Cure-on-demand, moisture-curable compositions having reactive silane functionality

• US 6,204,350 B1
• Filed: 09/16/1998
• Issued: 03/20/2001
• Est. Priority Date: 03/14/1997
• Status: Expired due to Term

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Boulos, Marie A., Everaerts, Albert I., Leir, Charles M., Moore, George G. I., Sherman, Audrey A., Liu, Junkang Jacob
• Primary Examiner(s): Dawson, Robert
• Assistant Examiner(s): Peng, Kuo-Liang
• Application Number:
  US09/153,967
• Time in Patent Office: 916 Days
• Field of Search: 427/515, 427/516, 427/195, 528/39, 528/23
• US Class Current: 528/23
• CPC Class Codes: C08K 5/5415 containing at least one Si—O bond
• CPC Class Codes: C08L 101/10 containing hydrolysable silane groups
• CPC Class Codes: C08L 2666/28 Non-macromolecular organic substances

Abstract

Cure-on-demand, moisture-curable compositions of one or more compounds comprising molecules having reactive silane functional groups and an acid generating material are taught herein. The acid generating material releases an acid upon exposure to heat, ultraviolet light, visible light, electron beam irradiation or microwave irradiation to initiate and accelerate the crosslinking reaction. Articles prepared using the moisture curable materials are also disclosed, as are methods of curing those materials.

Claims

1. A cure-on-demand, moisture-curable composition comprising:

(a) a compound comprising molecules bearing reactive silane functional groups having the structure;

wherein;

moiety A is an m-valent radical selected from fluoroalkyl radicals, fluoroaryl radicals, and polymeric radicals comprising a polymer selected from polysiloxane, polyolefin, polyester, polyphosphazene, fluorosilicone, fluorinated polyacrylate, fluorinated polyether, fluorinated polyester, and derivatives and combinations thereof;

p is an integer from 1 to 3;

m is an integer greater than or equal to 1;

each R¹ is individually selected from alkyl radicals and acyl radicals;

each R² is individually selected from hydrogen, alkyl radicals, acyl radicals and aryl radicals; and

G is an optional linking moiety which, when present, links radical A to the reactive silane functional groups; and

(b) an acid generating material that is free of ammonium salt and that liberates an acid that is capable of curing the moisture-curable composition;

wherein the reactive silane functional groups are the only acid curable groups present in the composition and wherein average reactive silane functionality of the moisture-curable composition is greater than two.

2. A cure-on-demand, moisture-curable composition according to claim 1, further comprising a reactive diluent.

3. A cure-on-demand, moisture-curable composition according to claim 1, wherein the composition is curable to provide a low surface energy material.

4. A cure-on-demand, moisture-curable composition according to claim 1, wherein the composition is curable to provide a release coating.

5. A cure-on-demand, moisture-curable composition according to claim 1, wherein the polymeric radical is of linear, branched, block or graft construction.

6. A cure-on-demand, moisture-curable composition according to claim 1, wherein A is selected from fluorosilicone, fluorinated polyacrylate, fluorinated polyether, or fluorinated polyester.

7. A cure-on-demand, moisture-curable composition according to claim 1, wherein each R¹ is individually selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms.

8. A cure-on-demand, moisture-curable composition according to claim 1, wherein each R² is individually selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms.

9. A cure-on-demand, moisture-curable composition according to claim 1, wherein m is an integer from 1 to 50.

10. A cure-on-demand, moisture-curable composition according to claim 1, wherein G is present and is selected from oxygen, alkylene radicals, arylene radicals and

wherein:

each R¹ is individually selected from alkyl radicals and acyl radicals;

each R² is individually selected from hydrogen, alkyl radicals, acyl radicals and aryl radicals;

q is an integer from 1 to 40; and

v is 0 or 1.

