Organopolysiloxane-polyurea block copolymer release agents

• US 5,290,615 A
• Filed: 08/31/1992
• Issued: 03/01/1994
• Est. Priority Date: 06/20/1986
• Status: Expired due to Term

• Current Assignee: Minnesota Mining and Manufacturing Co (3M Company)
• Original Assignee: Minnesota Mining and Manufacturing Co (3M Company)
• Inventors: Widerholt, Gary T., Tushaus, Leonard A.
• Primary Examiner(s): DEAN JR, RALPH H
• Application Number:
  US07/938,873
• Time in Patent Office: 547 Days
• Field of Search: 428/40, 428/425.5, 528/28, 528/38, 477/387
• US Class Current: 428/41.4
• CPC Class Codes: C08G 18/61 Polysiloxanes
• CPC Class Codes: C08G 2170/40 Compositions for pressure-sensitive adhesives
• CPC Class Codes: C08G 77/26 nitrogen-containing groups
• CPC Class Codes: C08G 77/458 containing polyurethane sequences
• CPC Class Codes: Y10T 428/1457 Silicon
• CPC Class Codes: Y10T 428/31551 Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• CPC Class Codes: Y10T 428/31598 Next to silicon-containing [silicone, cement, etc.] layer
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

Block copolymers having a repeating unit comprised of polysiloxane and urea segments are prepared by copolymerizing certain diaminopolysiloxanes with diisocyanates. The invention also provides novel diaminopolysiloxanes useful as precursors in the preparation of the block copolymers and a method of making such diaminopolysiloxanes. Pressure-sensitive adhesive compositions comprising the block copolymer are also provided as are sheet materials coated with the same.

Claims

1. A pressure-sensitive adhesive tape comprising a backing member having a first front side and a second back side, a layer of pressure-sensitive adhesive on said first side and a low adhesion backsize coating on said second side, said backsize coating comprising an organopolysiloxane-polyurea block copolymer comprising the condensation reaction product of an organopolysiloxane diamine reacted with at least one diisocyanate, and up to 95 weight percent of a diamine or dihydroxy chain extender wherein the organopolysiloxane has little contamination from monofunctional or non-functional silicone as determined by the ability of the tape to functionally adhere (PSTC-1) to a glass plate after being removed from said backsize coating.

2. The pressure-sensitive adhesive tape of claim 1 wherein the diisocyanate has the formula:

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

where;

Z is a divalent radical selected from phenylene, alkylene, aralkylene or cycloalkylene.

3. The pressure-sensitive adhesive tape of claim 1 wherein the diamine or dihydroxy chain extender has the formula:

space="preserve" listing-type="equation">H--A--B--A--H

where;

B is a divalent radical selected from alkylene, aralkylene, cycloalkylene, phenylene, polyethylene oxide, polytetramethylene oxide, polycaprolactone, or mixtures thereof;

A is a difunctional moiety selected from ##STR7## where G is hydrogen, an alkyl radical of 1 to 10 carbon atoms, phenyl, or an alkylene radical which completes a ring structure including B to form a heterocycle.

4. The pressure-sensitive adhesive tape of claim 2 wherein Z is selected from the group consisting of hexamethylene, methylene, bis-(phenylene), tetramethylene, isophorone, cyclohexylene, and methylene dicyclohexylene.

5. The pressure-sensitive adhesive tape of claim 1 wherein the organopolysiloxane diamine has a molecular weight as determined by acid titration of at least 2,000.

6. The pressure-sensitive adhesive tape of claim 1 wherein the organopolysiloxane diamine has a molecular weight as determined by acid titration of at least 4,000.

7. The pressure-sensitive adhesive tape of claim 1 wherein the organopolysiloxane diamine has the general formula:

##STR8## where;

R is at least 50% methyl with the balance of 100% of all R radicals being a monovalent alkyl or substituted alkyl radical having 2 to 12 carbon atoms, a vinylene radical, phenyl radical, or substituted phenyl radical group;

Y is an alkylene radical of 1 to 10 carbon atoms;

D is hydrogen, an alkyl radical of 1 to 10 carbon atoms or an alkylene radical which completes a ring structure including Y to form a heterocycl or phenyl; and

n is a number selected to provide a molecular weight as determined by acid titration of at least 2,000.

