JP2011052683A - Protective film for blade of wind power generator - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a means capable of prolonging the service life of a blade for wind power generation and easy to be repaired. <P>SOLUTION: A protective film for a blade capable of protecting a blade is attached to the surface of a blade of a wind power generator. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a blade of a wind turbine generator protected by a protective film having an adhesive layer, a protective film thereof, and a wind turbine generator having such a blade.

A blade for a wind power generator (hereinafter referred to as a blade) rotates in response to a flow of air, which is a fluid, and converts rotational energy into electricity. In order to efficiently rotate in response to a fluid flow, it is important to reduce the inertia force by reducing the weight of the blade. Moreover, since many blades of wind power generators have a total length of more than 50 m, the weight reduction of the blades leads to a reduction in size and weight of the device itself. Furthermore, in order to efficiently convert the fluid flow into the rotational motion of the blade, the design of the blade shape and the maintenance of the shape, the smoothness of the surface and the maintenance thereof are required.
As the blade member, lightweight metal materials such as aluminum and titanium have been used, but recently, fiber reinforced resin that is lighter than metal and has high strength and high rigidity due to the demand for further weight reduction and rigidity. Hereinafter, it is referred to as FRP). In particular, in the case of large-scale wind power generators, FRP is the mainstream.
Once installed, such a wind turbine generator continues to be used without being repaired. For example, it is inspected at most every five years. On the other hand, wind power generators are often installed in harsh climates. For example, in deserts, the difference in temperature between the temperature and the temperature is so great that it is exposed to strong sunlight and may be affected by sandstorms. Near the coast, in addition to wind and rain, it is affected by salt water and insects and wild birds collide. In the volcanic area, it may be affected by corrosive gas or ash.
Since the blade is always exposed to such a harsh natural environment, problems such as breakage, deformation, surface contamination, and surface peeling occur due to long-term use. When such a problem occurs, in addition to a decrease in conversion efficiency to electric power, there also arises a problem of poor appearance. Nevertheless, since the blades for wind power generation are huge, the repair thereof is not easy.
Regarding blade protection measures, a proposal to attach a cleaning device to a windmill (Patent Document 1) and a proposal to prevent surface contamination by directly forming a titanium oxide powder fixed layer or a photocatalyst coating layer on the surface of the blade (Patent Document 2).

JP 2002-115646 A JP 2007-120393 A

  However, in the conventional method, a special mechanism is built in the blade, or the blade surface is directly processed, and maintenance over time is required for the mechanism and the processing itself. In addition, it is ineffective against damage caused by collision of sand, insects, birds, etc., and maintenance work at the installation site is not easy.

  The present invention solves such a problem, and relates to protecting a blade by attaching a protective film to the blade surface of a wind power generator.

That is, the present invention is as follows.
[1] A protective film for blades that has a base material and an adhesive layer on one side of the base material, and is used by being attached to the blade surface of a wind power generator.
[2] The protective film for blades according to the above [1], wherein the substrate is a weather-resistant film.
[3] The above [2], wherein the weather-resistant film is selected from the group consisting of a polyolefin film, a polyester film, a urethane polymer film, a composite film containing an acrylic polymer and a urethane polymer, and a fluorine film. The protective film for a blade as described.
[4] The protective film for blades according to any one of [1] to [3], wherein the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is an acrylic pressure-sensitive adhesive.
[5] The protective film for blades according to any one of [1] to [4], wherein the pressure-sensitive adhesive layer is a bubble-containing pressure-sensitive adhesive layer.
[6] A blade protection method in which the blade protective film according to any one of [1] to [5] is attached to a blade surface of a wind power generator.
[7] A blade for a wind turbine generator whose surface is covered with a protective film.
[8] The blade according to [7], wherein the protective film has a base material made of a weather-resistant film and an adhesive layer formed on one surface of the base material.
[9] The blade according to [8], wherein the pressure-sensitive adhesive layer is an acrylic pressure-sensitive adhesive.
[10] The blade according to [8] or [9], wherein the pressure-sensitive adhesive layer is a bubble-containing pressure-sensitive adhesive layer.
[11] A wind power generator having the blade according to any one of [7] to [10].

The effect of one embodiment of the present invention is that the durability of the blade itself is improved because the deterioration of the FRP blade itself is suppressed by applying the protective film.
The effect of other embodiment of this invention is extending the lifetime maintenance and lifetime of a braid | blade by sticking to the braid | blade the protective film which has the surface which exhibits the contamination prevention effect like a fluorine treatment.
The effect of the other embodiment of the present invention is that the blade can be easily repaired even at the installation site because it is only necessary to replace the protective film of the contaminated or damaged portion.
The effect of the other embodiment of the present invention is that the pressure-sensitive adhesive layer exhibits good adhesion to the curved surface of the blade and the uneven surface (including the damaged portion during repair) by including bubbles in the pressure-sensitive adhesive layer. It is also possible to exhibit good repulsion resistance.
The effect of still another embodiment of the present invention is that it is possible to select a protective film or a surface treatment according to the installation location of the wind power generator without changing the structure or material of the blade itself.

  A protective film (hereinafter referred to as a protective film) to be affixed to the blade for a wind turbine generator according to the present invention includes at least a film-like or sheet-like base material (hereinafter referred to as a base material) and an adhesive layer formed thereon. Is provided. In the present invention, the term “film” includes a sheet. Therefore, the film is a broad concept including a long form, a roll form obtained by winding a long product, a single wafer form, a thick film, and a thin film. Moreover, a base material is the concept containing the aspect which formed the said film single-piece | unit and the surface treatment layer on this film. Various combinations of the base material and the pressure-sensitive adhesive layer are possible. Also, for example, when it is necessary to create a predetermined shape or conductive member on the surface of the blade for the purpose of lightning protection, it is not easy to process the FRP that is the main body of the blade because of its large area. And once it is processed, changes and repairs are not easy. On the other hand, if a protective film is utilized, the protective film can be affixed to the blade surface after a predetermined shape is fixed to the surface of the substrate in advance. In addition, since the shape and pattern required on the blade can be formed by coloring, surface treatment, and surface processing the protective film itself, the degree of freedom in design is increased and repair is easy.

  The form of the protective film of the present invention is not particularly limited. It is provided in various forms according to the application method for applying the blades of a large area smoothly without applying man-hours. For example, it can be provided in a roll shape in which a film having a predetermined width is wound. Moreover, it can also provide with the sheet | seat shape (single-sheet shape) cut | disconnected in advance by the shape according to the sticking form to a braid | blade. A sheet-like (sheet-fed) protective film is suitable for continuously covering a large area. Further, in the case of a sheet-like protective film, it is suitable for selectively replacing a soiled portion, a discolored portion, or a worn portion during repair. In addition, if the protective film is colored in various ways, a decorative effect of the blade can be imparted.

One of the effects of providing the protective film is that the surface of the blade body is protected by the film. In other words, if you remove the protective film after long-term use, the blade body surface that has not deteriorated will be exposed, so you can peel off the film without having to reattach the film. The use as the blade body surface is started, and there is an effect of extending the life of the blade.
On the other hand, the protective film of the present invention may be used as a repair film. In that case, a protective film may be applied to the whole or a part of the blade body surface that has been fouled by long-term use.

  The protective film may be a laminated protective film. As an example in which the base film has a two-layer structure, the first protective film is attached to the blade surface via an adhesive layer, and the second protective film is laminated thereon. As a method of laminating the first protective film and the second protective film, for example, a coextrusion molding method can be used. In the case of such a protective film having a multilayer structure, the first protective film surface that is not deteriorated is exposed only by peeling off the second protective film on the surface side, which is effective for repairability and long life. .

  With increasing demand for wind power generation, various blades have been proposed. For example, Japanese Patent Publication No. 2005-299620 proposes an assembly type blade. In such a prefabricated blade, the protection and strengthening of the joint is an important factor that determines the reliability of the blade. By using the protective film for blades of the present invention and sticking across such a joint part, water, dust, sand and gas can be prevented from entering from the joint part, and the joint part can be reinforced. The role of can also be demonstrated.

  One embodiment of the protective film of the present invention comprises a base material composed of a weather-resistant film having weather resistance and water resistance, and a pressure-sensitive adhesive layer having high durability, high heat resistance, and strong adhesive force. The material is subjected to contamination prevention treatment. It should be noted that the contamination prevention treatment for the substrate includes the case where the film itself has the contamination prevention performance. In this case, when the base material has flexibility, it can be easily attached to the deformed portion and the corner portion of the blade surface in the form of a film or sheet having a large area. However, the flexibility of the substrate is not an essential element. Even a film or the like having poor flexibility can be attached to a flat surface, or can be attached to a deformed portion or a corner portion of a blade surface by forming a sheet with a small area.

