KR19980702218A - Protective Polymeric Films for Metal Lamination - Google Patents

Abstract

The present invention provides a protective polymeric film that can be laminated to metal support 18 and provides protection against scratches, solvents and corrosion. The membrane is also used                 Aerosol valve installation When molding metal containers such as cups, can aids, bodies, bottoms, etc., they exhibit excellent compressibility and sealability. Protective Polymeric Membrane Shore D                 A scratch resistant layer 10, an adhesive layer 14, and a compressive layer 12 positioned between the scratch resistant layer and the adhesive layer with a hardness of 60 or more. In another embodiment                 The protective film includes a scratch resistant layer and an adjacent compressive adhesive layer. The film can be laminated by thermally activating the adhesive layer on the metal support.

Description

            Protective Polymeric Films for Metal Lamination         

The present invention is easily laminated to a metal support to protect it from scratches, solvents and corrosion, and when the laminate is used to form a metal container, excellent sealability and compressibility                 It relates to a protective polymerizable membrane to be shown.

Stacked on metal (e.g., tin-free steel, tin plate steel, and aluminum) to provide parts (e.g., aerosol valve installation cups, aerosol can aids or floors, paint cans,                 And protective polymeric films or coatings that can be molded into beverage containers, etc. are known in the art. Such membranes or coatings may be used to remove the underlying metal surface.                 Protects from corrosion and provides resistance to solvents and abrasion. For example, US Pat. No. 4,626,157 to Franek et al.                 With an upper can end member and a valve cup member molded from a metal stack comprising a polymerizable thin layer such as polyester or polypropylene placed on a support                 A method of making a metal container, such as an aerosol spray container, is described.

However, while these membranes provide resistance to corrosion, solvent and abrasion, due to the high modulus of the polypropylene membrane, metal / membrane laminates using polypropylene,                 It is not used to exhibit good sealing and compressibility in the manufacture of metal containers such as aerosol cans. In particular, this film is compression molded between two pieces of metal stacks.                 It does not form a good seal on the connection or seal. These poor seals can leak pressure propellants from the formed metal aerosol container from the metal stack.                 have.

It has also been found that polypropylene is difficult to adhere to various metal supports. Many industrial polypropylene membrane laminates in use today include urethane adhesives                 It is adhered using the same solvent-based adhesive. However, these adhesives are environmentally disadvantageous, leaving residual potential from the adhesive and gradually moving through the membrane stack.                 This is undesirable because it contaminates the contents of the metal container. In addition, inadequate curing of the adhesive may result in loss of adhesion of the film stack, in particular in the fabricated structure.                 Exposure to solvents may follow. As a result, polymer membranes have more recently been laminated to metal using thermoplastic adhesive resins. E.g,                 Heyes et al. US Pat. No. 4,980,210 discloses a metal sheet comprising an inner adhesive layer of an acid modified polyolefin resin and an outer layer of polyolefin.                 A two layered membrane bonded to the surface is described.

In order to solve the sealing and compressibility problems associated with prior polypropylene adhesive membranes, US Pat. No. 5,006,383 to Achille et al.                 An adhesive layer comprising a blend of polypropylene and very low density polyethylene and a rubber and a polar comonomer modified α-olefin polymer resin is taught. But these                 While the membrane exhibits good compressibility and formability, the membrane cannot provide sufficient resistance to abrasion and scratches. For example, handling, bulk packaging, and aerosols                 During shipping of the valve mounting cup, this membrane stack may be damaged by cutting, wear or perforation as the metal cups vibrate or move with each other. Also,                 If the stamping die or assembly mechanism is not completely aligned, it may be damaged during partial die stamping or molding. The protective polymerizable membrane is damaged                 In this case, the corrosion resistance of the aerosol valve installation cup is also weakened.

Therefore, it can be easily laminated without using a solvent-based adhesive in the support therein, exhibits excellent sealing and compressibility, and is resistant to scratch resistance and solvents and corrosion.                 Resistant protective films are still needed in the art.

