JP2007084795A - Adhesive sheet for glass protection and protective film for automobile glass - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive sheet for glass protection which is excellent in weather resistance, adhesion reliability, transparency and impact resistance and a protective film for automobile glasses which uses such an adhesive sheet for glass protection. <P>SOLUTION: The adhesive sheet for glass protection comprises an adhesive layer composed of an adhesive composition and a supporting body having a polyethylene/polypropylene/polyethylene three-layer structure. The adhesive composition contains, as the base polymer, a (meth)acrylic polymer containing, as monomer units, (A) 40-99.9 wt.% 2-ethylhexyl (meth)acrylate, (B) 0.1-10 wt.% functional group-containing (meth)acrylic monomer (B), and (C) 0-59.9 wt.% vinyl monomer which is copolymerizable with the component (A) and/or the component (B). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to pressure-sensitive adhesive sheets, and more particularly to pressure-sensitive adhesive sheets used for surface protection of an adherend having a glass surface. Moreover, this invention relates to the protective film for motor vehicle glass using the said adhesive sheet.

  In recent years, surface protection sheets have been used in various fields such as wooden products, metal products, glass products, plastic products, mainly electrical / electronic materials and precision machinery, in order to prevent damage such as scratches during storage and distribution processes. ing. Also, in the storage and distribution process of exported automobiles, a surface protective film with an adhesive layer formed on a polyolefin resin film is used to protect scratches on the automobile body (metal parts, plastic parts, etc.). It has been.

  However, in outdoor applications such as summer, when the temperature of the roof reaches 80 ° C or higher, such as the above-mentioned applications for automobiles, it is necessary to store ultraviolet light for a long period of time in the outdoor environment. There is a problem that it becomes difficult to peel off the protective film adhered to the glass surface due to deterioration of strength and flexibility due to heat and heat, and a rise in adhesive strength over time.

  In addition, in order to use it for protecting the surface of automobile glass, it is necessary to move each automobile at any time with a protective film attached in the process of storage and distribution, so transparency that does not hinder driving is required. .

  In addition, especially for export cars, temporary vehicles are often stored outdoors for several months to half a year before the finished vehicle reaches the customer. During such storage periods or during transportation, strong winds, typhoons, etc. When encountering severe weather, it has been found that there is a problem that the glass surface is damaged, such as scratches and cracks, due to pebbles and sand. Generally, in the case of damage to a painted part of an automobile, it can be partially repaired by refinishing, etc., but in the case of scratches or cracks on the glass part of the automobile, even a part of it can be repaired. Since the entire surface needs to be replaced, it becomes a big problem in terms of work and cost. For this reason, in recent years, a protective material for protecting a glass surface at the time of shipment and storage of an automobile or the like is being demanded.

  As an attempt to improve these problems, materials for protecting the glass surface have been proposed. For example, a surface protective film using a pressure-sensitive adhesive made of a polyethylene-vinyl acetate copolymer on a support made of polypropylene is disclosed (for example, see Patent Document 1). However, in such a proposal, even after storage at about 80 ° C. in an actual usage environment, adhesive residue is generated after peeling, which is insufficient in weather resistance and impact resistance, and is particularly safe to store and protect outdoors. Application to automotive glass, which is often done, has proved to be inadequate.

On the other hand, as a method different from the surface protection sheet, a glass protection device that covers a part of a windshield of an automobile with a cover sheet is disclosed (for example, see Patent Document 2). However, in this proposal, since it is inferior in cost and workability and inferior in transparency, it is insufficiently applied to automobile glass that requires individual automobiles to be moved at any time during storage and distribution processes.
JP 2001-150608 A JP 2004-106820 A

  In light of such circumstances, the present invention is a glass protective pressure-sensitive adhesive sheet excellent in weather resistance, adhesion reliability, transparency, and impact resistance, and automotive glass protection using the glass protective pressure-sensitive adhesive sheet. The object is to provide a film.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the above object can be achieved by the following pressure-sensitive adhesive sheets, and have completed the present invention.

That is, the pressure-sensitive adhesive sheets of the present invention are for glass protection,
As monomer units, (A) 2-ethylhexyl (meth) acrylate 40 to 99.9% by weight, (B) functional group-containing (meth) acrylic monomer 0.1 to 10% by weight, and (C) the above (A ) And / or (B), a pressure-sensitive adhesive layer comprising a pressure-sensitive adhesive composition based on a (meth) acrylic polymer containing 0 to 59.9% by weight of a vinyl-based monomer, and polyethylene A support having a three-layer structure comprising layer / polypropylene layer / polyethylene layer;
It is characterized by having.

  According to the present invention, as shown in the results of Examples, a pressure-sensitive adhesive layer made of a pressure-sensitive adhesive composition using a (meth) acrylic polymer having the above-mentioned specific monomer unit composition as a base polymer is formed into a polyethylene layer / polypropylene. The pressure-sensitive adhesive sheets formed on a support having a three-layer structure consisting of a layer / polyethylene layer have excellent weather resistance, adhesion reliability, transparency, and impact resistance.

  Although the details of the reason why the pressure-sensitive adhesive layer exhibits such properties are not clear, the pressure-sensitive adhesive layer using the (meth) acrylic polymer having the specific monomer unit composition described above and the support having the specific structure described above are used. By combining, it is presumed that weather resistance, adhesion reliability, transparency, and impact resistance can be achieved in a balanced manner.

  In the present invention, as monomer units, (A) 2-ethylhexyl (meth) acrylate 40 to 99.9% by weight, (B) functional group-containing (meth) acrylic monomer 0.1 to 10% by weight, and ( C) A (meth) acrylic polymer containing 0 to 59.9% by weight of a vinyl monomer copolymerizable with the above (A) and / or (B) is used. By using such a (meth) acrylic polymer as the base polymer of the pressure-sensitive adhesive composition, pressure-sensitive adhesive sheets having excellent weather resistance and reliability of adhesion to glass are obtained.

  The (meth) acrylic polymer in the present invention refers to an acrylic polymer and / or a methacrylic polymer. Further, (meth) acrylate refers to acrylate and / or methacrylate, and (meth) acrylic acid alkyl ester refers to acrylic acid alkyl ester and / or methacrylic acid alkyl ester.

  In the pressure-sensitive adhesive sheet of the present invention, the pressure-sensitive adhesive composition preferably further contains 0.1 to 5.0 parts by weight of a weather resistance stabilizer with respect to 100 parts by weight of the (meth) acrylic polymer. By containing a predetermined amount of such a weather stabilizer, the weather resistance is more reliably improved.

  In addition, the weather resistance stabilizer in the present invention refers to an ultraviolet absorber, a light stabilizer, or an antioxidant, and these compounds may be used alone as a weather resistance stabilizer, or a mixture of two or more thereof. May be used.

  Moreover, in the adhesive sheet of this invention, it is preferable that the said (B) functional group containing (meth) acrylic-type monomer is a hydroxyl group containing (meth) acrylate.

  Furthermore, in this invention, it is preferable that the gel fraction of the said adhesive layer is 70 to 98 weight%.

