TW592953B - Improved protective films - Google Patents

Abstract

Multilayer protective films that adhere well to many different surfaces and can be removed without leaving residues are provided. The films consist of a polyolefin backing layer(s) and an adhering layer consisting of an ethylene unsaturated ester copolymer layer containing a resin. The films have good tensile strength and stiffness at minimum thickness and can be produced by blown film and cast processes, mono and co-extrusion. The films are particularly useful for protecting automobiles during transportation and storage, a masterbatch of the resin in an ethylene polymer or copolymer to facilitate co-extrusion of the multilayer films is also provided.

Description

592953 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (1) The present invention relates to protective films, and in particular, to the protection of smooth objects such as glass or other transparent material surfaces, electrical objects, and displays. Films, and are particularly used to protect automobiles, especially during transportation and storage. It is known that thermoplastic resin films can be applied to automobile bodies for protection during transportation from production to point of sale and during storage. In some examples, a rhenium coating is used. When a thermoplastic resin film is used, the film typically includes a multilayer film including an adhesive layer and a protective backing layer. The adhesive layer is to ensure that the film adheres to the article, such as on a car under transportation and storage conditions; the protective back layer protects the main body and makes the film easy to handle when applied to the surface. An additional requirement for the adhesive layer of the film is that it can be immediately removed from the surface without leaving a residue. The film must also have good strength and puncture resistance, and be as thin as possible. In addition, the materials that can be used to make the film must be able to use economical manufacturing techniques, such as blown and cast films, single- or co-extruded, and need sufficient melt strength. Increasingly, automobiles are made from a variety of materials. In addition, different final finishes, especially paints, use different materials. For example, cars can contain metal body panels, rubber sealants, and plastic components such as bumpers. The metal plate is typically coated with a solvent-based coating system and the plastic ingredients are coated with a water-based coating system. These materials differ from the adhesive properties of the surface on which they are applied. Accordingly, there is a need for a type of protective film that is sufficiently adherent to various surfaces without leaving unpleasant deposits on any surface after removal. (Please read the notes on the back before filling this page)

This paper size applies to Chinese National Standard (CNS) A4 specifications (210X297 meals) -4- 592953 A7 B7 V. Description of the invention (2) (Please read the precautions on the back before filling this page) The currently used protective film is used as The back layer of polyolefin (usually polyethylene or polypropylene) is composed of an adhesive layer consisting of polyethylene or an ethylene vinyl acetate copolymer containing polyisobutylene. When such a film has sufficient adhesion to the car, it cannot be removed from the car without leaving annoying deposits on the surface. A further need for a protective film is that it can be applied at room temperature and must be adhered to the surface simply by pressing the film against the surface to be protected. Thus, when the film is applied to a complicated three-dimensional space object such as a car, it will obviously need, for example, the film can be easily heated to achieve sufficient adhesion. Although this film contains an adhesive layer of polyisobutylene as an adhesion promoter and can be applied at room temperature, the film tends to leave residue on the surface of the car when it is removed. This is believed to be due to the migration of polyisobutylene in the polymer film. The Intellectual Property Bureau of the Ministry of Economic Affairs (industrial and consumer cooperatives has printed a type of layered film that can be used as a protective film, which has been proposed in PCT Publication WO 91/06609, French Patent Certificate 296008 14, European Patent 28 1 694 and European Patent 5929 1 3 It includes a polyolefin backing layer and an ethylene, unsaturated ester copolymer. In particular, an ethylene vinyl acetate copolymer layer is used as an adhesive layer. However, we have found that if the vinyl acetate content in the adhesive layer is sufficiently high and To provide the required adhesion, this film will be too weak, too much obstructed, cannot be extruded immediately and will be on a roll. In addition, such patented protective films need to be applied under heat to ensure adequate adhesion. Patented in Japan Bulletin 54-1 60482 proposes a laminated film consisting of a polyethylene base layer up to 18 // m thick and a vinyl copolymer layer having a thickness of at least 10 // m, which can be used to protect metal sheets such as The size of the aluminum sheet is in accordance with the Chinese National Standard (CNS) A4 specification (210X 297 mm) -5-592953 Printed by A7 __B7 of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 __B7 V. Description of the invention (3) Steel sheet. Petroleum resin can be added to the ethylene vinyl acetate copolymer adhesive layer, and one embodiment shows that the ethylene vinyl acetate copolymer layer contains 2 parts by weight of petroleum resin. The film is used to protect aluminum, and Based on 7 (TC for lamination. UK patent application 2774729 is about a type of protective film, especially for plastic sheet processing, which is subsequently molded, which includes a polyethylene base layer and an ethylene vinyl acetate copolymer adhesive layer A laminated film composed of which the adhesion layer may include an adhesion promoting resin. US Patent 5 1 5498 1 mainly relates to a stretched adhesion film, and relates to an adhesion layer containing an ethylene unsaturated ester copolymer (containing a tackifier). Multilayer film with polyolefin backing layer. The unsaturated ester is preferably methyl acrylate, although vinyl acetate can be used. When a hydrocarbon resin tackifier is used, its softening point should be 10 ° C to 25 ° C. Although US Patent 5 1 5498 1 states that its film can be used for surface protection purposes. The use of the low softening point hydrocarbon resin tackifier makes the film too soft to be processed immediately and is effective for surface protection. Japanese Patent Publication JP 0423908 1 is a type of protective film for chemically colored stainless steel. The film is a layered film, which can be composed of a polyolefin backing layer and an adhesive layer of a polyolefin or ethylene vinyl acetate copolymer. The ethylene vinyl acetate copolymer The layer may contain a hydrocarbon resin. In Example 3, it relates to a film containing 6% vinyl acetate in an ethylene vinyl acetate copolymer. The film is thick and must be applied by heating to obtain the desired adhesion None of these patented films have been successfully used commercially to protect the car during its transportation. Accordingly, there remains a need for a film that can be easily manufactured, preferably co-extruded by blown film or casting Shaped, can be used as a roll and taken out of the roll, it can be applied at room temperature and it can be used for all types (please read the precautions on the back before filling this page) This paper size applies Chinese National Standard (CMS) A4 specification (210X297 mm) -6-592953 A7 B7 V. Description of the invention (4) The surface is fully adhered. The film and the surface to which it is adhered must be able to withstand the storage and transportation conditions to which it may be subjected. The film must have sufficient strength, stiffness, and puncture resistance, and the film must be able to be removed from various types of surfaces without leaving annoying deposits on the protected surface. The present invention provides such a film. The invention further provides a protective film, which comprises a polyolefin back layer and a co-extruded ethylene polymer or copolymer adhesive layer, and the adhesive layer contains 2 to 40 wt%, preferably 2 to 30 wt%, more preferably 3 to 30 wt%, more preferably 4 to 20 wt% and most preferably 5 to 15 wt% of resins having a softening point above 40 ° C, preferably above 50 ° C, and more preferably Above 60 ° C, the Vicat softening point of this co-extruded ethylene polymer or copolymer is below 90 ° C. The total thickness of the multilayer film should be less than 60 // m, preferably less than 55 // m, more preferably less than 50 // m, more preferably less than 45 // m, and more preferably less than 40 // m, the better is less than 35 // the better is less than 30 // m, the better is less than 25 // m, and the better is less than 20 / zm, the tensile strength at break (after ASTM Measured by D 8 82) is greater than 15 MPa, preferably greater than 20 MPa, and more preferably greater than 25 MPa, and the modulus is greater than 120 MPa, preferably greater than 150 MPa, and if necessary greater than 170 MPa, the best is The range is 130 to 170 MPa. The present invention further provides a film used as a protective film for automobiles. The film includes a polyolefin back layer and a co-extruded ethylene polymer or copolymer adhesive layer. The adhesive layer contains 2 to 30 wt%, preferably 3 to 30% by weight. 20 wt%, more preferably 4 to 15 wt. Softening point higher than 4 (TC resin, better than 50 ° C, more preferably higher than 60 ° C. Hydrocarbon resin softening point) measurement system Applicable in accordance with the standard of this paper. China National Standard (CNS) Α4 specification (210X297 mm) LT ·-a batch of clothing-(Please read the precautions on the back before filling this page)

