Curable compositions, methods of making and using the same, and articles therefrom

• US 20070054080A1
• Filed: 09/07/2005
• Published: 03/08/2007
• Est. Priority Date: 09/07/2005
• Status: Active Grant

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Qiu, Zai-Ming, Hulteen, John
• Granted Patent: US 7,279,210 B2
• Time in Patent Office: Days
• US Class Current: 428/40.100
• 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 83/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: C09D 133/16 Homopolymers or copolymers of esters containing halogen atoms
• CPC Class Codes: C09D 183/04 Polysiloxanes
• CPC Class Codes: C09J 2400/226 in the substrate
• CPC Class Codes: C09J 2400/283 in the substrate
• CPC Class Codes: C09J 2427/005 in the release coating
• CPC Class Codes: C09J 2433/005 in the release coating
• CPC Class Codes: C09J 2475/00 Presence of polyurethane
• CPC Class Codes: C09J 2483/00 Presence of polysiloxane
• CPC Class Codes: C09J 2483/005 in the release coating
• CPC Class Codes: C09J 7/201 characterised by the release coating composition on the carrier layer
• CPC Class Codes: C09J 7/21 Paper; Textile fabrics
• CPC Class Codes: C09J 7/22 Plastics; Metallised plastics
• CPC Class Codes: Y10T 428/14 Layer or component removable to expose adhesive
• CPC Class Codes: Y10T 428/1457 Silicon
• CPC Class Codes: Y10T 428/2848 Three or more layers
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

A curable composition comprises a fluoropolymer, a silicone having a plurality of vinyl groups, a silicone having a plurality of Si—H groups, and a hydrosilation catalyst. Reaction products of the curable composition are used as release materials for release liners and adhesive articles.

Claims

1. A curable composition comprising:

(a) a fluoropolymer that is a reaction product of components comprising a polyfunctional (meth)acrylate and a fluoroacrylate monomer represented by the formula;

wherein;

n is an integer in a range of from 1 to 6, inclusive,

wherein;

R is H or an alkyl group having 1 to 4 carbon atoms;

m is an integer in a range of from 2 to 8, inclusive;

R_f is C_nF_2n+1;

y is an integer in a range of from 0 to 6, inclusive;

q is an integer in a range of from 1 to 8, inclusive; and

A is a hydrocarbylene group;

p is an integer in a range of from 2 to 30, inclusive; and

R′

is H, CH₃, or F;

(b) a silicone having a plurality of vinyl groups;

(c) a silicone having a plurality of Si—

H groups; and

(d) a hydrosilation catalyst.

2. A curable composition according to claim 1, wherein the components further comprise a chain transfer agent.

3. A curable composition according to claim 1, wherein the fluoropolymer is a reaction product of components comprising a polyfunctional (meth)acrylate and a fluoroacrylate monomer represented by the formula:

4. A curable composition according to claim 1, wherein at least one of the silicones comprises a fluorosilicone.

5. A curable composition according to claim 1, wherein the polyfunctional (meth)acrylate is a polyethylene glycol di(meth)acrylate.

6. A curable composition according to claim 1, wherein the weight ratio of fluoropolymer to silicone is in a range of from 1:

2 to 5;

1, inclusive.

7. A method of making a composition comprising:

at least partially curing a curable composition, the curable composition comprising;

(a) a fluoropolymer that is a reaction product of components comprising a polyfunctional (meth)acrylate and a fluoroacrylate monomer represented by the formula;

wherein;

n is an integer in a range of from 1 to 6, inclusive,

wherein;

R is H or an alkyl group having 1 to 4 carbon atoms;

m is an integer in a range of from 2 to 8, inclusive;

R_{f l is Cn}F_2n+1;

y is an integer in a range of from 0 to 6, inclusive;

q is an integer in a range of from 1 to 8, inclusive; and

A is a hydrocarbylene group;

p is an integer in a range of from 2 to 30, inclusive; and

R′

is H, CH₃, or F;

(b) a silicone having a plurality of vinyl groups;

(c) a silicone having a plurality of Si—

H groups; and

(d) a hydrosilation catalyst.

8. A method according to claim 7, wherein the components further comprise a chain transfer agent.

9. A method according to claim 7, wherein the fluoropolymer is a reaction product of components comprising a polyfunctional (meth)acrylate and a fluoroacrylate monomer represented by the formula:

10. A method according to claim 7, wherein at least one of the silicones comprises a fluorosilicone.

11. A composition comprising a reaction product of a curable composition comprising:

(a) a fluoropolymer that is a reaction product of components comprising a polyfunctional (meth)acrylate and a fluoroacrylate monomer represented by the formula;

wherein;

n is an integer in a range of from 1 to 6, inclusive,

wherein;

R is H or an alkyl group having 1 to 4 carbon atoms;

m is an integer in a range of from 2 to 8, inclusive;

R_f is C_nF_2n+1;

y is an integer in a range of from 0 to 6, inclusive;

q is an integer in a range of from 1 to 8, inclusive; and

A is a hydrocarbylene group;

p is an integer in a range of from 2 to 30, inclusive; and

R′

is H, CH₃, or F;

(b) a silicone having a plurality of vinyl groups;

(c) a silicone having a plurality of Si—

H groups; and

(d) a hydrosilation catalyst.