  On the other hand, in the pressure-sensitive adhesive sheets of the present invention, the polypropylene layer of the support is a polypropylene homopolymer, or random copolymerization of 0.1 to 4 mol% of a monomer such as ethylene or butene to 96 to 99.9 mol% of polypropylene. It is preferable to contain 50 to 90% by weight of a random copolymer of polypropylene (random polypropylene). By using such a support, the weather resistance, adhesion reliability, transparency, and impact resistance are more balanced.

  Moreover, it is preferable that the thickness of the polypropylene layer of the said support body is 30-100 micrometers.

  Furthermore, in the pressure-sensitive adhesive sheets of the present invention, the scratch area ratio in the impact resistance test is preferably 0.20% or less, more preferably 0.16% or less, and 0.12% or less. Is more preferable. The pressure-sensitive adhesive sheets having the above values are particularly suitable for long-term storage outdoors and for glass protection applications through a distribution process.

In addition, the impact resistance test (impact resistance evaluation) in the present invention uses a sample in which a pressure-sensitive adhesive sheet prepared on a glass of a test piece is pasted, and a stepping stone testing machine (manufactured by Suga Test Instruments, JA) under the following test conditions. -400), and the flawed area ratio (%) per fixed area of each adherend after the test is calculated by the following formula and expressed numerically.
Scratch area rate (%) = [(total area of scratched part) / (total area)] × 100

  On the other hand, the automotive glass protective film of the present invention is characterized by using one or more of the above pressure-sensitive adhesive sheets. According to the protective film for automobile glass of the present invention, since the pressure-sensitive adhesive sheets having the above-described effects are used, it is excellent in weather resistance, adhesion reliability, transparency, and impact resistance for the surface protective film of automobile glass. It has a function.

  Hereinafter, embodiments of the present invention will be described in detail.

That is, the pressure-sensitive adhesive sheets of the present invention are for glass protection,
As monomer units, (A) 2-ethylhexyl (meth) acrylate 40 to 99.9% by weight, (B) functional group-containing (meth) acrylic monomer 0.1 to 10% by weight, and (C) the above (A ) And / or (B), a pressure-sensitive adhesive layer comprising a pressure-sensitive adhesive composition based on a (meth) acrylic polymer containing 0 to 59.9% by weight of a vinyl-based monomer, and polyethylene A support having a three-layer structure comprising layer / polypropylene layer / polyethylene layer;
It is characterized by having.

  The (meth) acrylic polymer used in the present invention includes, as monomer units, (A) 2-ethylhexyl (meth) acrylate 40 to 99.9% by weight, (B) a functional group-containing (meth) acrylic monomer 0. 1 to 10% by weight, and (C) 0 to 59.9% by weight of a vinyl monomer copolymerizable with the above (A) and / or (B) is used.

  As the component (A) in the present invention, 40 to 99.9% by weight of 2-ethylhexyl (meth) acrylate is used, more preferably 50 to 99% by weight, and 60 to 98% by weight. Is more preferable. In addition, if it is less than 40 weight%, the fall of the adhesive force with respect to a glass surface may be caused.

  As the component (B) in the present invention, a functional group-containing (meth) acrylic monomer is used. Such a functional group-containing (meth) acrylic monomer is mainly used for improving the adhesion to the substrate and improving the initial adhesion to the adherend.

  The functional group-containing (meth) acrylic monomer in the present invention refers to an acrylic monomer having a functional group such as one or more carboxyl groups, acid anhydride groups, and hydroxyl groups in the molecule. For example, a carboxyl group-containing monomer, Examples thereof include an acid anhydride group-containing monomer and a hydroxyl group-containing monomer. Of these, a hydroxyl group-containing monomer is preferably used.

  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. Of these, acrylic acid and methacrylic acid are particularly preferably used.

  Examples of the acid anhydride group-containing monomer include maleic anhydride and itaconic anhydride.

  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 mono Such as vinyl ether, and the like.

  In the present invention, the above-described functional group-containing (meth) acrylic monomer may be used alone or in combination of two or more, but the total content is (meth) acrylic. It is 0.01 to 10 weight% in the whole monomer of a system polymer, it is preferable that it is 0.01 to 7 weight%, and it is more preferable that it is 0.01 to 5 weight%. If it is less than 0.01% by weight, the adhesiveness to the substrate may be lowered. On the other hand, if it exceeds 10% by weight, the adhesive force may increase with time.

  As the component (C) in the present invention, a vinyl monomer copolymerizable with the above (A) and / or (B) is used. The vinyl monomer copolymerizable with the above (A) and / or (B) is mainly used as needed for the purpose of adjusting the initial adhesive force and the adhesive force with time, and further adjusting the cohesive force.

  As copolymerizable vinyl monomers, 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, and amide group-containing components Monomers, amino group-containing monomers, imide group-containing monomers, epoxy group-containing monomers, vinyl ether monomers and other components with functional groups that work as adhesion points and crosslinking points, and (meth) acrylic monomers with alkyl groups ( (Meth) acrylic acid alkyl ester), (meth) acrylic monomers having other alkyl groups ((meth) acrylic acid alkyl ester), and the like can be used as appropriate. These monomer compounds may be used alone or in admixture of two or more.

  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.

  Examples of the phosphoric acid group-containing monomer include 2-hydroxyethylacryloyl phosphate.

  Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.

  Examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, vinyl laurate, vinyl pyrrolidone, and the like.

  Examples of the aromatic vinyl monomer include styrene, chlorostyrene, chloromethylstyrene, α-methylstyrene, and benzyl (meth) acrylate.

  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 and the like Is given.

  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.

  Examples of the imide group-containing monomer include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, and itaconimide.

  Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate and allyl glycidyl ether.

  Examples of the vinyl ether monomer include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and the like.

  The (meth) acrylic acid alkyl ester is not particularly limited as long as it is a (meth) (meth) acrylate having an alkyl group having 2 to 14 carbon atoms, but preferably 3 to 13 carbon atoms. Are more preferred. The alkyl group having 5 or more carbon atoms may be either a straight chain or a branched chain, but is preferably a branched chain because of its low glass transition point.

  More specifically, for example, 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, 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, Decyl (meth) acrylate, n- dodecyl (meth) acrylate, isomyristyl (meth) acrylate, n- tridecyl (meth) acrylate, etc. n- tetradecyl (meth) acrylate. 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.

  Examples of other (meth) acrylic monomers having an alkyl group include silane-based monomers containing silicon atoms.

  In the present invention, copolymerizable vinyl monomers may be used alone or in admixture of two or more, but the total content is a single (meth) acrylic polymer. It is 0-59.9 weight% in the whole quantity body, It is preferable that it is 0-49.9 weight%, and it is more preferable that it is 0-39.9 weight%. If it exceeds 60% by weight, the initial adhesive force may be reduced.

  The (meth) acrylic polymer used in the present invention has a weight average molecular weight of 100,000 or more, preferably 250,000 or more, more preferably 400,000 or more. When the weight average molecular weight is smaller than 100,000, the durability is poor, and the adhesive force tends to be generated due to the reduced cohesive force of the pressure-sensitive adhesive layer. On the other hand, from the viewpoint of workability, the weight average molecular weight is preferably 1,000,000 or less. In addition, a weight average molecular weight is a polystyrene conversion value obtained by measuring by GPC (gel permeation chromatography).

