Impact resistant protective multilayer film

• US 6,444,311 B1
• Filed: 10/19/1999
• Issued: 09/03/2002
• Est. Priority Date: 10/19/1999
• Status: Expired due to Term

• Current Assignee: Saint-Gobain Performance Plastics Corporation (Compagnie De Saint-Gobain)
• Original Assignee: Saint-Gobain Performance Plastics Corporation (Compagnie De Saint-Gobain)
• Inventors: Zhou, Xixian, Friedman, Michael
• Primary Examiner(s): Thibodeau, Paul
• Assistant Examiner(s): ZACHARIA, RAMSEY E
• Application Number:
  US09/419,760
• Time in Patent Office: 1,050 Days
• Field of Search: 428/31, 428/195, 428/354, 428/355.AC, 428/421, 428/422, 428/520, 428/914, 428/523
• US Class Current: 428/354
• CPC Class Codes: B32B 2323/04 Polyethylene
• CPC Class Codes: B32B 2327/18 PTFE, i.e. polytetrafluoroethylene
• CPC Class Codes: B32B 2451/00 Decorative or ornamental articles wall paper B32B2607/02
• CPC Class Codes: B32B 27/08 of synthetic resin
• CPC Class Codes: B32B 27/304 comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
• CPC Class Codes: B32B 27/306 comprising vinyl acetate or vinyl alcohol (co)polymers
• CPC Class Codes: B32B 27/308 comprising acrylic (co)polymers
• CPC Class Codes: B32B 27/32 comprising polyolefins comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30
• CPC Class Codes: B32B 27/322 comprising halogenated polyolefins, e.g. PTFE
• CPC Class Codes: Y10S 428/914 Transfer or decalcomania
• CPC Class Codes: Y10T 428/2848 Three or more layers
• CPC Class Codes: Y10T 428/2891 including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof
• CPC Class Codes: Y10T 428/3154 Of fluorinated addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31544 Addition polymer is perhalogenated
• CPC Class Codes: Y10T 428/31928 Ester, halide or nitrile of addition polymer
• CPC Class Codes: Y10T 428/31938 Polymer of monoethylenically unsaturated hydrocarbon

Abstract

A clear multilayer film for coating synthetic environmental surfaces includes an exposed protective layer and an underlying cushioning layer. The exposed layer is primarily a polymer blend of a fluorine substituted olefin polymer, such as polyvinylidene fluoride, with an acrylic polymer. The cushioning layer is of a low modulus polymer selected from among impact modified acrylic polymer, ethylene vinyl acetate polymer and metallocene catalyzed polyethylene and having an elastic modulus below about 30,000 psi (207 MPa). The cushioning layer should be substantially free of all fluorinated polymers. The multilayer film can have an optional additional thermally adhesive layer of a blend of a fluorine substituted olefin polymer with an acrylic polymer. The multi layer film offers superior protection to such substrates as outdoor building siding, vehicle body panels, and signs from stains, weather conditions, and especially impact damage. Ally of the layers can also include fillers and additives adapted to provide a very low gloss appearance.

Claims

1. A multilayer film comprising

a protective layer of a blend comprising a fluorine substituted olefin polymer and an acrylic polymer,

a cushioning layer bonded to the protective layer and comprising an impact resistant polymer having an elastic modulus of less than 207 MPa and being free of any a fluoropolymer, and

a thermally adhesive layer in direct contact with the cushioning layer opposite the protective layer, and comprising a blend comprising a fluorine substituted olefin polymer and an acrylic polymer.

2. The multilayer film of claim 1 in which the thermally adhesive layer is free of adhesive primers.

3. The multilayer film of claim 1, in which the impact resistant polymer has an impact resistance of at least 30 J/m as measured by ASTM D-256.

4. The multilayer film of claim 3 in which all of the protective layer, the cushioning layer and the thermally adhesive layer have visible light transmission higher than 70% and haze less than 4%.

5. The multilayer film of claim 1 in which

the impact resistant polymer is a thermoplastic polymer selected from the group consisting of an impact-modified acrylic polymer, polytethylene vinyl acetate), metallocene catalyzed polyolefin, and a mixture of them,

the protective layer comprises about 45-95 parts by weight of a first fluorine substituted olefin polymer and about 5-55 parts by weight of a first acrylic polymer, and

the thermally adhesive layer comprises 5-55 parts by weight of a second fluorine substituted olefin polymer and 45-95 parts by weight of a second acrylic polymer,

in which the first and second fluorine substituted olefin polymers each is independently a fluorine substituted olefin polymer comprising a monomer selected from the group consisting of vinylidene fluoride, vinylfluoride, tetrafluoroethylene, hexafluoropropylene, trifluoroethylene, chlorotrifluoroethylene, ethylene-chlorotrifluoroethylene, and mixtures thereof, or a blend of such fluorine substituted olefin polymers,

in which the first and second acrylic polymers each independently comprise polymerized units of the following formula (I)

 

in which

X=H, or an alkyl group having from 1-4 carbon atoms, and

R=an alkyl group having from 1-4 carbon atoms, a glydidyl group or a hydroxyalkyl group having from 1-4 carbon atoms,

and all parts by weight are based on 100 parts by weight of total polymer components present in each layer.

6. The multilayer film of claim 5 in which the impact-modified acrylic polymer is present as a melt blend of particles having a core of a first composition and a shell surrounding the core of a second composition, and in which one of the two compositions comprises a copolymer of ethylene and a carboxylic compound selected from the group consisting of acrylic acid, methacrylic acid and mixtures thereof, and the other of the two compositions is an elastomer.

7. The multilayer film of claim 5 in which the impact-resistant polymer consists essentially of poly(ethylene vinylacetate).

8. The multilayer film of claim 5 in which the impact-resistant polymer consists essentially of a metallocene catalyzed polyolefin homopolymer, copolymer or mixture thereof and an adhesive promoting additive effective to improve adhesion between the impact-resistant polymer and adjacent layers.

9. The multilayer film of claim 5 in which the metallocene catalyzed poly olefin is polyethylene homopolymer, copolymer or mixture thereof.

10. The multilayer film of claim 1, in which the thermally adhesive layer has a composition identical to the protective layer.

11. The multilayer film of claim 1 in which at least one layer further comprises about 0.1-10 parts by weight per 100 parts of total polymer present in said layer of an ultraviolet light absorbing adjuvant, provided that said layer has visible light transmission higher than 70% and haze less than 4%.

12. A weather and stain resistant composite structure comprising

a substrate having a decorative surface, and

a multilayer film covering the substrate and comprising

a protective layer of a blend comprising a fluorine substituted olefin polymer and an acrylic polymer,

a cushioning layer bonded to the protective layer and comprising an impact resistant polymer having an elastic modulus of less than 207 MPa and being free of any fluoropolymer, and

a thermally adhesive layer between the cushioning layer and the substrate and in direct contact with the cushioning layer, which thermally adhesive layer comprises a blend of a fluorine substituted olefin polymer and an acrylic polymer.

13. The weather and stain resistant composite structure of claim 12 in which the structure has an impact resistance of at least 6.8 N·

m as measured by ASTM D3679.

14. The weather and stain resistant composite structure of claim 13 in which the substrate is a rigid structure selected from among a vehicle body panel, building siding, window frame, interior wall of a living space and a sign board.

15. The weather and stain resistant composite structure of claim 13, in which the substrate is a flexible structure selected from among a fabric, a curtain and an awning.