12. A composition according to claim 11, wherein the components further comprise a chain transfer agent.

13. A composition according to claim 11, wherein the fluoropolymer is a reaction product of components comprising a polyfunctional (meth)acrylate and a fluoroacrylate monomer represented by the formula:

14. A composition according to claim 11, wherein the polyfunctional (meth)acrylate is a polyethylene glycol di(meth)acrylate.

15. A composition according to claim 11, wherein the weight ratio of fluoropolymer to silicone is in a range of from 1:

2 to 5;

1, inclusive.

16. A release liner comprising a carrier and a release material, wherein the release material is present on at least one major surface of the carrier, and wherein the release material comprises a reaction product of a curable composition comprising:

(a) a fluoropolymer that is a reaction product of components comprising a polyfunctional (meth)acrylate and a fluoroacrylate monomer represented by the formula;

wherein;

n is an integer in a range of from 1 to 6, inclusive,

wherein;

R is H or an alkyl group having 1 to 4 carbon atoms;

m is an integer in a range of from 2 to 8, inclusive;

R_f is C_nF_2n+1;

y is an integer in a range of from 0 to 6, inclusive;

q is an integer in a range of from 1 to 8, inclusive; and

A is a hydrocarbylene group;

p is an integer in a range of from 2 to 30, inclusive; and

R′

is H, CH₃, or F;

(b) a silicone having a plurality of vinyl groups;

(c) a silicone having a plurality of Si—

H groups; and

(d) a hydrosilation catalyst.

17. A release liner according to claim 16, wherein the components further comprise a chain transfer agent.

18. A release liner according to claim 16, wherein the fluoropolymer is a reaction product of components comprising a polyfunctional (meth)acrylate and a fluoroacrylate monomer represented by the formula:

19. A release liner according to claim 16, wherein at least one of the silicones comprises a fluorosilicone.

20. A release liner according to claim 16, wherein the carrier comprises at least one of paper or a thermoplastic polymeric film.

21. A release liner according to claim 16, wherein the polyfunctional (meth)acrylate is a polyethylene glycol di(meth)acrylate.

22. A release liner according to claim 16, wherein the weight ratio of fluoropolymer to silicone is in a range of from 1:

2 to 5;

1, inclusive.

23. An adhesive article comprising:

a substrate having first and second opposed major surfaces;

a first layer of pressure sensitive adhesive in contact with at least a portion of the first major surface; and

a first release liner releasably bonded to at least a portion of the first adhesive layer, the first release liner comprising a first carrier and a first release material, wherein the first release material is present on at least one major surface of the first carrier, and wherein the first release material comprises a reaction product of a first curable composition comprising;

(a) a first fluoropolymer that is a reaction product of components comprising a polyfunctional (meth)acrylate and a fluoroacrylate monomer represented by the formula;

wherein;

n is an integer in a range of from 1 to 6, inclusive,

wherein;

R is H or an alkyl group having 1 to 4 carbon atoms;

m is an integer in a range of from 2 to 8, inclusive;

R_f is C_nF_2n+1;

y is an integer in a range of from 0 to 6, inclusive;

q is an integer in a range of from 1 to 8, inclusive; and

A is a hydrocarbylene group;

p is an integer in a range of from 2 to 30, inclusive; and

R′

is H, CH₃, or F; and

(b) a first silicone having a plurality of vinyl groups;

(c) a first silicone having a plurality of Si—

H groups; and

(d) a first hydrosilation catalyst.

24. An adhesive article according to claim 23, wherein the components further comprise a chain transfer agent.

25. An adhesive article according to claim 23, wherein the first fluoropolymer is a reaction product of components comprising a polyfunctional (meth)acrylate and a fluoroacrylate monomer represented by the formula:

26. An adhesive article according to claim 23, wherein at least one of the first silicones comprises a fluorosilicone.

27. An adhesive article according to claim 23, wherein the first carrier comprises at least one of paper or a thermoplastic polymeric film.

28. An adhesive article according to claim 23, wherein the first pressure sensitive adhesive comprises a silicone.

29. An adhesive article according to claim 23, wherein the first pressure sensitive adhesive comprises a tackified polydiorganosiloxane polyurea block copolymer.

30. An adhesive article according to claim 23, wherein the polyfunctional (meth)acrylate is a polyethylene glycol di(meth)acrylate.

31. An adhesive article according to claim 23, wherein the weight ratio of fluoropolymer to silicone is in a range of from 1:

2 to 5;

1, inclusive.

