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

• US 6,806,320 B2
• Filed: 11/15/2002
• Issued: 10/19/2004
• Est. Priority Date: 11/15/2002
• Status: Expired due to Term

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Xia, Jianhui, Nguyen, Lang N., Khandpur, Ashish K., Everaerts, Albert I., Ma, JingJing, DʼHaese, Francois C.
• Primary Examiner(s): Seidleck, James J.
• Assistant Examiner(s): Asinovsky, Olga
• Application Number:
  US10/295,810
• Publication Number:
  US 20040097658A1
• Time in Patent Office: 704 Days
• Field of Search: 525/330.3, 525/221, 525/222, 525/227, 525/299, 525/301, 525/75, 525/78, 525/80, 525/85, 525/191
• US Class Current: 525/330.3
• CPC Class Codes: C08F 293/005 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• 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 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: 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

Abstract

Described are melt-processable block copolymers and compositions, embodiments of which may be useful in applications such as pressure sensitive adhesive (PSA) or heat-activatable adhesive, comprising polymeric end block and polymeric B block, wherein end block comprises copolymer and the B block comprises homopolymer or copolymer.

Claims

1. A method of preparing a poly(meth)acrylate block copolymer, having meltflow temperature in the range from 50°

C. to 250°

C., the method comprising;

reacting at least one low glass transition temperature polymeric block and at least one high glass transition temperature copolymeric end block comprising first monomeric units and second monomeric units to form the block copolymer, wherein the low glass transition temperature polymeric block has a glass transition temperature of less than about 20°

C., and the high glass transition temperature copolymeric end block has a glass transition temperature of at least about 20°

C., and

selecting the second monomeric units to increase or decrease meltflow temperature of the block copolymer compared to a block copolymer that is otherwise similar but does not contain the second monomeric units,

wherein at least one of the low glass transition temperature polymeric block and the high glass transition temperature copolymeric end block is derived from one or more (meth)acrylate monomer.

2. The method of claim 1 wherein the block copolymer has a cohesive strength of at least 5,000 minutes measured according to ASTM D 3654.

3. The method of claim 1 comprising selecting the second monomeric units to decrease meltflow temperature of the block copolymer compared to a block copolymer that is otherwise similar but does not contain the second monomeric units,

wherein the block copolymer has a cohesive strength of at least 10,000 minutes measured according to ASTM D 3654.

4. The method of claim 1 wherein the copolymer comprises high glass transition temperature copolymeric end block having a glass transition temperature of the copolymeric block between 20°

C. to 200°

C.

5. The method of claim 1 comprising selecting the second monomeric units to desirably increase meltflow temperature of the block copolymer compared to a block copolymer that is otherwise similar but does not contain the second monomeric units,

wherein the block copolymer has a cohesive strength of at least 10,000 minutes measured according to ASTM D 3654.

6. The method of claim 5 wherein the copolymer comprises copolymeric end blocks having a glass transition temperature of from 20°

C. to 200°

C.

7. The method of claim 5 wherein the copolymer comprises copolymeric end blocks having a glass transition temperature of the copolymeric block from 100°

C. to 200°

C.

8. The method of claim 1 wherein end block copolymer comprises first monomeric units selected from the group consisting of linear and branched alkyl(meth)acrylates, cycloaliphatic monomeric units, and aromatic monomeric units, and

second monomeric units selected from the group consisting of cycloaliphatic and aromatic monomeric units.

9. The method of claim 1 wherein end block copolymer comprises first monomeric units selected from the group consisting of linear and branched alkyl(meth)acrylates, and

second monomeric units selected from the group consisting of cycloaliphatic and aromatic monomeric units.

10. The method of claim 9 wherein the first monomeric unit is methyl methacrylate, and the second monomeric unit is selected from the group consisting of benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, phenylacrylate, phenyl methacrylate, phenethyl acrylate, phenethyl methacrylate, 2-naphthyl acrylate, 2-naphthyl methacrylate, adamantyl acrylate, adamantyl methacrylate, styrene, alpha-methylstyrene, and t-butylstyrene.

11. The method of claim 8 wherein the method is used to prepare a pressure sensitive adhesive composition comprising the block copolymer.

12. The method of claim 11 wherein the pressure sensitive adhesive composition comprises tackifier.

13. The method of claim 11 further comprising the step of crosslinking the pressure sensitive adhesive composition.

14. The method of claim 11 wherein the pressure sensitive adhesive composition comprises 10 to 200 parts by weight tackifier based on 100 parts by weight block copolymer.