1T Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the 8th Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 592953 A7 B7 V. Description of the invention (5) Ring and ball softening point method, according to ASTM E-28 (Version 1 996) . When the film is used for automobile protection, the film should have a peel strength (measured via D 5458) of at least 150, preferably at least 300, for both water-based and solvent-based surface coatings. The best is at least 500, most preferably at least 600 cN per 25 mm. In this type of film, the choice of polymer for each layer and the nature of the resin can be changed according to the better film properties. The back layer of the multilayer film contains a polyolefin and provides an adhesive layer to the protective body. The adhesive layer is an ethylene polymer or copolymer containing a hydrocarbon resin therein, which can provide adhesion to the protected surface. The polymer or various polymers selected as the backing layer should provide sufficient melt strength so that the multilayer film can be made by blow co-extrusion, casting co-extrusion, or any other suitable method. The back layer is an ethylene or propylene polymer or copolymer and needs to have sufficient melt strength so that the layered film can be made by a blown film or cast film method. Among them, the ethylene or propylene polymer or copolymer of the layered film produced by blown film co-extrusion molding should have a melt index (which is measured by ASTM D 1 23 8) in the range of 0.1 to 10; preferably in the range of i to 7 Among them, the melting index of the film produced by casting and co-extrusion is preferably 2 to 12, more preferably 4 to 15 and most preferably 5 to 12. The backing layer should be low crystalline, and when it is a polymer of ethylene, it can be an ethylene homopolymer or a copolymer of ethylene and other alpha olefins, such as up to 30 wt% dagger to Ci ^ olefins. The back layer can also provide the main body of laminar film strength and puncture resistance, and it is therefore preferred that its density be 0.915 to 0.964 g / cm3. Ethylene polymers or copolymers prepared using a metallocene catalyst are preferred. This backing paper size is in accordance with Chinese National Standard (CNS) A4 (210X297). (Please read the precautions on the back before filling this page)