11. A cure-on-demand, moisture-curable composition according to claim 1, wherein:

G is —

CH₂CH₂—

;

m is 6;

p is 1 or 2;

R¹ is —

CH₂CH₃;

R² is —

CH₃; and

A is;

12. A cure-on-demand, moisture-curable composition according to claim 1, wherein:

G is —

CH₂CH₂—

;

m is 6;

p is 3;

R¹ is —

CH₂CH₃; and

A is;

13. A cure-on-demand, moisture-curable composition according to claim 1, wherein said acid generating material is capable of generating acid upon exposure to ultraviolet light, visible light, or electron beam irradiation.

14. A cure-on-demand, moisture-curable composition according to claim 1, wherein said acid generating material liberates an acid that has a pKa of less than about 3.

15. A cure-on-demand, moisture-curable composition according to claim 1, wherein said acid generating material liberates an acid that has a pKa of less than about 1.

16. A cure-on-demand, moisture-curable composition according to claim 1, wherein said acid generating material is selected from the group consisting of carboxylate esters, sulfonate esters, and onium salts.

17. A cure-on-demand, moisture-curable composition according to claim 1, wherein said acid generating material is an onium salt having the structure:

18. A cure-on-demand, moisture-curable composition according to claim 1, wherein said acid generating material is di(dodecylphenyl)iodonium hexafluoroantimonate.

19. A cure-on-demand, moisture-curable composition according to claim 1, comprising:

(a) 0 to about 100 parts by weight of a compound according to structure (I) wherein A is a polymeric radical;

(b) 0 to about 100 parts by weight of a compound according to structure (I) wherein A is a non-polymeric radical, the sum of (a) and (b) being 100 parts by weight;

(c) about 0.5 to about 20 parts by weight of an onium salt based on 100 parts by weight of (a) plus (b); and

(d) about 0.03 to about 0.1 parts by weight of a sensitizer based on 100 parts by weight (a) plus (b).

31. An article comprising a substrate and a layer of a cure-on demand moisture-curable composition according to claim 1 on the substrate.

33. An article according to claim 1 wherein the moisture-curable composition is coated on the substrate using an electrostatically-assisted coating method.

34. An article according to claim 33 wherein the moisture-curable composition is coated on the substrate using electrospray.

36. An article according to claim 31 wherein the moisture-curable composition has been cured.

40. An article according to claim 36 wherein the article is a release liner.

41. An article according to claim 40 wherein the article is a differential release liner.

47. A method of curing a composition comprising the steps of:

(a) providing a moisture-curable composition according to claim 1;

(b) activating the acid generating material to provide an acid; and

(c) allowing the composition to cure.

20. A cure-on-demand, moisture-curable composition comprising:

(a) a compound comprising molecules bearing reactive silane functional groups; and

(b) an acid generating material having the structure;

wherein;

R³ is selected from the group consisting of alkyl and fluoroalkyl groups;

R⁴ represents hydrogen or an alkyl group; and

R⁵ and R⁶ each independently represent an alkyl group, or R⁵ and R⁶ together with the carbon atom to which they are attached form a ring.

21. A cure-on-demand, moisture-curable composition according to claim 20, further comprising a reactive diluent.

22. A cure-on-demand, moisture-curable composition according to claim 20, wherein the composition is curable to provide a low surface energy material.

38. An article comprising a substrate and a layer of the moisture-curable composition of claim 20 on the substrate, wherein the moisture-curable composition has been cured.

23. A cure-on-demand, moisture-curable composition comprising:

(a) a compound comprising molecules bearing reactive silane functional groups; and

(b) an acid generating material having the structure;

wherein;

R⁷ is a fluoroalkyl group; and

each of R⁸, R⁹ and R¹⁰ independently represent an alkyl group, or R⁸ and R⁹ together with the carbon to which they are attached form a ring.

24. A cure-on-demand, moisture-curable composition according to claim 23, further comprising a reactive diluent.

25. A cure-on-demand, moisture-curable composition according to claim 23, wherein the composition is curable to provide a low surface energy material.

39. An article comprising a substrate and a layer of the moisture-curable composition of claim 23 on the substrate, wherein the moisture-curable composition has been cured.

