護フィルム22を剥がす際に、切り込み部24の先端に設けられた引き裂き防止部26により、保護フィルム22が裂けにくくなる。 In the protective film 22, a tear preventing portion 26 connected to the cut portion 24 is formed at the inner end of the cut portion 24. The tear preventing unit 26 is an opening sectioned by a curve. Therefore, for example, when the protective film 22 attached to the wheel is peeled off, the protective film 22 is not easily torn by the tear preventing portion 26 provided at the tip of the cut portion 24.
 [第3の実施の形態]
 図4は、第3の実施の形態に係る保護フィルムの正面図である。本実施の形態に係る保護フィルム28は、一方の面から他方の面へ空気が通過できる通気部30が形成されている以外は、第1の実施の形態に係る保護フィルム10と同様である。なお、図4において、セパレータは省略されている。
[Third Embodiment]
FIG. 4 is a front view of the protective film according to the third embodiment. The protective film 28 according to the present embodiment is the same as the protective film 10 according to the first embodiment, except that a ventilation portion 30 through which air can pass from one surface to the other surface is formed. In FIG. 4, the separator is omitted.
 通気部30が形成されている保護フィルム28をホイールに貼り付けることで、ホイールの内外の圧力差が緩和され、ホイールからの保護フィルムの剥離が抑制される。なお、通気部30は、製造の容易性から保護フィルム28とセパレータが一体の状態で形成される。そのため、セパレータにも通気部30が形成されているが、セパレータには必ずしも通気部は必要ない。 By sticking the protective film 28 in which the ventilation part 30 is formed on the wheel, the pressure difference between the inside and outside of the wheel is alleviated and the peeling of the protective film from the wheel is suppressed. In addition, the ventilation part 30 is formed in the state in which the protective film 28 and the separator were integrated from the ease of manufacture. Therefore, although the ventilation part 30 is formed also in the separator, the ventilation part is not necessarily required for the separator.
 なお、本実施の形態に係る通気部30は、複数形成されている。これにより、通気部30が一つの場合と比較して、ホイールの内外の圧力差がより緩和される。また、複数の通気部30は、環状に配列されている。特に本実施の形態に係る複数の通気部30は、保護フィルム10の中心に対して同心状に配列されている。また、複数の通気部30は、等間隔に配列されている。これにより、ホイールの内外の圧力差を緩和するように通気部30を通過する空気の流れは、保護フィルム10の周方向に等間隔な場所で発生することになる。そのため、保護フィルム10には、ホイールから剥離する方向の力が接着面に均一に働くため、保護フィルム10がホイールから剥離しにくくなる。 Note that a plurality of ventilation portions 30 according to the present embodiment are formed. Thereby, compared with the case where the ventilation part 30 is one, the pressure difference inside and outside of a wheel is relieve | moderated more. Moreover, the some ventilation | gas_flowing part 30 is arranged in cyclic | annular form. In particular, the plurality of ventilation portions 30 according to the present embodiment are arranged concentrically with respect to the center of the protective film 10. Moreover, the some ventilation | gas_flowing part 30 is arranged at equal intervals. Thereby, the flow of air passing through the ventilation portion 30 so as to relieve the pressure difference between the inside and outside of the wheel is generated at equal intervals in the circumferential direction of the protective film 10. Therefore, since the force in the direction of peeling from the wheel acts uniformly on the adhesive surface of the protective film 10, the protective film 10 is difficult to peel from the wheel.
 [第4の実施の形態]
 図5は、第4の実施の形態に係る保護フィルムの正面図である。本実施の形態に係る保護フィルム32は、一方の面から他方の面へ空気が通過できる通気部30が形成されている以外は、第2の実施の形態に係る保護フィルム22と同様である。なお、図5において、セパレータは省略されている。本実施の形態に係る保護フィルム32おける通気部30の働きは、第3の実施の形態で説明した通りである。
[Fourth Embodiment]
FIG. 5 is a front view of the protective film according to the fourth embodiment. The protective film 32 according to the present embodiment is the same as the protective film 22 according to the second embodiment except that a ventilation portion 30 through which air can pass from one surface to the other surface is formed. In FIG. 5, the separator is omitted. The function of the ventilation portion 30 in the protective film 32 according to the present embodiment is as described in the third embodiment.
 [第5の実施の形態]