592953 A7 B7 V. Description of the invention (6) It can be a multilayer structure, and one layer of the multilayer structure is derived from an ethylene polymer or copolymer obtained from a catalysis of a metallocene. Polyolefin backing layers are preferably ethylene or propylene homopolymers or copolymers, and ethylene polymers or copolymers are more preferred because of their higher adhesion during co-extrusion. The density and melt index of the polyolefin, preferably the polyethylene backing layer, are chosen to provide the desired strength (tensile strength), stiffness (modulus) and puncture resistance. The necessary melt strength in extrusion and casting. It is desirable to use a film containing two or more backing layers, where one type of polyolefin is used to provide a layer with the desired properties (such as tensile strength and / or modulus), and another type of polyolefin is used to provide Another desirable property is melt strength. For example, a low-density polyethylene layer can be used to provide stiffness and melt strength, while a layer derived from a metallocene-catalyzed polymer can be used to provide enhanced tensile strength and puncture resistance at low thicknesses. The back layer may contain additives such as stabilizers, antioxidants, anti-embolic agents, and lubricant additives. Various films are used to protect various items, such as cars parked outdoors for a long time, and the back layer should contain stabilizers to protect from degradation by ultraviolet light, such as degradation that occurs under prolonged exposure to sunlight. Pigments can be added, and such films can be opaque, transparent, shiny, or dull. The film can be recessed by any known method. This back layer may also contain a resin such as petroleum hydrocarbon resin, polyterpene resin, or rosin ester to give film stiffness, wherein the presence of the resin should make it occupy 5 to 20% by weight, and the softening point is 80 ° C. To 160 ° C, preferably 85 ° C to 15 (TC 'better is 90 ° C to 140 ° C, more preferably 95 ° C to 140 ° C, the best paper size applies Chinese national standards (CNS) A4 specification (210X297 mm) (Please read the notes on the back before filling out this page) Binding and printing Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-9- 592953 A7 B7 V. Description of Invention (7) ( Please read the notes on the back before filling out this page) The floor temperature is 100 ° C to 140 ° C. Suitable resins will include those marketed by ExxonMobil Chemical® under the trade name " EMPR ·· (I_xxonM_bil Eplymer lesin). Examples of this EMPR-series resin are EMPR-100, 101, 102, 103, 104, 1 12, 113, 114, 124. Other resins may include hydrogenated and partially hydrogenated C9 resins, such as those produced by Arakawa Chemical Company. Arkon®P and M-series, Regalite®R and S-series from Eastman Chemical Company [j. Rosin esters from Arizona Chemical Company such as Sylvalite® series, terpene-based resins such as Sylvares® series, and other resins within the scope of this patent application. Intellectual Property Bureau, Ministry of Economic Affairs, Consumer Consumption Cooperative The preferred thickness for printing various layers depends on the processing ability of the polymer and the desired properties. Typically, the thickness of the adhesive layer is 5 to 30 // m, preferably 10 to 25 // m, and more preferably Between 10 and 20 // m, and the thickness of the backing layer between 10 and 50 / zm, preferably between 15 and 40 // m, and more preferably between 20 and 40 // m, and The overall thickness of the protective film is not more than 60 // m, preferably not more than 50 // m, more preferably not more than 40 / zm, and not less than 25 / zm. A preferred film system consists of a three-layer film It consists of an adhesive layer with a thickness of at least 10 // m, preferably 10 // m to 20 // m, and the thickness of both the middle layer and the back layer is between 15 and 30 // m. It is co-extruded with the protective backing layer through casting or blown film technology. 0 is also preferred. The melting point of the adhesive layer (which is measured according to ASTM D 3418) is lower than 100 ° C, and is preferably In a 60 ° C to l〇〇 ° C., Preferably within 70 ° C and 95 ° C, more preferably by at 70 ° C and 90 ° C. The best is to apply the Chinese National Standard (CNS) A4 specification (210X297 mm) at the paper size. &Quot; -10- 592953 A7 B7 V. Description of the invention (8) The combination of the disclosed melting point and Vicat softening point Ethylene polymers and copolymers (Please read the notes on the back before filling out this page) This adhesive layer may contain stabilizers, antioxidants, etc. to improve resistance to processing and / or environmental degradation. The film may contain conventional pigments and colorants such as titanium dioxide. Calcium carbonate can also be used. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This adhesive layer can be an ethylene homopolymer or copolymer. When it is a copolymer, it may be a copolymer of ethylene and another C3 to olefin. Alternatively, it may be a copolymer of ethylene and an unsaturated ester. Ethylene unsaturated esters are preferred, and we prefer an ester containing 10 to 40 wt%, more preferably 12 to 30 wt%, and more preferably 15 to 20 wt% unsaturated esters. The optimal range for blown film operation is 10 wt% to 20 wt% unsaturated esters, and for cast film operations this can be extended to 10 wt% to 30% wt% unsaturated esters. We have also found that when the ethylene unsaturated ester copolymer contains 10 to 30 wt% of the ester and its melt index is between 0.1 and 15, preferably between 1 and 10 and more preferably between 1.5 and 3. It can be co-extruded with the back layer, but there is no nasty polymer melted inwardly in the melt of the casting method, or the melt strength is lost in the blown film method. The Vicat softening point of the adhesive layer (which is measured by ASTM D 1 525) is preferably below 90 ° C, preferably 40 ° C to 85 ° C, especially 6 (TC to 80 ° C. When used) Ethylene unsaturated ester copolymer, the unsaturated ester can be vinyl acetate, vinyl propionate, higher esters, C! -C8 acrylate, C ^ -Cs methyl acrylate, can be alone or combined together .The preferred ones are vinyl acetate and methyl acrylate, the latter can provide thermal stability. The ester content should be 12 to 20 wt% and the melting index of unsaturated ester copolymers should not be greater than 25. This paper is applicable China National Standard (CNS) A4 Specification (210X 297mm) -11-Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 592953 A7 _____B7 V. Description of the Invention (9) The better is not more than 20, and the better is not more than 1 5. The production of ethylene unsaturated ester copolymers can be made by solution polymerization and / or high pressure free radical methods. The ester content is expressed as a wt% relationship to ethyl acetate. When esters of different molecular weights are used, they should be on a Moore basis. Adjust the weight range. Commercially available ethylene acetate can be used in the present invention Examples of ene ester copolymers include evatane EVA copolymer supplied by Atofina, Lotryl EMA, Lotryl EMA supplied by Atofina Greenlfex, EVA supplied by Polimeri Europe, Alcudia-PA supplied by Repsol, DuPont ( DuPont) Elvax EVA, Escorene Ultra supplied by ExxonMobil Chemical. Alternatively, the adhesive layer may be low density polyethylene ('LDPE'), which contains both low and medium density polyethylene with a density of 0.910 to 0.940 g / cm3. Low density polyethylene includes copolymers and terpolymers of ethylene. Various types of comonomers typically include olefins. The ethylene content will typically account for at least 80 wt% of polyethylene copolymers and terpolymers. Such polymers The typical preparation of copolymers and copolymers can be coordinated polymerization by metallocene catalysis according to methods well known in polymer technology. Low density polyethylene with a density of 0.9 40 g / cm3 and lower is particularly suitable for production Adhesive layer of the film of the present invention. Examples of commercially available low density polyethylenes that can be used in the present invention include Escorene LDPE from ExxonMobil Chemical, and Stamy from DSM lanLD, Polyethylene from Dow, LDPE from Borealis, Novex LDPE from BP, Riblene from Polimeri Euorpa, PE from Repsol Alcudia. This high-pressure polymerization can be performed in a conventional autoclave or tubular reactor. The paper size applies to the Chinese National Standard (CNS) A4 specification (2) 0X297 mm. (Please read the precautions on the back before filling this page)