The present invention can be easily laminated to a metal support to this need, is resistant to scratches, solvents and corrosion and is used to mold metal containers.                 By providing a protective polymeric film that exhibits sealability and compressibility. The membrane can be prepared by conventional coextrusion techniques.

According to one aspect of the invention, the adhesive layer constituting 5 to 25% of the total film thickness, the scratch resistant layer and the adhesive layer constituting 5 to 40% of the total film thickness and                 A protective polymerizable membrane is provided comprising a compressive layer positioned between the scratch resistant layer and constituting 40 to 80% of the total film thickness. ASTM of Scratch Resistant Layer                 The D2240 Shore D hardness is preferably at least 60, and the Shore D hardness of the adhesive and compressible layer is less than the scratch resistant layer. In addition, the scratch resistant layer                 The ASTM D3363 pencil hardness is at least 3B, preferably at least B.

Preferably, the adhesive layer comprises an ethylenically unsaturated copolymer of vinyl acetate, ethyl acetate, ethyl methacrylate, methyl acrylic acid, acrylic acid or carbon monoxide;                 Homopolymers of ethylene or propylene; Copolymers of ethylene and propylene; Ionomers of ethylene and methacrylic acid or acrylic acid; Maleic anhydride modified polyethylene;                 Polyamides; Polyurethane; Or a group consisting of compatible blends thereof. The adhesive layer is preferably thermally activated to be laminated to the metal support                 Solvent free.

The scratch resistant layer is preferably selected from the group consisting of polypropylene, polyethylene, polyesters, polyamides and combinations thereof. Once the shield is metal                 When laminated to the support, a hard scratch resistant layer acts to protect the underlying metal from scratches and provide resistance to solvents and corrosion. Randomly scratch resistant                 The layer can be applied with a curable hard paint selected from urethane, epoxy, acrylic and silicone to increase scratch resistance.

The scratch resistant layer may contain inorganic fillers to further cure the layer and increase scratch resistance. Using chemicals or radiation-induced crosslinkers                 It is also possible to further increase the hardness and scratch tolerance of the scratch resistant layer.

The compressible layer is preferably a homopolymer of ethylene or propylene, a copolymer of ethylene and propylene, ethylene-propylene rubber, thermoplastic olefin elastomer resins,                 Styrene block copolymers, polyurethanes and combinations thereof. The compressible layer has a protective film laminated and used on a metal support to provide excellent sealing properties in the manufacture of metal containers.                 And soft polymeric membrane layers that provide compressibility. In a preferred embodiment of the present invention the compressive layer is formed by foaming with a chemical blowing agent                 Improve.

The protective polymerizable membrane of the present invention preferably has a thickness of 0.5 to 20.0 mils (0.013 to 0.51 mm). Protective Polymeris in Preferred Embodiments of the Invention                 The film is bonded to one or more major surfaces of the metal support to form a metal stack, wherein the film comprises the scratch resistant, adhesive and compressible layers described above.                 Suitable metal supports have a thickness of 5 to 100 mils (0.13 to 2.5 mm), preferably 5 to 15 mils (0.13 to 0.38 mm). protect                 The polymerizable film is preferably laminated by thermally activating the adhesive layer and bonding the adhesive layer to the metal stack. The membrane is subjected to 180 degree peel test according to ASTM D-903.                 Peel adhesion of at least 5.01 b / in (0.89 kg / cm) to metals upon application. Thus, the scratch resistant layer is exposed to the exposed exterior of the metal stack.                 It becomes a protective layer and a soft compressible layer remains between the adhesive layer and the scratch resistant layer. The protective film protects the underlying metal from scratches that expose the metal to solvents and corrosion.                 To protect the support.