  In the present invention, the weather-resistant film can be used as a protective film for blades (for example, 2 years or more, preferably 5 years or more, more preferably about 10 years) for use (maintaining the blade protection function). There is no particular limitation as long as it is present. Examples thereof include various plastic films such as polyolefin films, polyester films, fluorine films, urethane polymer films, or composite films containing acrylic polymers and urethane polymers, and more preferably anti-aging agents and ultraviolet absorbers. A film in which a chemically inert pigment or the like is blended, or a laminated film of different or similar plastics, a laminated film of a plastic film and a metal foil, a film obtained by metal vapor deposition on a plastic film, or the like can be used.

  Hereinafter, as an embodiment of the present invention, a protective film having a weather resistant film and an adhesive layer will be described. In addition, this invention is not limited to embodiment shown below, As long as it has the concept of this invention, various embodiment is included.

  One embodiment of the protective film of the present invention uses, as a base material, a highly durable film surface-treated so as to have a pollution prevention effect, or a film made of a material having a pollution prevention effect. In this embodiment, the base material is attached to the blade surface via an adhesive layer.

  High durability films include films that can withstand long-term use outdoors, polyolefin films such as polypropylene homopolymer and polypropylene random polymer, polyester films such as polyethylene terephthalate (PET) film, and urethane films. , A composite film containing an acrylic polymer and a urethane polymer, or a fluorine film.

(Polyolefin film)
The polyolefin-based film is made of a polyolefin-based thermoplastic resin. Examples of the polyolefin-based thermoplastic resin include those having a polymer containing an α-olefin having 4 to 12 carbon atoms as a main component, polyethylene-based resins, polypropylene-based resins, and ethylene-vinyl acetate copolymers.

  Specifically, for example, olefin polymers such as low density polyethylene, linear low density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene / propylene copolymers, ethylene 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene / 1-octene copolymer, ethylene / propylene / butene copolymer, ethylene / acrylic Polyolefin films such as methyl acid copolymer, ethylene / methyl methacrylate copolymer, ethylene / vinyl acetate copolymer, ethylene / ethyl acrylate copolymer, ethylene / vinyl alcohol copolymer, polyvinyl chloride, and polyvinylidene chloride Etc.

(Polyester film)
Examples of the polyester film include a polyethylene terephthalate (PET) film and a polybutylene terephthalate (PBT) film.

(Urethane polymer film)
Examples of the urethane polymer film include films made of various urethane polymers having a urethane bond in the main chain, obtained by reacting diisocyanate with diol or diamine.

(Fluorine film)
Examples of the fluorine-based film include polytetrafluoroethylene (PTFE), a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether (PFA), a copolymer of tetrafluoroethylene and hexafluoropropylene (FEP), and polychlorotriethylene. Examples thereof include films of fluoroethylene (PCTFE), a copolymer of tetrafluoroethylene and ethylene (ETFE), polyvinylidene fluoride (PVdF), polyvinyl fluoride (PVF), and the like.

(Composite film)
On the other hand, a composite film containing an acrylic polymer and a urethane polymer is a composite film having flexibility and water resistance on a curved surface while achieving both high strength and high elongation at break. Such a composite film can be used for various parts such as a flat surface, a curved surface, or a corner portion of a blade.

(Acrylic polymer for composite film)
The acrylic polymer contained in the composite film is an acrylic component containing at least a (meth) acrylic acid monomer and a monofunctional (meth) acrylic monomer having a glass transition temperature (Tg) of the homopolymer of 0 ° C. or higher. What is obtained is preferred. More preferably, the acrylic component further includes a monofunctional (meth) acrylic monomer having a glass transition temperature (Tg) of the homopolymer of less than 0 ° C.

  In the composite film, the (meth) acrylic acid monomer is a (meth) acrylic monomer having a carboxyl group, and examples thereof include acrylic acid, methacrylic acid, maleic acid, and crotonic acid. Among these, acrylic acid is particularly preferable. The content of the (meth) acrylic acid monomer in the acrylic component is 1% by weight or more and 15% by weight or less, and preferably 2% by weight or more and 10% by weight or less. If the content of the (meth) acrylic acid monomer is less than 1% by weight, it takes a long time for the reaction, making it very difficult to form a film, and there may be a problem that the strength of the film is not sufficient. . When the content of the (meth) acrylic acid monomer exceeds 15% by weight, the water absorption rate of the film increases, which may cause a problem in water resistance. In the present invention, the (meth) acrylic acid monomer greatly affects the compatibility with the urethane component and the acrylic component, and is an essential component having a very important function.

  In the composite film, examples of the monofunctional (meth) acrylic monomer having a Tg of 0 ° C. or higher include acryloylmorpholine, isobornyl acrylate, dicyclopentanyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, and lauryl acrylate. It is done. These may be used alone or in combination of two or more.

  In the composite film, it is more preferable to use at least one selected from the group consisting of acryloylmorpholine, isobornyl acrylate, and dicyclopentanyl acrylate as a monofunctional (meth) acrylic monomer having a Tg of 0 ° C. or higher. It is more preferable to use acryloyl morpholine and / or isobornyl acrylate, or acryloyl morpholine and / or dicyclopentanyl acrylate, and it is particularly preferable to use isobornyl acrylate.

  The content of the monofunctional (meth) acrylic monomer having a Tg of 0 ° C. or higher is preferably 20 wt% or more and 99 wt% or less in the acrylic component, and is 30 wt% or more and 98 wt% or less. Is more preferable. If the content of this monofunctional (meth) acrylic monomer is less than 20% by weight, there may be a problem that the strength of the film is not sufficient, and if it exceeds 99% by weight, the film becomes too rigid and brittle. There is.

  In the composite film, the monofunctional (meth) acrylic monomer having a Tg of less than 0 ° C. includes, for example, n-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isobutyl acrylate, 2-methoxyethyl acrylate, tetrahydro Examples include furfuryl acrylate, phenoxyethyl acrylate, ethoxyethyl acrylate, and 3-methoxybutyl acrylate. These may be used alone or in combination of two or more.

In the composite film, it is particularly preferable to use n-butyl acrylate as a monofunctional (meth) acrylic monomer having a Tg of less than 0 ° C.
A monofunctional (meth) acrylic monomer having a Tg of less than 0 ° C. may not be contained (content is 0% by weight), but if contained, the content is from 0% by weight in the acrylic component. The amount is preferably 50% by weight or less, more preferably more than 0% by weight and 45% by weight or less. When the content of the monofunctional (meth) acrylic monomer exceeds 50% by weight, there may be a problem that the strength of the film is not sufficient.

  The type, combination, amount of use, and the like of the (meth) acrylic monomer are appropriately determined in consideration of compatibility with urethane, polymerizability at the time of photocuring such as radiation, and characteristics of the high molecular weight obtained.

  In the composite film, together with the (meth) acrylic monomer, vinyl acetate, vinyl propionate, styrene, acrylamide, methacrylamide, mono- or diester of maleic acid, and derivatives thereof, N-methylolacrylamide, glycidyl acrylate, glycidyl methacrylate, N , N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl methacrylamide, 2-hydroxypropyl acrylate, N, N-dimethylacrylamide, N, N-diethylacrylamide, imide acrylate, N-vinylpyrrolidone, oligoester acrylate, ε-caprolactone acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, methoxylated cyclododecatri Down acrylate may be copolymerized monomer such as methoxyethyl acrylate. Note that the types and amounts of the monomers to be copolymerized are appropriately determined in consideration of the characteristics of the composite film.

  In addition, other polyfunctional monomers can be added within a range that does not impair the characteristics. Polyfunctional monomers include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol. Examples include tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, urethane acrylate, epoxy acrylate, and polyester acrylate. Particularly preferred is trimethylolpropane tri (meth) acrylate.

  The polyfunctional monomer may be contained in an amount of 1 part by weight or more and 20 parts by weight or less based on 100 parts by weight of the (meth) acrylic monomer. If the content of the polyfunctional monomer is 1 part by weight or more, the cohesive force of the composite film is sufficient, and if it is 20 parts by weight or less, the elastic modulus does not become too high, and the unevenness of the adherend surface is reduced. Can follow.

