Silicone copolymer modified release tapes

• US 5,866,222 A
• Filed: 07/18/1997
• Issued: 02/02/1999
• Est. Priority Date: 07/18/1997
• Status: Expired due to Term

• Current Assignee: 3M Company
• Original Assignee: 3M Company
• Inventors: Seth, Jayshree, Kinning, David J., Bany, Stephen W.
• Primary Examiner(s): PEZZUTO, HELEN LEE
• Application Number:
  US08/896,708
• Time in Patent Office: 564 Days
• Field of Search: 428/40.1, 428/41.4, 442/87, 442/99
• US Class Current: 428/41.4
• CPC Class Codes: C08G 18/61 Polysiloxanes
• 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: C09D 151/08 grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• 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: C09D 183/10 Block or graft copolymers containing polysiloxane sequences obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C09D151/08, C09D153/00
• CPC Class Codes: Y10T 428/14 Layer or component removable to expose adhesive
• CPC Class Codes: Y10T 428/1457 Silicon
• CPC Class Codes: Y10T 442/223 Organosilicon containing
• CPC Class Codes: Y10T 442/2328 Organosilicon containing

Abstract

There is provided a block, segmented or graft copolymer having polyorganosiloxane segments and self-associating hard segments, which copolymer is capable of forming a solid, generally non-tacky release coating without the requirement of curing. The release coating comprises the polyorganosiloxane copolymer admixed with an MQ resin wherein the amount of MQ resin is generally between 1 and 30 weight percent of the polyorganosiloxane content preferably 1 to 20 weight percent. The MQ resin modifies the copolymer release material to have a higher release than the copolymer itself, generally at least 10 percent and preferable at least 20 percent up to 50 percent or higher with the readhesion values decreasing by 50 percent or less, preferably 40 percent or less.

Claims

1. A release coated backing material comprising a backing web having a first face and a second face, at least the first face having a substantially tack free release coating of a blend of a MQ resin and a thermoplastic copolymer having polyorganosiloxane segments and hard segments having a Tg of at least 20°

C. wherein the amount of MQ resin is between 1 and 30 weight percent of the polyorganosiloxane content.

2. The release coated backing material of claim 1 wherein the amount of MQ resin is between 1 and 20 weight percent of the polyorganosiloxane content.

3. The release coated backing material of claim 1 wherein the hard segments have a Tg of at least about 65°

C.

4. The release coated backing material of claim 1 wherein the polyorganosiloxane is a polyalkylsiloxane.

5. The release coated backing material of claim 4 wherein the polyalkylsiloxane alkyl groups contain one to six carbon atoms.

6. The release coated backing material of claim 5 wherein the alkyl groups are predominately methyl.

7. The release coated backing material of claim 4 wherein the polyorganosiloxane copolymer is a segmented copolymer.

8. The release coated backing material of claim 4 wherein the polyorganosiloxane segments have a molecular weight of at least about 1000.

9. The release coated backing material of claim 4 wherein the polyorganosiloxane segments have a molecular weight of from 2000 to 20000.

10. The release coated backing material of claim 4 wherein the polyorganosiloxane segments have a molecular weight of from 4000 to 10000.

11. The release coated backing material of claim 1 wherein the hard segments comprise an isocyanate reaction product.

12. The release coated backing material of claim 1 wherein the MQ resin comprises MQ silicate resins, MQD silicate resins, MQT silicate resins or combinations thereof.

13. The release coated backing material of claim 12 wherein the MQ resin has a number average molecular weight from about 100 to 50,000.

14. The release coated backing material of claim 1 wherein the backing web comprises a woven, nonwoven, knitted, film or laminate thereof.

15. The release coated backing material of claim 1 further comprising a pressure-sensitive adhesive on the second face.

16. The release coated backing material of claim 1 wherein a polyorganosiloxane used to form the copolymer is preferably substantially difunctional or monofunctional to obtain segmented or graft copolymers.

17. The release coated backing material of claim 1 wherein the polyorganosiloxane contains reactive group(s) selected from vinyl, hydroxy, mercapto, thio, amino, carboxy or the like, which is reacted with primary hard segment group selected from a vinyl, ester, isocyanate, amine, carboxylic acid or the like.