In another aspect of the invention there is provided a protective polymerizable membrane comprising a scratch resistant layer and an adjacent layer having compressive and adhesive properties. The compressible adhesive layer has a total film thickness of 10                 And the scratch resistant layer comprises 10 to 90% of the total film thickness. The Shore D hardness of the scratch resistant layer is at least 60 and compressible                 The Shore D hardness of the adhesive layer is less than the scratch resistant layer. In addition, the ASTM D3363 pencil hardness of the scratch resistant layer is at least 3B, preferably B                 That's it.

The compressible adhesive layer is preferably ethylenically unsaturated of vinyl acetate, ethyl acetate, ethyl methacrylate, methyl acrylic acid, acrylic acid or carbon monoxide.                 Copolymers; Homopolymers of ethylene or propylene; Copolymers of ethylene and propylene; Ethylene and methacrylic acid or acrylic acid are ionomers; Graft anhydride                 Copolymers; Polyamides; Polyurethane; Or a group consisting of compatible blends thereof. Preferably the compressive adhesive layer is foamed.

The scratch resistant layer is preferably selected from the group consisting of polypropylene, polyethylene, polyester, polyamide or combinations thereof. Scratch resistant                 The layer may be applied or crosslinked with a curable paint, or include the organic filler to increase scratch resistance.

The protective polymeric film of the present invention can be laminated to metals such as tin free steel, tin plate steel and aluminum. In one embodiment of the invention the protective polymerizable membrane                 It can be laminated to tin plate steel to form an aerosol valve mounting cup. The protective film of the present invention helps aerosol cans, can bottoms, paint cans, metal trays, fans                 It may be machined into many other parts, including the like.

Thus, it is a feature of the present invention to provide a protective polymerizable membrane that can be laminated to a metal support. Other features of the present invention are directed to scratches, solvents and corrosion                 It is to provide a protective polymerizable membrane that provides resistance and exhibits excellent sealing and compressibility when used in the manufacture of metal containers. These features of the invention, other                 Features and advantages will be apparent from the following detailed description, the accompanying drawings, and the appended claims.

1 is a cross sectional view of a protective polymeric membrane of the present invention showing a scratch resistant layer, a compressible layer and an adhesive layer.

2 is a cross-sectional view of another embodiment of a protective film comprising a scratch resistant layer and a compressive adhesive layer.

3 is a variation of the embodiment shown in FIG. 1 in which a film is laminated to a metal support.

4 is a perspective view of an aerosol valve installation cup molded from the protective membrane of the present invention.

Protective polymerizable membranes and membrane / metal laminates of the present invention provide several properties not obtained by prior art protective membranes. The present invention has excellent compressibility and sealability                 Along with the soft membrane layer shown, a hard membrane layer is used that is resistant to nicks and abrasions that expose and corrode underlying metal surfaces. The membrane of the present invention is a solvent                 The glass adhesive film layer can be thermally activated to easily deposit on a metal support, and the resulting metal stack is a metal protected from scratches, solvents and corrosion.                 It can be molded into a container. The bond formed between the adhesive film layer and the metal support is strong and durable. Depending on the desired end use, the laminate of the present invention                 After 30 days of immersion in methylene chloride, it is possible to withstand two layers and peeling of the membrane from the metal support.

The protective polymerizable membrane of the present invention comprises a three-layer film comprising an adhesive layer, a compressive and scratch resistant layer or an adjacent layer having a compressive and adhesive property with a scratch resistant layer.                 It may comprise a two-layer film comprising.

1 shows one embodiment of the protective polymerizable membrane of the present invention. The film is provided between the scratch resistant layer 10, the adhesive layer 14, and the scratch resistant layer and the adhesive layer.                 Positioned compressible layer 12. Shore D durometer hardness of the scratch resistant layer is at least 60 as tested according to ASTM D2240. ASTM                 Pencil scratch resistance of grade 3B or higher according to D 3363 is also preferred. Suitable membranes for use as scratch resistant layers include polypropylene, polyethylene,                 Polyesters, polyamides and combinations thereof having the required hardness. Olefin resins such as polypropylene and polyethylene are preferred, but other suitable                 Resins include polyesters and polyamides or nylon resins. However, the scratch resistant layer is at least 80% to provide the desired scratch resistance.                 Preference is given to being made of polypropylene.