(Urethane polymer for composite film)
The urethane polymer is obtained by reacting a diol with a diisocyanate. In general, a catalyst is used for the reaction between the hydroxyl group of the diol and the isocyanate. However, the reaction can be performed without using an environmental load catalyst such as dibutyltin dilaurate or tin octoate.

(Polyol for urethane polymer)
Examples of the low molecular weight diol include divalent alcohols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, and hexamethylene glycol.

  Moreover, as a high molecular weight diol, polyether polyol obtained by addition polymerization of ethylene oxide, propylene oxide, tetrahydrofuran or the like, or the above-mentioned divalent alcohol, 1,4-butanediol, 1,6-hexanediol And polyester polyols composed of polycondensates of alcohols such as adipic acid, azelaic acid and sebacic acid, acrylic polyols, carbonate polyols, epoxy polyols and caprolactone polyols. Among these, for example, polyoxytetramethylene glycol (PTMG), polyalkylene carbonate diol (PCD) and the like are preferably used.

  Examples of the acrylic polyol include a homopolymer or copolymer of a hydroxyl group-containing (meth) acrylic monomer, and a copolymer of a hydroxyl group-containing substance and a (meth) acrylic monomer. Examples of the epoxy polyol include an amine-modified epoxy resin.

  In the composite film, the diol can be used alone or in combination in consideration of solubility in a (meth) acrylic monomer, reactivity with isocyanate, and the like. When the strength is required, it is effective to increase the amount of the urethane hard segment by the low molecular weight diol. When importance is attached to elongation, a diol having a large molecular weight is preferably used alone. Polyether polyols are generally inexpensive and have good water resistance, and polyester polyols have high strength. In the present invention, the type and amount of polyol can be freely selected according to the use and purpose, and the properties of the base material to be applied, reactivity with isocyanate, compatibility with acrylic component, etc. Also from the viewpoint, the kind, molecular weight, and usage amount of the polyol can be selected as appropriate.

(Diisocyanate for urethane polymer)
Examples of the diisocyanate include aromatic, aliphatic and alicyclic diisocyanates, dimers and trimers of these diisocyanates. Examples of aromatic, aliphatic, and alicyclic diisocyanates include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), naphthylene diisocyanate (NDI), and phenolene diisocyanate (PPDI). m-tetramethylxylylene diisocyanate (TMXDI), methylcyclohexane diisocyanate (hydrogenated TDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexane diisocyanate (hydrogenated PPDI), bis (isocyanatomethyl) cyclohex Xan (hydrogenated XDI), norbornene diisocyanate (NBDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), butanediiso Aneto, hexamethylene diisocyanate 2,4-trimethyl hexamethylene diisocyanate to 2,4,4-trimethyl like. Moreover, these dimers, trimers, and polyphenylmethane diisocyanate are used. Examples of the trimer include isocyanurate type, burette type, and allophanate type, and can be used as appropriate.

  Among these, in particular, methylcyclohexane diisocyanate (hydrogenated TDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexane diisocyanate (hydrogenated PPDI), bis (isocyanatomethyl) cyclohexane (hydrogenated) XDI), norbornene diisocyanate (NBDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), butane diisocyanate, 2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Aliphatic and alicyclic diisocyanates are preferably used. This is because it is not preferable to use an aromatic diisocyanate containing a benzene ring because a colored substance having a conjugated structure is easily generated by a photoreaction. In the present invention, it does not contain a benzene ring, is hardly yellowed, and has no yellow color. Modified aliphatic and alicyclic diisocyanates are preferably used.

  These diisocyanates can be used alone or in combination. From the viewpoints of the characteristics of the support to which the composite film is applied (applied or the like), solubility in acrylic monomers, reactivity with hydroxyl groups, and the like, the type and combination of diisocyanates may be appropriately selected.

  In the present invention, the urethane polymer is hexamethylene diisocyanate (HDI), hydrogenated tolylene diisocyanate (HTDI), hydrogenated 4,4-diphenylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), and hydrogenated xylene diisocyanate. It is preferably formed using at least one diisocyanate selected from the group consisting of (HXDI), and hydrogenated xylene diisocyanate is particularly preferable.

  In the present invention, the amount of the diol component and diisocyanate component used to form the urethane polymer is preferably [NCO] / [OH] (equivalent ratio) of 1.1 or more and 2.0 or less. More preferably, it is 12 or more and 1.60 or less, and particularly preferably 1.15 or more and 1.40 or less. If the [NCO] / [OH] (equivalent ratio) is less than 1.1, the molecular weight of the urethane polymer becomes too high, the viscosity of the composite film precursor (syrup solution) becomes large, and the work in the subsequent sheeting process can be performed. It can be difficult. On the other hand, when [NCO] / [OH] (equivalent ratio) exceeds 2.0, the molecular weight of the urethane polymer becomes small, and the breaking strength tends to decrease.

(Acrylic component / urethane component ratio in composite film)
In the present invention, the ratio of the acrylic component and the urethane component forming the composite film is a weight ratio, and the acrylic component / urethane component is 0.25 or more and 4.00 or less, preferably 0.429 or more, 2 .333 or less, particularly preferably 0.538 or more and 1.857 or less. When the acrylic component / urethane component is less than 0.25, the viscosity of the syrup solution becomes large, and the work may be difficult in the subsequent sheet forming step. On the other hand, when the acrylic component / urethane component exceeds 4.00, the amount of urethane polymer in the composite film becomes less than 25%, the tensile strength at break is lowered, and it may not be practically used.

  A hydroxyl group-containing (meth) acrylic monomer may be added to the urethane polymer. By adding a hydroxyl group-containing (meth) acrylic monomer, a (meth) acryloyl group can be introduced to the molecular end of the urethane prepolymer, and copolymerization with the (meth) acrylic monomer is imparted to the urethane component. The compatibility between the acryl component and the acrylic component is increased, and SS (stress-strain) characteristics such as breaking strength can be improved. As the hydroxyl group-containing (meth) acrylic monomer used here, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, or the like is used. It is preferable that the usage-amount of a hydroxyl-containing (meth) acrylic-type monomer is 0.1-10 weight part with respect to 100 weight part of urethane polymers, More preferably, it is 1-5 weight part.

(Film stabilizer)
Further, from the viewpoint of weather resistance, it is possible to appropriately perform a treatment using a weather resistance stabilizer on a weather resistant film (including a composite film).

  The treatment using the weather resistance stabilizer (ultraviolet absorber, light stabilizer, antioxidant) can be performed on the surface of the resin layer by application treatment, transfer treatment, kneading into the resin layer, or the like.

(UV absorber)
As the ultraviolet absorber, for example, known ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and benzoate-based ultraviolet absorbers can be appropriately used. These ultraviolet absorbers may be used alone or in combination of two or more.

Examples of the benzotriazole ultraviolet absorber include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, benzenepropanoic acid and 3- (2H-benzotriazol-2-yl) -5- ( Ester compound with 1,1-dimethylethyl) -4-hydroxy (C ₇ -C ₉ side chain and linear alkyl), octyl-3- [3-tert-butyl-4-hydroxy-5- (5- Chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) Phenyl] propionate, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-pheni) Ethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, methyl -3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction product, 2- (2H-benzotriazol-2-yl) -P-cresol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol, 2- (2H-benzotriazol-2-yl) -4 , 6-Di-tert-pentylphenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) pheno 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], methyl-3- (3- (2H- Reaction product of benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate with polyethylene glycol 300, 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methyl Phenol, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimido-methyl) -5-methylphenyl] benzotriazole, 2,2′-methylenebis [6- (benzotriazol-2-yl) ) -4-tert-octylphenol] and the like.

Moreover, as a hydroxyphenyl triazine type ultraviolet absorber, for example, 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl and [ _(C 10 _{-C 16,} predominantly alkyloxy _C 12 _{-C 13)} reaction products of methyl] oxirane, 2- (2,4-dihydroxyphenyl) -4,6-bis - (2,4-dimethylphenyl ) -1,3,5-triazine and the reaction product of (2-ethylhexyl) glycidic acid ester, 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-di Butoxyphenyl) -1,3,5-triazine, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- (2 -Hydro And xyl-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine.

  Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-n-octyloxybenzophenone.

  Examples of the benzoate UV absorber include 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate.