  In addition, the glass transition temperature (Tg) of the (meth) acrylic polymer is desirably 0 ° C. or lower (usually −100 ° C. or higher), and preferably −10 ° C. or lower for the reason that the adhesive performance is easily balanced. When the glass transition temperature is higher than 0 ° C., the polymer is difficult to flow and the wetting of the adherend is insufficient, and there is a tendency to cause blisters generated between the adherend and the adhesive layer of the adhesive sheet. is there. 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 adopt 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 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).

  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.

  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 performed at about 60 to 80 ° C. for about 4 to 10 hours under an inert gas stream such as nitrogen.

  A polymerization initiator, a chain transfer agent, and the like used for radical polymerization are not particularly limited and can be appropriately selected and used.

  Examples of the polymerization initiator used in the present invention 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′-dimethyleneisobutylamidine) ), 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (manufactured by Wako Pure Chemical Industries, Ltd., VA-057), azo initiators, potassium persulfate, ammonium persulfate, etc. Persulfate, di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, -Sec-butylperoxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1 , 1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di (t -Hexylperoxy) peroxide initiators such as cyclohexane, t-butyl hydroperoxide, hydrogen peroxide, peroxides such as combinations of persulfate and sodium bisulfite, peroxides and sodium ascorbate And redox initiators combined with reducing agents. That, without being limited thereto.

  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 weight with respect to 100 parts by weight of the monomer. Is preferably about 0.02 to 0.5 parts by weight.

  In the present invention, 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.

  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.

  These chain transfer agents may be used alone or in combination of two or more, but the total content is 0.01 to 0. About 1 part by weight.

  The (meth) acrylic polymer of the present invention has the above-described configuration. The pressure-sensitive adhesive composition in the present invention is based on the above (meth) acrylic polymer.

  The pressure-sensitive adhesive composition of the present invention is more excellent in weather resistance, heat resistance, and the like by crosslinking the (meth) acrylic polymer using a crosslinking agent. 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. A compound, an epoxy compound, an oxazoline compound, a melamine resin, an aziridine derivative, a metal chelate compound, or the like is used. These compounds may be used alone or in combination.

  Among these, examples of the polyisocyanate compound include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, aliphatic isocyanates such as hexamethylene diisocyanate, and emulsion type isocyanates.

  More specifically, examples of the polyisocyanate compound include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate, Aromatic diisocyanates such as 4-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (trade name Coronate L, manufactured by Nippon Polyurethane Industry), trimethylol Propane / hexamethylene diisocyanate trimer adduct (made by Nippon Polyurethane Industry, trade name Coronate HL), hexamethylene diisocyanate Isocyanurate of (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 polyisocyanate compounds may be used alone or in admixture of two or more.

  Examples of the oxazoline compound include 2-oxazoline, 3-oxazoline, 4-oxazoline, 5-keto-3-oxazoline, and Epocros (manufactured by Nippon Shokubai Co., Ltd.). 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), polyglycidylamine compounds such as tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, diglycidylaniline, diglycidyl-o-toluidine, and the like. . These compounds may be used alone or in combination.

  Examples of the melamine resin include hexamethylol melamine and water-soluble melamine resin.

  Examples of the aziridine derivative include a commercial product name HDU (manufactured by Mutual Pharmaceutical Company), a product name TAZM (manufactured by Mutual Pharmaceutical Company), a product name TAZO (manufactured by Mutual Pharmaceutical Company), and the like. These compounds may be used alone or in combination.

  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.

  The amount of these crosslinking agents to be used is appropriately selected depending on the balance with the (meth) acrylic polymer to be crosslinked, and further depending on the intended use as the pressure-sensitive adhesive sheet. In order to obtain sufficient weather resistance and heat resistance due to the cohesive strength of the (meth) acrylic polymer, generally 1 to 10 parts by weight is contained with respect to 100 parts by weight of the (meth) acrylic polymer. It is more preferable that 2 to 8 parts by weight is contained. When the content is less than 1 part by weight, 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, causing adhesive residue. Tend. On the other hand, when the content exceeds 10 parts by weight, the initial adhesive strength of the pressure-sensitive adhesive layer is insufficient, the cohesive strength of the polymer is large, the fluidity is lowered, and the wetness to the adherend becomes insufficient. , Tend to cause peeling.

  Moreover, the pressure-sensitive adhesive sheets of the present invention are more weather resistant by further containing 0.1 to 5.0 parts by weight of a weather resistance stabilizer in the pressure-sensitive adhesive composition with respect to 100 parts by weight of the (meth) acrylic polymer. And excellent removability. The weather resistance stabilizer is preferably used in an amount of 0.1 to 3.0 parts by weight, more preferably 0.1 to 2.0 parts by weight.

  The weathering stabilizer in the present invention means an ultraviolet absorber, a light stabilizer, or an antioxidant, and these compounds may be used alone as a weathering stabilizer, or a mixture of two or more thereof. May be.

  As an ultraviolet absorber, well-known ultraviolet absorbers, such as a benzotriazole type ultraviolet absorber, a triazine type ultraviolet absorber, a benzophenone type ultraviolet absorber, can be used suitably, for example. These ultraviolet absorbers may be used alone or in combination of two or more.

  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.

  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.

  Furthermore, the pressure-sensitive adhesive composition of the present invention may contain other known additives, such as powders such as colorants and pigments, dyes, surfactants, plasticizers, tackifiers, 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.

  On the other hand, the pressure-sensitive adhesive layer of the present invention is composed of a pressure-sensitive adhesive composition having the above (meth) acrylic polymer as a base polymer. Moreover, the adhesive layer of this invention can also be formed from what formed by bridge | crosslinking the said adhesive composition. At this time, the crosslinking of the pressure-sensitive adhesive composition is generally performed after the application of the pressure-sensitive adhesive composition, but the pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition after crosslinking may be transferred to a support or the like. Is possible.

  The method for forming the pressure-sensitive adhesive layer on the support is not particularly limited. For example, the pressure-sensitive adhesive composition is applied to a release-treated separator, and the polymerization solvent is dried and formed to form the pressure-sensitive adhesive layer on the support. Or a method of applying the pressure-sensitive adhesive composition on a support and drying and removing the polymerization solvent to form a pressure-sensitive adhesive layer on the support. 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. Further, when the pressure-sensitive adhesive composition is coated on a support to produce a pressure-sensitive adhesive sheet, the composition contains at least one solvent (solvent) other than the polymerization solvent so that it can be uniformly coated on the support. May be newly added.

  Examples of the solvent used in the present invention include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, mesitylene, methanol, ethanol, n-propanol, isopropanol, water, and various types. Examples include aqueous solutions. These solvents may be used alone or in combination of two or more.

  Moreover, as a formation method of the adhesive layer of this invention, the well-known method used for manufacture of adhesive sheets 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. Is given.

  The surface of the pressure-sensitive adhesive layer may be subjected to surface treatment such as corona treatment, plasma treatment, or ultraviolet treatment.