18. The release coated backing material of claim 17 wherein the polyorganosiloxane is a polyalkylsiloxane and the hard segment groups are substantially difunctional.

19. The release coated backing material of claim 1 wherein the polyorganosiloxane copolymer is a graft copolymer.

20. The release coated backing material of claim 19 wherein the polyorganosiloxane is the graft segment formed from substantially monofunctional macromers.

21. The release coated backing material of claim 19 wherein the polyorganosiloxane is the backbone segment having one or more reactive groups.

22. The release coated backing material of claim 1 wherein the copolymer has polyvinyl hard segments formed by free radical polymerization.

23. The release coated backing material of claim 22 wherein the polyvinyl hard segments are formed by in situ reaction of reactive polyorganosiloxane with free radically polymerizable vinyl monomers, with optional free radically polymerizable monomer or macromer modifiers such as polar monomers.

24. The release coated backing material of claim 23 wherein the free radically polymerizable vinyl monomers comprise styrene, vinyl acetate, vinyl chloride, acrylic or methacrylic esters of nontertiary alcohols or combinations thereof.

25. The release coated backing material of claim 7 wherein the segmented copolymer is comprising a primary hard segment formed from a diisocyanate used to forming a polyurea or polyurethane in conjunction with a terminally functional diamine or diol polyorganosiloxane with optional chain extending soft or hard segments.

26. The release coated backing material of claim 25 wherein the diisocyanates comprises 2,6-toluene diisocyanate, p-phenylene diisocyanate, methylene bis(o-chlorophenyl diisocyanate), methylenediphenylene-4,4'"'"'-diisocyanate, polycarbodiimide-modified methylenediphenylene diisocyanate, (4,4'"'"'-diisocyanato-3,3'"'"',5,5'"'"'-tetraethyl) diphenylmethane, 4,4'"'"'-diisocyanato-3,3'"'"'-dimethoxybiphenyl(o-dianisidine diisocyanate), 5-chloro-2,4-toluene diisocyanates, m-xylylene diisocyanate, tetramethyl-m-xylylene diisocyanate 1,4-diisocyanatobutane, 1,6-diisocyanatohexene, 2,2,4-trimethylhexyl diisocyanate, 1,12-diisocyanatododecane, 2-methyl-1,5-diisocyanatopentane, and cycloaliphatic diisocyanates such as methylene-dicyclohexylene-4,4'"'"'-diisocyanate, and 3-isocyanatomethyl-3,5,5-trimethyl-cyclohexyl isocyanate and mixtures thereof.

27. The release coated backing material of claim 26 wherein the primary hard segments are formed from diisocyanates which can be represented by the formula:

space="preserve" listing-type="equation">OCN--Z--NCO

wherein Z is a polyvalent radical selected from arylene or alkylene radicals having from 6 to 20 carbon atoms, alkylene or cycloalkylene radicals having from 6 to 20 carbon atoms, and mixtures thereof.

28. The release coated backing material of claim 25 wherein the diisocyanates comprises 2,6-toluene diisocyanate, methylenediphenylene-4,4'"'"'-diisocyanate, polycarbodiimide-modified methylenediphenyl diisocyanate, o-dianisidine diisocyanate, tetramethyl-m-xylylene diisocyanate, methylenedicyclohexylene-4,4'"'"'-diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 2,2,4-trimethylhexyl diisocyanate, 1,6-diisocyanatohexane, and cyclohexylene-1,4-diisocyanate and mixtures thereof.

29. The release coated backing material of claim 1 where the release coating is hot melt coated.

30. The release coated backing material of claim 16 wherein the polyorganosiloxane is a diamine represented by the formula:

##STR2## including those having number average molecular weights in the range of about 700 to 150,000,

D is individually selected from hydrogen, alkyl radicals having from 1 to 10 carbon atoms, phenyl radicals, or can form a ring structure with Y to form a heterocycle having from about 6 to 20 carbon atoms,

Y is individually selected from an alkylene radical having from 1 to 10 carbon atoms, an aralkyl radical or an aryl radical,

R is individually selected from substituted or unsubstituted radicals such as a monovalent alkyl or cycloalkyl radical having from 2 to 12 carbon atoms, a substituted alkyl radical having from 2 to 12 carbon atoms, a vinyl radical, a phenyl radical, a substituted phenyl radical, however at least 50 percent of the R radicals should be methyl,

p is 5 or more.