The scratch resistant layer 10 may be applied with urethane, epoxy, acrylic or silicone and a hard curable paint. Inorganic fillers or chemicals or radiation-induced                 Additives such as crosslinkers can be used to further increase the hardness and scratch resistance of the scratch resistant layer.

Compressible layer 12 may be produced from homopolymers of ethylene or propylene, copolymers of ethylene and propylene, ethylene-propylene or other olefin rubbers.                 Thermoplastic elastomers such as styrene block copolymers, polyurethanes or combinations of these resins are also suitable for use in the present invention. The compressible layer is preferably                 Foaming is accomplished using chemical blowing agents such as sodium bicarbonate-citric acid blend or azodicarbonamide. Foamed compressible layer is an improvement over conventional extruded solid layers                 Provides compressibility.

Suitable adhesive polymers useful as the adhesive layer 14 include vinyl acetate, ethyl acetate, ethyl methacrylate, methyl acrylic acid, acrylic acid and carbon monoxide.                 Ethylenically unsaturated copolymers, including but not limited to. Other examples are homopolymers of ethylene or propylene, copolymers of ethylene and propylene, ethylene                 And ionomers of methyl acrylic acid or acrylic acid, graft anhydride copolymers, polyamides, polyurethanes and compatible blends thereof. The adhesive layer is a compressible layer                 And easily adhered to the metal support.

Usually, the scratch resistant layer is 5 to 40% of the total film thickness, the compressible layer is 40 to 80% of the total film thickness, and the adhesive layer is 5 to 40% of the total film thickness.                 Constitutes 25%. More preferred structures for three-layer films include scratch resistant layers that constitute 20% of the total thickness, compressible layers that constitute 65% of the total thickness, and overall                 It is an adhesive layer constituting 15% of the thickness.

Another aspect of the invention is shown in FIG. 2, where the film comprises a compressive adhesive layer 16 and a scratch resistant layer 10. In this embodiment the compressive adhesive layer is                 Preferably, 75% of the total film thickness and the scratch resistant layer constitute 25% of the total film thickness.

The scratch resistant layer may comprise polypropylene, polyethylene, polyester, polyamide and combinations thereof, with polypropylene being most preferred. Compressibility                 Suitable resins for use as adhesive layers are ethylenically unsaturateds of vinyl acetate, ethyl acetate, ethyl methacrylate, methyl acrylic acid, acrylic acid and carbon monoxide.                 Copolymers, homopolymers of ethylene or propylene, copolymers of ethylene and propylene, ionomers of ethylene and methyl acrylic acid or acrylic acid, graft anhydride                 Copolymers, polyamides, polyurethanes and compatible blends thereof.

The protective polymerizable membrane of the present invention is preferably produced by co-extrusion in conventional mold membrane lines or tubular blown membrane lines. The layers are coextruded together and produced                 The protective film can be thermally laminated to a metal support using a hot roll laminator. The metal stack is shown in FIG. 3, where the adhesive layer 14 is attached to the metal support.                 Bonded with the scratch resistant layer to form an outer protective layer for the metal. Metal cans can be applied with the same or different protective films on one or both sides                 have.

The resulting metal stack is used to form a variety of components such as aerosol valve installation cups, aerosol can aids, aerosol can bottoms, paint cans, metal cans or trays, and the like.                 Can be prepared. 4 shows an aerosol valve installation cup 20 formed by stamping a metal stack formed from the protective film of the present invention. Compressibility                 The layer 12 allows the membrane to be easily compressed to make such a part, and when the aerosol valve installation cup is later crimped into the can body, such as a crimping operation.                 Provides excellent seal

It should also be appreciated that the protective film can be laminated on both sides of the metal support. For example, the film thickness is 5 to 5 on the inner surface of the aerosol valve installation cup.                 Form a sealing gasket of 10 mils (0.13-0.25 mm) and a scratch-resistant, corrosion-resistant coating on the outer surface of the cup from 1 to 2 mils (0.025-0.05 mm)                 Can be formed.