Commercially available benzotriazole ultraviolet absorbers include, for example, “TINUVIN PS” manufactured by BASF Japan as 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, benzenepropanoic acid BASF Japan Ltd. as an ester compound of 2- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy (C ₇ -C ₉ side chain and straight chain alkyl) "TINUVIN 384-2", octyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl- 3- [3-tert-Butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole) “TINUVIN 109” manufactured by BASF Japan Ltd. as a mixture with 2-yl) phenyl] propionate, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol As “TINUVIN 900” manufactured by BASF Japan Ltd., 2- (2H-benzotriazol-2-yl) -6-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl ) Reaction product of “TINUVIN 928” manufactured by BASF Japan Ltd. as methyl and methyl-3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 “TINUVIN 1130” manufactured by BASF Japan, 2- ( “TINUVIN P” manufactured by BASF Japan Ltd. as H-benzotriazol-2-yl) -p-cresol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert -“TINUVIN 326” manufactured by BASF Japan Ltd. as 2-butyl) phenol, “TINUVIN 328” manufactured by BASF Japan Ltd. as 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol, 2 -(2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol "TINUVIN 329", 2,2'-methylenebis [6- (2H) manufactured by BASF Japan -Benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) pheno ] “TINUVIN 360” manufactured by BASF Japan Ltd., reaction of methyl-3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate with polyethylene glycol 300 As a product, “TINUVIN 213” manufactured by BASF Japan Ltd., “TINUVIN 571” manufactured by BASF Japan Ltd. as 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol, 2- [2-hydroxy -3 (3,4,5,6-tetrahydrophthalimido-methyl) -5-methylphenyl] benzotriazole, "Sumisorb 250" manufactured by Sumitomo Chemical Co., Ltd., 2,2'-methylenebis [6- (benzotriazole-2- Yl) -4-tert-octylphenol ADEKA made of "ADKSTAB LA31", and the like as.

Moreover, as a commercially available hydroxyphenyl triazine type ultraviolet absorber, for example, 2- (4,6-bis (2,4-dimethylphenyl) -1-3,5-triazin-2-yl)- 5-hydroxyphenyl and oxirane _[(C 10 ~C _16, mainly _C 12 _{-C 13} alkyloxy) methyl oxirane] reaction product and 1-methoxy-2-propanol as BASF Japan Ltd. of "TINUVIN 400" with Reaction of 2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine with (2-ethylhexyl) -glycidic acid ester "TINUVIN 405" manufactured by BASF Japan, 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- ( , 4-dibutoxyphenyl) -1,3,5-triazine, “TINUVIN 460” manufactured by BASF Japan, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5 “TINUVIN 1577” manufactured by BASF Japan Ltd. as 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) as [(hexyl) oxy] -phenol ) -1,3,5-triazine includes “TINUVIN 479” manufactured by BASF Japan.

  Examples of commercially available benzophenone ultraviolet absorbers include “CHIMASSORB 81” manufactured by BASF Japan. Examples of the benzoate UV absorber include “TINUVIN 120” manufactured by BASF Japan Ltd. as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate. It is done.

  In this invention, the said ultraviolet absorber can be used individually or in combination of 2 or more types.

  The total amount of the ultraviolet absorber used is preferably 0.1% by weight or more and 4.0% by weight or less with respect to 100% by weight of the composite film precursor, and is 0.5% by weight or more and 2.0% by weight or less. More preferably, it is as follows. If the content of the UV absorber is 0.1% by weight or more, absorption of UV light causing deterioration or coloring is sufficient, and if it is 4.0% by weight or less, coloring by the UV absorber itself is caused. There is no.

(Light stabilizer)
As the light stabilizer, for example, a known light stabilizer such as a hindered amine light stabilizer or a benzoate light stabilizer can be appropriately used. These light stabilizers may be used alone or in combination of two or more.

  The addition amount of the light stabilizer is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and still more preferably about 0.1 to 1 part by weight with respect to 100 parts by weight of the base polymer of each resin layer. .

  The light stabilizer used in the present invention is preferably a hindered amine light stabilizer (HALS), and the hindered amine light stabilizer preferably has, for example, a structure represented by the following formula (I).

(In the formula, R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ are each independently a hydrogen atom, an optionally substituted alkyl group, or an alkoxy group.)

  As a commercially available hindered amine light stabilizer, for example, as a light stabilizer that is a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, “TINUVIN 622” (manufactured by BASF Japan), a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and N, N ′, N ″, N ′ '' -Tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7- As a light stabilizer which is a one-to-one reaction product with diazadecane-1,10-diamine, “TINUVIN 119” (manufactured by BASF Japan), dibutylamine, 1,3-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine As a light stabilizer that is a polycondensation product with TINUVIN 2020 (manufactured by BASF Japan), poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine- 2,4-diyl} {2,2,6,6-tetramethyl-4-piperidyl} imino] hexamethylene {(2,6,6-tetramethyl-4-piperidyl) imino}) as a light stabilizer "TINUVIN 944" (manufactured by BASF Japan Ltd.), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl seba “TINUVIN 765” (manufactured by BASF Japan) as a light stabilizer that is a mixture with Kate, and “TINUVIN 770” as a light stabilizer that is bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate ( BASF Japan), decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester (1,1-dimethylethyl hydroperoxide) and octane As a light stabilizer which is a product, “TINUVIN 123” (manufactured by BASF Japan Ltd.), bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) ) -4-hydroxyphenyl] methyl] butyl malonate as a light stabilizer “TINUVIN 144” (BASF Japan) Product), reaction product of cyclohexane and N-butyl-2,2,6,6-tetramethyl-4-piperidineamine-2,4,6-trichloro-1,3,5-triazine peroxide As a light stabilizer which is a reaction product of 2-aminoethanol with “TINUVIN 152” (manufactured by BASF Japan), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1 , 2,2,6,6-pentamethyl-4-piperidyl sebacate is a light stabilizer such as “TINUVIN 292” (manufactured by BASF Japan).

  In the present invention, the hindered amine light stabilizer can be used alone or in combination of two or more. The total amount of these hindered amine light stabilizers used is 100% by weight of the composite film precursor. 0.1 wt% or more and 4.0 wt% or less is preferable, and 0.5 wt% or more and 2.0 wt% or less is more preferable. When the amount of the hindered amine light stabilizer used is 0.1% by weight or more, the deterioration preventing function is sufficiently expressed, and when it is 4.0% by weight or less, coloring by the light stabilizer itself is not caused.

(Antioxidant)
As the antioxidant, for example, known antioxidants such as hindered phenol-based antioxidants, phosphorus-based processing heat stabilizers, lactone-based processing heat stabilizers, sulfur-based heat stabilizers can be appropriately used. These antioxidants may be used alone or in combination of two or more.

  The amount of the antioxidant added is preferably 3 parts by weight or less, more preferably 1 part by weight or less, and still more preferably about 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the base polymer of each resin layer. It is.

  In addition, fillers, pigments, colorants, flame retardants, antistatic agents and the like that do not impair the effects of the present invention can be added within a range that does not impair the effects of the present invention. These additives are used in normal amounts depending on the type.

(Substrate surface treatment)
In one embodiment of the protective film of the present invention, one aspect of the surface treatment having an antifouling effect is a coat layer (surface treatment layer) made of a fluoroethylene vinyl ether copolymer on the surface opposite to the adhesive layer of the film. Is formed. The fluoroethylene vinyl ether copolymer is preferably one represented by the following formula (II) having fluoroethylene units and vinyl ether units alternately.

In the formula (II), X represents fluorine, chlorine or bromine, R _a represents H or a C _{1 to} C ₁₀ alkyl group, R _b represents a C _{1 to} C ₁₆ alkyl group, and R _c represents C It represents an alkylene group having ₁ -C _16. Note that m and n are integers.

  The weight average molecular weight of the fluoroethylene vinyl ether alternating copolymer is 1,000 to 2,000,000, preferably 5,000 to 1,000,000, and more preferably 10,000 to 500,000. is there. In the present invention, m and n in the above formula (II) are selected in the range where the weight average molecular weight of the fluoroethylene vinyl ether alternating copolymer is 1,000 to 2,000,000.