 図6は、第5の実施の形態に係る保護フィルムの正面図である。本実施の形態に係る保護フィルム34は、第3の実施の形態に係る保護フィルム28と同様に、複数の通気部36が環状に等間隔で形成されている。第3の実施の形態に係る保護フィルム28と第5の実施の形態に係る保護フィルム34は、通気部の形状が異なっている以外は、構成は同じである。第5の実施の形態に係る通気部36は、円弧状に形成されているスリットである。そのため、ホイールが静止している状態では、保護フィルム34が貼り付けられているホイールの内側に水や汚染物が侵入しにくくなっている。また、ホイールが回転している状態では、通気部36を通過する空気の流れなどにより円弧状のスリットが変形し、空気がより流通しやすくなる。
[Fifth Embodiment]
FIG. 6 is a front view of the protective film according to the fifth embodiment. As with the protective film 28 according to the third embodiment, the protective film 34 according to the present embodiment has a plurality of ventilation portions 36 formed in a ring at regular intervals. The protective film 28 according to the third embodiment and the protective film 34 according to the fifth embodiment have the same configuration except that the shape of the ventilation portion is different. The ventilation portion 36 according to the fifth embodiment is a slit formed in an arc shape. Therefore, when the wheel is stationary, it is difficult for water and contaminants to enter the inside of the wheel to which the protective film 34 is attached. Further, in the state where the wheel is rotating, the arc-shaped slit is deformed by the flow of air passing through the ventilation portion 36 and the like, and the air is more easily distributed.
 なお、通気部36のスリットは、円弧が保護フィルム34の中心から外側に向かって形成されているが、円弧が保護フィルム34の中心に向かって形成されていてもよい。 In addition, although the circular arc is formed toward the outside from the center of the protective film 34, the circular arc may be formed toward the center of the protective film 34.
 [第6の実施の形態]
 図7は、第6の実施の形態に係る保護フィルムの正面図である。本実施の形態に係る保護フィルム38は、第4の実施の形態に係る保護フィルム32と同様に、複数の通気部36が環状に等間隔で形成されている。第4の実施の形態に係る保護フィルム32と第6の実施の形態に係る保護フィルム38は、通気部の形状が異なっている以外は、構成は同じである。第6の実施の形態に係る通気部36も、円弧状に形成されているスリットである。本実施の形態に係る保護フィルム38における通気部36の働きは、第5の実施の形態で説明した通りである。
[Sixth Embodiment]
FIG. 7 is a front view of the protective film according to the sixth embodiment. As with the protective film 32 according to the fourth embodiment, the protective film 38 according to the present embodiment has a plurality of ventilation portions 36 formed annularly at equal intervals. The protective film 32 according to the fourth embodiment and the protective film 38 according to the sixth embodiment have the same configuration except that the shape of the ventilation portion is different. The ventilation part 36 according to the sixth embodiment is also a slit formed in an arc shape. The function of the ventilation portion 36 in the protective film 38 according to the present embodiment is as described in the fifth embodiment.
 以上、本発明を各実施の形態をもとに説明した。この実施の形態は例示であり、それらの各構成要素や各処理プロセスの組合せにいろいろな変形例が可能なこと、またそうした変形例も本発明の範囲にあることは当業者に理解されるところである。 The present invention has been described based on each embodiment. This embodiment is an exemplification, and it will be understood by those skilled in the art that various modifications can be made to combinations of the respective constituent elements and processing processes, and such modifications are also within the scope of the present invention. is there.
 なお、各実施の形態に係る保護フィルムの切り込み部、切り欠き部、通気部などの数や位置は、保護フィルムの貼り付け対象となるホイールの大きさや形状に応じて適宜選択すればよい。 In addition, what is necessary is just to select suitably the number and position, such as a notch part of a protective film which concerns on each embodiment, a notch part, and a ventilation | gas_flowing part, according to the magnitude | size and shape of the wheel which adheres a protective film.
 10 保護フィルム、 12 基材層、 14 粘着剤層、 16 セパレータ、 18 切り欠き部、 18a 先端部、 22 保護フィルム、 24 切り込み部、 26 引き裂き防止部、 28 保護フィルム。 10 protective film, 12 base material layer, 14 adhesive layer, 16 separator, 18 notch, 18a tip, 22 protective film, 24 cut, 26 tear prevention, 28 protective film.
 本発明は、自動車などの車両のホイールに貼り付けられる保護フィルムに利用できる。 The present invention can be used for a protective film attached to a wheel of a vehicle such as an automobile.

