Relating to thermosetting adhesive films

• US 10,577,523 B2
• Filed: 07/25/2014
• Issued: 03/03/2020
• Est. Priority Date: 07/26/2013
• Status: Active Grant

• Current Assignee: Zephyros, Inc.
• Original Assignee: Zephyros, Inc.
• Inventors: Miller, Ira, Czaplicki, Michael, Awkal, Michel
• Primary Examiner(s): Freeman, John D
• Application Number:
  US14/907,164
• Publication Number:
  US 20160160087A1
• Time in Patent Office: 2,048 Days
• CPC Class Codes: C08J 2363/00 Characterised by the use of epoxy resins; Derivatives of epoxy resins
• CPC Class Codes: C08J 2367/00 Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
• CPC Class Codes: C08J 2463/00 Characterised by the use of epoxy resins; Derivatives of epoxy resins
• CPC Class Codes: C08J 5/128 Adhesives without diluent
• CPC Class Codes: C09J 163/00 Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
• CPC Class Codes: C09J 171/00 Adhesives based on polyethers obtained by reactions forming an ether link in the main chain based on polyacetals C09J159/00; based on epoxy resins C09J163/00; based on polythioether-ethers C09J181/02; based on polyethersulfones C09J181/06; Adhesives based on derivatives of such polymers
• CPC Class Codes: C09J 2301/122 the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
• CPC Class Codes: C09J 2301/124 the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
• CPC Class Codes: C09J 2301/414 presence of a copolymer
• CPC Class Codes: C09J 2400/263 in the substrate
• CPC Class Codes: C09J 2451/00 Presence of graft polymer
• CPC Class Codes: C09J 2461/00 Presence of condensation polymers of aldehydes or ketones
• CPC Class Codes: C09J 2463/00 Presence of epoxy resin
• CPC Class Codes: C09J 2463/006 in the substrate
• CPC Class Codes: C09J 2467/006 in the substrate
• CPC Class Codes: C09J 2471/00 Presence of polyether
• CPC Class Codes: C09J 2477/006 in the substrate
• CPC Class Codes: C09J 2479/086 in the substrate
• CPC Class Codes: C09J 5/00 Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
• CPC Class Codes: C09J 5/06 involving heating of the applied adhesive
• CPC Class Codes: C09J 7/00 : Adhesives in the form of films or foils
• CPC Class Codes: C09J 7/10 : without carriers
• CPC Class Codes: C09J 7/21 : Paper; Textile fabrics
• CPC Class Codes: C09J 7/35 : Heat-activated
• CPC Class Codes: Y10T 428/1476 : Release layer
• CPC Class Codes: Y10T 428/31515 : As intermediate layer

Abstract

Flexible films of thermosetting adhesive materials which are non-tacky to the touch are storage stable at room temperature and can be cured at elevated temperature with a short cure time and can be cured to produce a tough flexible adhesive layer including bonding to oily surfaces, the materials are particularly useful in bonding together dissimilar substrates.

Claims

1. An article comprising:

a curable thermosetting epoxy resin based adhesive film,

a coating of liquid, tacky epoxy resin free of a curing agent applied to the adhesive film, and

a release liner disposed on the coating so that the article is adapted for reeling and unreeling at room temperature,

wherein the adhesive film is;

i) non-tacky to the touch at room temperature;

ii) flexible prior to cure; and

iii) storage stable;

wherein the adhesive film is derived from a mixture of;

a.) phenoxy resin;

b.) an elastomer/epoxy resin adduct;

c.) a core shell material; and

d.) a curing agent;

wherein the adhesive film is configured to form an adhesive bond with a metal surface having a corrosion preventive oi;

wherein the adhesive bond has a shear strength of no less than about 90% or more of an adhesive bond between the adhesive film and a metal surface free of corrosion preventive oil when the metal surface is provided with a layer of about 3 g/m²of the corrosion preventive oil, and

wherein the coating is configured to be cured by the curing agent of the adhesive film.

2. The article according to claim 1, wherein the adhesive film can be cured in no more than 45 minutes at a temperature no higher than 190°

C.

3. The article according to claim 2, wherein the adhesive film is foamable.

4. The article according to claim 1, wherein the adhesive film can be cured at a temperature in the range 130°

C. to 190°

C.

5. The article according to claim 4, wherein the adhesive film has an uncured thickness between 0.2 and 3.0 mm.

6. The article according to claim 4, wherein the adhesive film has a density of from 1.1 to 1.5 g/ml.

7. The article according to claim 1, wherein the adhesive film contains from 15 to 40 wt % of the phenoxy resin, from 5 to 40 wt % of the elastomer epoxy resin adduct, and from 5 to 25 wt % of the core shell material.

8. The article according to claim 7, wherein the article is supported by a carrier.

9. The article according to claim 8, wherein the carrier is a fibrous carrier or fleece selected from:

a woven mat, a knit mat, or a random mat; and

wherein the fibrous carrier or fleece is derived from;

glass, polyester, polyimide, carbon, or aramid fibers.

10. The article according to claim 9, wherein the adhesive film is an uncured film and the article is on one or both sides of the fibrous carrier.

11. The article according to claim 7, wherein the adhesive film is a cured adhesive film derived from the curable adhesive film.

12. The article according to claim 11, wherein the article includes a fibrous carrier.

13. The article according to claim 12, wherein the cured adhesive film has a lap sheer resistance greater than 20 mPa.

14. A laminar structure comprising a metal substrate and a fiber reinforced resin substrate, wherein the cured adhesive film of the article according to claim 11 is released from the release liner and bonds the metal substrate and the fiber reinforced resin substrate together.

15. The article according to claim 7, wherein the adhesive film contains 0.001 to 7% by weight of the curing agent.

16. The article according to claim 15, wherein the curing agent includes a curing agent accelerator.

17. The article according to claim 1, wherein the coating is a bisphenol-A or bisphenol-F based epoxy resin.

18. The article according to claim 1, wherein the coating is applied to only one surface of the adhesive film.

19. The article according to claim 1, wherein the coating is applied to opposing surfaces of the adhesive film.

20. A process for the manufacture of the article of claim 1, comprising extruding the adhesive film

at a temperature in the range 70 to 120°

C. and calendering the extrudate to a thickness in the range 0.3 to 2 mm.