The weight average molecular weight of the fluoroethylene vinyl ether alternating copolymer can be measured by the GPC method.
The measuring method of GPC method is shown below. That is, the fluoroethylene vinyl ether alternating copolymer is adjusted to 2.0 g / L using a THF solution and then allowed to stand for 12 hours. Thereafter, this solution is filtered through a 0.45 μm membrane filter, and GPC measurement is performed on the filtrate under the following measurement conditions using “HLC-8120GPC” manufactured by Tosoh Corporation as an analyzer.
Measurement condition:
Column TSKgel GMH-H (S) x 2
Column size 7.8 mmI. D x 300mm
Eluent THF
Flow rate 0.5mL / min
Detector RI
Column temperature 40 ° C
Injection volume 100μL

  In addition, it is preferable that the base material has a coating layer on one surface of the composite film and a pressure-sensitive adhesive layer on the other surface. The thickness of the coat layer is preferably 2 to 100 μm, more preferably 5 to 50 μm, and still more preferably 8 to 40 μm. When the thickness of the coat layer is less than 2 μm, a defect site where the coat layer is not formed, such as pinholes, is likely to occur, and the characteristics of the coat layer may not be sufficiently exhibited. On the other hand, if the thickness exceeds 100 μm, the physical properties of the coating layer may deteriorate the physical properties of the composite film.

(Crosslinking of composite film and coat layer)
In the protective film of one embodiment of the present invention, the coat layer is preferably crosslinked with the composite film and has a crosslinking point. A structure having a crosslinking point can be obtained, for example, by combining the component constituting the coat layer and the component constituting the composite film to form a crosslinking point. For example, if there is a residual isocyanate group in the isocyanate used to form the coat layer, this residual isocyanate group can react with the hydroxyl group of the urethane polymer / acrylic monomer mixture to form a crosslinking point. Alternatively, if the hydroxyl group of the fluoroethylene vinyl ether alternating copolymer used for forming the coating layer remains, it can react with the isocyanate group present in the coating solution for composite film to form a crosslinking point. it can. Therefore, in the present invention, when the composite film coating solution is applied, it is preferable that the residual isocyanate group or the residual hydroxyl group exists in the coat layer in a state where it can react. Moreover, it is preferable to apply the composite film coating solution before the crosslinking reaction of the coating layer is completely completed.

  Thus, if the coat layer and the composite film form a cross-linked structure, excellent adhesion can be exhibited, so the surface coat layer should keep excellent adhesion to the composite film for a long period of time. Can do. Therefore, even if an application sheet is affixed for positioning the protective film, the surface coat layer does not peel off when the application sheet is peeled off.

  In order for the surface coat layer and the composite film to form a cross-linked structure, the surface coat layer needs to be composed of an alternating copolymer of fluoroethylene vinyl ether, and an acrylic polymer and a urethane polymer are used as the composite film. It is necessary to contain.

  In one embodiment of the present invention, any method may be used as long as the surface coat layer and the composite film can form a crosslinked structure. For example, after the surface coat layer is applied, dried and cured, the composite film coating solution can be applied to form a crosslinking point with the coat layer surface semi-cured. Alternatively, if the remaining isocyanate group can react even when the surface is completely cured, a composite film coating solution can be applied thereon to form a crosslinking point. Therefore, it is preferable that the crosslinked structure is appropriately designed in consideration of the types and amounts of components used for forming the coat layer and the composite film. For example, in a state in which the remaining isocyanate group can react, a crosslinked structure can be formed by applying a composite film coating solution within 24 hours and causing a photocuring reaction. In addition, if the remaining isocyanate group can react and is stored at about 5 ° C., a crosslinked structure can be formed by applying a composite film coating solution within 5 days and allowing it to undergo photocuring reaction. it can. If a hydroxyl group-containing monomer is reacted with the isocyanate crosslinking agent in advance, the residual isocyanate group can be reacted even after being stored at 50 ° C. for one week or longer.

(Manufacture of coat layer)
In one embodiment of the present invention, a fluoroethylene vinyl ether alternating copolymer is dissolved in a solvent, and a polyfunctional isocyanate is added thereto to form a coating layer coating solution, and this solution is used to form a coating layer. . For example, this solution is applied onto a polyethylene film that has been subjected to a release treatment, and dried to form a coat layer. On this coat layer, a mixture containing a urethane polymer and an acrylic monomer (composite film coating solution) was applied, and the coat layer was crosslinked to the composite film by irradiating ultraviolet rays or the like (the composite film was coated). It is possible to obtain a laminate having a structure in which the layers are crosslinked.

  Alternatively, after reacting the hydroxyl group-containing monomer and the polyfunctional isocyanate, a fluoroethylene vinyl ether alternating polymer is added, and a coating layer is formed using this solution. For example, this solution is applied onto a peeled PET film and dried to form a coat layer. On this coating layer, a coating solution for a composite film containing an acrylic monomer and a urethane polymer was applied, and cured by irradiation with ultraviolet rays or the like, whereby the coating layer was crosslinked to the composite film (the composite film was coated). It is possible to obtain a laminate having a structure in which the layers are crosslinked.

  Examples of the polyfunctional isocyanate having two or more isocyanate groups in the molecule include hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, ethylene diisocyanate, 1 , 4-tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, norbornene diisocyanate, etc., bifunctional isocyanate, Desmodur N3200 (manufactured by Sumika Bayer Urethane Co., Ltd.), Coronate L, HL, HX (manufactured by Nippon Polyurethane Co., Ltd.), Trifunctional isocyanates such as Takenate D-140N, D-127, D-110N (Mitsui Chemicals) are listed. In the present invention, these polyfunctional isocyanates can be used alone or in combination of two or more.

  When reacting a hydroxyl group-containing monomer with a polyfunctional isocyanate, the ratio of the number of moles of hydroxyl group [OH] of the hydroxyl group-containing monomer to the number of moles of isocyanate group [NCO] of the polyfunctional isocyanate ([OH] / [NCO]) Is 0.05 to 0.5, preferably 0.05 to 0.4, and more preferably 0.05 to 0.3.

  The hydroxyl group-containing monomer has one or more hydroxyl groups in the molecule and one or more (meth) acryl groups in the molecule. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 1,4-cyclohexanedimethanol monoacrylate, and 1,4-cyclohexane. Xanthodimethanol monomethacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, pentaerythritol acrylate and the like. In the present invention, these hydroxyl group-containing monomers can be used alone or in combination of two or more.

(Multi-layer base material)
In one embodiment of the present invention, the base material can be laminated with another film on one side of the composite film (the side on which the coating layer is not provided) within a range that does not impair the effects of the present invention. Examples of materials for forming other films include polyester resins such as polyethylene terephthalate (PET), polyolefin resins such as polyethylene (PE) and polypropylene (PP), polyimide (PI), and polyetheretherketone (PEEK). Besides thermoplastic resins such as polyvinyl chloride (PVC), polyvinylidene chloride resins, polyamide resins, polyurethane resins, polystyrene resins, acrylic resins, fluorine resins, cellulose resins, polycarbonate resins, etc. And thermosetting resins. In addition, when providing the said coating layer, it is preferable to arrange | position a coating layer in the position of the outermost layer of a base material.

(Thickness of base material)
The thickness of the entire substrate is not particularly limited, but the thickness of the entire substrate is preferably 2 μm or more and 500 μm or less, more preferably 12 μm or more and 400 μm or less. When the substrate has a multilayer structure, the thickness of each layer (that is, each film) is not particularly limited, but the thickness of each layer is preferably 2 μm or more and 500 μm or less, more preferably 12 μm or more and 400 μm or less.

(Adhesive layer)
The protective film of one embodiment of the present invention has an adhesive layer on one side of the substrate. As the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer, general materials such as acrylic, rubber-based, and silicone-based materials can be used. However, low temperature adhesiveness, high temperature retention, and cost are considered. Then, an acrylic adhesive is preferable.

  For the pressure-sensitive adhesive layer having a strong adhesive force, for example, an acrylic pressure-sensitive adhesive is suitable. The acrylic pressure-sensitive adhesive is an acrylic copolymer obtained by copolymerizing a monomer component mainly composed of (meth) acrylic acid ester and a monomer component having a functional group such as a carboxyl group or a hydroxyl group (even if there are two or more types). Good).

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate , N-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, iso Sil (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, Examples include octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, and the like. These alkyl (meth) acrylates can be used alone or in combination of two or more.