26. A cure-on-demand, moisture-curable composition comprising:

(a) a compound comprising molecules bearing reactive silane functional groups having the structure;

wherein;

moiety A is an m-valent radical;

p is an integer from 1 to 3;

m is an integer greater than or equal to 1;

each R¹ is individually selected from alkyl radicals and acyl radicals;

each R² is individually selected from hydrogen, alkyl radicals, acyl radicals and aryl radicals; and

G has the structure;

wherein each R¹ is individually selected from alkyl radicals and acyl radicals;

each R² is individually selected from hydrogen, alkyl radicals, acyl radicals and aryl radicals;

q is an integer from 1 to 40; and

v is 0 or 1; and

(b) an acid generating material that is free of ammonium salt;

wherein the reactive silane functional groups are the only acid curable groups present in the composition.

27. A cure-on-demand, moisture-curable composition comprising:

(a) a compound comprising molecules bearing reactive silane functional groups and comprising a polymeric material that is essentially free of basic groups selected from the group consisting of amide, urea, urethane, and sulfonamide groups; and

(b) an acid generating material that is free of ammonium salt and that liberates an acid that is capable of curing of the moisture-curable composition;

wherein the reactive silane functional groups are the only acid curable groups present in the composition and wherein average reactive silane functionality of the moisture-curable composition is greater than two.

28. A cure-on-demand, moisture-curable composition according to claim 27, wherein said acid generating material liberates an acid that has a pKa of less than about 3.

29. A cure-on-demand, moisture-curable composition according to claim 27, further comprising a reactive diluent.

30. A cure-on-demand, moisture-curable composition according to claim 27, wherein the composition is curable to provide a low surface energy material.

32. An article comprising a substrate and a layer of a cure-on demand moisture-curable composition according to claim 27 on the substrate.

35. An article according to claim 27 wherein the moisture-curable composition is coated on the substrate using an electrostatically-assisted coating method.

37. An article according to claim 32 wherein the moisture-curable composition has been cured.

42. An article comprising:

(A) a release liner comprising;

(a) a substrate; and

(b) a layer of a cure-on-demand moisture-curable composition on the substrate,

wherein the cure-on-demand, moisture-curable composition comprises;

(1) a compound comprising molecules bearing reactive silane functional groups; and

(2) an acid generating material that is free of ammonium salt;

wherein the reactive silane functional groups are the only acid curable groups present in the composition; and

(B) an adhesive layer.

43. An electrostatically-assisted coatable, cure-on-demand, moisture-curable composition comprising:

(a) a compound comprising molecules bearing reactive silane functional groups; and

(b) an acid generating material that is free of ammonium salt and is electroconductivity enhancing;

wherein the reactive silane functional groups are the only acid curable groups present in the composition.

44. An electrostatically-assisted coatable, cure-on-demand, moisture-curable composition according to claim 43 wherein the composition is electrosprayable.

45. An electrostatically-assisted coatable, cure-on-demand, moisture-curable composition according to claim 43 wherein the acid generating material is selected from the group consisting of (4-octyloxyphenyl)diphenylsulfonium tetrakis(3,5-bis-trifluoromethyl phenyl)borate;

tris(dodecylphenyl)sulfonium tetrakis(3,5-bis-trifluoromethyl phenyl)borate;

bis(dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate;

(4-octyloxyphenyl)phenyliodonium tetrakis(3,5-bis-trifluoromethyl phenyl)borate; and

(tolylcumyl)iodonium tetrakis(pentafluorophenyl)borate.

46. An electrostatically-assisted coatable, cure-on-demand, moisture-curable composition according to claim 43, further comprising an electroconductivity enhancer.

48. A silicone pressure-sensitive adhesive composition comprising:

(a) 20 to about 80 parts by weight of an urea-linked reactive silane functional polysiloxane having the structure;

wherein;

p is an integer from 1 to 3;

each R¹ is individually selected from the group consisting of alkyl radicals and acyl radicals;

each R² is individually selected from the group consisting of hydrogen, alkyl radicals, acyl radicals and aryl radicals;

Y is a divalent radical that independently is an alkylene radical of 1 to 10 carbon atoms, an aralkylene radical or an arylene radical; and

A corresponds to the following formula;

wherein R³ is a vinyl radical or an alkyl moiety and x=100-2000;

(b) 80 to about 20 parts by weight of a silicate tackifying resin, wherein the sum of (a) and (b) is 100 parts by weight;

(c) and about 0.5 to about 20 parts by weight of a condensation catalyst or an acid generating material, based on 100 parts by weight of (a) plus (b).