-12- 592953 A7 B7 V. Description of the invention (10). Depending on the polymerization conditions, polymerization using a metallocene catalyst will impart a special polymer structure. Among them, special conditions are selected based on the needs of the product. A linear low-density polymer 'produced by a metallocene catalyst (m-LLDPE) can be used to form the back layer of the present invention. Typically, it is a copolymer of ethylene and at least one alpha olefin having at least four carbon atoms such as 1-butene, 1-hexene, 1.octene, and the like. Typically, the metallocene homopolymer or copolymer is made using a mono- or di-cyclopentadienyl transition metal catalyst, combined with an aluminum nf alkane activator and / or a non-coordinating anion. In solution, slurry, high pressure, or gas phase. This catalytic system may be supported or unsupported ' and the cyclopentadienyl ring may be substituted or unsubstituted. Titanium, rhenium, and dopants are the preferred transition metals. Several commercial products made using the catalyst / activator composition are commercially available from ExxonMobil Chemical Company under the trade names EXCEED® and EXACT®, or from Dow Chemical Company under the trade names ENGAGE® and AFFINITY® . The copolymer prepared by the above metallocene should have a polydispersity of less than 4, and the composition distribution width index (CDBI) is 50% or higher, preferably higher than 60%, and even more preferably higher than 70%. . In a specific embodiment, the CDBI is above 80%, even more preferably above 90%, and even more preferably above 95%. In a specific embodiment, the CDBI of the polyethylene copolymer is between 60 and 85%, and even more preferably between 65 and 85%. The Composition Distribution Width Index (CDBI) is a measurement of the composition distribution of monomers in a polymer chain, and its measurement procedures are described in PCT publication WO93 / 03093, published on February 18, 1993, including when measuring CDBI, its weight The average paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) Approval-(Please read the precautions on the back before filling out this page), 11 Printed by the 8th Industrial Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs- 13- 592953 A 7 B7 V. Description of the invention (11) The stratification with molecular weight (Mw) below 15,000 will be ignored. The m-LLDPE production method can be performed using a metallocene catalyst such as those described above and using a low-pressure single or multiple reactor. Possible methods are: gas phase (slurry and solution) or a combination thereof. The preferred m-LLDPE used in the present invention has a density higher than 0.915 g / cm3. The resin added to the adhesive layer of the ethylene polymer or copolymer should be compatible with the ethylene polymer or copolymer, so that only a small (if any) resin migrates to the surface layer of the produced adhesive layer, because it is in the film After removal, deposits will be left on the protected surface. This resin may be selected from aliphatic hydrocarbon resins, at least partially hydrogenated aliphatic hydrocarbon resins, aliphatic / aromatic hydrocarbon resins, at least partially hydrogenated aliphatic aromatic resins, cycloaliphatic hydrocarbon resins, at least partially hydrogenated Cycloaliphatic resins, cycloaliphatic / aromatic hydrocarbon resins, cycloaliphatic / aromatic hydrocarbon trees at least partially hydrogenated, aromatic hydrocarbon resins at least partially hydrogenated, natural resins such as terpene trees, Phenol, terpene phenol, rosin or rosin esters. The softening point of the resin should be higher than 40 ° C, preferably between 40 ° C and 130 ° C, more preferably between 60 ° C and 130 ° C, and more preferably between 80 ° C and Between 130 ° C and more preferably between 80 ° C and 12 ° C. We prefer to use hydrocarbon petroleum resins or rosin esters. We prefer to have some aromaticity in the resin, as this has been found to improve the unsaturation with ethylene Compatibility of ester copolymers. The preferred aromaticity is 5 to 40%, which is measured by 4 NMR. This resin can be hydrogenated by conventional methods to reduce reactivity, odor, color, and improve color stability. This resin can be partially hydrogenated or substantially the size of this paper applies Chinese National Standard (CNS) A4 specifications (210X297 mm) Approval-(Please read the precautions on the back before filling this page) Order the staff of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperatives -14-592953 Printed by the Consumer Cooperatives of the Intellectual Property Office of the Ministry of Economic Affairs A7 ____B7 V. Invention Description (12) Hydrogenated. If used here at least partially hydrogenated means that the material contains less than 90% Protonic protons, preferably those with less than 75% olefinic protons The better ones have less than 50% olefin protons, the better have less than 40% hydrocarbon storage protons, the better have less than 25% olefin protons, and the better have less than 15% olefin protons. Protons have less than 10% olefin protons, better have less than 9% olefin protons, better have less than 8% olefin protons, and more have less than 7 % Olefin protons, and the better ones have less than 6% olefin protons. For this user, substantially hydrogenation means that after hydrogenation, the material contains less than 5% olefin protons, and the better ones have Less than 4% olefin protons, more preferably less than 3% olefin protons, more preferably less than 2% olefin protons, more preferably less than 1% olefin protons, more preferably One has less than 0.5% olefin protons, more preferably has less than 0.1% olefin protons, and more preferably has less than 0.05% olefin protons. The degree of hydrogenation is typically performed to bond the aromatic bonds Minimize and better avoid the hydrogenation of aromatic bonds. The aromatic content of the resin species can be adjusted to suit the polarity of the ethylene unsaturated ester copolymer. Particularly preferred The lipids are those sold by ExxonMobil Chemical under the name " EMPR11 (XοnM_bil £ _〇lymer Kesin), especially EMPR 1 00 to 1 25. The choice of resin is based on maximum compatibility with the polymer, such as non-hydrogenated inclusion Aromatic cyclopentadiene-based resins (EMPR 1 1 4) can be used especially with ethylene vinyl acetate copolymers. Alternatively, other resins described herein such as rosin esters and terpenoid resins can be used. We have also found that the partially hydrogenated C9 petroleum resin series is particularly useful. It is particularly suitable (please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) -15- 592953 A7 B7 V. Description of the invention (13) Use of resins as described here includes EMFR-series resins (g_xxon win obil functional R_esins) such as EMFR-100 and 101, commercially available from ExxonMobil Chemical Company, hydrogenated and partially hydrogenated C9 trees Months such as Arkon®P and M-series from Arakawa Chemical Company are like ArkonTM M90, M100, M115 and M135, Regalite®R from Eastman Chemical Company and S-series 歹 [], EastotacTM resin, PiccotacTMC5 / C9 resin, and RegalrezTM aromatics, produced from Arizona Chemical Company's rosin esters such as Sylvalite® series, and terpene-based resins such as Sylvares® series, are commercially available SylvaresTM (R) modified styrene-alpha methylstyrene resin, styrenated terpene resin, Zonatac terpend-aromatic resin, and terpene phenol resin from Arizona Chemical Company. SylvatacTM & SylvaliteTM rosin esters, commercially available from Norsole n aliphatic aromatic resins in Cray Valley, France, DertopeneTM 15 ene resins commercially available from DRT Chemical Company, WingtackTM ET and EXTRA commercially available from Goodyear Chemical Company , ForalTM, PentalynTM, and? 61 * 1! 1 & 1: / 111 ^ Rosin and rosin esters are commercially available from QuintoneTM acid modified C5 resin, C5 / C9 resin, and acid modified C5 / C9 resin from Nippon Zeon, Japan, and are commercially available LXTM mixed aromatic / cycloaliphatic resins from Neville Chemical Company are commercially available C1 ear ο hydrogenated ifS pseudo aromatic resins from Yasuhara, and other resins within the scope of this patent application. The foregoing embodiments are illustrative only and should not be taken as limiting. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -----·-· Clothing-(Please read the precautions on the back before filling this page), 11 Intellectual Property of the Ministry of Economic Affairs Printed by Bureau 8 Industrial Cooperatives Co., Ltd. 16-592953 A7 ____B7_ 5. Description of the invention (14) The better one is that the resin can be added to the adhesive layer through the matrix mixture. The matrix mixture can be copolymerized with the ethylene polymer or its copolymer before co-extrusion. The materials are mixed to form an adhesive layer, which is generally mixed in the feed hopper of the extruder. The precursor mixture is composed of a resin and a polymer (generally an ethylene polymer or a copolymer thereof), and the precursor mixture is compatible with an ethylene polymer or copolymer used to make an adhesive film. The precursor mixture of the present invention typically has 20 to 70 wt% resin and 80 to 30 wt% polymer, preferably 20 to 60 wt% resin and 80 to 40 wt% polymer, and more preferably 30 to 60 wt%. % Resin with 70 to 40 wt% polymer. When the adhesive layer is made of an ethylenically unsaturated ester copolymer, it is preferable that the polymer in the matrix mixture is also an ethylenically unsaturated ester copolymer, preferably the same unsaturated ester. However, the ester content of the polymer used in the matrix mixture may be lower than the ester content of the polymer in the copolymer from which the adhesive layer is made, making it easier to handle the matrix mixture. Accordingly, in another specific embodiment, the present invention provides a matrix mixture comprising 20 to 70 wt% of a resin having a softening point higher than 40 ° C, and 80 to 30 wt% of a Vicat softening point lower than 90 ° C ethylene polymer or copolymer. The use of a matrix mixture results in better dispersion and compatibility of the polymer and resin in the final film. The resins and ethylene polymers and copolymers of this type that can be used to make the matrix mixture are those described herein regarding the adhesive layer in the protective film. It may be different from the polymer to be added to the matrix mixture. For example, this resin may be mixed with a polymer in a matrix mixture, and the matrix mixture may then be added to a different polymer. Parental blends are often recommended to ensure good mixing of all ingredients. This is because the paper size of resin and polymer is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) '~~ (Please read the precautions on the back before filling this page). * Tr Staff of Intellectual Property Bureau, Ministry of Economic Affairs Printed by Consumer Cooperatives 592953 A7 B7 Intellectual Property Bureau of the Ministry of Economic Affairs (printed by Industrial and Consumer Cooperatives V. Invention Description (15)) The molecular weight and viscosity of materials are very different, and direct blending usually results in poor mixing. The film of the invention can be a cast film or a film produced by blow co-extrusion. The latter is better. We have found that to co-extrude a film with the desired properties immediately, an ethylene unsaturated ester copolymer can be used. Especially ethylene vinyl acetate copolymer, its melt index is 0.1 to 20, containing 10 to 30 wt% vinyl acetate (for example, for blown film, preferably between 10 and 20 wt%) and Contains between 3 and 15 wt% resin, preferably between 5 and 10 wt% resin, with a low density polyethylene backing layer. We have found that this type of film can be applied to a variety of surfaces, including automotive coatings Metal-clad and bumper (fender ) Both surfaces, for example to provide protection during transportation, are applied to the surface at room temperature (~ 2CTC). This application can cause sufficient adhesion between the ethylene unsaturated ester copolymer layer and the surface, It is not possible to transport the vehicle at normal transport speeds, and at a speed of up to 130 km / hr, within the period that the vehicle is transported. We have also found that it can be transported from different surfaces of the vehicle via, for example, Peeling removes this film without damaging the final finish of the surface without leaving annoying deposits on the surface. The invention also covers protecting other surfaces. Consumer goods such as displays such as glass, plastic, liquid crystal displays, etc., white items , Acrylic surface, such as plastic glass (Plexiglass), or any object that needs to be protected against damage before use, such as scratch resistance, impact. However, the present invention is particularly used for surface protection during transportation. The present invention will be composed of the following Explanation of the examples. (Please read the notes on the back before filling out this page} This paper size applies to China National Standard (CNS) A4 210 X 297 mm) -18- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 592953 A7 B7 V. Description of the invention (16) The following polymers and hydrocarbon resins will be used in such examples. Polymers and Hydrocarbon Resin A ) Metallocene-catalyzed ethylene and octene copolymer plastics' with a density of 0.8 82, a melt index of 1 and a melting point of 66.6 ° C, and a Vicat softening point of 53.7 ° C, marketed by ExxonMobil Chemical's product name Exact 8201.