32. An adhesive article according to claim 23, further comprising:

a second layer of pressure sensitive adhesive in contact with at least a portion of the second major surface; and

a second release liner releasably bonded to at least a portion of the second adhesive layer, the second release liner comprising a second carrier and a second release material, wherein the second release material is present on at least one major surface of the second carrier, and wherein the second release material comprises a reaction product of a second curable composition comprising;

(a) a second fluoropolymer that is a reaction product of components comprising a second polyfunctional (meth)acrylate and a second monomer represented by the formula;

wherein;

n is an integer in a range of from 1 to 6, inclusive,

wherein;

R is H or an alkyl group having 1 to 4 carbon atoms;

m is an integer in a range of from 2 to 8, inclusive;

R_f is C_nF_2n+1;

y is an integer in a range of from 0 to 6, inclusive;

q is an integer in a range of from 1 to 8, inclusive; and

A is a hydrocarbylene group;

p is an integer in a range of from 2 to 30, inclusive; and

R′

is H, CH₃, or F; and

(b) a second silicone having a plurality of vinyl groups;

(c) a second silicone having a plurality of Si—

H groups; and

(d) a second hydrosilation catalyst.

33. An adhesive article according to claim 32, wherein the components further comprise a chain transfer agent.

34. An adhesive article according to claim 32, wherein the second fluoropolymer is a reaction product of components comprising a second polyfunctional (meth)acrylate and a fluoroacrylate monomer represented by the formula:

35. An adhesive article according to claim 32, wherein at least one of the second silicones comprises a fluorosilicone.

36. An adhesive article according to claim 32, wherein the first and second release liners are not identical.

37. An adhesive article comprising:

a substrate having first and second opposed major surfaces;

a layer of pressure sensitive in contact with at least a portion of the first major surface; and

a low adhesion backsize bonded to the second major surface, wherein the low adhesion backsize comprises a reaction product of a curable composition comprising;

(a) a fluoropolymer that is a reaction product of components comprising a second polyfunctional (meth)acrylate and a second monomer represented by the formula;

wherein;

n is an integer in a range of from 1 to 6, inclusive,

wherein;

R is H or an alkyl group having 1 to 4 carbon atoms;

m is an integer in a range of from 2 to 8, inclusive;

R_f is C_nF_2n+1;

y is an integer in a range of from 0 to 6, inclusive;

q is an integer in a range of from 1 to 8, inclusive; and

A is a hydrocarbylene group;

p is an integer in a range of from 2 to 30, inclusive; and

R′

is H, CH₃, or F;

(b) a silicone having a plurality of vinyl groups;

(c) a silicone having a plurality of Si—

H groups; and

(d) a hydrosilation catalyst.

38. An adhesive article according to claim 37, wherein the components further comprise a chain transfer agent.

39. An adhesive article according to claim 37, wherein the fluoropolymer is a reaction product of components comprising a polyfunctional (meth)acrylate and a fluoroacrylate monomer represented by the formula:

40. An adhesive article according to claim 37, wherein at least one of the silicones comprises a fluorosilicone.

41. An adhesive article according to claim 37, wherein at least a portion of the layer of pressure sensitive adhesive contacts the low adhesion backsize.

42. An adhesive article according to claim 37, wherein the polyfunctional (meth)acrylate is a polyethylene glycol di(meth)acrylate.

43. An adhesive article according to claim 37, wherein the weight ratio of fluoropolymer to silicone is in a range of from 1:

2 to 2;

1, inclusive.

44. An adhesive article according to claim 37, wherein the first pressure sensitive adhesive comprises a silicone.

45. An adhesive article according to claim 38, wherein the first pressure sensitive adhesive comprises a tackified polydiorganosiloxane polyurea block copolymer.

46. An adhesive article comprising:

a substrate having first and second opposed major surfaces;

a layer of a first release material bonded to at least a portion of the first major surface;

a layer of a second release material bonded to at least a portion of the second major surface;

a layer of a first pressure sensitive adhesive releasably bonded to at least a portion of the layer of the first release material;

a layer of a second pressure sensitive adhesive releasably bonded to at least a portion of the layer of the second release material;

a first substrate bonded to at least a portion of the layer of the first pressure sensitive;

a second substrate bonded to at least a portion of the layer of the second pressure sensitive;

wherein at least one of the layer of the first release material and the layer of the second release material comprises a reaction product of a curable composition comprising;

(a) a fluoropolymer that is a reaction product of components comprising a second polyfunctional (meth)acrylate and a second monomer represented by the formula;

wherein;

n is an integer in a range of from 1 to 6, inclusive,

wherein;

R is H or an alkyl group having 1 to 4 carbon atoms;

m is an integer in a range of from 2 to 8, inclusive;

R_f is C_nF_2n+1;

y is an integer in a range of from 0 to 6, inclusive;

q is an integer in a range of from 1 to 8, inclusive; and

A is a hydrocarbylene group;

p is an integer in a range of from 2 to 30, inclusive; and

R′

is H, CH₃, or F;

(b) a silicone having a plurality of vinyl groups;

(c) a silicone having a plurality of Si—

H groups; and

(d) a hydrosilation catalyst.

47. An adhesive article according to claim 46, wherein the components further comprise a chain transfer agent.

48. An adhesive article according to claim 46, wherein the layers of first and second pressure sensitive adhesives and/or their associated layers of first and second release materials, respectively, are selected such that the release of each layer of pressure sensitive from its associated layer of release material occurs at a different level of applied peel force.