49. An article comprising a substrate and a layer of a silicone pressure-sensitive adhesive according to claim 48 on the substrate.

50. A cure-on-demand, moisture-curable composition comprising:

(a) a compound comprising molecules bearing reactive silane functional groups having the structure;

wherein;

moiety A is an m-valent radical selected from fluorosilicone, fluorinated polyacrylate, fluorinated polyether, fluorinated polyester, and combinations thereof;

p is an integer from 1 to 3;

m is an integer greater than or equal to 1;

each R¹ is individually selected from alkyl radicals and acyl radicals;

each R² is individually selected from hydrogen, alkyl radicals, acyl radicals and aryl radicals; and

G is an optional linking moiety which, when present, links radical A to the reactive silane functional groups; and

(b) an acid generating material that is free of ammonium salt and that liberates an acid that is capable of curing the moisture-curable composition;

wherein the reactive silane functional groups are the only acid curable groups present in the composition.

51. A cure-on-demand, moisture-curable composition comprising:

(a) a compound comprising molecules bearing reactive silane functional groups having the structure;

wherein;

moiety A is an m-valent radical selected from the group consisting of fluoroalkyl radicals, fluoroaryl radicals, and polymeric radicals comprising a polymer selected from polysiloxane, polyolefin, polyester, polyphosphazene, fluorosilicone, fluorinated polyacrylate, fluorinated polyether, fluorinated polyester, and derivatives and combinations thereof;

p is an integer from 1 to 3;

m is an integer greater than or equal to 1;

each R¹ is individually selected from alkyl radicals and acyl radicals;

each R² is individually selected from hydrogen, alkyl radicals, acyl radicals and aryl radicals; and

G is a linking moiety that links radical A to the reactive silane functional groups and is selected from oxygen, alkylene radicals, arylene radicals and

wherein;

each R¹ is individually selected from alkyl radicals and acyl radicals;

each R² is individually selected from hydrogen, alkyl radicals, acyl radicals and aryl radicals;

q is an integer from 1 to 40; and

v is 0 or 1; and

(b) an acid generating material that is free of ammonium salt and that liberates an acid that is capable of curing the moisture-curable composition;

wherein the reactive silane functional groups are the only acid curable groups present in the composition.

52. A cure-on-demand, moisture-curable composition comprising:

(a) a compound comprising molecules bearing reactive silane functional groups having the structure;

wherein;

moiety A is an m-valent radical selected from the group consisting of fluoroalkyl radicals, fluoroaryl radicals, and polymeric radicals comprising a polymer selected from polysiloxane, polyolefin, polyester, polyphosphazene, fluorosilicone, fluorinated polyacrylate, fluorinated polyether, fluorinated polyester, and derivatives and combinations thereof;

p is an integer from 1 to 3;

m is an integer greater than or equal to 1;

each R¹ is individually selected from alkyl radicals and acyl radicals;

each R² is individually selected from hydrogen, alkyl radicals, acyl radicals and aryl radicals; and

G is an optional linking moiety which, when present, links radical A to the reactive silane functional groups; and

(b) an acid generating material that is free of ammonium salt and that liberates an acid that is capable of curing the moisture-curable composition;

wherein the reactive silane functional groups are the only acid curable groups present in the composition and wherein the composition comprises;

(i) 0 to about 100 parts by weight of a compound according to structure (I) wherein A is a polymeric radical;

(ii) 0 to about 100 parts by weight of a compound according to structure (I) wherein A is a non-polymeric radical, the sum of (i) and (ii) being 100 parts by weight;

(iii) about 0.5 to about 20 parts by weight of an onium salt based on 100 parts by weight of (i) plus (ii); and

(iv) about 0.03 to about 0.1 parts by weight of a sensitizer based on 100 parts by weight (i) plus (ii).