B) Ethylene vinyl acetate copolymer. It has a melt index of 3, contains 28 wt% vinyl acetate, and has a melting point of 70 ° C and a Vicat softening point of 43 ° C. It is marketed by ExxonMobil Chemical. Its product name is Escorene. Ultra FL 00328. C) Ethylene vinyl acetate copolymer with a melt index of 14, containing 18 wt% vinyl acetate, a melting point of 82 ° C, and a Vicat softening point of 52 ° C. It is marketed by ExxonMobil Chemical and its name is Escorene. Ultra FL 01418 D) Low-density polyethylene with a melt index of 0.7 and a density of 0.923, and a melting point of 11 (TC, with Vicat softening point of 96t, marketed by ExxonMobil Chemical, and its name is ExxonMobil LID 150 E). Its melt index is 0.75 and density is 0.9280. It is marketed by ExxonMobil Chemical and its name is ExxonMobil LID 170 F) hydrogenated cyclopentadiene resin. It is marketed by ExxonMobil Chemical and its name is EMPR 104 (softening point (SP ) 125t :, Tg 75 ° C, Μη 3 60 a mu) The paper size is applicable to Chinese National Standard (CNS) A4 (210X29? Mm) (Please read the precautions on the back before filling this page)

-19- 592953 A7 B7 V. Description of the invention (17) G) Hydrogenated cyclopentadiene resin, marketed by EuOnMobil Chemical, and its product name is EMPR 114 (SP 118t :, Tg 68 ° C, Mη 3 30 amu) H) Ethylene vinyl acetate copolymer, which contains 18 wt% vinyl acetate, has a melt index of 1.7, and a melting point of 85.5 ° C and a Vicat softening point of 62 ° C. Marketed by ExxonMobil Chemical. Its product name is Escorene Ultra FL 00218 I) Ethylene vinyl acetate copolymer containing 28 wt% ethyl acetate, with a melt index of 7 and a Vicat softening point of 41.5 ° C

ExxonMobil Chemical is marketed under the name Escorene Ultra FL 00728 J) Low density polyethylene with a melt index of 3 and a density of 0.9335 ′ is marketed by ExxonMobil Chemical under the name ExxonMobil LID 151

K) Linear low-density copolymers of ethylene and hexene, with a melt index of 2.5 and a density of 0.918, derived from the use of metallocene catalysis and marketed by ExxonMobil Chemical under the trade name of more than 2518 CB L) metallocene-catalyzed ethylene, Octene copolymer plastic, with a density of 0.882 and a melt index of 3, is marketed by ExxonMobil Chemical under the trade name Exact8203. M) A metallocene polymerized linear low-density polyethylene with a melt index of 1 and a density of 0.918. It is marketed by ExxonMobil Chemical and its name exceeds 1018 CA. Example 1 In order to show the adhesive properties of the film that can form the adhesive layer in the film of the present invention, the paper size is applicable to the Chinese national standard (0 milk) 8 4 specifications (210 fathers 297 males). Clothing-(Please read the back first (Notes to fill out this page)

Printed by the 1T Intellectual Property Bureau of the Ministry of Economic Affairs, the Industrial Cooperative Consumer Cooperative, -20- 592953 Printed by the Consumer Property Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, 5. Description of the Invention (18), from the formula shown in Table 1, the usual antioxidants are added, The single-layer film shown in Table 1 was made on the cast film extruder line of the Collin laboratory. This extrusion is between 150 ° C and 180 ° C, with a pressure of about 35 bar, using a die gap of 0.6 mm, and an output of 3.5 kg / hr. According to ASTM-D 5458, the adhesiveness or adhesion of the glue when applied to a steel plate coated with a solvent-based coating and a water-based coating is shown in Table 1. The adhesion or adhesion between the protective film and the coated surface, measured in cN, is the force required to separate the 25 mm film sample from the slope of the horizontal adhesion line. This line is located at 50% of the total distance. Table 1 Adhesion of film polymer modulator film thickness (β m) on solvent-based coated steel plate (cN / 25mm) Adhesion on water-based coated steel plate (cN / 25 mm) 1 Η 50 55-2 C 31 65 48 3 95% C + 5% F 33 120 75 4 90% C + 10% F 33 200 120 5 90% C + 10% G 32 180 180 Films 2 to 5 were tested during vehicle driving tests. Apply each film to the application area (hood / hood and top / front bumper / fender) for a perfect wash. Apply it by hand with a revolving roller and smooth it with a light brush. The hood temperature is about 23t and the bumper temperature is about 18 ° C. This test (Please read the notes on the back before filling this page)