  In this invention, it is preferable to adjust the addition amount of an isocyanate type crosslinking agent so that the gel fraction of the bridge | crosslinked adhesive layer may be 70 to 98 weight%, and it is added so that it may become 80 to 97 weight% It is more preferable to adjust the amount, and it is more preferable to adjust the addition amount so as to be 85 to 97% by weight. When the gel fraction is less than 70% by weight, the cohesive force is lowered, so that durability and curved surface adhesion may be inferior, and when it exceeds 98% by weight, adhesion may be inferior.

The gel fraction of the pressure-sensitive adhesive composition in the present invention means that after the dry weight W ₁ (g) of the pressure-sensitive adhesive layer is immersed in ethyl acetate, the insoluble content of the pressure-sensitive adhesive layer is taken out from the ethyl acetate and dried. The weight W ₂ (g) was measured, and the value calculated as (W ₂ / W ₁ ) × 100 was taken as the gel fraction (% by weight).

More specifically, for example, W ₁ (g) (about 100 mg) of a pressure-sensitive adhesive layer after crosslinking was collected on a tetrafluoroethylene resin film (manufactured by Nitto Denko, Nittofuron, NTF1122, pore size: 0.2 μm). Next, the sample was immersed in ethyl acetate at about 23 ° C. for 7 days, then, the sample was taken out and dried at 130 ° C. for 2 hours, and W ₂ (g) of the obtained adhesive layer was measured. By applying W ₁ and W ₂ to the above formula, the gel fraction (% by weight) was determined.

  In order to adjust to a predetermined gel fraction, it is necessary to fully consider the influence of the crosslinking treatment conditions (heat treatment temperature, heating time, etc.) as well as adjusting the addition amount of the isocyanate-based crosslinking agent.

  Moreover, this crosslinking process may be performed at the temperature at the time of the drying process of an adhesive layer, and you may carry out by providing a crosslinking process process separately after a drying process.

  In addition, in this invention, it produces so that the thickness after drying of the said adhesive layer may be 5-50 micrometers, Preferably it is about 10-30 micrometers.

  When the pressure-sensitive adhesive is exposed on such a surface, the pressure-sensitive adhesive layer may be protected with a release-treated sheet (release sheet, separator, release liner) until it is put to practical use.

  Examples of the constituent material 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, a plastic film 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. For example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, 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 5 to 200 μm, preferably about 5 to 100 μm.

  For the above separator, if necessary, mold release 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.

  In the above production method, the release-treated sheet (release sheet, separator, release liner) can be used as it is as a separator for pressure-sensitive adhesive sheets, and the process can be simplified.

  The pressure-sensitive adhesive layer of the present invention has the above-described configuration.

  The pressure-sensitive adhesive sheets of the present invention are formed by forming a pressure-sensitive adhesive layer having the above-described structure on one side or both sides of a support.

  In addition, in this invention, sheets mean a planar material and usually include what is called a tape and a film.

  As the support of the present invention, a resin layer having a three-layer structure consisting of polyethylene layer / polypropylene layer / polyethylene layer is used.

  For the support, a resin layer having a multilayer structure including at least a three-layer structure composed of a polyethylene layer / polypropylene layer / polyethylene layer can be used, and other layers may be provided between the layers and on the surface without impairing the effects of the present invention. May be included.

  Polypropylene is a material having excellent transparency and heat resistance and a certain level of impact resistance, but it is difficult to obtain sufficient adhesion to the pressure-sensitive adhesive layer. Therefore, in the present invention, the polyethylene layer is provided on the pressure-sensitive adhesive layer side as described above, and the outer layer on the surface side is also provided with a polyethylene layer in order to suppress the phenomenon such as curling. The present inventors have found that the pressure-sensitive adhesive sheets exhibit a good balance between weather resistance and adhesiveness.

  Considering outdoor use in particular, a polyethylene layer made of a polyethylene resin layer is used as the outermost layer from the viewpoint of weather resistance and impact resistance. Examples of polyethylene resin layers include ethylene polymers (low density, high density, linear low density, etc.), olefin polymers such as ethylene / α-olefin copolymers, ethylene / vinyl acetate copolymers, ethylene / methacrylic acid. Examples thereof include a resin layer composed of an olefin polymer of ethylene and another monomer such as a methyl copolymer, an ethylene / propylene copolymer, and an ethylene / propylene / α-olefin copolymer. Use of these polyethylene layers is preferable in terms of weather resistance, impact resistance, transparency, and adhesion to the outermost layer and other layers.

  The polyethylene unit content in the polyethylene layer is preferably 60% by weight or more, more preferably 70% by weight or more, and still more preferably 80% by weight or more. When the content of the polyethylene unit is less than 50% by weight, the anchoring force with the pressure-sensitive adhesive layer is reduced, and adhesive residue tends to occur when the adhesive strength is increased or when the adhesive strength increases with time. The outermost layer may be a resin stretched or non-stretched. These polyethylene resin layers may be used alone or in combination of two or more.

  The thickness of the polyethylene layer is generally 3 to 30 μm, particularly 5 to 20 μm, but is not limited thereto.

  A polypropylene resin layer is used as the polypropylene layer. Examples of the polypropylene resin layer include a propylene polymer (homopolymer, a random copolymer polymer in which ethylene other than propylene or another comonomer is randomly inserted in the molecular chain (hereinafter referred to as random polypropylene), and ethylene in the molecular chain. A block copolymer obtained by block copolymerization (hereinafter referred to as a block polypropylene), and a commercial block polypropylene is not limited to a pure block copolymer, but other than the block copolymer in a homopolymer matrix. By-products such as ethylene and ethylene / propylene rubber are often present as a mixture, but these are also known as block polypropylene), known as thermoplastic elastomer (TPE) and thermoplastic polyolefin resin (TPO). Have Impact copolymer (impact copolymer usually contains up to about 50% ethylene / propylene rubber in a homopolymer matrix. TPO and TPE have a higher rubber content than block polypropylene. A resin layer comprising an olefin polymer of propylene and another monomer such as an olefin polymer such as an ethylene / propylene copolymer, a propylene / α-olefin copolymer, and an ethylene / propylene / α-olefin copolymer. can give. Use of these polypropylene layers is preferable in terms of weather resistance, impact resistance, transparency, and adhesion to the outermost layer and other layers.

  The polypropylene unit content in the polypropylene layer is preferably 60% by weight or more, more preferably 70% by weight or more, and still more preferably 80% by weight or more. When the content of the polypropylene unit is less than 50% by weight, the heat resistance is inferior, and floating tends to occur during outdoor use. The polypropylene layer may be a resin stretched or non-stretched. These polypropylene resin layers may be used alone or in combination of two or more.

  The thickness of the polypropylene layer is generally 30 to 150 μm, particularly 30 to 100 μm, but is not limited thereto.

  Further, in order to improve the adhesion between the polyethylene layer and the polypropylene layer, a method of adding a modifier to the polypropylene layer, or a method of using a polypropylene resin layer containing a polyethylene unit for the polypropylene layer, etc. Can be used.

  Examples of the resin used for the polypropylene layer in order to improve the adhesiveness described above include amorphous soft polypropylene-based materials and polypropylene block copolymers (block polypropylene). A more specific example is tough selenium (manufactured by Sumitomo Chemical).