  The following monomer components can be copolymerized with the alkyl (meth) acrylate. Examples of copolymerizable monomer components include monomers containing carboxyl groups such as (meth) acrylic acid, itaconic acid, maleic acid, crotonic acid, fumaric acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, and the like. ; 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxy (meth) acrylate Hydroxyl group-containing monomers such as octyl, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) -methyl acrylate; glycidyl (meth) acrylate, methyl glycidyl ( Meta) Acry Glycidyl group-containing monomers such as acrylate; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (Meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, (meth) acryloylmorpholine, N-vinyl-2-piperidone, N-vinyl- 3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-2-pyrrolidone, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, N-cyclohexyl Maleimide, N-phenylmaleimide, N-actyl Roirupirorijin, tert- butylaminoethyl (meth) nitrogen-containing monomers such as acrylates, styrene, derivatives of styrene, monomers such as vinyl acetate. One or more of these monomers can be used by copolymerizing with (meth) acrylic acid ester as required.

  The pressure-sensitive adhesive used in the protective film of one embodiment of the present invention is at least one selected from the group consisting of 2-ethylhexyl acrylate and isononyl acrylate, and at least selected from the group consisting of acrylic acid and methacrylic acid. It is preferable to include one kind of carboxyl group-containing monomer. That is, the pressure-sensitive adhesive used in the present invention uses a copolymer obtained by copolymerizing 2-ethylhexyl acrylate, isononyl acrylate and the like as a main monomer and a carboxyl group-containing monomer such as acrylic acid and methacrylic acid. Can do.

(Bubble-containing adhesive layer)
The pressure-sensitive adhesive layer in one embodiment of the protective film of the present invention may be a bubble-containing pressure-sensitive adhesive layer. When air bubbles are contained in the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer can exhibit good adhesion to a curved surface or an uneven surface, and can also exhibit good repulsion resistance.

  Basically, it is desirable that the bubbles contained in the bubble-containing pressure-sensitive adhesive layer be closed-cell type bubbles, but closed-cell type bubbles and open-cell type bubbles may be mixed.

  In addition, such bubbles usually have a spherical shape (particularly true spherical shape), but may have an irregular spherical shape. The average bubble diameter (diameter) of the bubbles is not particularly limited, and can be selected from a range of, for example, 1 to 1000 μm, preferably 10 to 500 μm, and more preferably 30 to 300 μm.

  The gas component contained in the bubbles (the gas component that forms bubbles may be referred to as “bubble-forming gas”) is not particularly limited, and is an air other than an inert gas such as nitrogen, carbon dioxide, or argon. Various gas components such as can be used. As the bubble forming gas, when a reaction such as a polymerization reaction is performed in a state in which the bubble forming gas is contained, it is important to use a gas that does not inhibit the reaction. As the bubble forming gas, nitrogen is preferable from the viewpoint of not inhibiting the reaction and from the viewpoint of cost.

  The amount of bubbles in the pressure-sensitive adhesive layer is not particularly limited, and can be appropriately selected according to the use of the pressure-sensitive adhesive tape in which the pressure-sensitive adhesive layer is used. For example, for the total volume of the pressure-sensitive adhesive layer It can be 10% or more, preferably 11% or more, and more preferably 12% or more. The upper limit of the amount of bubbles in the pressure-sensitive adhesive layer is not particularly limited, and can be, for example, 50% or less, preferably 40% or less, and more preferably 30% or less.

In the pressure-sensitive adhesive layer containing such bubbles (sometimes referred to as “bubble-containing pressure-sensitive adhesive layer”), the form in which bubbles are formed is not particularly limited. Examples of the bubble-containing pressure-sensitive adhesive layer include (1) an acrylic pressure-sensitive adhesive composition (“bubble-containing (photopolymerizable)” previously mixed with a gas component (bubble-forming gas) that forms bubbles. A foam-containing pressure-sensitive adhesive layer in which bubbles are formed using (a) a (photopolymerizable) acrylic pressure-sensitive adhesive composition containing a foaming agent. And a bubble-containing pressure-sensitive adhesive layer in which bubbles are formed.
In one embodiment of the present invention, a bubble-containing pressure-sensitive adhesive layer in which bubbles are formed by using a bubble-containing photopolymerizable acrylic pressure-sensitive adhesive composition is suitable as the bubble-containing pressure-sensitive adhesive layer. The amount of bubbles in the bubble-containing photopolymerizable acrylic pressure-sensitive adhesive composition can be appropriately selected from a range corresponding to the amount of bubbles in the bubble-containing pressure-sensitive adhesive layer.

The method for mixing the bubbles is not particularly limited, and a known bubble mixing method can be used. For example, as an example of a foaming device, a stator having a large number of fine teeth on a disk having a through hole in the center, and a stator with teeth are opposed to each other. And a device having a rotor with teeth.
Adhesive precursor is introduced between the teeth on the stator and the teeth on the rotor in this device, and the gas component (bubble forming gas) is bonded to form bubbles through the through-hole while rotating the rotor at high speed. By introducing into the agent precursor, a bubble-containing pressure-sensitive adhesive composition in which the bubble-forming gas is finely dispersed and mixed in the pressure-sensitive adhesive precursor can be obtained.

  In order to suppress or prevent the coalescence of bubbles, it is preferable to continuously perform the steps from the mixing of bubbles to the formation of the bubble-containing pressure-sensitive adhesive layer as a series of steps. That is, the bubble-containing pressure-sensitive adhesive layer is prepared by mixing bubbles as described above to prepare a bubble-containing pressure-sensitive adhesive composition, and then using the bubble-containing pressure-sensitive adhesive composition, It is preferably formed using a forming method.

  On the other hand, when the bubble-containing pressure-sensitive adhesive layer is a bubble-containing pressure-sensitive adhesive layer in which bubbles are formed by using a photopolymerizable acrylic pressure-sensitive adhesive composition containing a foaming agent, It does not restrict | limit in particular, For example, it can select suitably from a well-known foaming agent. In addition, as a foaming agent, a thermally expansible microsphere etc. can be used, for example.

  The bubble-containing pressure-sensitive adhesive layer can also be produced by blending hollow microspheres in the pressure-sensitive adhesive composition. Examples of the hollow microspheres used for the bubble-containing pressure-sensitive adhesive layer include hollow inorganic microspheres and hollow organic microspheres. Specifically, as the hollow inorganic microspheres, for example, glass hollow balloons such as hollow glass balloons; metal compound hollow balloons such as hollow alumina balloons; porcelain hollow balloons such as hollow ceramic balloons, etc. Is mentioned. Examples of the hollow organic microsphere include resin hollow balloons such as hollow acrylic balloons and hollow vinylidene chloride balloons. The surface of the hollow microsphere may be subjected to various surface treatments (for example, low surface tension treatment with a silicone compound, a fluorine compound, or the like).

  Although it does not restrict | limit especially as a particle size (average particle diameter) of a hollow microsphere, For example, it can select from the range of 1-500 micrometers (preferably 5-200 micrometers, More preferably, 10-100 micrometers).

The specific gravity of the hollow microspheres is not particularly limited, for example, 0.1 to 0.8 g / cm ³ (preferably 0.12 / cm ³⁾ can be selected from the range of. If the specific gravity of the hollow microspheres is less than 0.1 g / cm ³ , the hollow microspheres may be lifted when the hollow microspheres are mixed with the pressure-sensitive adhesive constituting the bubble-containing pressure-sensitive adhesive layer and mixed. Since it becomes large, it becomes difficult to uniformly disperse the hollow microspheres. On the other hand, when it is larger than 0.8 g / cm ³ , it becomes expensive and the production cost increases.

  The amount of the hollow microspheres used is not particularly limited, and is, for example, a range that is 10 to 50% by volume (volume%), preferably 15 to 40% by volume with respect to the total volume of the bubble-containing pressure-sensitive adhesive layer. You can choose from. If the amount of the hollow microspheres used is less than 10% by volume with respect to the total volume of the bubble-containing pressure-sensitive adhesive layer, the effect of adding the hollow microspheres tends to be reduced, whereas 50 If the amount used exceeds volume%, the adhesive force of the bubble-containing pressure-sensitive adhesive layer tends to decrease.

(Properties of protective film)
The thickness of the pressure-sensitive adhesive layer is not particularly limited and can be arbitrarily set. The thickness of the bubble-containing pressure-sensitive adhesive layer is preferably 0.1 mm or more and 2.0 mm or less, more preferably 0.2 mm or more and 1.2 mm or less. The thickness of the pressure-sensitive adhesive layer not containing bubbles is preferably 10 μm or more and 500 μm or less, more preferably 20 μm or more and 200 μm or less.

  As one embodiment of the present invention, the pressure-sensitive adhesive layer is formed by, for example, applying a solvent-based or emulsion-based pressure-sensitive adhesive directly to a substrate and drying it. It is possible to apply a method in which a layer is formed and the pressure-sensitive adhesive layer is bonded to a substrate.