Claims (10)

  1.  基材層と、
     前記基材層の一方の面に設けられた粘着剤層とを有するホイール用保護フィルムであって、
     前記ホイール用保護フィルムは、外縁から内側に向かって1以上の切り込み部が形成されていることを特徴とするホイール用保護フィルム。
    A base material layer;
    A protective film for a wheel having a pressure-sensitive adhesive layer provided on one surface of the base material layer,
    The wheel protective film is characterized in that one or more incisions are formed from the outer edge toward the inner side.
  2.  前記切り込み部の内側の端部に、該切り込み部と連なる引き裂き防止部が形成されていることを特徴とする請求項1に記載のホイール用保護フィルム。 2. The protective film for a wheel according to claim 1, wherein a tear preventing portion connected to the cut portion is formed at an inner end portion of the cut portion.
  3.  前記引き裂き防止部は、曲線で区画された開口部であることを特徴とする請求項2に記載のホイール用保護フィルム。 3. The protective film for a wheel according to claim 2, wherein the tear preventing portion is an opening section defined by a curve.
  4.  前記ホイール用保護フィルムは、円形であり、
     前記切り込み部は、等間隔に複数配列されていることを特徴とする請求項1乃至3のいずれか1項に記載のホイール用保護フィルム。
    The wheel protective film is circular,
    4. The wheel protective film according to claim 1, wherein a plurality of the cut portions are arranged at equal intervals. 5.
  5.  基材層と、
     前記基材層の一方の面に設けられた粘着剤層とを有するホイール用保護フィルムであって、
     前記ホイール用保護フィルムは、外縁部に1以上の切り欠き部が形成されていることを特徴とするホイール用保護フィルム。
    A base material layer;
    A protective film for a wheel having a pressure-sensitive adhesive layer provided on one surface of the base material layer,
    The wheel protective film is characterized in that one or more notches are formed in an outer edge portion.
  6.  前記切り欠き部は、中心に近い先端部がR形状であることを特徴とする請求項5に記載のホイール用保護フィルム。 6. The protective film for a wheel according to claim 5, wherein the cutout portion has an R shape at a tip portion close to the center.
  7.  前記ホイール用保護フィルムは、円形であり、
     前記切り欠き部は、等間隔に複数配列されていることを特徴とする請求項5または6に記載のホイール用保護フィルム。
    The wheel protective film is circular,
    The wheel protective film according to claim 5 or 6, wherein a plurality of the notches are arranged at equal intervals.
  8.  前記ホイール用保護フィルムは、一方の面から他方の面へ空気が通過できる通気部が形成されていることを特徴とする請求項1乃至7のいずれか1項に記載のホイール用保護フィルム。 The wheel protective film according to any one of claims 1 to 7, wherein the protective film for a wheel is formed with a ventilation portion through which air can pass from one surface to the other surface.
  9.  前記通気部は、スリットであることを特徴とする請求項8に記載のホイール用保護フィルム。 The wheel protective film according to claim 8, wherein the ventilation portion is a slit.
  10.  前記スリットは、円弧状に形成されていることを特徴とする請求項9に記載のホイール用保護フィルム。 The wheel protective film according to claim 9, wherein the slit is formed in an arc shape.
PCT/JP2012/003367 2011-07-05 2012-05-23 Protection film for wheel WO2013005368A1 (en)

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WO2018235772A1 (en) * 2017-06-21 2018-12-27 シャープ株式会社 Display panel provided with protective film

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JP2020179032A (en) * 2019-04-26 2020-11-05 株式会社洗車の王国 Golf club head protective sheet
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JPWO2017199463A1 (en) * 2016-05-16 2019-02-14 株式会社寺岡製作所 Adhesive composition and adhesive tape
WO2018235772A1 (en) * 2017-06-21 2018-12-27 シャープ株式会社 Display panel provided with protective film

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