To make the invention easier to understand, reference is made to the following examples, which are intended to illustrate the invention and not to limit the scope thereof.

Three layer protective polymerizable membranes are prepared according to the invention in conventional mold membrane lines. The scratch resistant layer, which constitutes 25% of the total film thickness, consists of polypropylene homopolymer (Himont ProFaxTM PD-064). The compressible layer constitutes 60% of the total film thickness and consists of a blend of 50% polypropylene (Himont ProFaxTM PD-064) and 50% ultra low density polyethylene (Dow Chemical ATTANE ^R 4201). The adhesive layer constitutes 15% of the total film thickness and consists of a blend of 60% maleic anhydride modified linear low density polyethylene (Quantam Chemical Plexar ™ 360) and 40% maleic anhydride modified high density polyethylene (Quantam Chemical Plexar ™ 206). Each layer is extruded from a temperature of 400 to 410 ° F. (204 to 210 ° C.) to a die temperature of 410 ° F. (210 ° C.). The coextruded membrane is quenched and rolled onto a 100 ° F. (38 ° C.) mold roll. The resulting 8.0 mil (0.2 mm) thick film is thermally laminated with a 10.5 mil (0.27 mm) tin plate steel at 350 ° F. (177 ° C.) using a hot roll laminator. The membrane exhibits at least 10.0 lb / in (1.8 kg / cm) peel adhesion when subjected to 180 degree peel test using an Instron Tensile Tester (ASTM D-903). The resulting stack is successfully stamped onto a multi-position running die with an aerosol valve installation cup. The membrane maintains good adhesion to the molded installation cup.

Example 2

A three-layer 8.0 mil (0.2 mm) thick coextruded membrane is produced in a conventional mold membrane line. Outer scratch resistant layer, 25% of total membrane gauge                 Random copolymer (Himont Profax 7531). The compressible layer (60% of the membrane gauge) is made of polypropylene random copolymer (Himont Profax                 7531) a blend of 50% and very low density polyethylene (Dow Chemical ATTANE 4202). The adhesive layer (15% of the membrane gauge) is maleic acid                 Anhydrous Modified Linear Low Density Polyethylene (Quantam Chemical Plexcar 360) 60% and Maleic Anhydride Modified High Density                 40% blend of polyethylene (Quantam Chemical Plexar 206). Each layer at 400-410 ° F (204-210 ° C)                 At a die temperature of 410 ° F. (210 ° C.). The membrane is quenched on a 100 ° F. (38 ° C.) mold roll and rolled into a roll. 8.0mil (0.2mm) thick                 The film is thermally laminated using a hot roll laminator at 350 ° F. (177 ° C.) in 10.5 mil (0.27 mm) tin plate steel. The resulting stack is installed with an aerosol valve                 The cup is successfully stepped onto the multi-position running die.

Example 3

Another 8.0 mil (0.2 mm) three layer protective polymeric film was prepared as in Example 1. The scratch resistant layer, which constitutes 25% of the total film thickness, consists of polypropylene homopolymer (Himont ProFaxTM PD-064). The compressible layer, which constitutes 60% of the total film thickness, consists of an ultra low density metallocene catalyst ethylene copolymer (Dow AFFINITY ^R RL-1840). The adhesive layer, which constitutes 15% of the total film thickness, consists of 100% maleic anhydride modified linear low density polyethylene (Quantam Chemical Plexar ™ 360). Each layer is coextruded as described in Example 1, the resulting film is quenched and thermally laminated to 10.5 mil (0.27 mm) tin plate steel.

