Silicone pressure sensitive adhesives

• US 5,961,770 A
• Filed: 11/16/1998
• Issued: 10/05/1999
• Est. Priority Date: 07/05/1996
• Status: Expired due to Term

• Current Assignee: Dow Corning Corporation (Dow, Inc.)
• Original Assignee: Dow Corning Corporation (Dow, Inc.)
• Inventors: Fenton, William Neal, Cifuentes, Martin Eric
• Primary Examiner(s): Short, Patricia A.
• Application Number:
  US09/192,690
• Time in Patent Office: 323 Days
• Field of Search: 156/60, 156/329, 525/477
• US Class Current: 156/329
• CPC Class Codes: C08L 2666/28 Non-macromolecular organic substances
• 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: C09J 183/04 Polysiloxanes
• CPC Class Codes: C09J 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 C09J151/08, C09J153/00
• CPC Class Codes: Y10T 156/10 Methods of surface bonding and/or assembly therefor

Abstract

The present invention relates to pressure sensitive adhesive compositions which are prepared by heating a mixture of a polydiorganosiloxane, a silicone resin copolymer, and an organic amine compound or metal salt thereof, and then adding an organic peroxide or azo compound to the resultant reaction product. The silicone pressure sensitive adhesives of this invention are useful in preparing articles such as pressure sensitive tapes, labels, emblems and other decorative or informational signs.

Claims

1. A method of making an article of manufacture comprising:

(I) applying a silicone pressure sensitive adhesive composition to at least one surface of a substrate, wherein the silicone pressure sensitive adhesive composition is obtained by a method comprising;

(i) heating a mixture comprising;

(A)(i) a hydroxyl-terminated polydiorganosiloxane having a viscosity of from 100 to 10,000,000 mm² /s at 25°

C. or

(ii) a mixture of (a) a hydroxyl-terminated polydiorganosiloxane and (b) a polydiorganosiloxane selected from (i) polydiorganosiloxanes terminated with monovalent hydrocarbon radicals free of aliphatic unsaturation or (ii) alkenyl-terminated polydiorganosiloxanes wherein said mixture has a viscosity of from 100 to 10,000,000 mm^2/ s at 25°

C.;

(B) a soluble silicone resin comprising R₃ SiO_1/2 siloxane units and SiO_4/2 units, wherein R is selected from a monovalent hydrocarbon or halohydrocarbon radical free of aliphatic unsaturation and having from 1 to 20 carbon atoms, an alkenyl radical, or a hydroxyl radical; and

(C) an organic amine compound selected from the group consisting of primary amines, secondary amines, and tertiary amines, or a metal salt of an organic amine compound selected from the group consisting of carboxylic acid salts of organic amines and quaternary ammonium salts to form a reaction product having a solids content of at least 70% and a viscosity of up to 200,000 millipascal-seconds at 25°

; and

(ii) adding (D) an organic peroxide or azo compound to the reaction product of (i); and

(II) heating the silicone pressure sensitive adhesive composition and the substrate to cure the composition.

2. A method according to claim 1, wherein the method further comprises (III) contacting a solid support with the substrate having the adhesive composition cured thereon after step (II) whereby the solid support and the substrate are adhered together.

3. A method according to claim 1, wherein the mixture of step (i) further comprises a solvent.

4. A method according to claim 3, wherein the method further comprises stripping the reaction product of step (i) prior to step (ii).

5. A method according to claim 3, wherein the mixture of step (i) further comprises a rare earth metal salt of a fatty acid.

6. A method according to claim 1, wherein the mixture of step (i) further comprises a rare earth metal salt of a fatty acid.

