Block copolymer hot-melt processable adhesives, methods of their preparation, and articles therefrom

• US 6,734,256 B1
• Filed: 09/25/2000
• Issued: 05/11/2004
• Est. Priority Date: 12/29/1998
• Status: Expired due to Term

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Ma, JingJing, DʼHaese, Francois C., Everaerts, Albert I.
• Primary Examiner(s): Seidleck, James J.
• Assistant Examiner(s): Asinovsky, Olga
• Application Number:
  US09/646,975
• Time in Patent Office: 1,324 Days
• Field of Search: 525/299, 525/271, 525/272
• US Class Current: 525/299
• CPC Class Codes: C08F 293/00 Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule on to polymers modified by introduction of unsaturated end groups C08F290/02
• CPC Class Codes: C08F 293/005 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• CPC Class Codes: C08F 297/02 using a catalyst of the anionic type
• CPC Class Codes: C08F 297/026 polymerising acrylic acid, methacrylic acid or derivatives thereof
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• 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: C08L 53/00 Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• CPC Class Codes: C09D 153/00 Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
• CPC Class Codes: C09J 153/00 Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
• CPC Class Codes: C09J 2453/00 Presence of block copolymer
• CPC Class Codes: C09J 7/35 Heat-activated
• CPC Class Codes: C09J 7/387 Block-copolymers
• CPC Class Codes: Y10T 428/31855 Of addition polymer from unsaturated monomers

Abstract

Hot-melt processable adhesive, such as pressure-sensitive-adhesive (PSA) or heat-activatable adhesive, compositions of the present invention possess a broad formulation latitude and adequate cohesive strength after application for use in high performance applications. Hot-melt processable adhesives of the invention comprise at least one block copolymer comprising at least two A blocks and at least one B block. The A and B blocks are derived from monoethylenically unsaturated monomers, which monomers result in saturated polymer backbones without the need for subsequent hydrogenation upon their polymerization. Preferably, the block copolymer is a (meth)acrylate block copolymer.

Claims

1. A composition comprising:

100 parts by weight of at least one block copolymer comprising at least two A blocks and at least one B block, wherein the A block is derived from at least one monoethylenically unsaturated monomer selected from the group consisting of (meth)acrylates, styrenes and vinyl esters, and wherein the B block is derived from at least one monoethylenically unsaturated monomer selected from the group consisting of (meth)acrylates, acrylamides and vinyl esters, and the boundaries between microdomains comprising the A blocks and a continuous phase comprising the B blocks are essentially free of tapered structures; and

at least 40 parts by weight of at least one tackifier based on total weight of the block copolymer;

wherein said composition is a hot melt processable adhesive.

2. The composition of claim 1, wherein the block copolymer comprises at least one of:

(A-B-A) triblocks, -(A-B)_n- multiblocks, (A-B)_n- star blocks, and combinations thereof.

3. The composition of claim 1, wherein the block copolymer is a linear block copolymer.

4. The composition of claim 1, wherein the adhesive composition has a cohesive strength of at least about 2,000 minutes when measured according to ASTM D 3654.

5. The composition of claim 1, wherein the adhesive composition has a cohesive strength of at least about 6,000 minutes when measured according to ASTM D 3654.

6. The composition of claim 1, wherein the adhesive composition has a cohesive strength of at least about 10,000 minutes when measured according to ASTM D 3654.

7. The composition of claim 1, wherein the adhesive composition has a zero shear displacement when tested according to Shear Displacement test described herein.

8. The composition of claim 1, wherein the A blocks are polymers independently derived from a monoethylenically unsaturated monomer, which as a homopolymer has a glass transition temperature (Tg) of greater than about 20°

C.

9. The composition of claim 8, wherein the monoethylenically unsaturated monomer is a (meth)acrylate monomer.

10. The composition of claim 8, wherein a homopolymer of the monoethylenically unsaturated monomer has a glass transition temperature of about 20°

C. to about 200°

C.

11. The composition of claim 8, wherein a homopolymer of the monoethylenically unsaturated monomer has a glass transition temperature of about 50°

C. to about 150°

C.

12. The composition of claim 8, wherein the monoethylenically unsaturated monomer is a vinyl-terminated monomer.

13. The composition of claim 8, wherein the monoethylenically unsaturated monomer is a styrene.

14. The composition of claim 1, wherein the A blocks each independently have a weight average molecular weight of less than about 50,000.

15. The composition of claim 1, wherein the A blocks each independently have a weight average molecular weight of about 3,000 to about 30,000.

16. The composition of claim 1, wherein the A blocks each independently have a weight average molecular weight of about 5,000 to about 15,000.

17. The composition of claim 1, wherein the B block is a polymer derived from a monoethylenically unsaturated monomer, which as a homopolymer has a glass transition temperature (Tg) of less than about 20°

C.

18. The composition of claim 1, wherein the B block is a polymer derived from a (meth)acrylate monomer.

19. The composition of claim 17, wherein a homopolymer of the monoethylenically unsaturated monomer has a glass transition temperature of about −

70°

C. to about 20°

C.

20. The composition of claim 17, wherein a homopolymer of the monoethylenically unsaturated monomer has a glass transition temperature of about −

60°

C. to about 0°

C.