15. The method of claim 11 wherein the pressure sensitive adhesive composition comprises plasticizer.

16. The method of claim 11 wherein the pressure sensitive adhesive composition comprises tackifier and plasticizer.

17. The method of claim 11 wherein the composition is a pressure sensitive adhesive having a cohesive strength of at least 2,000 minutes measured according to ASTM D 3654.

18. A melt-processable poly(meth)acrylate block copolymer, the block copolymer comprising

at least one high glass transition temperature copolymeric end block having a glass transition temperature of at least about 20°

C., and

at least one low glass transition temperature polymeric block having a glass transition temperature of less than about 20°

C.,

wherein high glass transition temperature copolymeric end block comprises first monomeric units and second monomeric units, the second monomeric units increasing or decreasing meltflow temperature of the block copolymer compared to a similar block copolymer that does not contain the second monomeric units,

wherein at least one of the high glass transition temperature copolymeric end block and the low glass transition temperature polymeric block is derived from one or more (meth)acrylate monomer, and

the meltflow temperature of the block copolymer is in the range from 50°

C. to 250°

C.

19. The block copolymer of claim 18 wherein the second monomeric unit increases the meltflow temperature of the block copolymer relative to a similar block copolymer having end blocks of the homopolymeric first monomeric units.

20. The block copolymer of claim 18 wherein the second monomeric unit decreases the meltflow temperature of the block copolymer relative to a similar block copolymer having end blocks of homopolymeric first monomeric units.

21. The block copolymer of claim 18 wherein the block copolymer is a pressure sensitive adhesive having a cohesive strength of at least 2,000 minutes measured according to ASTM D 3654.

22. The block copolymer of claim 18 comprising

first monomeric units selected from the group consisting of linear and branched alkyl(meth)acrylates, and

second monomeric units selected from the group consisting of cycloaliphatic and aromatic monomeric units.

23. The block copolymer of claim 18 wherein the first monomeric unit is methyl methacrylate, and

the second monomeric unit is selected from the group consisting of benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, phenylacrylate, phenyl methacrylate, phenethyl acrylate, phenethyl methacrylate, 2-naphthyl acrylate, 2-naphthyl methacrylate, adamantyl acrylate, adamantyl methacrylate, styrene, alpha-methylstyrene, and t-butylstyrene.

24. A melt processable, thermoplastic poly(meth)acrylate block copolymer comprising

at least one soft polymeric block having a glass transition temperature of less than about 20°

C., and

at least two hard copolymeric end blocks having a glass transition temperature of from 20°

C. to 200°

C. and comprising

first monomeric units selected from the group consisting of linear and branched alkyl(meth)acrylates, cycloaliphatic monomeric units, and aromatic monomeric units, and

second monomeric units selected from the group consisting of cycloaliphatic monomeric units, aromatic monomeric units, and low glass transition temperature linear or branched alkyl acrylate or alkyl methacrylate monomeric units, and

wherein the block copolymer has a meltflow temperature in the from 50°

C. to 250°

C.

25. The copolymer of claim 24 wherein end block copolymer comprises

first monomeric units selected from the group consisting of linear and branched alkyl(meth)acrylates, and

second monomeric units selected from the group consisting of cycloaliphatic and aromatic monomeric units.

26. The copolymer of claim 25 wherein the first monomeric unit is methyl methacrylate, and the second monomeric unit is selected from the group consisting of benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, phenylacrylate, phenyl methacrylate, phenethyl acrylate, phenethyl methacrylate, 2-naphthyl acrylate, 2-naphthyl methacrylate, adamantyl acrylate, adamantyl methacrylate, styrene, alpha-methylstyrene, and t-butylstyrene.

27. A melt processable, thermoplastic block copolymer comprising

at least one soft polymeric block having a glass transition temperature of less than about 20°

C., and

at least two hard copolymeric end blocks having a glass transition temperature of from 20°

C. to 200°

C. and comprising

first monomeric units selected from the group consisting of ethylenically unsaturated polymerizable cycloaliphatic monomeric units, and

second monomeric units selected from the group consisting of ethylenically unsaturated polymerizable aromatic monomeric units, and

wherein the block copolymer has a meltflow temperature in the range from 50°

C. to 250°

C.