Adhesive oxyhalopolymer composites

• US 6,428,887 B1
• Filed: 01/27/1999
• Issued: 08/06/2002
• Est. Priority Date: 01/30/1998
• Status: Expired due to Term

• Current Assignee: Integument Technologies, Inc.
• Original Assignee: Integument Technologies, Inc.
• Inventors: Koloski, Timothy S., Naab, Douglas J., Vargo, Terrence G.
• Primary Examiner(s): OGDEN JR, NECHOLUS
• Application Number:
  US09/239,108
• Time in Patent Office: 1,287 Days
• Field of Search: 428/411.14, 428/421, 428/416, 428/343, 156/302
• US Class Current: 428/343
• CPC Class Codes: B32B 7/12 using interposed adhesives or interposed materials with bonding properties
• CPC Class Codes: C09J 2427/006 in the substrate
• CPC Class Codes: C09J 7/245 Vinyl resins, e.g. polyvinyl chloride [PVC]
• CPC Class Codes: Y10T 156/1097 Lamina is running length web
• CPC Class Codes: Y10T 428/28 Web or sheet containing structurally defined element or component and having an adhesive outermost layer
• CPC Class Codes: Y10T 428/31522 Next to metal
• CPC Class Codes: Y10T 428/3154 Of fluorinated addition polymer from unsaturated monomers

Abstract

There is disclosed adhesive-oxyhalopolymer composites having surface hydrogen and oxygen or oxygen functionality groups wherein the oxygen or oxygen functionality sites are chemically bonded to an adhesive material forming a stable and permanent bond with surprisingly and unexpected superior bond strength. The adhesive-oxyhalopolymer composites comprise an oxyhalopolymer prepared from a halopolymer having from about 1 to 100 percent of surface halogens permanently substituted with hydrogen and oxygen or oxygen-containing groups of which from about 3 to about 30 percent of the substituted halogens are replaced with oxygen or oxygen-containing groups and from about 70 to about 97 percent of the substituted halogens are replaced with hydrogen atoms and the oxyhalopolymer is chemically bonded to an adhesive material.

Claims

1. An adhesive-oxyhalopolymer composite comprising:

(a) an oxyhalopolymer prepared from a halopolymer in which from 1 to 100 percent of surface halogens are permanently substituted with hydrogen and oxygen or oxygen-containing groups of which from about 3 to about 30 percent of the substituted halogens are replaced with oxygen or oxygen-containing groups and from about 70 to about 97 percent of the substituted halogens are replaced with hydrogen atoms; and

(b) an adhesive material engaged with said oxyhalopolymer and chemically bonded to the oxygen or oxygen-containing groups of the oxyhalopolymer.

2. The adhesive-oxyhalopolymer composite according to claim 1 wherein the surface halogen is at least one member selected from the group consisting of fluorine, chlorine, bromine and iodine.

3. The adhesive-oxyhalopolymer composite according to claim 1 wherein the oxyhalopolymer is selected from a group consisting of an oxyfluoropolymer and oxychlorofluoropolymer.

4. The adhesive-oxyhalopolymer composite according to claim 1 wherein the adhesive material is a member selected from the group consisting of epoxy, aqueous based adhesive, solvent based adhesive, acrylic adhesive, fluorine based adhesives, polyester adhesive, heat sealable, pressure sensitive rubber adhesive, pressure sensitive acrylic adhesive, pressure sensitive silicone adhesive and release coating adhesive.

5. The adhesive-oxyhalopolymer composite according to claim 3 wherein the adhesive material is a member selected from the group consisting of epoxy, aqueous based adhesive, fluorine based adhesive, solvent based adhesive, acrylic adhesive, polyester adhesive, heat sealable adhesive, pressure sensitive rubber adhesive, pressure sensitive acrylic adhesive, pressure sensitive silicone adhesive and release coating adhesive.

6. The adhesive-oxyhalopolymer composite according to claim 1 wherein from about 20 to about 85 of the surface halogen atoms are substituted with hydrogen and oxygen or oxygen-containing groups.

7. The adhesive-oxyhalopolymer composite according to claim 1 wherein the halopolymer is a member selected from the group consisting of FEP, PTFE, ePTFE, MFA, PFA, ECTFE, PCTFE and PVDF.

8. The adhesive-oxyhalopolymer composite according to claim 1 wherein the composite is bonded onto a substrate selected from the group consisting of metals, non-metals, plastics and ceramics.

9. The adhesive-oxyhalopolymer composite according to claim 1 wherein the composite is bonded to a carbon steel substrate.

10. The adhesive-oxyhalopolymer composite according to claim 1 wherein:

(a) the halopolymer is a film having first and second sides wherein each side has a surface and with the surface of at least the first side having up to 98 percent of surface halogens permanently substituted with hydrogen and oxygen or oxygen-containing groups of which from about 3 to about 30 percent of the substituted halogens are replaced with oxygen or oxygen-containing groups and from about 70 to about 97 percent of the substituted halogens are replaced with hydrogen atoms to form an oxyhalopolymer on at least the first side; and

(b) the adhesive material engaged with said oxyhalopolymer and chemically bonded to the oxygen or oxygen-containing groups on at least the first side of the oxyhalopolymer.

11. The adhesive-oxyhalopolymer composite according to claim 1 wherein the chemical bond between the oxyhalopolymer and adhesive is characterized by resistance to chemical attack, ultraviolet radiation, temperature extremes and humidity.

