Multilayer polyurethane protective films

• US 10,213,992 B2
• Filed: 12/15/2014
• Issued: 02/26/2019
• Est. Priority Date: 04/29/2005
• Status: Active Grant

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Ho, Charlie C., Halford, Kenneth J.
• Primary Examiner(s): Shah, Samir
• Application Number:
  US14/570,454
• Publication Number:
  US 20150099113A1
• Time in Patent Office: 1,534 Days
• Field of Search: None
• CPC Class Codes: B32B 2250/03 3 layers
• CPC Class Codes: B32B 2250/24 All layers being polymeric
• CPC Class Codes: B32B 2307/402 Coloured
• CPC Class Codes: B32B 2307/412 Transparent
• CPC Class Codes: B32B 2405/00 Adhesive articles, e.g. adhesive tapes
• CPC Class Codes: B32B 2571/00 Protective equipment
• CPC Class Codes: B32B 2571/02 defensive, e.g. armour plates or anti-ballistic clothing
• CPC Class Codes: B32B 2605/00 Vehicles
• CPC Class Codes: B32B 2605/12 Ships
• CPC Class Codes: B32B 2605/18 Aircraft
• CPC Class Codes: B32B 27/08 of synthetic resin
• CPC Class Codes: B32B 27/16 specially treated, e.g. irradiated
• CPC Class Codes: B32B 27/34 comprising polyamides
• CPC Class Codes: B32B 27/36 comprising polyesters
• CPC Class Codes: B32B 27/40 comprising polyurethanes
• CPC Class Codes: B32B 37/15 with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
• CPC Class Codes: B32B 37/153 at least one layer is extruded and immediately laminated while in semi-molten state
• CPC Class Codes: B32B 37/24 with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate B32B37/15 takes precedence
• CPC Class Codes: B32B 38/0008 Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation heat treatment B32B38/0036
• CPC Class Codes: B32B 7/12 using interposed adhesives or interposed materials with bonding properties
• CPC Class Codes: C09J 2203/306 : for protecting painted surfaces, e.g. of cars
• CPC Class Codes: C09J 2301/162 : the carrier being a laminate constituted by plastic layers only
• CPC Class Codes: C09J 2475/006 : in the substrate
• CPC Class Codes: C09J 7/25 : based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
• CPC Class Codes: C09J 7/255 : Polyesters
• CPC Class Codes: C09J 7/29 : Laminated material metallised plastics C09J7/22
• CPC Class Codes: Y10T 156/10 : Methods of surface bonding and/or assembly therefor
• CPC Class Codes: Y10T 428/2848 : Three or more layers
• CPC Class Codes: Y10T 428/31507 : Of polycarbonate
• CPC Class Codes: Y10T 428/31554 : Next to second layer of polyamidoester

Abstract

A multilayer protective film comprising a first layer, a second layer and a PSA layer. The first layer at least comprises a polyester-based polyurethane, a polycarbonate-based polyurethane or a combination or blend of both. The second layer at least comprises a polycaprolactone-based thermoplastic polyurethane. The PSA layer comprises a pressure sensitive adhesive. One major surface of the first layer is bonded to one major surface of the second layer, and the PSA layer is bonded to an opposite major surface of the second layer such that the second layer is sandwiched between the first layer and the PSA layer.

Claims

1. A multilayer protective film comprising:

a first layer comprising a polyurethane, said polyurethane being a polyester-based polyurethane, a polycarbonate-based polyurethane or a combination of both;

a second layer comprising a polycaprolactone-based thermoplastic polyurethane; and

a PSA layer comprising a pressure sensitive adhesive,

wherein said first layer is bonded to one major surface of said second layer and said PSA layer is bonded to an opposite major surface of said second layer such that said second layer is sandwiched between said first layer and said PSA layer, and said multilayer protective film is clear, transparent, and passes the “

Staining and Discoloration Test”

after being exposed to at least one of the fluids from the group consisting of grease, tar, transmission fluid, motor oil, fuel oil, diesel oil, gear oil, and SUNOCO lub/grease.

2. The film according to claim 1, wherein the polyurethane of said first layer is the reaction product of a polyol and at least an aliphatic triisocyanate, and said polyol is a polyester polyol, a polycarbonate polyol or a combination of both.

3. The film according to claim 1, wherein the polyurethane of said first layer is an aliphatic polyurethane.

4. The film according to claim 1, wherein the polyurethane of said first layer is a slightly crosslinked polyurethane that exhibits at least enough melting or at least enough softening, when heated, to form a bond that passes the “

Tape Snap Adhesion Test”

after at least one of the aging conditions (a) Water Immersion in 40°

C. water bath for 7 days, (b) Fog chamber exposure on a rack at about a 30 degree angle and exposed for 7 days at 38°

C. in a chamber with 100% condensation, and (c) Salt spray exposure on a rack at about a 30 degree angle and exposed for 7 days at 35°

C. using a 5% sodium chloride solution in a salt fog chamber.

5. The film according to claim 1, wherein the polyurethane of said first layer is a solvent-based polyurethane.

6. A vehicle comprising a body part having a painted surface protected by said multilayer protective film according to claim 1.