This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -21 592953 A7 B7 V. Description of invention (19) Including driving 8 km at 40 to 70 km / hr, driving at 120 km / hr Steer 2.5 km, stop and repeat the steps in reverse order. Figure 1 shows the film performance on a coated metal automotive hood. As can be seen in Figure 1, Film 2 (without hydrocarbon resin) showed traces of peeling from the surface during the first half of the test, and severe peeling at the end of the test. Films 3 (5% hydrocarbon resin) and films 4 and 5 (10% hydrocarbon resin) showed no signs of peeling after complete testing. The film was easily removed and no deposition was observed on the coating surface. Similar results were also observed on the surface of the coated thermoplastic resin bumper, with Film 2 showing a peeling similar to that on the hood surface. Films 3 and 4 showed no peeling at all. Example 2 The compound of polymer VII and polymer I was prepared using 10% resin G. A compound of resin G and polymer A was also prepared for comparison. All compounds are stabilized with customary antioxidants. On the Collin extruder line, using polymer J and polymer K as backing layers, all such compounds were co-extruded into a cast film. The nature of the back layer and the adhesive layer is shown in Table 2. Each film was adhered to a steel coated with a water-based acrylic coating. Adhesion to metals coated with water-based acrylic coatings was 1% tangent modulus measured with ASTM D 882, tensile strength measured with ASTM 882, and elongation at break measured with ASTM D 882. Each film The obtained and results are shown in Table 2. This paper size applies to China National Standard (CNS) 8-4 specification (21〇χ297297) (Please read the precautions on the back before filling this page)

Printed by 1T Intellectual Property Bureau, Ministry of Economic Affairs, M Industrial Consumer Cooperative, -22- 592953 A7 B7 V. Description of the invention (2) Table 2 Total film thickness of film identification (/ m) Adhesive force (cN) 1% tangent modulus ( MPa) Tensile MD at break (MPa) MD at elongation at break (%) Back layer adhesive layer 6 26 / zm Poly 11 β m 90% 39 80 209 +/- 10 34.4 + / 352 +/- 33 Compound J Polymer H + -2.4 10% resin G 7 27 // m poly 12 / zm 90% 39 160 182 +/- 7 26.0 + / 358 +/- 37 compound J polymer A + -2.2 10% resin G 8 26 // m poly 14 β m90% 40 550 174 +/- 14 26.0 + / 337 +/- 31 Compound J Polymer I + 10% -1.8 Resin G 9 Intermediate layer: 14 // m90% 44 625 155 +/- 2 27.8+ / 451 +/- 28 19 // 111 polymer 0, polymer I + 10% -L6 back layer: resin G ll // m90% polymer K + 10% polymer J 10 26 // m poly 14 // m poly 40 200 182 +/- 7 30.4 + / 386 +/- 41 Compound J Compound I -2.3 MD = machine direction (please read the precautions on the back before filling this page) Employees ’Intellectual Property Bureau of the Ministry of Economy Co-operative printing thus adding the hydrocarbon resin according to the invention can improve this Smooth surface plastic viscosity or adhesion. Films 8 and 9 using polymer I containing 10% resin G as the adhesive layer showed the highest adhesion. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) -23- 592953 A7 B7 V. Description of the invention (21) Films 5, 7, 8 and 9 are tested on automobiles in field tests . (Please read the notes on the back before filling out this page) Apply each film to the hood of one car and the bumper of another car. The driving criteria are the same as in the first embodiment. The normal temperature was 18 ° C in each test. For any film containing hydrocarbon resin, no peeling marks were seen on the hood or bumper test. In addition, as observed by FIG. 3, no residue was seen on the car after the film was removed from the hood. The test on the hood is shown in Figure 2 and the test on the bumper is shown in Figure 4. The membranes were left on the bumper for further testing for 7 days, during which time the vehicle was applied to urban local roads at speeds between 50 and 100 km / hr. Films 5, 7 and 9 were removed without leaving a residue. This vehicle was then driven 800 km, with driving speeds of up to 130 km / hi * for several hours. The weather conditions are variable, including clouds, heavy rain and wind, and the temperature varies between 11 and 15 ° C. After being applied to the car, after travelling (or 10 days), the film 8 remained on the bumper and was removed without leaving a residue. Example 3 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs To evaluate the adhesion of potential adhesive layer films 2 to 5 and the adhesion of two pure plastic films, polymer A (film 11) and L were tested in a road test (Film 12 A. Road test conditions for the experiment: Each film is manually applied to the car body and bumper at 54 ° C. This paper size applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm)) -24- 592953 A7 _B7 V. Description of the invention (22) (Please read the precautions on the back before filling this page) At 5 0-7 0 km / hi: Drive the car for 10 minutes at 70- 120 km / hr Drive for 10 minutes. Then stop the car and record the result in the halfway bar. Then perform the reverse journey and record the final result. Test result: The car body starts halfway. Final conclusion film 2 Remove the part with satisfactory adhesion Unsatisfactory removal of film 3 Satisfactory adhesion Not removed Satisfactory film not removed 11 Satisfactory adhesion partial removal Total removal of unsatisfactory film 12 Satisfactory Removal of sticky parts The unsatisfactory bumper started halfway. The final conclusion. Film 2 Satisfactory adhesion. Partial removal. Satisfactory adhesion. 3 Satisfactory adhesion. Not removed. Satisfactory film. 4 Satisfactory adhesion has not been removed. Satisfactory film has not been removed. 11 Satisfactory adhesion has been removed. All unsatisfactory films have been removed. 12 Satisfactory adhesion has been removed. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics. B. Laboratory test is to simulate the adhesion of the film on the car and the bumper. A laboratory test is set up on the Zwick tensile test device. In this test, The film is pressed on two different steel plates, one of which is coated with a water-based coating and the other of which is a paper size that applies the Chinese National Standard (CNS) A4 (210X297 mm) -25- 592953 7 Β 5 2. Description of the invention (23) Coating with solvent-based coating (Please read the precautions on the back before filling this page) Follow ASTM D 545 8 to fix the board on a prying (wedge) at an angle of 45 degrees, and use 100 mm The film was peeled from the board at a speed of 1 / min. The adhesive force of the separation film was measured from the inclined surface of the horizontal adhesion line, in cN, at a distance of 50 cm from the board at a distance of 5 cm, and at a distance of 100% from the board (1 0cm). This film can be used to indicate film performance. The results are shown in Table 3. Compared to the control film without hydrocarbon resin, all the films containing hydrocarbon resin achieved higher adhesion. Resin G contained The film has the best adhesion. Table 3 Film solvent-based coating Water-based coating thickness 50% distance 100% distance 50% distance 100% distance cN) (cN) (cN) Force (cN) 2 31 65 105.3 +/- 14 48 66.4 +/- 4 3 33 120 180.0 +/- 33 75 146.3 +/- 28 4 33 200 285.6 +/- 63 120 194 +/- 16 5 32 180 323.8 +/- 63 180 287.2 +/- 48 Printed by Consumer Consumption Cooperative of Intellectual Property Bureau, Ministry of Economy Example 4