12. The adhesive-oxyhalopolymer composite according to claim 10 wherein the second side of the halopolymer has up to 98 percent of said surface halogens permanently substituted with hydrogen and oxygen or oxygen-containing groups of which from about 3 to about 30 percent of the substituted halogens are replaced with oxygen or oxygen-containing groups and from about 70 to about 97 percent of the substituted halogens are replaced with hydrogen atoms wherein the oxygen or oxygen-containing groups are covalently bonded to a transition metal or a conductive metallic film.

13. The adhesive-oxyhalopolymer composite according to claim 12 wherein the transition metal is bonded to an adhesive.

14. The adhesive-oxyhalopolymer composite according to claim 1 wherein the oxygen containing group is a hydroxyl group.

15. An adhesive-oxyhalopolymer composite, which comprises a halogenated polymer having an outer surface modified with hydrogen and oxygen or oxygen containing groups substituted for at least a portion of the halogen atoms thereon to provide an oxyhalopolymer;

and an adhesive material engaged with said oxyhalopolymer and chemically bonded to the oxygen or oxygen containing groups of the oxyhalopolymer.

16. A method of making a permanently bonded adhesive-oxyhalopolymer composite, comprising a halogenated polymer having an outer surface modified with hydrogen and oxygen or oxygen containing groups substituted for at least a portion of the halogen atoms thereon to provide an oxyhalopolymer and an adhesive material engaged with said oxyhalopolymer and chemically bonded to the oxygen or oxygen containing groups of the oxyhalopolymer which method comprises the steps of:

(a) providing a halopolymer;

(b) modifying the halopolymer wherein from 1 to 100% percent of surface halogens are permanently substituted with hydrogen and oxygen or oxygen-containing groups to a depth of from about 10 to 100 Å

thereby forming an oxyhalopolymer; and

(c) contacting the oxyhalopolymer with an adhesive material to facilitate the forming of a chemical bond between the oxygen or oxygen-containing sites of the oxyhalopolymer and the adhesive material.

17. The method of making a permanently bonded adhesive-oxyhalopolymer composite according to claim 16 wherein from about 3 to about 30 percent of the substituted halogens are replaced with oxygen or oxygen-containing groups and from about 70 to about 97 percent of the substituted halogens are replaced with hydrogen atoms.

18. The method of making a permanently bonded adhesive-oxyhalopolymer composite according to claim 16 wherein the oxyhalopolymer is selected from a group consisting of an oxyfluoropolymer and oxychlorofluoropolymer.

19. The method of making a permanently bonded adhesive-oxyhalopolymer composite according to claim 16 wherein the adhesive material is a member selected from the group consisting of epoxy, aqueous based adhesive, solvent based adhesive, acrylic adhesive, polyester adhesive, fluorine based adhesive, heat sealable adhesive, pressure sensitive rubber adhesive, pressure sensitive acrylic adhesive, pressure sensitive silicone adhesive and release coating adhesive.

20. The method of making a permanently bonded adhesive-oxyhalopolymer composite according to claim 16 wherein from about 20 to about 85 percent of the surface halogens are substituted with hydrogen and oxygen or oxygen-containing groups.

21. The method of making a permanently bonded adhesive-oxyhalopolymer composite according to claim 16 wherein the halopolymer is a member selected from the group consisting of FEP, PTFE, ePTFE, MFA, PFA ECTFE, PCTFE and PVDF.

22. The method of making a permanently bonded adhesive-oxyhalopolymer composite according to claim 16 wherein the chemical bond is covalent.

23. An adhesive-oxyhalopolymer composite prepared according to claim 16.

24. A method of making a permanently bonded adhesive-oxyhalopolymer composite using a non-halogenated base substrate, said composite comprising a halogenated polymer having an outer surface modified with hydrogen and oxygen or oxygen containing groups substituted for at least a portion of the halogen atoms thereon to provide an oxyhalopolymer and an adhesive material engaged with said oxyhalopolymer and chemically bonded to the oxygen or oxygen containing groups of the oxyhalopolymer, the method comprising the steps of:

(a) providing the non-halogenated base substrate selected from the group consisting of polymeric, ceramic and metallic materials;

(b) halogenating the surface of the non-halogenated base substrate with molecularly bonded halogen atoms or a halocarbon polymer film to form a halopolymer on the surface of the non-halogenated base substrate;

(c) modifying the halopolymer wherein from 1 to 100% percent of surface halogens are permanently substituted with hydrogen and oxygen or oxygen-containing groups to a depth of from about 10 to 100 Å

thereby forming an oxyhalopolymer; and

(d) contacting the oxyhalopolymer of step (c) with an adhesive material to facilitate the forming of a chemical bond between the oxygen or oxygen-containing sites of the oxyhalopolymer and the adhesive material.

25. A method of making an adhesive-oxyhalopolymer composite, comprising:

contacting an oxyhalopolymer with an adhesive material to form a composite, wherein at least one surface of said oxyhalopolymer comprises from about 1 to about 100 percent of surface halogens permanently substituted with hydrogen and oxygen or oxygen-containing groups of which from about 3 to about 30 percent of the substituted halogens are replaced with oxygen or oxygen-containing groups and from 70 to about 97 percent of the substituted halogens are replaced with hydrogen atoms, said adhesive material chemically bonded to said oxyhalopolymer.

26. An adhesive-oxyhalopolymer composite made according to the method of claim 25.