8. The pressure-sensitive adhesive tape of claim 1 wherein the copolymer comprises from about 15 to 70% hard segments.

9. The pressure-sensitive adhesive tape of claim 7 wherein R is methyl.

10. The pressure-sensitive adhesive tape of claim 1 wherein the chain extender is a diamine.

11. The pressure-sensitive adhesive tape of claim 10 wherein the diamine is polytetramethylene oxide diamine with a molecular weight as determined by acid titration of from 5,000 to 25,000 and a functionality approaching 2.

12. The pressure-sensitive adhesive tape of claim 1 wherein the organopolysiloxane diamine has a molecular weight as determined by acid titration of at least 5,000.

13. The pressure-sensitive adhesive tape of claim 1 wherein the low adhesion backsize coating is not cured.

14. A release film for a pressure-sensitive adhesive tape comprising a backing member having a first front side and a second back side, a low adhesion backsize coating on at least said first side, said backsize coating comprising a non-crosslinked organopolysiloxane-polyurea block copolymer comprising the condensation reaction product of an organopolysiloxane diamine reacted with at least one diisocyanate, and up to 95 weight percent of a diamine or dihydroxy chain extender wherein the organopolysiloxane has little contamination from monofunctional or non-functional silicone as determined by the ability of a pressure-sensitive adhesive tape to functionally adhere (PSTC-1) to a glass plate after being removed from said backsize coating.

15. The release film of claim 14 wherein the diisocyanate has the formula:

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

where;

Z is a divalent radical selected from phenylene, alkylene, aralkylene or cycloalkylene.

16. The release film of claim 14 wherein the diamine or dihydroxy chain extender has the formula:

space="preserve" listing-type="equation">H--A--B--A--H

where;

B is a divalent radical selected from alkylene, aralkylene, cycloalkylene, phenylene, polyethylene oxide, polytetramethylene oxide, polycaprolactone, or mixtures thereof;

A is a difunctional moiety selected from ##STR9## where G is hydrogen, an alkyl radical of 1 to 10 carbon atoms, phenyl, or an alkylene radical which completes a ring structure including B to form a heterocycle.

17. The release film of claim 14 wherein the organopolysiloxane diamine has a molecular weight as determined by acid titration of at least 2,000.

18. The release film of claim 14 wherein the organopolysiloxane diamine has a molecular weight as determined by acid titration of at least 4,000.

19. The release film of claim 14 wherein the organopolysiloxane diamine has the general formula:

##STR10## where;

R is at least 50% methyl with the balance of 100% of all R radicals being a monovalent alkyl or substituted alkyl radical having 2 to 12 carbon atoms, a vinylene radical, phenyl radical, or substituted phenyl radical group;

Y is an alkylene radical of 1 to 10 carbon atoms;

D is hydrogen, an alkyl radical of 1 to 10 carbon atoms or an alkylene radical which completes a ring structure including Y to form a heterocycle or phenyl; and

n is a number selected to provide a molecular weight as determined by acid titration of at least 2,000.

20. The release film of claim 14 wherein the copolymer comprises from about 15 to 70% hard segments.

21. The release film of claim 18 wherein R is methyl.

22. The release film of claim 14 wherein the chain extender is a diamine.

23. The release film of claim 22 wherein the diamine is polytetramethylene oxide diamine with a molecular weight as determined by acid titration of from 5,000 to 25,000 and a functionality approaching 2.

24. The release film of claim 14 wherein the organopolysiloxane diamine has a molecular weight as determined by acid titration of at least 5,000.

25. A method for forming a release coating on a backing member having a first front face and a second back face comprising the steps of;

providing a storage stable solution of a non-crosslinked organopolysiloxane-polyurea block copolymer formed by a condensation reaction of an organopolysiloxane diamine with at least one diisocyanate and up to 95weight percent of a diamine or dihydroxy chain extender with little or no residue contamination from monofunctional or non-functional silicones,

coating said storage stable solution onto the backing member, having first and second faces, on at least said first face, and

forming an elastomeric film layer release coating on said backing member of said non-crosslinked organopolysiloxane-polyurea block copolymer, without chemical crosslinking of the block copolymer, wherein the film layer is characterized by the ability of a pressure-sensitive adhesive to be removably adhered thereto such that the pressure-sensitive adhesive will functionally adhere (PSTC-1) to a glass plate after being removed from said release coating.

26. The method of claim 25 wherein the film layer is formed by evaporation of the solvent for the storage-stable solution.

27. The method of claim 26 further comprising coating said second face of said backing member with a layer of pressure-sensitive adhesive.