  Among them, the polypropylene layer preferably contains 0 to 50% by weight of amorphous soft polypropylene material, and more preferably 5 to 40% by weight. When the content of the amorphous soft polypropylene material is 50% by weight or more, the heat resistance may be inferior.

  Moreover, it is preferable that content of the polyethylene unit in the said polypropylene layer is 0 to 20 weight%. When the content of the polyethylene unit is 20% by weight or more, the polypropylene unit and the polyethylene unit are easily phase-separated, and transparency may not be obtained.

  The thickness of the resin layer (support) including the above-described three-layer structure is generally 40 to 170 μm, particularly 50 to 120 μm, but is not limited thereto.

  In addition, in order to improve adhesion with other resin layers, pressure-sensitive adhesive layers, undercoats, etc., the surface of the support (or each resin layer) is subjected to a surface treatment such as corona treatment, plasma treatment, or ultraviolet treatment. May be. Moreover, you may perform a back surface process to a support body (resin layer).

  In addition, from the viewpoint of weather resistance, the support (or each resin layer) can be appropriately treated with a weather stabilizer within a range that does not impair the transparency of the present invention.

  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.

  As an ultraviolet absorber, well-known ultraviolet absorbers, such as a benzotriazole type ultraviolet absorber, a triazine type ultraviolet absorber, a benzophenone type ultraviolet absorber, can be used suitably, for example. These ultraviolet absorbers may be used alone or in combination of two or more.

  The amount of the ultraviolet absorber added 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. .

  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. .

  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.

  Moreover, within the range which does not impair the effect of this invention, arbitrary additives, such as a flame retardant, an inert inorganic particle, an organic particle, a lubricant, and an antistatic agent, can also be mix | blended with the said support body (or each resin layer). .

  Moreover, when using especially for a surface protection film, it is preferable that it is a resin film which has a heat resistance and solvent resistance as a support body, and has a flexibility. When the support film (support) has flexibility, the pressure-sensitive adhesive composition can be applied by a roll coater or the like, and can be wound into a roll.

  In addition, the support (resin layer) may include a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, mold release with silica powder, and antifouling treatment or acid treatment, if necessary. Antistatic treatment such as alkali treatment, primer treatment, coating type, kneading type, and vapor deposition type can also be performed.

  Moreover, a surface coat layer, for example, a hard coat layer and a soft coat layer can be appropriately provided on the support (resin 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 more excellent in abrasion resistance, chemical resistance, a weather resistance, anti-fogging property, etc.

  Furthermore, in the pressure-sensitive adhesive sheets of the present invention, the scratch area ratio in the impact resistance test is preferably 0.20% or less, more preferably 0.16% or less, and 0.12% or less. Is more preferable. The pressure-sensitive adhesive sheets having the above values are particularly suitable for long-term storage outdoors and for glass protection applications through a distribution process.

In addition, the impact resistance test (impact resistance evaluation) in the present invention uses a sample in which a pressure-sensitive adhesive sheet prepared on a glass of a test piece is pasted, and a stepping stone testing machine (manufactured by Suga Test Instruments, JA) under the following test conditions. -400), and the flawed area ratio (%) per fixed area of each adherend after the test is calculated by the following formula and expressed numerically.
Scratch area rate (%) = [(total area of scratched part) / (total area)] × 100

  Moreover, the protective film for automobile glass of the present invention is characterized by using one or more of the above pressure-sensitive adhesive sheets. According to the protective film for automobile glass of the present invention, since the pressure-sensitive adhesive sheets having the above-described effects are used, it has a function excellent in weather resistance, adhesion reliability, transparency, and impact resistance. For this reason, it becomes a thing especially suitable for the surface protection film for motor vehicle glass protection which passes through the long-term storage in the outdoors etc. and a distribution process.

  In the present invention, the protective film for automobile glass means a film for protecting a glass surface of an automobile or the like indoors / outdoors, for example, a small automobile, a normal passenger car, a large automobile, a special vehicle, a heavy machine, or a motorcycle. It is used for the purpose of protecting the glass surface.

  By having the above-mentioned configuration, the present invention provides pressure-sensitive adhesive sheets excellent in weather resistance, adhesion reliability, transparency, and impact resistance for protecting the surface of glass. Furthermore, by using the above-mentioned pressure-sensitive adhesive sheets, a surface excellent in weather resistance, adhesion reliability, transparency, and impact resistance, particularly suitable for long-term storage outdoors and the like for protecting automobile glass through a distribution process It becomes a protective film.

  Hereinafter, examples and the like specifically showing the configuration and effects of the present invention will be described, but the present invention is not limited to these. In addition, the evaluation item in an Example etc. measured as follows.

<Measurement of molecular weight>
The weight average molecular weight was measured using a GPC apparatus (manufactured by Tosoh Corporation, HLC-8120GPC). The measurement conditions are as follows.
・ Eluent: THF
・ Flow rate: 0.5ml / min
・ Measurement temperature: 40 ℃
-Column: TSKgel GMH-H (S) (2)
・ Detector: Differential refractometer (RI)
The weight average molecular weight was determined in terms of polystyrene.

<Measurement of glass transition temperature (Tg)>
The glass transition temperature (Tg) (° C.) was determined by the following formula using the following literature values as the glass transition temperature Tgn (° C.) of the homopolymer of each monomer.
Formula: 1 / (Tg + 273) = Σ [Wn / (Tgn + 273)]
[Wherein, Tg (° C.) is the glass transition temperature of the copolymer, Wn (−) is the weight fraction of each monomer, Tgn (° C.) is the glass transition temperature of the homopolymer of each monomer, and n is the type of each monomer Represents. ]
Literature values:
2-ethylhexyl acrylate: -70 ° C
Hydroxyethyl acrylate: -15 ° C
-Ethyl acrylate: -22 ° C
・ Methyl methacrylate: 105 ℃

<Measurement of initial adhesive strength>
The prepared pressure-sensitive adhesive sheet (machine direction: 150 mm x 20 mm long) is attached to a slide glass (Matsuro Glass Industrial Co., Ltd., MICRO SLIDE GLASS). The sample (a) for evaluation was obtained by allowing it to stand for 30 minutes in the environment described above.

  Next, the adhesive force (when the pressure-sensitive adhesive sheet was peeled off with the universal tensile tester (manufactured by Shimadzu Corp., Autograph) at a tensile speed (crosshead speed) of 300 mm / min and a peeling angle of 180 ° was used for the evaluation sample (a). N / 20 mm). The measurement was performed in an environment of 23 ° C. × 50% RH.

<Measurement of high-speed peel adhesion>
The prepared pressure-sensitive adhesive sheet (150 mm × 20 mm) is attached to a slide glass (Matsuro Glass Industrial Co., Ltd., MICRO SLIDE GLASS) and pressure-bonded by a method of reciprocating a 2 kg roller, and is 30 in an environment of 23 ° C. × 50% RH. The sample for evaluation (b) was obtained by leaving it for a minute.