In order to evaluate both the adhesion and mechanical properties of the film of the present invention, the following β-molds were prepared using the following * items as the adhesive layer and then co-extruded from the casting: polymer Η plus antioxidant plus 10% resin G paper size Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -26- 592953 A7 _B7_ V. Description of the invention (24)

Polymer I plus antioxidant plus 10% resin G Polymer A plus antioxidant plus 10% resin G

Table 4 Film backing layer, middle layer, adhesive layer 13 8 // m 90% polymer K 10% polymer J 22 // m polymer J 14 // m 90% polymer Η 10% resin G 6 26 // m polymerization Polymer J ΙΙβΙΊΪ 90% polymerΗ 10% resin G 14 23 // m polymer J 18 / zm 90% polymerΗ 10% resin G 9 11 / zm 90% polymer K 10% polymer J 19 // m Polymer J 14 μm 90% polymer I 10% resin G 8 26 // 111 polymer 1 14 μm 90% polymer I 10% resin G 10 26 // m polymer J 14 / zm polymer I 15 27 // m polymer J 12 // m 90% polymer A 10% resin G 16 27 // m polymer J 12 // m polymer A (Please read the precautions on the back before filling this page). ·

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1T. The properties of such films were measured on a Zwick tensile test device, and the results are shown in Table 5. This paper size applies Chinese National Standard (CNS) A4 specification (210 × 29? Mm) -27- 592953 A7 _____B7 V. Description of invention (25) Table 5 Film thickness (#m) 1% tangent modulus in MD direction ( MPa) Tensile strength at break in the MD direction (MPa) Elongation at break in the MD direction 6 39 209 +/- 10 MPa 34.4 +/- 2.4 MPa 352 +/- 33% 8 40 174 +/- 14 MPa 26.0 +/- 1.8 MPa 337 +/- 31 9 43 155 +/- 2 MPa 27.8 +/- 1.6 MPa 451 +/- 28% 10 42 182 +/- 7 MPa 30.4 + Λ2.3 MPa Γ 386 + Λ41 11 40 182 +/- 7 MPa 26.0 +/- 2.2 MPa 358 +/- 37% Each film is adhered to water-based acrylic coated steel. Through peeling at a rate of 100 mm / min, the adhesion of various films on steel coated with a water-based acrylic coating was measured, and the results are shown in Table 6 as shown. Adhesion was measured immediately after application, after 24 hours of application, and for film 6 after 48 hours of application. (Please read the precautions on the back before filling this page)

， 1T Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives. The paper size is applicable. National Standard (CNS) A4 Specification (210X 297 mm) -28- 592953 A7 B7 V. Description of Invention (26) Table 6 Film Thickness ( β m) Adhesive force at 50% distance (cN) Adhesive force at full distance (cN) 8 —1 40 525 787 +/- 132 9 44 525 735 +/- 47 10 40 100 157 +/- 42 11 Call 39 140 219 +/- 26 16 39 80 102 +/- 7 after 24 hr 8 __ 40 550 778 +/- 160 9 _ 44 625 910 +/- 50 10 _ 40 200 240 +/- 13 11 _ 39 160 277.6 +/- 58 16 39 80 120 +/- 12 after 48 Hr 9 38 55 90.4 +/- 18 Reference: 5 32 340 455 +/- (Please read the notes on the back before filling this page) Wisdom of the Ministry of Economy Printed in Table 6 of the Consumer Affairs Cooperative of the Property Bureau, it is shown that the use of the adhesive layer modified by resin G can improve the adhesion and surpass the control film containing no hydrocarbon resin. Comparative Example 6 Two kinds of co-extruded films without resin were used as blown films to provide the following films: Film 17: Polymer A (12 // m) (as adhesive layer) / 90% polymer M with 10% content Polymer D (28 / zm) Membrane 18: Polymer B (12 // m) (as adhesive layer) / 90% polymer M with 10% of polymer D and polymer E (3 2 / zm) Various films were applied to automobiles and tested in field trials: using 40/5 0 km / hi ·, both films satisfactorily adhered to automobiles, but at 70 km / ln ·, both films They are blown off from the car, especially from the paper size of the bumper. The Chinese national standard (CNS) A4 specification (210X297 mm) is applied. -29- > 7 ^ 592953 A7 B7 5. The description of the invention (27). Brief description of the drawing Figure 1 shows the performance of the film on the car hood / hood surface painted on the car. 0 Figure 2 shows the performance of the film on the car hood / hood surface painted on the car. No residue was seen on the car. Figure 4 shows the performance of the film on the bumper / fender surface painted on the car (please read the precautions on the back before filling out this page). Industrial and consumer cooperatives print this paper and apply the Chinese National Standard (CN'S) A4 specification (210X29? Mm) -30-

Claims (1)