7. A method according to claim 1, wherein the hydroxyl-terminated polydiorganosiloxane is a polydiorganosiloxane having the general formula

8. A method according to claim 7, wherein R¹ is selected from methyl, phenyl, or vinyl.

9. A method according to claim 1, wherein the hydroxyl-terminated polydiorganosiloxane is selected from a polydiorganosiloxane having its formula selected from

HOMe₂ SiO(Me₂ SiO)_a SiMe₂ OH,

HOMe₂ SiO(Me₂ SiO)₀.94a (Ph₂ SiO)₀.06a SiMe₂ OH,

HOPh₂ SiO(Me₂ SiO)₀.94a (Ph₂ SiO)₀.06a SiPh₂ OH,

HOMe₂ SiO(Me₂ SiO)₀.95a (MeViSiO)₀.05a SiMe₂ OH,

HOVi₂ SiO(Me₂ SiO)₀.95 a(MeViSiO)₀.05a SiVi₂ OH, or

HOR₂ SiO(Me₂ SiO)₀.88a (Ph₂ SiO)₀.12a SiR₂ OH

wherein each R is independently selected from methyl, phenyl, or vinyl, and a has a value such that the viscosity of the polydiorganosiloxane ranges from 1,000 to 500,000 mm² /s when measured at 25°

C.

10. A method according to claim 1, wherein the monovalent hydrocarbon radicals free of aliphatic unsaturation are selected from methyl or phenyl.

11. A method according to claim 1, wherein the alkenyl radical is vinyl.

12. A method according to claim 1, wherein (b)(i) is selected from

Me₃ SiO(Me₂ SiO)_a SiMe₃, Me₃ SiO(Me₂ SiO)₀.95a (MeViSiO)₀.05a SiMe₃, or

Me₃ SiO(Me₂ SiO)₀.5a (MePhSiO)₀.5a SiMe₃ wherein Me, Vi, and Ph denote methyl, vinyl and phenyl, respectively, and a has a value such that the viscosity of the polydiorganosiloxane ranges from 1,000 to 500,000 mm² /s when measured at 25°

C.

13. A method according to claim 1, wherein (b)(ii) is selected from

ViMe₂ SiO(Me₂ SiO)_a SiMe₂ Vi, ViMe₂ SiO(Me₂ SiO)₀.95a (MePhSiO)₀.05a SiMe₂ Vi,

ViMe₂ SiO(Me₂ SiO)₀.98a (MeViSiO)₀.02a SiMe₂ Vi,

PhMeViSiO(Me₂ SiO)_a SiPhMeVi, or

PhMeViSiO(Me₂ SiO)₀.8a (MePhSiO)₀.1a (Ph₂ SiO)₀.1a SiPhMeVi, wherein Me, Vi, and Ph denote methyl, vinyl and phenyl, respectively, and a has a value such that the viscosity of the polydiorganosiloxane ranges from 1,000 to 500,000 mm² /s when measured at 25°

C.

14. A method according to claim 1, wherein R is selected from methyl, phenyl, vinyl, or hydroxyl.

15. A method according to claim 1, wherein the molar ratio of R₃ SiO_1/2 units to SiO_4/2 units is from 0.5 to 1.3.

16. A method according to claim 1, wherein (B) has a number average molecular weight of 3,000 to 7,500.

17. A method according to claim 1, wherein (C) is selected from methylamine, ethylamine, propyl amine, hexylamine, butanolamine, butylamine, dimethylamine, diethylamine, diethanolamine, dipropylamine, dibutylamine, dihexylamine, ethylamylamine, propylhexylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, pyridine, methyldipropylamine, tripropanolamine, methylpropylhexylamine, diethylammonium acetate, butylammonium octoate, trimethylammonium laurate, tetramethylammonium acetate, methylethyldibutylammonium chloride, dioctadecyldimethylammonium chloride, methylimidazole, or imidazole.

18. A method according to claim 1, wherein (D) is selected from benzoyl peroxide, dichlorobenzoyl peroxide, or azobisisobutyronitrile.

19. A method according to claim 1, wherein the reaction product of Step (i) has a solids content of at least 75% and a viscosity of up to 150,000 millipascal-seconds at 25°

C.

20. A method according to claim 1, wherein the reaction product of Step (i) has a solids content of at least 80% and a viscosity of up to 100,000 millipascal-seconds at 25°

C.