  The protective film of one embodiment of the present invention preferably has a 100% modulus of 1.0 MPa or more and 10.0 MPa or less, more preferably 1.50 MPa or more and 8.0 MPa or less, and particularly preferably 2. It is 0 MPa or more and 6.0 MPa or less. If the 100% modulus at 23 ° C. is 1.0 MPa or more and 10 MPa or less, the protective film has a good balance between flexibility and rigidity, and has excellent workability for applying to curved surfaces such as curved portions and corner portions. Yes.

  Here, the 100% modulus at 23 ° C. is a unit when a tensile test is performed at a tensile speed of 200 mm / min, a distance between chucks of 50 mm, and a room temperature (23 ° C.), a stress-strain curve is obtained, The stress per area.

  The protective film of one embodiment of the present invention preferably has a breaking elongation of 200% or more and 1,000% or less, more preferably 250% or more and 800% or less, and particularly preferably 300% or more and 600%. % Or less. If the elongation at break is 200% or more, the pressure-sensitive adhesive sheet is sufficiently stretched at the time of sticking, so that the work of sticking to a curved surface or the like is not reduced. Further, if the elongation at break is 1,000% or less, the pressure-sensitive adhesive sheet will not grow too much at the time of sticking, and the sticking work will not be reduced.

  Here, the elongation at break means that the pressure-sensitive adhesive sheet (width 1 cm, length 13 cm) is subjected to a tensile test at a tensile speed of 200 mm / min, a distance between chucks of 50 mm, and room temperature (23 ° C.). The value divided by the distance (50 mm).

  The protective film of one embodiment of the present invention preferably has a breaking strength of 10 MPa or more and 100 MPa or less, more preferably 15 MPa or more and 90 MPa or less, and particularly preferably 20 MPa or more and 80 MPa or less. Within this range, when the sand or pebbles collide, the surface of the adhesive sheet is not damaged, the aesthetic appearance of the blade for the wind turbine generator is not impaired, and can easily follow the curved surface of the blade. .

  Here, the breaking strength is a force when the pressure-sensitive adhesive sheet breaks by performing a tensile test on the pressure-sensitive adhesive sheet (width 1 cm × length 13 cm) at a tensile speed of 200 mm / min, a distance between chucks of 50 mm and room temperature (23 ° C.). To tell.

  Although there is no limitation in particular in the thickness of a protective film, This thickness becomes like this. Preferably they are 20 micrometers or more and 3000 micrometers or less, More preferably, they are 40 micrometers or more and 2000 micrometers or less.

  The protective film of one embodiment of the present invention is required to be transparent in order to reflect the color and the like of the painted surface of the adherend to the appearance as it is. You may use it as a protective film, coloring with the same color, or coloring with another color.

(Method for producing protective film)
The manufacturing method of the protective film of one Embodiment of this invention is described below. For example, first, a surface coating layer is formed by applying a coating solution for a surface coat layer on the release treatment surface of a release-treated polyethylene terephthalate film (temporary support 1), and then a coating solution for a composite film thereon. Is applied, and a transparent separator or the like is placed thereon, and ultraviolet rays or the like are irradiated thereon to form a composite film while forming a crosslinking point, and then the separator is removed. Separately, a pressure-sensitive adhesive layer coating solution is applied to the release-treated surface of the release-treated polyester film (temporary support 2) to form a pressure-sensitive adhesive layer. Thereafter, the pressure-sensitive adhesive layer can be superimposed on the composite film surface to obtain a protective film. In addition, although it becomes the layer structure of the polyethylene terephthalate film (temporary support 1) / surface coat layer / composite film / adhesive layer / peeled polyester film (temporary support 2) by which peeling processing was carried out here. The temporary support 1 and the temporary support 2 are not particularly included in the structure of the protective film of the present invention because they are peeled and removed during use, that is, when the protective film is applied and applied. However, these temporary support 1, temporary support 2 and the like can be appropriately provided as necessary, and these configurations belong to the technical scope of the present invention.

  The protective film of one embodiment of the present invention can achieve both high strength and high elongation at break, and is excellent in flexibility with respect to a curved surface. Furthermore, in the protective film of one embodiment of the present invention, the coat layer is firmly adhered to the composite film, and the coat layer may be peeled off even if positioning is performed using an application sheet during the pasting operation, for example. There is no. Therefore, it is suitable as a protective film for blades for wind power generators.

Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited thereto. In the following examples, unless otherwise specified, parts means parts by weight,
% Means weight%.

  First, measurement methods and evaluation methods used in the following examples will be described.

<Measurement method and evaluation method>
(1) Evaluation of weather resistance (yellowing resistance) Each sample of the protective film for blades was made to reciprocate a 2 kg roller on a white painted plate (white test plate made by Nippon Test Panel, dull steel plate “JIS G3141”). Then, they were bonded by pressure bonding and left at 23 ° C. for 24 hours. Then, each sample was installed in a sunshine weather tester (manufactured by Suga Test Instruments Co., Ltd.), and irradiated with light (300 to 700 nm, 255 W / m ² ) for 1,000 hours. The protective film for blades was visually observed to confirm discoloration (yellow), and it was determined that there was no discoloration (OK) and discoloration (NG).

(2) Evaluation of stain resistance Adhering the protective film for blades to a white paint plate (made by Nippon Test Panel Co., Ltd., dull steel plate “JIS G3141” white acrylic baking) by reciprocating a 2 kg roller once. And left at 23 ° C. for 24 hours. Thereafter, using a stepping stone tester (manufactured by Suga Test Instruments Co., Ltd.), a stone having a diameter of 2 to 5 mm at 0.4 MPa was applied to the blade protective film on the white painted plate. Then, the dirt on the surface of the protective film for blades was wiped off with a cloth, and it was observed whether or not the dirt was wiped off. When the dirt was wiped off, it was determined that there was no adhesion (OK), and when the dirt was not wiped off, it was determined that there was adhesion (NG).

Example 1
A blade protective film having the following laminated structure was produced.
[Layer structure] Fluorine coat (surface treatment) / acrylic-urethane composite film or sheet (base material) / hyper joint H9008 (adhesive layer)

<Manufacturing method>
1. Preparation of acrylic-urethane composite film composition (step 1)
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, 13.74 parts of acrylic acid (AA), 97.52 parts of isobornyl acrylate (IBXA) as acrylic monomers, n-butyl acrylate 26.10 parts of (BA) and 100 parts of polyoxytetramethylene glycol (PTMG) (number average molecular weight 650, manufactured by Mitsubishi Chemical Corporation) as a polyol were added and stirred while hydrogenated xylylene diisocyanate (Takenate). 600 (H6XDI) manufactured by Mitsui Chemicals, Inc. was added dropwise, reacted at 65 ° C. for 12 hours, and 5.55 parts of 4-hydroxybutyl acrylate (4-HBA) was added. By stirring for a time, a (urethane polymer-acrylic monomer) mixture was obtained.
Thereafter, as a photopolymerization initiator, 0.15 part of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (“Irgacure 819” manufactured by BASF Japan Ltd.), trimethylolpropane triacrylate ( 2- (4,6-bis (2,4-dimethylphenyl) -1-3,5-triazin-2-yl) -5-hydroxyphenyl and oxirane [(C _{10 to} C ₁₆ , mainly C _{12 to} C ₁₃ alkyloxy) methyloxirane] and an ultraviolet absorber (“TINUVIN 400” manufactured by BASF Japan Ltd.) comprising 1-methoxy-2-propanol. 1.25 parts, and bis (2,2,6,6-tetramethyl-1- (o 1.25 parts of a reaction product of tiloxy) -4-piperidinyl) ester, 1,1-dimethylethyl hydroperoxide and octane (“TINUVIN 123” manufactured by BASF Japan Ltd.) was added, and urethane polymer and acrylic A mixture of monomers (acrylic-urethane composite film composition) was obtained.

2. Preparation of fluorine coating treatment (Step 2)
To 100 parts of a 50% solution of fluoroethylene vinyl ether in xylene and toluene (“LF600” manufactured by Asahi Glass Co., Ltd.), 11.9 parts of an isocyanate crosslinking agent (manufactured by Nippon Polyurethane Co., Ltd.) Coronate HX "), 0.35 parts of dibutyltin laurate (" OL1 "manufactured by Tokyo Fine Chemical Co., Ltd.) as a catalyst, xylene diluent (solid content concentration 0.1%), 98 .2 parts of toluene and 11.0 parts of methyl ethyl ketone (MEK) were added to prepare a fluorine coating agent (solid content rate 28%).