Example 4

A three layer protective polymeric film was prepared as in Example 1. The scratch resistant layer (25% of the total film thickness) consists of polypropylene homopolymer (Himont ProFaxTM PD-064). The compressible layer (60% of the total film thickness) is combined with a blend of 50% polypropylene (Himont ProFaxTM PD-191) and 50% ultra low density polyethylene (Dow Chemical ATTANE ^R 4201) sodium bicarbonate-citric acid based foam concentrate (Henley HydrocerolTM) CF-20) 2.5 phr. The endothermic blowing agent is activated during extrusion to produce an ultrafine, independent foam blowing agent compressed layer. The adhesive layer, which constitutes 15% of the total film thickness, consists of 100% maleic anhydride modified linear low density polyethylene (Quantam Chemical Plexar ™ 360). Each layer is extruded as described in Example 1, the resulting film is quenched and thermally laminated to 10.5 mil (0.27 mm) tin plate steel.

Example 5

As in Example 1, the scratch resistant layer (25% of the total film thickness), which is a polypropylene homopolymer (Himont ProFaxTM PD-064),                 65% polypropylene (Himont ProFaxTM PD-064) and ethylene-propylene rubber (Exxon Chemical VistalonTM 37089P)                 A three layer protective polymeric film is prepared comprising a compressive layer (60% of the total film thickness) of 35% of the blend. The adhesive layer is maleic anhydride modified linear low density                 100% polyethylene (Quantam Chemical Plexar ™ 360). Each layer was extruded as described in Example 1 and the resulting                 The film is quenched and thermally laminated to tinplate steel.

Example 6

Two-layer 8.0 mil (0.2 mm) thick polymer membranes are prepared in conventional mold membrane lines. The scratch resistant layer, which constitutes 80% of the total film thickness, consists of 50% polypropylene (ProFaxTM PD-064) and 50% ultra low density polyethylene blend (ATTANE ^R 4201). The adhesive layer, which constitutes 20% of the total film thickness, consists of a blend of 60% linear low density polyethylene (PlexarTM PD-064) and 40% high density polyethylene (PlexarTM 360). The resulting membrane is thermally laminated with tin plate steel and stamped into an aerosol valve mounting cup as described in Example 1.

Example 7

Polypropylene, polyethylene, Plexar adhesives and formulations, including those described in Examples 1-5, were prepared using hot plate presses.                 Heat-compress with 0.125 in (0.32 cm) flakes. Next, the polymer flakes were subjected to a durometer tester (Pacific Transducer Corp. Model).                 Test durometer hardness according to ASTM D2240 using 409 type D). The results are shown in Table 1.

Example 8

The scratch resistance of the flakes is measured in Example 7 using the pencil hardness test (ASTM D-3363). Leads ranging from 6H (hard) to 6B (soft)                 Hardness or hardness of the various polymer blends given in Example 7 using one set of Eberhard Faber Design Drawing 3800 pencils of hardness.                 Quantify scratch resistance. The results are shown in Table II.

As is evident, flakes containing polypropylene or blends of polypropylene and very low density polyethylenes exhibit the highest scratch resistance.

Example 9

Of relatively poor resistance to membrane laminates containing 100% polypropylene protective layer and 50% polypropylene and 50% ultra low density polyethylene.                 For comparison, the aerosol valve installation cups prepared from the laminates described in Examples 1 and 6, respectively, were subjected to vibration stirrer evaluation. Aerosol Valve Installation Cups for Each Sample                 Five are placed in a 9 oz empty glass bottle installed on a Lab-Line Instruments multiband stirrer. Five identical metal stack installation cups in each bottle                 Stir vigorously with an instrument setting of 10 (maximum) for 5 minutes. The cup is then removed and 10 times the form, scratch or abrasion damage of the nick on the side of the membrane stack.                 Inspect with a magnifying glass. The cup of Example 6 (50% polypropylene-50% ultra low density polyethylene top layer) shows an average of 22 surface damage nicks in the stack,                 The cup of Example 1 (100% polypropylene top layer) shows only nine surface damage nicks.