7. The film according to claim 1, wherein the polyurethane of said first layer comprises an anionic surfactant.

8. The film according to claim 7, wherein the anionic surfactant comprises a sulfosuccinate type anionic surfactant.

9. The film according to claim 1, wherein the polyurethane of said first layer comprises a UV light absorber.

10. The film according to claim 9, wherein said UV light absorber comprises 2-ethylhexyl α

-cyano-α

-β

′

diphenylacrylate.

11. The film according to claim 1, wherein the polyurethane of said first layer comprises an aziridine crosslinker.

12. The film according to claim 1, wherein the polyurethane of said first layer comprises dicyclohexylmethane diisocyanate.

13. The film according to claim 12, wherein the polyurethane of said first layer further comprises an aliphatic polyisocyanate.

14. The film according to claim 1, wherein the polyurethane of said first layer comprises a poly(cycloaliphatic carbonate) polyol.

15. A method of making the multilayer protective film according to claim 1, said method comprising:

(a) forming a first layer comprising a polyurethane, the polyurethane being a polyester-based polyurethane, a polycarbonate-based polyurethane or a combination of both;

(b) forming a second layer comprising a polycaprolactone-based thermoplastic polyurethane;

(c) forming a PSA layer comprising a pressure sensitive adhesive;

(d) bonding one major surface of the first layer to one major surface of the second layer; and

(e) bonding the PSA layer to an opposite major surface of the second layer,

wherein the second layer is sandwiched between the first layer and the PSA layer.

16. The method according to claim 15, wherein said forming a second layer further comprises:

extruding the polycaprolactone-based thermoplastic polyurethane at an elevated temperature through a die to form the second layer.

17. The method according to claim 16, wherein said bonding the first layer further comprises:

laminating the one major surface of the first layer to the one major surface of the second layer, after said extruding and while the one major surface of the second layer is at an elevated temperature that is sufficiently higher than room temperature to facilitate adequate bonding between the first layer and the second layer.

18. The method according to claim 16, wherein said bonding the first layer further comprises:

laminating one major surface of the first layer to one major surface of the second layer after said extruding and with at least the one major surface of the first layer and the second layer being at a temperature that does not facilitate adequate bonding between the first layer and the second layer; and

heating the one major surface of the second layer to an elevated temperature that is sufficiently higher than room temperature to facilitate adequate bonding between the first layer and the second layer during said laminating,

wherein said heating occurs before or during said laminating.

19. The method according to claim 18, further comprising:

releasably laminating an opposite major surface of the second layer to a releasable carrier web after said extruding.

20. A multilayer protective film comprising:

a first layer comprising a polyurethane, said polyurethane being a polyester-based polyurethane, a polycarbonate-based polyurethane or a combination of both;

a second layer comprising a polycaprolactone-based thermoplastic polyurethane; and

a PSA layer comprising a pressure sensitive adhesive,

wherein said first layer is bonded to one major surface of said second layer and said PSA layer is bonded to an opposite major surface of said second layer such that said second layer is sandwiched between said first layer and said PSA layer, adhesion between said first layer and said second layer passes the “

Tape Snap Adhesion Test”

, said multilayer protective film passes the “

Staining and Discoloration Test”

, and said first layer has an exposed major surface with the appearance of having been cast onto a smooth major surface of a releasable carrier web, dried and the carrier web removed.

21. The film according to claim 20, wherein said film is colored.

22. A method of making the multilayer protective film according to claim 20, said method comprising:

(a) forming a first layer comprising a polyurethane, the polyurethane being a polyester-based polyurethane, a polycarbonate-based polyurethane or a combination of both;

(b) forming a second layer comprising a polycaprolactone-based thermoplastic polyurethane;

(c) forming a PSA layer comprising a pressure sensitive adhesive;

(d) bonding one major surface of the first layer to one major surface of the second layer; and

(e) bonding the PSA layer to an opposite major surface of the second layer,

wherein the second layer is sandwiched between the first layer and the PSA layer.

23. The method according to claim 22, wherein said forming a first layer further comprises:

coating an aqueous-based or solvent-based polyurethane dispersion onto the releasable carrier web.

24. A method of making a multilayer protective film, said method comprising:

forming a first layer comprising a polyurethane, the polyurethane being a polyester-based polyurethane, a polycarbonate-based polyurethane or a combination of both;

forming a second layer comprising a polycaprolactone-based thermoplastic polyurethane by extruding the polycaprolactone-based thermoplastic polyurethane at an elevated temperature through a die to form the second layer;

forming a PSA layer comprising a pressure sensitive adhesive;

bonding one major surface of the first layer to one major surface of the second layer by laminating one major surface of the first layer to one major surface of the second layer after said extruding and with at least the one major surface of the first layer and the second layer being at a temperature that does not facilitate adequate bonding between the first layer and the second layer, and heating the one major surface of the second layer to an elevated temperature that is sufficiently higher than room temperature to facilitate adequate bonding between the first layer and the second layer during said laminating, with said heating occurring before or during said laminating;

bonding the PSA layer to an opposite major surface of the second layer;

releasably laminating an opposite major surface of the second layer to a releasable carrier web after said extruding;

exposing the opposite major surface of the second layer, after said releasably laminating; and

corona treating the opposite major surface of the second layer, after said exposing and before said bonding the PSA layer,

wherein the second layer is sandwiched between the first layer and the PSA layer.