  Subsequently, the adhesive force (N / 20 mm) when the pressure-sensitive adhesive sheet was peeled off at a tensile speed of 30 m / min and a peeling angle of 180 ° was measured for the evaluation sample (b) with a high-speed peel tester (manufactured by Tester Sangyo). The measurement was performed in an environment of 23 ° C. × 50% RH.

<Evaluation of weather resistance>
The produced pressure-sensitive adhesive sheet (150 mm × 50 mm) is attached to a slide glass (Matsuro Glass Industrial Co., Ltd., MICRO SLIDE GLASS) and pressure-bonded by a method of reciprocating a 2 kg roller, and is 30 in an environment of 23 ° C. × 50% RH. The sample for evaluation (c) was obtained by leaving it for a minute.

The sample for evaluation (c) was treated with xenon weather (Ci4000 Xenon Weather Ometer manufactured by ATLAS) for 500 hours in accordance with ISO 4892-2. More specifically, a processing step of 120 minutes per cycle consisting of segment 1 (light irradiation 102 minutes, spray-off) and segment 2 (light irradiation 18 minutes, spray-on) was performed. In addition, in segment 1 and segment 2, irradiation illuminance: 0.50 W / m ² (at 340 nm), black panel temperature: 65 ° C., test bath temperature: 40 ° C., relative humidity: 50%, and rack spray-off conditions. . Then, it returned to room temperature (about 23 degreeC), and obtained the sample for evaluation (c ').

  Subsequently, the pressure-sensitive adhesive after the accelerated weathering test was performed when the pressure-sensitive adhesive sheet was peeled off from the evaluation sample (c ′) with a universal tensile testing machine (manufactured by Shimadzu Corp., Autograph) at a tensile speed of 300 mm / min and a peeling angle of 180 °. The force (N / 20 mm) was measured. The measurement was performed in an environment of 23 ° C. × 50% RH.

<Constant load test>
The prepared pressure-sensitive adhesive sheet (150 mm × 50 mm) is attached to a slide glass (Matsuro Glass Industrial Co., Ltd., MICRO SLIDE GLASS) and pressure-bonded by a method of reciprocating a 2 kg roller, and is 48 in an environment of 23 ° C. × 50% RH. The sample for evaluation (d) was obtained by leaving it for a period of time.

Next, the sample for evaluation (d) was put into a thermostat bath prepared at 80 ° C., aged for 30 minutes, then a 1 g load was applied to the end, and the adhesive sheet peeled off the glass surface after 15 minutes The state of was observed. The evaluation criteria are as follows.
・ If no adhesive residue has occurred: ○
・ If adhesive residue has occurred: ×

<Evaluation of transparency>
The visible light total light transmittance (%) (spectrophotometer, MPS-2000, manufactured by Shimadzu Corporation) of the produced adhesive sheet was measured and evaluated according to JIS K 7361-1. In the application of the present invention, the total light transmittance is preferably 50 or more, and more preferably 70 or more.

  Further, the haze value (%) (HAZEMETER HM150, manufactured by Murakami Color Research Laboratory) of the produced pressure-sensitive adhesive sheet was measured and evaluated according to JIS K7136. In addition, in the use of the present invention, the haze value is preferably 10 or less, and more preferably 5 or less.

<Evaluation of impact resistance>
The impact resistance was evaluated by preparing a sample with a pressure-sensitive adhesive sheet prepared on glass with a test piece size (tempered glass, manufactured by Fujiwara Kogyo Co., Ltd., thickness: 5 mm). A test was performed by JA-400), and the scratch area ratio (%) per fixed area of each adherend after the test was calculated by the following formula and evaluated.
Scratch area rate (%) = [(total area of scratched part) / (total area)] × 100
The test conditions were as follows.
・ Air pressure: 0.50 MPa (5 kgf / cm ² )
・ Blowing distance: 350mm
・ Stepping stone amount: about 200g / 10sec
-Stone size: 3-5mm in diameter
・ Test specimen dimensions: Width 90mm x Height 145mm
Test environment: 23 ° C x 50% RH

<Preparation of (meth) acrylic polymer>
[Acrylic polymer (A)]
In a reaction vessel equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a cooler, 100 parts by weight of 2-ethylhexyl acrylate, 4 parts by weight of hydroxyethyl acrylate, 2,2′-azobisisobutyronitrile as a polymerization initiator (Kishida Chemical Co., Ltd.) 0.2 parts by weight and ethyl acetate were charged, nitrogen gas was introduced while gently stirring, and the atmosphere was purged with nitrogen. Then, the temperature of the liquid in the flask was kept at around 60 ° C. for 10 hours. Acrylic polymer (A) solution (solid content 50% by weight) was prepared. The acrylic polymer (A) had a weight average molecular weight of 5.4 × 10 ⁵ and Tg = −68 ° C.

[Acrylic polymer (B)]
In a reaction vessel equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser, 2-ethylhexyl acrylate 50 parts by weight, ethyl acrylate 50 parts by weight, methyl methacrylate 5 parts by weight, hydroxyethyl acrylate 4 parts by weight, a polymerization initiator As a dibenzoyl peroxide (manufactured by NOF Corporation, Niper BW) 0.2 parts by weight and toluene, nitrogen gas was introduced with gentle stirring, and the atmosphere was replaced with nitrogen. The polymerization reaction was carried out for 10 hours, and an acrylic polymer (B) solution (solid content 50% by weight) was prepared. The acrylic polymer (B) had a weight average molecular weight of 4.7 × 10 ⁵ and Tg = −43 ° C.

[Example 1]
(Preparation of adhesive solution)
2 parts by weight of aromatic polyisocyanate (manufactured by Nippon Polyurethane Industry, Coronate L) as a cross-linking agent and dioctyltin dilaurate (manufactured by Tokyo Fine Chemicals, ENBILIZER) as an additive for 100 parts by weight of the solid content of the acrylic polymer (A) solution. OL-1) 0.035 parts by weight, 0.2 parts by weight of TINUVIN XT850 (manufactured by Ciba Specialty Chemicals) as a light stabilizer, and 0.5 parts by weight of TINUVIN X234 (manufactured by Ciba Specialty Chemicals) as an ultraviolet absorber In addition, the mixture was uniformly mixed and stirred to prepare an acrylic pressure-sensitive adhesive solution (1).

(Preparation of adhesive sheet)
The acrylic pressure-sensitive adhesive solution (1) was prepared by using a polyethylene / polypropylene / polyethylene three-layer film (polyethylene layer: LDPE (low density polyethylene), Novakch LF580 (manufactured by Nippon Polyethylene), polypropylene layer: Excelen EPX (manufactured by Sumitomo Chemical Co., Ltd., KS37F3). 80 parts by weight, 20 parts by weight of tough selenium (manufactured by Sumitomo Chemical Co., Ltd., T3712), 0.2 parts by weight of weathering agent (manufactured by Ciba Specialty Chemicals, TINUVIN 622LD), 0.2 part by weight of CHIMASSORB 2020FDL (manufactured by Ciba Specialty Chemicals) IRGANOX HP2225 (manufactured by Ciba Specialty Chemicals) 0.2 parts by weight, thickness: polyethylene layer / polypropylene layer / polyethylene layer = 10 μm / 80 μm / 10 μm, total thickness: 100 μm) It was coated on the corona-treated surface of the lens layer, and heated at 80 ° C. 3 min, the thickness after drying to form a pressure-sensitive adhesive layer of 20 [mu] m.