While specific representative aspects and detailed descriptions are shown to illustrate the invention, those skilled in the art will recognize the methods and apparatus described herein in the appended claims.                 It is apparent that various modifications can be made without departing from the scope of the present invention.

Claims (13)

a) scratch resistant layer tested according to ASTM D2240 having a Shore D durometer hardness of at least 60 and constituting 5-40% of the total protective film thickness; b) a homopolymer of ethylene or propylene, a copolymer of ethylene and propylene, an ethylene-propylene rubber, an elastomeric olefin resin adjacent to the scratch resistant layer,                 Compressible layers comprising 40% to 80% of the total protective film thickness, including styrene block copolymers, polyurethanes or combinations thereof; And c) ethylenically unsaturated copolymers of vinyl acetate, ethyl acetate, ethyl methacrylate, methyl acrylic acid, acrylic acid or carbon monoxide adjacent to the compressible layer,                 Homopolymers of ethylene or propylene, copolymers of ethylene and propylene, ionomers of ethylene and methacrylic acid or acrylic acid, maleic anhydride modified polyethylene,                 Make up 5 to 25% of the total protective film thickness, including polyamide, polyurethane, or compatible blends thereof, and peel 180 degrees according to ASTM D903                 An adhesive layer capable of exhibiting at least 5.01 b / in (0.89 kg / cm) of peel adhesion to the metal support upon testing, wherein the overall protective film thickness is 0.5                 To 20.0 mil (0.01 to 0.51 mm). The membrane of claim 1, wherein the scratch resistant layer comprises at least 80% polypropylene. The membrane of claim 1, wherein the compressible layer consists essentially of a blend of polypropylene and polyethylene. The membrane of claim 1 wherein the adhesive layer consists essentially of a blend of maleic anhydride modified polyethylene. An adhesive layer bonded to one or more major surfaces of the metal support and constituting 5-25% of the total film thickness, compressible of 40-80% of the total film thickness                 Layer, a protective polymeric film comprising a scratch resistant layer constituting 5-40% of the total film thickness, wherein the Shore D hardness of the scratch resistant layer is 60                 The metal laminate having the above-mentioned and having a Shore D hardness of the adhesive layer and the compressible layer less than the scratch resistant layer. The method of claim 6, wherein the adhesive layer is an ethylenically unsaturated copolymer of vinyl acetate, ethyl acetate, methyl methacrylate, methyl acrylic acid, acrylic acid or carbon monoxide,                 Homopolymers of ethylene or propylene, copolymers of ethylene and propylene, ionomers of ethylene and methacrylic acid or acrylic acid, maleic anhydride modified polyethylene,                 A metal laminate selected from the group consisting of polyamides, polyurethanes or compatible blends thereof. 7. The metal of claim 6 wherein the scratch resistant layer is selected from the group consisting of polypropylene, polyethylene, polyester, polyamides and combinations thereof                 Laminates. The method of claim 6, wherein the compressible layer is a homopolymer of ethylene or propylene, a copolymer of ethylene and propylene, ethylene-propylene rubber, olefin resin, styrene block                 Metallic laminates comprising copolymers, polyurethanes or combinations thereof. The metal laminate of claim 6, wherein the compressible layer is foamed. The metal laminate of claim 6, wherein the scratch resistant layer comprises a curable coating film selected from the group consisting of urethane, epoxy, acrylic, and silicone. 7. The metal stack of claim 6, wherein the scratch resistant layer comprises an inorganic filler. The metal laminate of claim 6, wherein the scratch resistant layer is crosslinked. An adhesive layer laminated on a metal and constituting 5 to 25% of the total film thickness, a compressive layer constituting 40 to 80% of the total film thickness, 5 to 5 of the total film thickness                 A scratch resistant layer comprising 40%, the Shore D hardness of the scratch resistant layer being at least 60 and the Shore D hardness of the adhesive and compressible layers being scratch resistant                 An aerosol valve installation cup molded from less than one layer of protective polymerizable membrane.