31. The release coated backing material of claim 30 wherein the polydialkylsiloxane is substantially pure polydialkylsiloxane diamine.

32. The release coated backing material of claim 30 wherein the polydialkylsiloxane diamine comprises polydimethylsiloxane diamine, polydiphenylsiloxane diamine, polytrifluoropropylmethylsiloxane diamine, polyphenylmethylsiloxane diamine, polydiethylsiloxane diamine, polydivinylsiloxane diamine, polyvinylmethylsiloxane diamine, poly(5-hexenyl)methylsiloxane diamine, mixtures and copolymers thereof.

33. The release coated backing material of claim 1 wherein the MQ resin has a number average molecular weight of about 100 to about 50,000.

34. The release coated backing material of claim 1 wherein the MQ resin has a number average molecular weight of about 500 to about 20,000 with primarily methyl substituents.

35. The release coated backing material of claim 1 wherein the release coating comprises a blend further comprising fillers, plasticizers and other property modifiers in amounts ranging from 0 to about 80 weight percent of the blend which modifiers do not adversely effect the overall release properties of the release coating.

36. The release coated backing material of claim 1 wherein the copolymer further comprises non-silicone soft segments.

37. The release coated backing material of claim 36 wherein the non-silicone soft segments are primarily difunctional.

38. The release coated backing material of claim 16 wherein the copolymers further comprises chain extenders comprising short chain divinyls, diamines such as hexamethylene diamine, xylylene diamine, 1,3-di(4-piperidyl)propane (DIPIP), N(-2-aminoethyl propylmethyldimethoxysilane (DAS), piperazine 1,3-diaminopentane (DAMP), 1,4 diaminopentane, piperidyl propane or short chain diols such as 1,4-butanediol, ethylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1-6-hexanediol, 1,4-cylcohexane dimethanol and the like.

39. The release coated backing material of claim 38 wherein the non-silicone soft segments are chain extenders comprising polymeric diamines or diols such as polyethylene oxide diamine, polypropylene oxide diamine, polytetramethylene oxide diamine or diols such as polytetramethylene oxide glycol, polyethylene oxide glycol, polyethylene oxide glycol, polypropylene oxide glycol, polycaprolactone glycol, and the like.

40. The release coated backing material of claim 1 wherein the polyorganosiloxane copolymers are comprised of 2 to 90 weight percent hard segment and 98 to 10 weight percent polyorganosiloxane, with chain extending agents comprising from 0 to 80 weight percent of the copolymer.

41. The release coated backing material of claim 40 wherein the hard segment comprises from 2 to 90 weight percent of the copolymer.

42. The release coated backing material of claim 40 wherein the hard segment comprises from 5 to 60 weight percent of the polyorganosiloxane copolymer.

43. The release coated backing material of claim 40 wherein the hard segment comprises 15 to 50 weight percent of the copolymer.

44. The release coated backing material of claim 15 wherein the pressure-sensitive adhesive provided on the second face of the web backing comprises a tackified elastomer based adhesive.

45. The release coated backing material of claim 15 wherein the pressure-sensitive adhesive provided on the second face of the web backing comprises a A-B type block copolymer elastomer where the A blocks are predominately polyarenes and the B blocks are predominately polydienes tackified with solid and/or liquid tackifiers.

46. The release coated backing material of claim 1 wherein the release coating'"'"'s release value with MQ resin is at least 10 percent higher than without the MQ resin.

47. The release coated backing material of claim 1 wherein the release coating'"'"'s release value with MQ resin is at least 20 percent higher than without the MQ resin.

48. The release coated backing material of claim 1 wherein the release coating'"'"'s release value with MQ resin is at least 50 percent higher than without the MQ resin.