  Subsequently, an LDPE (low density polyethylene) film (manufactured by Okura Kogyo Co., Ltd., 100 μm) was bonded to the pressure-sensitive adhesive layer as a separator to prepare a pressure-sensitive adhesive sheet.

[Example 2]
(Preparation of adhesive solution)
3 parts by weight of aromatic polyisocyanate (manufactured by Nippon Polyurethane Industry, Coronate L) as a cross-linking agent and dioctyltin dilaurate (manufactured by Tokyo Fine Chemicals, ENBILIZER) as an additive for 100 parts by weight of the solid content of the acrylic polymer (A) solution. OL-1) 0.035 parts by weight and 0.2 parts by weight of TINUVIN XT850 (manufactured by Ciba Specialty Chemicals) as a light stabilizer were added and mixed and stirred uniformly to prepare an acrylic pressure-sensitive adhesive solution (2).

(Preparation of adhesive sheet)
The acrylic adhesive solution (2) is a polyethylene / polypropylene / polyethylene three-layer film (polyethylene layer: LDPE (low density polyethylene), Novakch LF580 (manufactured by Nippon Polyethylene), polypropylene layer: Excelen EPX (manufactured by Sumitomo Chemical Co., Ltd., KS37F3). 80 parts by weight, 20 parts by weight of tough selenium (manufactured by Sumitomo Chemical Co., Ltd., T3712), 0.2 parts by weight of weathering agent (manufactured by Ciba Specialty Chemicals, TINUVIN 622LD), 0.2 part by weight of CHIMASSORB 2020FDL (manufactured by Ciba Specialty Chemicals) IRGANOX HP2225 (manufactured by Ciba Specialty Chemicals) 0.2 parts by weight, thickness: polyethylene layer / polypropylene layer / polyethylene layer = 10 μm / 55 μm / 10 μm, total thickness: 75 μm) It was coated on the corona-treated surface of the emission layer, and heated at 80 ° C. 3 min, the thickness after drying to form a pressure-sensitive adhesive layer of 15 [mu] m.

  Subsequently, an LDPE (low density polyethylene) film (manufactured by Okura Kogyo Co., Ltd., 100 μm) was bonded to the pressure-sensitive adhesive layer as a separator to prepare a pressure-sensitive adhesive sheet.

Example 3
(Preparation of adhesive solution)
3 parts by weight of aromatic polyisocyanate (manufactured by Nippon Polyurethane Industry, Coronate L) as a cross-linking agent and dioctyltin dilaurate (manufactured by Tokyo Fine Chemicals, ENBILIZER) as an additive for 100 parts by weight of the solid content of the acrylic polymer (A) solution. OL-1) 0.05 part by weight and 0.25 part by weight of TINUVIN X234 (manufactured by Ciba Specialty Chemicals) as an ultraviolet absorber were added and mixed and stirred uniformly to prepare an acrylic pressure-sensitive adhesive solution (3).

(Preparation of adhesive sheet)
The acrylic pressure-sensitive adhesive solution (3) was prepared by using a polyethylene / polypropylene / polyethylene three-layer film (polyethylene layer: LDPE (low density polyethylene), Novakch LF580 (manufactured by Nippon Polyethylene), polypropylene layer: Excelen EPX (manufactured by Sumitomo Chemical Co., Ltd., KS37F3). 80 parts by weight, 20 parts by weight of tough selenium (manufactured by Sumitomo Chemical Co., Ltd., T3712), 0.2 parts by weight of weathering agent (manufactured by Ciba Specialty Chemicals, TINUVIN 622LD), 0.2 part by weight of CHIMASSORB 2020FDL (manufactured by Ciba Specialty Chemicals) IRGANOX HP2225 (manufactured by Ciba Specialty Chemicals) 0.2 parts by weight, thickness: polyethylene layer / polypropylene layer / polyethylene layer = 10 μm / 80 μm / 10 μm, total thickness: 100 μm) It was coated on the corona-treated surface of the lens layer, and heated at 80 ° C. 3 min, the thickness after drying to form a pressure-sensitive adhesive layer of 20 [mu] m.

  Subsequently, an LDPE (low density polyethylene) film (manufactured by Okura Kogyo Co., Ltd., 100 μm) was bonded to the pressure-sensitive adhesive layer as a separator to prepare a pressure-sensitive adhesive sheet.

Example 4
(Preparation of adhesive solution)
4 parts by weight of aromatic polyisocyanate (manufactured by Nippon Polyurethane Industry, Coronate L) as a cross-linking agent and dioctyltin dilaurate (manufactured by Tokyo Fine Chemicals, ENBILIZER) as an additive for 100 parts by weight of the solid content of the acrylic polymer (A) solution. OL-1) 0.035 parts by weight, and 0.1 parts by weight of TINUVIN XT850 (manufactured by Ciba Specialty Chemicals) as a light stabilizer were added and uniformly mixed and stirred to prepare an acrylic pressure-sensitive adhesive solution (4).

(Preparation of adhesive sheet)
The acrylic pressure-sensitive adhesive solution (4) was prepared by using a polyethylene / polypropylene / polyethylene three-layer film (polyethylene layer: LDPE (low density polyethylene), Novakch LF580 (manufactured by Nippon Polyethylene), polypropylene layer: Excelen EPX (manufactured by Sumitomo Chemical Co., Ltd., KS37F3). 80 parts by weight, 20 parts by weight of tough selenium (manufactured by Sumitomo Chemical Co., Ltd., T3712), 0.2 parts by weight of weathering agent (manufactured by Ciba Specialty Chemicals, TINUVIN 622LD), 0.2 part by weight of CHIMASSORB 2020FDL (manufactured by Ciba Specialty Chemicals) IRGANOX HP2225 (manufactured by Ciba Specialty Chemicals) 0.2 parts by weight, thickness: polyethylene layer / polypropylene layer / polyethylene layer = 10 μm / 30 μm / 10 μm, total thickness: 50 μm) It was coated on the corona-treated surface of the emission layer, and heated at 80 ° C. 3 min, the thickness after drying to form a pressure-sensitive adhesive layer of 20 [mu] m.

  Subsequently, an LDPE (low density polyethylene) film (manufactured by Okura Kogyo Co., Ltd., 100 μm) was bonded to the pressure-sensitive adhesive layer as a separator to prepare a pressure-sensitive adhesive sheet.

Example 5
(Preparation of adhesive solution)
2 parts by weight of aromatic polyisocyanate (manufactured by Nippon Polyurethane Industry, Coronate L) as a cross-linking agent and dioctyltin dilaurate (manufactured by Tokyo Fine Chemicals, ENBILIZER) as an additive for 100 parts by weight of the solid content of the acrylic polymer (B) solution. OL-1) 0.005 parts by weight, 0.2 parts by weight of TINUVIN XT850 (manufactured by Ciba Specialty Chemicals) as a light stabilizer, and 0.5 parts by weight of TINUVIN X234 (manufactured by Ciba Specialty Chemicals) as an ultraviolet absorber In addition, the mixture was uniformly mixed and stirred to prepare an acrylic pressure-sensitive adhesive solution (5).