3. Fabrication of base material (step 3)
The fluorine coating treatment agent obtained in Step 2 is applied onto a 75 μm-thick polyethylene terephthalate (PTE) film previously peel-treated as a temporary support, and dried and cured at a temperature of 140 ° C. for 3 minutes to provide temporary support. A 10 μm-thick fluoroethylene vinyl ether alternating copolymer layer was formed on the body. After the fluoroethylene vinyl ether alternating copolymer layer is cured, it is allowed to stand, and then on the fluoroethylene vinyl ether alternating copolymer layer between the 4th day (72 hours) and the 7th day (168 hours), The acrylic-urethane composite film composition produced in Step 1 was applied so that the thickness after curing was 290 μm, and a second PET film that had been previously peeled off was overlaid thereon as a separator. This second PET film surface is irradiated with ultraviolet rays using a metal halide lamp (illuminance 290 mW / cm ² , light amount 4,600 mJ / cm ² ) to advance photocuring of the acrylic-urethane composite film composition, On the temporary support, a fluoroethylene vinyl ether alternating copolymer layer and an acrylic-urethane composite film were formed in this order, and a laminate in which a second PET film (separator) was further laminated thereon was produced.

4). Production of protective film for blade (step 4)
The second PET film (separator) is peeled from the laminate produced in Step 3, and a double-sided pressure-sensitive adhesive tape (trade name: Hyper Joint H9008, manufactured by Nitto Denko Corporation, thickness) on the exposed acrylic-urethane composite film. : 800 μm) was attached, and then the temporary support on the fluoroethylene vinyl ether alternating copolymer layer was peeled off to prepare a protective film for blades. The used double-sided pressure-sensitive adhesive tape is a grade having excellent heat resistance and water resistance and high adhesive strength. The protective film for blades of Example 1 has a fluorine coating layer having a thickness of about 10 μm formed on one side of an acrylic-urethane composite film and a strong pressure-sensitive adhesive layer on the other side.

(Example 2)
A blade protective film having the following constitution was produced.
[Layer structure] Fluorine coat (surface treatment) / PET film (base material) / Hyper joint H9008 (adhesive layer)
<Manufacturing method>
The same fluorine coating treatment agent as in Example 1 was applied to one side of a PET film (trade name: X10S, manufactured by Toray Industries, Inc., thickness 188 μm), dried and cured at a temperature of 140 ° C. for 3 minutes, and a thickness of 10 μm. A fluoroethylene vinyl ether alternating copolymer layer was formed. Furthermore, the protective film for blades was produced by sticking the double-sided adhesive tape (Brand name: Hyperjoint H9008, Nitto Denko Co., Ltd. thickness: 800 micrometers) on the other surface of PET film.

(Example 3)
A blade protective film having the following constitution was produced.
[Layer structure] PTFE film (base material) / Hyper joint H9008 (adhesive layer)
<Manufacturing method>
Double-sided adhesive tape (trade name: Hyperjoint H9008, Nitto Denko) on one side of a polytetrafluoroethylene (tetrafluoroethylene, PTFE) film (thickness: 85 μm, trade name: NTF-1122, manufactured by Nitto Denko Corporation) A protective film for blades was produced by attaching a product manufactured by Co., Ltd., thickness: 800 μm.

Example 4
A blade protective film having a bubble-containing pressure-sensitive adhesive layer was produced.
[Layer structure] Fluorine coat (surface treatment) / acrylic-urethane composite film or sheet (base material) / bubble-containing pressure-sensitive adhesive layer

<Manufacturing method>
1. Preparation of bubble-containing pressure-sensitive adhesive composition Irgacure 651 (0.05) as a photopolymerization initiator was added to a monomer mixture in which 2-ethylhexyl acrylate (90 parts by weight) and acrylic acid (10 parts by weight) were mixed as monomer components. Parts by weight) and Irgacure 184 (0.05 parts by weight) were mixed and mixed. Irgacure is a trade name of BASF Japan.
Composition (syrup) partially polymerized by irradiating the mixture with ultraviolet rays (UV) until the viscosity of the mixture (BH viscometer, No. 5 rotor, 10 rpm, measurement temperature: 30 ° C.) reaches about 15 Pa · s. ) Was produced. Thereafter, as a surfactant, the trade name “Surflon S-393” (manufactured by AGC Seimi Chemical Co., Ltd .; perfluoroalkyl surfactant) is converted into a solid content, and all monomer components (2-ethylhexyl acrylate and acrylic acid) 0.7 weight part was added with respect to 100 weight part, and it mixed and produced the adhesive precursor. The pressure-sensitive adhesive precursor is put into a beaker, and while introducing nitrogen gas into the pressure-sensitive adhesive precursor by bubbling from the bottom, the bubbles are mixed into the bubble-containing pressure-sensitive adhesive precursor by a homomixer so as to bite the bubbles. A bubble-containing pressure-sensitive adhesive composition was obtained.

2. Preparation of bubble-containing pressure-sensitive adhesive layer The thickness of the bubble-containing pressure-sensitive adhesive composition after drying and curing on the release-treated surface of a polyethylene terephthalate substrate (process separator) that has been subjected to a release treatment on one side After coating to 0.8 mm, a polyethylene terephthalate base material (separator for cover) that has been subjected to a release treatment on one side is bonded so that the release treatment surface comes into contact with the black light lamp. UV irradiation was carried out at 4.0 mW / cm ² for 10 minutes, and the bubble-containing pressure-sensitive adhesive was cured to produce a bubble-containing pressure-sensitive adhesive layer.

3. Attachment of the bubble-containing pressure-sensitive adhesive layer to the protective film From the bubble-containing pressure-sensitive adhesive layer obtained by producing the bubble-containing pressure-sensitive adhesive layer, the cover separator was peeled to expose the pressure-sensitive adhesive surface. On the other hand, the 2nd PET film (separator) was peeled from the laminated body produced at step 3 of Example 1, the acrylic-urethane composite film surface was exposed, and the bubble-containing adhesive layer was stuck. Finally, the temporary support on the fluoroethylene vinyl ether alternating copolymer layer was peeled off to produce a protective film for blades. The used double-sided pressure-sensitive adhesive tape is a grade having excellent heat resistance and water resistance and high adhesive strength. The protective film for blades of Example 4 is one in which a fluorine coating layer having a thickness of about 10 μm is formed on one surface of an acrylic-urethane composite film and a bubble-containing pressure-sensitive adhesive layer is formed on the other surface.

  As shown in Table 1, each of Examples 1 to 4 has good weather resistance and has a contamination prevention layer on the surface, so that the effect of preventing adhesion of dirt can be exhibited. When used as a protective film for a blade, it is effective in preventing the blade from being deteriorated.

  The blade protective film for wind power generators of the present invention can be used for exterior surfaces of vehicles (automobiles, trains, airplanes, etc.) that require weather resistance in addition to blade protection.

  This application claims the priority based on Japanese Patent Application No. 2009-184134 for which it applied on August 7, 2009, The whole of this application is integrated in this specification by reference.

Claims (11)

  A protective film for blades, which has a base material and an adhesive layer on one side of the base material, and is used by being attached to the blade surface of a wind turbine generator.   The blade protective film according to claim 1, wherein the substrate is a weather resistant film.   The blade according to claim 2, wherein the weather resistant film is selected from the group consisting of a polyolefin film, a polyester film, a urethane polymer film, a composite film including an acrylic polymer and a urethane polymer, and a fluorine film. Protective film.   The protective film for blades according to any one of claims 1 to 3, wherein the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is an acrylic pressure-sensitive adhesive.   The said adhesive layer is a bubble containing adhesive layer, The protective film for blades of any one of Claims 1-4.   The blade protection method which affixes the protective film for blades of any one of Claims 1-5 on the blade surface of a wind power generator.   A blade for wind power generators whose surface is covered with a protective film.   The blade according to claim 7, wherein the protective film has a base material made of a weather resistant film and an adhesive layer formed on one surface of the base material.   The blade according to claim 8, wherein the pressure-sensitive adhesive layer is an acrylic pressure-sensitive adhesive.   The blade according to claim 8 or 9, wherein the pressure-sensitive adhesive layer is a bubble-containing pressure-sensitive adhesive layer.   A wind turbine generator having the blade according to any one of claims 7 to 10.