21. The composition of claim 1, wherein the A blocks and B block are each independently derived from a monomer having a structure as follows:

,

wherein;

R¹ is H or CH₃; and

R² is a hydrocarbon group, such that R² for each A block has a total number of carbon atoms differing by at least two from R² for the B block.

22. The composition of claim 1, wherein the B block has a weight average molecular weight of about 30,000 to about 500,000 grams per mole.

23. The composition of claim 1, wherein the B block has a weight average molecular weight of about 70,000 to about 200,000 grams per mole.

24. The composition of claim 1, wherein the block copolymer is polymerized via a living free-radical polymerization method.

25. The composition of claim 1, wherein the block copolymer is polymerized via living anionic polymerization.

26. The composition of claim 1, wherein polydispersity of the block copolymer is about 2.0 or less.

27. The composition of claim 1, wherein polydispersity of the block copolymer is about 1.5 or less.

28. The composition of claim 1, wherein the A blocks are each essentially free of segments derived from a monomer used to prepare the B block.

29. The composition of claim 1, wherein the B block is essentially free of segments derived from a monomer used to prepare the A blocks.

30. The composition of claim 1, wherein the block copolymer is polymerized without using iniferters.

31. The composition of claim 1, wherein the block copolymer is essentially free of iniferter residue.

32. The composition of claim 1, further comprising at least one additive.

33. The composition of claim 32, wherein the additive is compatible with the B block.

34. The composition of claim 32, wherein the additive is selected from the group consisting of A-block compatible resins, (A-B) diblock copolymers, plasticizers, photocrosslinkers, stabilizers, pigments, fillers, and medicaments.

35. The composition of claim 1, wherein elastomeric components in the composition consist essentially of the block copolymer.

36. The composition of claim 1, wherein the composition comprises an (A-B-A) triblock copolymer and an (A-B) diblock copolymer.

37. The composition of claim 1, wherein the tackifier comprises about 60 parts by weight to about 140 parts by weight based on total weight of the block copolymer.

38. The composition of claim 1, wherein the tackifier comprises about 80 parts by weight to about 120 parts by weight based on total weight of the block copolymer.

39. The composition of claim 1, wherein the adhesive composition is a pressure-sensitive-adhesive composition.

40. The composition of claim 1, wherein the adhesive composition is a heat-activatable adhesive composition.

41. A substrate at least partially coated with the composition of claim 1.

42. The substrate of claim 41, wherein the composition is chemically crosslinked.

43. A tape comprising:

a backing having a first and second side; and

the composition of claim 1 coated on at least a portion of the first side of the backing.

44. The tape of claim 43, wherein the composition of claim 1 is solvent-coated on the first side of the backing.

45. A method of preparing a hot-melt processable adhesive, comprising the steps of:

providing 100 parts by weight of at least one block copolymer comprising at least two A blocks and at least one B block, wherein the A block is derived from at least one monoethylenically unsaturated monomer selected from the group consisting of (meth)acrylates, styrenes and vinyl esters, and wherein the B block is derived from at least one monoethylenically unsaturated monomer selected from the group consisting of (meth)acrylates, acrylamides and vinyl esters, and wherein the boundaries between microdomains comprising the A blocks and a continuous phase comprising the B blocks are essentially free of tapered structures; and

blending at least 40 parts by weight of at least one tackifier based on total weight of the block copolymer with the block copolymer.

46. The method of claim 45, further comprising the step of polymerizing the block copolymer.

47. The method of claim 46, wherein the step of polymerizing the block copolymer does not use iniferters.

48. The method of claim 45, further comprising the step of applying the hot-melt adhesive to at least a portion of a substrate.

49. The method of claim 48, wherein the step of applying the hot-melt processable adhesive comprises hot-melt processing the hot-melt processable adhesive.

50. A composition comprising:

100 parts by weight of at least one block copolymer comprising at least two A blocks and at least one B block, wherein the B block is derived from monoethylenically unsaturated monomers comprising at least one of a (meth)acrylate monomer or a vinyl-terminated monomer, which as a homopolymer has a glass transition temperature (Tg) of less than about 20°

C., and the A blocks are polymers independently derived from a (meth)acrylate monomer, which as a homopolymer has a glass transition temperature (Tg) of greater than about 20°

C., and the boundaries between microdomains comprising the A blocks and a continuous phase comprising the B blocks are essentially free of tapered structures; and

at least 40 parts by weight of at least one tackifier based on total weight of the block copolymer;

wherein said composition is a hot melt processable adhesive.

51. A composition comprising:

100 parts by weight of at least one block copolymer comprising at least two A blocks and at least one B block, wherein the A and B blocks are each independently derived from a monomer having a structure as follows;

 

wherein;

R¹ is H or CH₃; and

R² is a hydrocarbon group, such that R² for each A block has a total number of carbon atoms differing by at least two from R² for the B block, and the boundaries between microdomains comprising the at least two A blocks and a continuous phase comprising the at least one B block are essentially free of tapered structures; and

at least 40 parts by weight of at least one tackifier based on total weight of the block copolymer;

wherein said composition is a hot melt processable adhesive.