592953 A8 B8 C8 _____ D8 _ VI. Scope of patent application 1 1 · A multilayer protective film containing an adhesive layer and a co-extruded back layer, in which the back layer is polyolefin, the adhesive, and the adhesive layer contains 2 to 40 wt% softening An ethylene polymer or copolymer of a resin having a point higher than 40 ° C, wherein the adhesive layer is an ethylene polymer or copolymer having a Vicat softening point lower than 90 ° C. 2. The multilayer protective film according to item 1 of the patent application scope, wherein the adhesive layer contains 2 to 30 wt% of the resin. 3. If the multilayer protective film of item 1 or item 2 of the patent application scope, in which the Vicat softening point of the ethylene polymer or copolymer of the adhesive layer is 40t to 90 ° C. The multilayer protective film of item 2, wherein the adhesive layer is an ethylene polymer or copolymer having a melting point below 100 ° C. 5. The multilayer protective film as claimed in item 1 or item 2 of the patent application, wherein the adhesive layer is an ethylene polymer or copolymer having a melting point in the range of 651 to 100 ° C. 6. If the multi-layer protective film of the first or the second item of the patent application scope is a film made by blow-moulding and co-extrusion. 7 · If the multi-layer protective film of item 1 or 2 of the patent application scope is made by casting co-extrusion molding. 8. The multilayer protective film according to item 6 of the application, wherein the backing layer is derived from a polymer having a melt index of 0.1 to 10. _9. The multilayer protective film according to item 7 of the patent application, wherein the back layer is derived from a polymer having a melt index of 2 to 12. 1 〇 Such as the application of the scope of the first or second layer of the patent. Protective film, wherein the back layer is derived from the density of 0.915 to 0.964 ethylene polymer or co-paper size, using Chinese National Standard (CNS) A4 specifications (210X297 mm): '^-(Please read the notes on the back before filling out this page}, 1T. Line · Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 592953 ABCD Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. Polymers with a patent scope of 2. Apply for a multilayer protective film in the scope of item 1 or 2 of the patent scope, in which the back layer is a polymer produced by free-radical metallocene-catalyzed polymerization. 12 · If a patent is applied The multilayer protective film of the scope of item 1 or item 2, wherein the adhesive layer comprises an ethylene-CkGa olefin copolymer. 1 3 · If the multilayer protective film of the scope of the patent application item 1 or item 2, the adhesive layer is derived from ethylene Copolymers with unsaturated esters. 14. The multilayer protective film according to the scope of patent application No. 13, wherein the copolymer of ethylene and unsaturated esters is a copolymer of ethylene and vinyl acetate. Multilayer Protective film, in which the copolymer of ethylene and vinyl acetate contains 2 to 30% by weight of ethyl acetate. 16 If the multilayer protective film of the first or the second item of the patent application scope, the overall thickness is less than 60 / / m. 17. If the multilayer protective film of the first or second item of the patent application scope has a breaking tensile strength greater than 15 mPa. 1 8. If the multilayer protective film of the first or the second item of patent application scope, the The modulus is greater than 120 mPa. 1 9. If the multilayer protective film of item 1 or item 2 of the patent application range, wherein the thickness of the adhesive layer is 5 to 30 // m. 20. If the item of patent application range 1 or 2 item The multilayer protective film of item 'wherein the thickness of the back layer or each layer is 10 to 50 / zm. 2 1. The multilayer protective film of item 1 or item 2 of the scope of patent application', wherein the resin contains at least a partially hydrogenated aromatic compound Cyclopentane =-Resin This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm) (Please read the precautions on the back before filling out this page). Installation · 1T line -32- 592953 A8 B8 C8 D8 Sixth, the scope of patent application is 3 22 · —a kind of parent mixture, which contains 20 to 70 wt% of Chemical black accounts for resins still below 40 ° C, and 80 to 30% by weight of vinyl polymers or copolymers with a Vicat softening point below 90C. 23. For example, the parent mixture of the 22nd patent application, where the resin The softening point of the polymer is 80 ° C to 130 ° C. 24. If the parent mixture of the patent application No. 22 or 23, the Vicat softening point of the ethylene polymer or copolymer ranges from 50t: to 90. (: 〇25. If the parent mixture of the scope of patent application No. 22 or 23 'where the melting point of the ethylene polymer or copolymer is lower than 10 (TC. 26. If the parent mixture of the scope of patent application No. 25, where ethylene is polymerized The melting point of the polymer or copolymer is in the range of 65 ° C to 10 ° C. 27. The parent mixture of item 22 or 23 in the scope of the patent application, wherein the ethylene polymer or copolymer is a copolymer of ethylene and an unsaturated ester. 28. For example, the parent mixture of item 27 of the patent application, where the unsaturated ester is vinyl acetate. 29. The parent mixture of item 22 or 23 of the patent application, where the resin is an aromatic cyclopentadiene resin. 3 0 · If the parent mixture of the scope of patent application No. 22 or 23 ', where the resin is a C9 aromatic resin. 3 1 · If the base mixture of the scope of patent application No. 29, the resin is at least partially hydrogenated. 3 2 · If patent is applied The parent mixture of scope item 30, in which the resin is at least partially hydrogenated. This paper size applies to China National Standard (CNS) A4 (210X297 mm) _ (Please read the precautions on the back first (Fill in this page) • Binding · Printed by the Consumers 'Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 592953 Α8 Β8 C8 D8 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. Scope of patent application 4 3 3 The parent mixture of item 2 or 23 should be used for making protective film .. 34. — A method for making a multilayer film, which includes co-extruding a back layer and an adhesive layer, wherein the back layer contains a polyolefin and is adhered. The layer is an ethylene polymer comprising a copolymer of 2 to 40 wt% of a resin having a softening point higher than 40 ° C, wherein the adhesive layer is obtained by blending an ethylene polymer or copolymer with a resin under high shear conditions to form Concentrate containing 20 to 70 wt% resin, and then blending this concentrate with the ethylene polymer or copolymer of the adhesive layer, and co-extruding the resulting blend with the back layer to form a multilayer film 35. The method according to item 34 of the patent application, wherein the concentrate is blended with the ethylene polymer and copolymer so that the adhesive layer contains 2 to 30 wt% of the resin. Method 35 in which the adhesive layer The Vicat softening point of the ethylene polymer or copolymer is between 4 ° C and 90 ° C. 37. The method according to item 34 or 35 of the patent application, wherein the adhesive layer is an ethylene polymer having a melting point of less than 10 ° C Or a copolymer. 38. The method of claim 34 or 35, wherein the back layer is derived from a polymer having a melt index of 0.1 to 10. 39. The method of claim 34 or 35, The back layer is derived from an ethylene polymer or copolymer having a density of 0.915 to 0.9 64. 40. The method according to item 34 or 35 of the application, wherein the back layer is a polymer produced by catalytic polymerization of a metallocene. 41. The method of claim 34 or 35, wherein the adhesive layer comprises an ethylene-C3-C1 () a olefin copolymer. This Zhang's scale is applicable to China National Standard (CNS) A4 specifications (21〇 × 297ΑίΓ) -34- (Please read the precautions on the back before filling this page) Installation, 1T. Line 592953 A8 B8 C8 D8 ---- " ~ * -------- VI. Application for patent scope 5 42. If the method of patent application scope item 34 or 35, the back layer is derived from the copolymer of ethylene and unsaturated ester. 43. The method according to item 42 of the scope of patent application, wherein the copolymer of ethylene and an unsaturated ester is a copolymer of ethylene and vinyl acetate. 44. The method of claim 34 or 35, wherein the resin comprises at least a partially hydrogenated aromatic cyclopentadiene resin. 45. If the method of the scope of patent application No. 34 or 35, the intermediate layer is co-extruded between the adhesive layer and the back layer. (Please read the precautions on the back before filling out this page). Binding and Binding Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper size applies to China National Standard (CNS) A4 (210X297 mm)