Adhesive for bonding to low surface energy surfaces

• US 7,163,741 B2
• Filed: 07/01/2003
• Issued: 01/16/2007
• Est. Priority Date: 02/02/2000
• Status: Expired due to Term

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Momchilovich, Bradley S., Gehlsen, Mark D., Ma, Jingjing, Khandpur, Ashish K., Stradinger, John J.
• Primary Examiner(s): SZEKELY, PETER A
• Application Number:
  US10/610,950
• Publication Number:
  US 20040082700A1
• Time in Patent Office: 1,295 Days
• Field of Search: 428/141, 428/304.4, 428/316.6, 428/317.1, 428/317.3, 428/317.5, 428/317.7, 428/355.BL, 428/355.EN, 524/505, 521/143, 521/148
• US Class Current: 428/355.0BL
• CPC Class Codes: B32B 5/18 characterised by features of a layer of foamed material
• CPC Class Codes: C08F 297/044 using a coupling agent
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 2666/24 Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
• CPC Class Codes: C09J 151/003 grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds C09J151/04, C09J151/06 take precedence
• CPC Class Codes: C09J 153/02 Vinyl aromatic monomers and conjugated dienes
• CPC Class Codes: C09J 2433/006 in the substrate
• CPC Class Codes: C09J 7/26 Porous or cellular plastics
• CPC Class Codes: C09J 7/387 Block-copolymers
• CPC Class Codes: Y10T 428/24355 Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
• CPC Class Codes: Y10T 428/249953 Composite having voids in a component [e.g., porous, cellular, etc.]
• CPC Class Codes: Y10T 428/249981 Plural void-containing components
• CPC Class Codes: Y10T 428/249982 With component specified as adhesive or bonding agent
• CPC Class Codes: Y10T 428/249983 As outermost component
• CPC Class Codes: Y10T 428/249984 Adhesive or bonding component contains voids
• CPC Class Codes: Y10T 428/249985 Composition of adhesive or bonding component specified
• CPC Class Codes: Y10T 428/2878 including addition polymer from unsaturated monomer
• CPC Class Codes: Y10T 428/2883 including addition polymer of diene monomer [e.g., SBR, SIS, etc.]
• CPC Class Codes: Y10T 428/31855 Of addition polymer from unsaturated monomers

Abstract

A novel polymodal asymmetric elastomeric block copolymer and a pressure sensitive adhesive, tape and adhesive backed article made therefrom, such as a polymer foam article having a substantially smooth surface prepared by melt-mixing a polymer composition and a plurality of microspheres, at least one of which is an expandable polymeric microsphere, under process conditions, including temperature and shear rate, selected to form an expandable extrudable composition; and extruding the composition through a die.

Claims

1. An article comprising a pressure sensitive adhesive in combination with a backing having first and second major surfaces, the adhesive having a rubber phase and comprising:

(a) 100 parts by weight of a polymodal asymmetric elastomeric block copolymer;

(b) at least one tackifier capable of increasing the T_g of the rubber phase of the adhesive, said at least one tackifier being present in an amount sufficient to raise the calculated Fox T_g of the rubber phase of the adhesive to greater than 245°

K;

(c) 0 to about 50 parts by weight of a crosslinking agent; and

(d) 0 to about 300 parts by weight of a plasticizer;

wherein the polymodal asymmetric elastomeric block copolymer has the formula QnY and comprises from about 4 to about 40 percent by weight of a polymerized monovinyl aromatic compound and from about 96 to about 60 percent by weight of polymerized conjugated diene, wherein;

Q represents an individual arm of the block copolymer and has the formula S-B;

n represents the number of arms Q in the block copolymer and is a whole number of at least 3; and

Y is the residue of a multifunctional coupling agent; and

further wherein;

(a) S is a nonelastomeric polymer segment endblock of a polymerized monovinyl aromatic homopolymer, there being at least two different molecular weight endblocks in the copolymer, a higher molecular weight endblock and a lower molecular weight endblock, wherein;

(i) the number average molecular weight of the higher molecular weight endblock (Mn)H is in the range of from about 5,000 to about 50,000;

(ii) the number average molecular weight of the lower molecular weight endblock (Mn)L is in the range of from about 1,000 to about 10,000; and

(iii) the ratio (Mn)H/(Mn)L is at least 1.25; and

(b) B is an elastomeric polymer segment midblock which connects each arm to the residue of a multifunctional coupling agent (Y) and comprises a polymerized conjugated diene or combination of conjugated dienes; and

wherein the adhesive forms a layer on at least a portion of at least one of the major surfaces of the backing and the article exhibits a 180°

peel adhesion on high density polyethylene of at least 80 N/dm.

