Pressure-sensitive adhesive composition, process for the preparation thereof and pressure-sensitive adhesive sheets

• US 6,432,475 B1
• Filed: 12/07/1999
• Issued: 08/13/2002
• Est. Priority Date: 12/08/1998
• Status: Expired due to Fees

• Current Assignee: Nitto Denko Corporation
• Original Assignee: Nitto Denko Corporation
• Inventors: Kamifuji, Fumiko, Yamamoto, Michiharu, Moroishi, Yutaka, Okada, Kenichi, Doi, Tomoko
• Primary Examiner(s): Dawson, Robert
• Assistant Examiner(s): Feely, Michael J
• Application Number:
  US09/456,912
• Time in Patent Office: 980 Days
• Field of Search: 428/413, 428/500, 428/523, 526/135, 526/145-147, 526/93, 526/320, 427/208.4, 525/94
• US Class Current: 427/208.4
• CPC Class Codes: C08F 293/005 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• 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: Y10T 428/31511 Of epoxy ether
• CPC Class Codes: Y10T 428/31855 Of addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31938 Polymer of monoethylenically unsaturated hydrocarbon

Abstract

A pressure-sensitive adhesive composition having well-balanced pressure-sensitive adhesive force and cohesive force without causing any safety or economy problems, a process for the preparation of the same and pressure-sensitive adhesive sheets using the same are disclosed. The pressure-sensitive adhesive composition comprises a crosslinked polymer obtained by crosslinking a block copolymer comprising at least two of a styrene-based polymer block A and an acrylic polymer block B having a structural unit represented by the general formula (1):—[CH₂═C(R¹)COOR²]— wherein R¹ represents a hydrogen atom or methyl group, and R² represents a C_2-14 alkyl group, bonded each other, such as A-B or B-A type block copolymer and A-B-A type block copolymer.

Claims

1. A process for the preparation of a pressure-sensitive adhesive composition, which comprises subjecting a styrene-based monomer and an acrylic monomer represented by the general formula (1A):

CH₂═

C(R¹)COOR² wherein R¹ represents a hydrogen atom or methyl group, and R² represents a C_2-14 alkyl group, to a living radical polymerization in an appropriate order of monomers using a polymerization initiator in the presence of a transition metal and its ligand to produce a block copolymer comprising at least two of a styrene-based polymer block A and an acrylic polymer block B bonded to each other, and then subjecting said block copolymer to crosslinking to produce a crosslinked polymer,

wherein said styrene-based monomer and said acrylic monomer are subjected to a living radical polymerization together with at least one monomer selected from the group consisting of a monomer having an epoxy group in its molecule and a monomer having a hydroxyl group in its molecule.

2. The process for the preparation of a pressure-sensitive adhesive composition as claimed in claim 1, wherein said block copolymer is an A-B type or B-A type block copolymer.

3. The process for the preparation of a pressure-sensitive adhesive composition as claimed in claim 2, wherein said styrene-based polymer block A is present in an amount not exceeding 50% by weight based on the total weight of said block copolymer.

4. The process for the preparation of a pressure-sensitive adhesive composition as claimed in claim 1, wherein said block copolymer is an A-B-A type block copolymer.

5. The process for the preparation of a pressure-sensitive adhesive composition as claimed in claim 4, wherein said styrene-based polymer block A is present in an amount not exceeding 60% by weight based on the total weight of said block copolymer.

6. The process for the preparation of a pressure-sensitive adhesive composition as claimed in claim 1, 2, 3, 4 or 5, wherein said block copolymer contains a hydroxyl group in its polymer chain and is heat-crosslinked with addition of a polyfunctional isocyanate to the hydroxyl group.

7. The process for the preparation of a pressure-sensitive adhesive composition as claimed in claim 1, 2, 3, 4 or 5, wherein said block copolymer contains an epoxy group in its polymer chain and is irradiated with ultraviolet rays with addition of an onium salt-based curing catalyst thereto to epoxy-crosslink.

8. The process for the preparation of a pressure-sensitive adhesive composition as claimed in claim 7, wherein said block copolymer contains at least two epoxy groups per molecule.

9. The process for the preparation of a pressure-sensitive adhesive composition as claimed in claim 8, wherein said epoxy groups are incorporated in said block copolymer at or in the vicinity of the end of the polymer chain thereof.

10. The process for the preparation of a pressure-sensitive adhesive composition as claimed in claim 7, wherein said block copolymer contains at least one epoxy group and at least one hydroxyl group per molecule.

11. The process for the preparation of a pressure-sensitive adhesive composition as claimed in claim 10, wherein said epoxy groups are incorporated in said block copolymer at or in the vicinity of the end of the polymer chain thereof and said hydroxyl groups are incorporated in said block copolymer at or in the vicinity of the polymer chain thereof.

12. The process for the preparation of a pressure-sensitive adhesive composition as claimed in claim 7, wherein said block copolymer contains at least two hydroxyl groups per molecule and is epoxy-crosslinked with addition of the onium salt-based curing catalyst and an epoxy-based crosslinking agent to the hydroxyl group.

13. The process for the preparation of a pressure-sensitive adhesive composition as claimed in claim 12, wherein said hydroxyl groups are incorporated in said block copolymer at or in the vicinity of the end of the polymer chain thereof.

14. The process for the preparation of a pressure-sensitive adhesive composition as claimed in claim 1, wherein said transition metal is Cu, Ru, Fe, Rh, V or Ni and its ligand is a bipyridine derivative, mercaptan derivative or trifluorate derivative.

15. The process for the preparation of a pressure-sensitive adhesive composition as claimed in claim 14, wherein a combination of said transition metal and said ligand is Cu⁺¹-bipyridine complex.

16. The process for the preparation of a pressure-sensitive adhesive composition as claimed in claim 1, wherein said polymerization initiator is an ester- or styrene-based derivative containing a halogen in α

-position.

17. The process for the preparation of a pressure-sensitive adhesive composition as claimed in claim 1, wherein said polymerization initiator contains an epoxy group or hydroxyl group in its molecule.

18. A process for the preparation of pressure-sensitive adhesive sheets comprising

preparing a pressure-sensitive adhesive composition by subjecting a styrene-based monomer and an acrylic monomer represented by the general formula (1A):

CH₂═

C(R¹)COOR² wherein R¹ represents a hydrogen atom or methyl group, and R2 represents a C_2-14 alkyl group, to a living radical polymerization in an appropriate order of monomers using a polymerization initiator in the presence of a transition metal and its ligand to produce a block copolymer comprising at least two of a styrene-based polymer block A and an acrylic polymer block B bonded to each other, and then subjecting said block copolymer to crosslinking to produce a crosslinked polymer,

wherein said styrene-based monomer and said acrylic monomer are subjected to a living radical polymerization together with at least one monomer selected from the group consisting of a monomer having an epoxy group in its molecule and a monomer having a hydroxyl group in its molecule, and

providing a layer of the pressure-sensitive adhesive composition on a support.