(Preparation of adhesive sheet)
The acrylic pressure-sensitive adhesive solution (5) is obtained by using a polyethylene / polypropylene / polyethylene three-layer film (polyethylene layer: LDPE (low density polyethylene), Novakch LF580 (manufactured by Nippon Polyethylene), polypropylene layer: Excelen EPX (manufactured by Sumitomo Chemical Co., Ltd., KS37F3). 80 parts by weight, 20 parts by weight of tough selenium (manufactured by Sumitomo Chemical Co., Ltd., T3712), 0.2 parts by weight of weathering agent (manufactured by Ciba Specialty Chemicals, TINUVIN 622LD), 0.2 part by weight of CHIMASSORB 2020FDL (manufactured by Ciba Specialty Chemicals) IRGANOX HP2225 (manufactured by Ciba Specialty Chemicals) 0.2 parts by weight, thickness: polyethylene layer / polypropylene layer / polyethylene layer = 10 μm / 30 μm / 10 μm, total thickness: 50 μm) It was coated on the corona-treated surface of the emission layer, and heated at 80 ° C. 3 min, the thickness after drying to form a pressure-sensitive adhesive layer of 15 [mu] m.

  Subsequently, an LDPE (low density polyethylene) film (manufactured by Okura Kogyo Co., Ltd., 100 μm) was bonded to the pressure-sensitive adhesive layer as a separator to prepare a pressure-sensitive adhesive sheet.

Example 6
(Preparation of adhesive solution)
3 parts by weight of aromatic polyisocyanate (manufactured by Nippon Polyurethane Industry, Coronate L) as a cross-linking agent and dioctyltin dilaurate (manufactured by Tokyo Fine Chemicals, ENBILIZER) as an additive for 100 parts by weight of the solid content of the acrylic polymer (B) solution. OL-1) 0.020 part by weight, TINUVIN XT850 (manufactured by Ciba Specialty Chemicals) as a light stabilizer, 0.2 part by weight, TINUVIN X234 (manufactured by Ciba Specialty Chemicals) as an ultraviolet absorber, 0.25 part by weight In addition, the mixture was uniformly mixed and stirred to prepare an acrylic pressure-sensitive adhesive solution (6).

(Preparation of adhesive sheet)
The acrylic pressure-sensitive adhesive solution (6) is obtained by using a polyethylene / polypropylene / polyethylene three-layer film (polyethylene layer: LDPE (low density polyethylene), Novakch LF580 (manufactured by Nippon Polyethylene), polypropylene layer: Excelen EPX (manufactured by Sumitomo Chemical Co., Ltd., KS37F3). 80 parts by weight, 20 parts by weight of tough selenium (manufactured by Sumitomo Chemical Co., Ltd., T3712), 0.2 parts by weight of weathering agent (manufactured by Ciba Specialty Chemicals, TINUVIN 622LD), 0.2 part by weight of CHIMASSORB 2020FDL (manufactured by Ciba Specialty Chemicals) IRGANOX HP2225 (manufactured by Ciba Specialty Chemicals) 0.2 parts by weight, thickness: polyethylene layer / polypropylene layer / polyethylene layer = 10 μm / 30 μm / 10 μm, total thickness: 50 μm) It was coated on the corona-treated surface of the emission layer, and heated at 80 ° C. 3 min, the thickness after drying to form a pressure-sensitive adhesive layer of 20 [mu] m.

  Subsequently, an LDPE (low density polyethylene) film (manufactured by Okura Kogyo Co., Ltd., 100 μm) was bonded to the pressure-sensitive adhesive layer as a separator to prepare a pressure-sensitive adhesive sheet.

[Comparative Example 1]
(Preparation of adhesive solution)
As a pressure-sensitive adhesive sheet of Comparative Example 1, Glassguard tesa 50550 (manufactured by Beiersdorf Aktiengesellschaft), thickness: 60 μm, pressure-sensitive adhesive: polyethylene-vinyl acetate copolymer (vinyl acetate content: 40 to 80% by weight, 14 μm), support: polypropylene System resin, 46 μm) was used.

  In accordance with the above method, measurement of the adhesive strength of the prepared adhesive sheet (initial adhesive strength, high-speed peel adhesive strength), weather resistance evaluation (adhesive strength after weather resistance test, constant load test), transparency evaluation, and resistance The impact property was evaluated. The obtained results are shown in Table 1.

  From the results of Table 1 above, when the pressure-sensitive adhesive sheet prepared according to the present invention was used (Examples 1 to 6), in any of the examples, excellent transparency and adhesion to glass and removability were observed. It can be seen that (adhesion reliability) is excellent. Furthermore, in any of the examples, it can be seen that there is no significant change in adhesive strength after the weather resistance test, no adhesive residue, and excellent impact resistance.

  On the other hand, unlike the configuration of the present invention, when a polyethylene-vinyl acetate copolymer is used (Comparative Example 1), the impact resistance is not sufficient, and the durability after treatment for practical conditions for outdoor use. (Constant load test) also showed inadequate results. Therefore, it has been clarified that the pressure-sensitive adhesive sheet of the comparative example is not yet sufficient for protecting outdoor glass such as automobile glass that particularly requires weather resistance and impact resistance.

  From the above, it can be seen that the pressure-sensitive adhesive sheets of the present invention are excellent in weather resistance, adhesion reliability, transparency, and impact resistance for glass surface protection.

Claims (7)

As monomer units, (A) 2-ethylhexyl (meth) acrylate 40 to 99.9% by weight, (B) functional group-containing (meth) acrylic monomer 0.1 to 10% by weight, and (C) the above (A ) And / or (B), a pressure-sensitive adhesive layer comprising a pressure-sensitive adhesive composition based on a (meth) acrylic polymer containing 0 to 59.9% by weight of a vinyl-based monomer, and polyethylene A support having a three-layer structure comprising layer / polypropylene layer / polyethylene layer;
A pressure-sensitive adhesive sheet for protecting a glass, comprising:   The pressure-sensitive adhesive sheet for glass protection according to claim 1, further comprising 0.1 to 5.0 parts by weight of a weather resistance stabilizer in the pressure-sensitive adhesive composition with respect to 100 parts by weight of the (meth) acrylic polymer.   The pressure-sensitive adhesive sheet for glass protection according to claim 1 or 2, wherein the (B) functional group-containing (meth) acrylic monomer is a hydroxyl group-containing (meth) acrylate.   The pressure-sensitive adhesive sheet for glass protection according to any one of claims 1 to 3, wherein the polypropylene layer of the support contains 50 to 90% by weight of a polypropylene homopolymer or a polypropylene random copolymer.   The pressure-sensitive adhesive sheet for glass protection according to any one of claims 1 to 4, wherein the polypropylene layer of the support has a thickness of 30 to 100 µm.   The pressure-sensitive adhesive sheet for glass protection according to any one of claims 1 to 5, wherein a scratch area ratio in an impact resistance test is 0.20% or less. The protective film for motor vehicle glass which used 1 or more types of adhesive sheets for glass protection in any one of Claims 1-6.