2. The article according to claim 1, wherein the backing comprises a foam.

3. The article according to claim 1, wherein the backing further comprises a release surface.

4. The article according to claim 1, wherein the backing comprises a foam tape comprising the same or a different polymodal asymmetric elastomeric block copolymer, and the adhesive is in the form of a layer on at least one of the major surfaces of the foam tape.

5. The article according to claim 1, wherein the backing comprises an acrylic foam tape core, and the adhesive is in the form of at least one co-extruded layer on the foam tape core.

26. An article according to claim 2 wherein the backing is co-extruded with the pressure sensitive adhesive.

27. An article according to claim 1 wherein the backing comprises a foam tape comprising a polymodal asymmetric elastomeric block copolymer.

28. An article according to claim 27 wherein the pressure sensitive adhesive is a layer coextruded with the backing.

6. An article comprising a pressure sensitive adhesive in combination with a backing having first and second major surfaces, wherein the backing is in the form of a foam, at least one of the major surfaces of which is substantially smooth having an Ra value less than about 75 micrometers, as measured by laser triangulation profilometry, and the foam comprises a plurality of microspheres, at least one of which is an expandable polymeric microsphere, the adhesive having a rubber phase and comprising:

(a) 100 parts by weight of a polymodal asymmetric elastomeric block copolymer;

(b) at least one tackifier capable of increasing the T_g of the rubber phase of the adhesive, said at least one tackifier being present in an amount sufficient to raise the calculated Fox T_g of the rubber phase of the adhesive to greater than 245°

K;

(c) 0 to about 50 parts by weight of a crosslinking agent; and

(d) 0 to about 300 parts by weight of a plasticizer;

wherein the polymodal asymmetric elastomeric block copolymer has the formula QnY and comprises from about 4 to about 40 percent by weight of a polymerized monovinyl aromatic compound and from about 96 to about 60 percent by weight of polymerized conjugated diene, wherein;

Q represents an individual arm of the block copolymer and has the formula S-B;

n represents the number of arms Q in the block copolymer and is a whole number of at least 3; and

Y is the residue of a multifunctional coupling agent; and

further wherein;

(a) S is a nonelastomeric polymer segment endblock of a polymerized monovinyl aromatic homopolymer, there being at least two different molecular weight endblocks in the copolymer, a higher molecular weight endblock and a lower molecular weight endblock, wherein;

(i) the number average molecular weight of the higher molecular weight endblock (Mn)H is in the range of from about 5,000 to about 50,000;

(ii) the number average molecular weight of the lower molecular weight endblock (Mn)L is in the range of from about 1,000 to about 10,000; and

(iii) the ratio (Mn)H/(Mn)L is at least 1.25; and

(b) B is an elastomeric polymer segment midblock which connects each arm to the residue of a multifunctional coupling agent (Y) and comprises a polymerized conjugated diene or combination of conjugated dienes;

wherein the adhesive forms a layer on at least a portion of at least one of the major surfaces of the backing and the article exhibits a 180°

peel adhesion on high density polyethylene of at least 80 N/dm.

8. An article according to claim 6 wherein the adhesive comprises a blend of the polymodal asymmetric elastomeric block copolymer and a second polymer.

9. An article according to claim 8 wherein the polymer comprises an acrylate or methacrylate adhesive polymer or copolymer, an acrylate-insoluble polymer, an elastomer containing ultraviolet radiation-activatable groups, or a pressure sensitive or hot melt adhesive prepared from non-photopolymerizable monomers.

10. An article according to claim 8 wherein the polymer comprises a copolymer of an acrylate or methacrylate monomer and a monoethylenically unsaturated co-monomer.

11. An article according to claim 10 wherein the monoethylenically unsaturated co-monomer comprises acrylic acid.

12. An article according to claim 6 wherein the backing comprises an elastomeric block copolymer foam.

13. An article according to claim 6 wherein the backing comprises a polymodal asymmetric elastomeric block copolymer foam.

14. An article according to claim 6 wherein the backing comprises an acrylic foam.

15. An article according to claim 6 wherein at least one adhesive layer is crosslinked.

16. An article according to claim 6 wherein the article exhibits a 180°

peel adhesion on high density polyethylene of at least 100 N/dm.

7. An article comprising a pressure sensitive adhesive in the form of a foam having at least one substantially smooth major surface having an Ra value less than about 75 micrometers, as measured by laser triangulation profilometry, the foam comprising a plurality of expandable polymeric microspheres in combination with at least one other polymer composition in the form of a plurality of discrete structures bonded to or embedded in the foam, and the adhesive having a rubber phase and comprising:

(a) 100 parts by weight of a polymodal asymmetric elastomeric block copolymer;

(b) at least one tackifier capable of increasing the T_g of the rubber phase of the adhesive, said at least one tackifier being present in an amount sufficient to raise the calculated Fox T_g of the rubber phase of the adhesive to greater than 245°

K;

(c) 0 to about 50 parts by weight of a crosslinking agent; and

(d) 0 to about 300 parts by weight of a plasticizer;

wherein the polymodal asymmetric elastomeric block copolymer has the formula QnY and comprises from about 4 to about 40 percent by weight of a polymerized monovinyl aromatic compound and from about 96 to about 60 percent by weight of polymerized conjugated diene, wherein;

Q represents an individual arm of the block copolymer and has the formula S-B;

n represents the number of arms Q in the block copolymer and is a whole number of at least 3; and

Y is the residue of a multifunctional coupling agent; and

further wherein;

(a) S is a nonelastomeric polymer segment endblock of a polymerized monovinyl aromatic homopolymer, there being at least two different molecular weight endblocks in the copolymer, a higher molecular weight endblock and a lower molecular weight endblock, wherein;

(i) the number average molecular weight of the higher molecular weight endblock (Mn)H is in the range of from about 5,000 to about 50,000;

(ii) the number average molecular weight of the lower molecular weight endblock (Mn)L is in the range of from about 1,000 to about 10,000; and

(iii) the ratio (Mn)H/(Mn)L is at least 1.25; and

(b) B is an elastomeric polymer segment midblock which connects each arm to the residue of a multifunctional coupling agent (Y) and comprises a polymerized conjugated diene or combination of conjugated dienes;

wherein the foam adhesive exhibits a 180°

peel adhesion on high density polyethylene of at least 80 N/dm.

17. An article comprising a foam backing having first and second major surfaces and an adhesive layer on at least a portion of at least one of the major surfaces wherein the article exhibits a 180°

peel adhesion on high density polyethylene of at least 80 N/dm, and at least one of the foam backing or adhesive has a rubber phase and comprises;

(a) 100 parts by weight of a polymodal asymmetric elastomeric block copolymer;

(b) at least one tackifier capable of increasing the T_g of the rubber phase of the adhesive, said at least one tackifier being present in an amount sufficient to raise the calculated Fox T_g of the rubber phase to greater than 245°

K;

(c) 0 to about 50 parts by weight of a crosslinking agent; and

(d) 0 to about 300 parts by weight of a plasticizer;

wherein the polymodal asymmetric elastomeric block copolymer has the formula QnY and comprises from about 4 to about 40 percent by weight of a polymerized monovinyl aromatic compound and from about 96 to about 60 percent by weight of polymerized conjugated diene, wherein;

Q represents an individual arm of the block copolymer and has the formula S-B;

n represents the number of arms Q in the block copolymer and is a whole number of at least 3; and

Y is the residue of a multifunctional coupling agent; and

further wherein;

(a) S is a nonelastomeric polymer segment endblock of a polymerized monovinyl aromatic homopolymer, there being at least two different molecular weight endblocks in the copolymer, a higher molecular weight endblock and a lower molecular weight endblock, wherein;

(i) the number average molecular weight of the higher molecular weight endblock (Mn)H is in the range of from about 5,000 to about 50,000;

(ii) the number average molecular weight of the lower molecular weight endblock (Mn)L is in the range of from about 1,000 to about 10,000; and

(iii) the ratio (Mn)H/(Mn)L is at least 1.25; and

(b) B is an elastomeric polymer segment midblock which connects each arm to the residue of a multifunctional coupling agent (Y) and comprises a polymerized conjugated diene or combination of conjugated dienes.

18. An article according to claim 17 wherein the foam backing comprises polymodal asymmetric elastomeric block copolymer.

19. An article according to claim 17 wherein the foam backing comprises an acrylic foam.

20. An article according to claim 17 wherein at least one of the adhesive layers comprises polymodal asymmetric elastomeric block copolymer.

21. An article according to claim 17 wherein at least one of the adhesive layers comprises a copolymer of an acrylate or methacrylate monomer and a monoethylenically unsaturated co-monomer.

22. An article according to claim 17 wherein the foam backing or at least one adhesive layer is crosslinked.

23. An article according to claim 17 wherein the foam backing and the adhesive layers on the first and second major surfaces comprise polymodal asymmetric elastomeric block copolymer.

24. An article according to claim 17 wherein the adhesive layer on the first major surface comprises polymodal asymmetric elastomeric block copolymer and the adhesive layer on the second major surface comprises an acrylic adhesive.

25. An article according to claim 17 wherein the article exhibits a 180°

peel adhesion on high density polyethylene of at least 100 N/dm.

29. An article according to claim 24 wherein the foam backing comprises an acrylic foam.