Silicone pressure sensitive adhesive compositions

• US 5,916,981 A
• Filed: 03/24/1997
• Issued: 06/29/1999
• Est. Priority Date: 03/24/1997
• Status: Expired due to Term

• Current Assignee: Dow, Inc.
• Original Assignee: Dow, Inc.
• Inventors: Fenton, William Neal, Cifuentes, Martin Eric
• Primary Examiner(s): Glass, Margaret W.
• Application Number:
  US08/822,844
• Time in Patent Office: 827 Days
• Field of Search: 525/477, 428/447, 156/329, 524/284, 524/490, 524/251, 524/322, 524/391, 524/379, 524/385, 524/361, 524/378, 524/268, 522/60, 522/62
• US Class Current: 525/477
• CPC Class Codes: C08G 77/44 containing only polysiloxane sequences
• CPC Class Codes: C08L 2666/28 Non-macromolecular organic substances
• 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 428/31663 As siloxane, silicone or silane

Abstract

This invention relates to pressure sensitive adhesive compositions which are obtained by a method comprising reacting a mixture of at least one polydiorganosiloxane, at least one silicone resin copolymer, at least one silanol condensation catalyst, and at least one solvent or plasticizer having a boiling point of at least 200° C., to form a reaction product, 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 silicone pressure sensitive adhesive composition obtained by a method comprising the steps of

(I) reacting a mixture comprising

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

C.;

(B) at least one soluble silicone resin consisting essentially of at least one R₃ SiO_1/2 unit and at least one SiO_4/2 unit, wherein R is independently 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 wherein the molar ratio of R₃ SiO_1/2 units to SiO_4/2 units is from 0.5;

1 to 1.2;

1;

(C) at least one silanol condensation catalyst selected from the group consisting of liquid catalysts having a boiling point of less than 200°

C. and catalysts which are solid at room temperature; and

(D) at least one solvent or plasticizer having a boiling point of at least 200°

C. to form a reaction product; and

(II) adding (E) an organic peroxide or azo compound to the reaction product of (I).

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

3. A composition 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.

4. A composition 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.

5. A composition according to claim 1, wherein R is independently selected from methyl, phenyl, vinyl, or hydroxyl, the molar ratio of R₃ SiO_1/2 units to SiO_4/2 units is from 0.6:

1 to 1;

1, and (B) has a number average molecular weight of 3,000 to 7,500.

6. A composition according to claim 1, wherein (C) is selected from alkali metal hydroxides, alkali metal alkoxides, alkali metal carbonates, alkali metal silanolates, amines, carboxylic acid salts of amines, quaternary ammonium salts, carboxylic acids, or metal salts of carboxylic acids.

7. A composition according to claim 1, wherein (C) is selected from trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, methyldipropylamine, tripropanolamine, pyridine, N-methylimidazole, methylpropylhexylamine, acetic acid, propanoic acid, butanoic acid, formic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, stearic acid, potassium formate, or potassium acetate.

8. A composition according to claim 1, wherein (D) is selected from the group consisting of aliphatic hydrocarbons, glycol ethers, esters, alcohols, ester alcohols, ketones, kerosenes, naphthas, petrolatums, carboxylic acids having at least six carbon atoms, and amines having at least nine carbon atoms.

9. A composition according to claim 1, wherein (D) is selected from the group consisting of dodecane, tridecane, tetradecane, 1-tetradecene, pentadecane, hexadecane, octadecane, nonadecane, diethylene glycol ethyl ether, diethylene glycol butyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol butyl ether, ethylene glycol phenyl ether, propylene glycol phenyl ether, aromatic based glycol ethers, diethylene glycol butyl ether acetate, pine oil, mineral seal oil, tridecyl alcohol, trimethyl pentane diol isobutyrate, isophorone, nonanoic acid, caproic acid, caprylic acid, oleic acid, linoleic acid, linolenic acid, dodecylamine, hexadecylamine, octadecylamine, dimethyldodecylamine, dicocoamine, methyldicocoamine, dimethyl cocoamine, dimethyltetradecylamine, dimethylhexadecylamine, dimethyloctadecylamine, dimethyl tallow amine, dimethyl nonylamine, di(hydrogenated-tallow)amine, and methyldi(hydrogenated-tallow)amine.

10. A composition according to claim 1, wherein the mixture of step (I) further comprises a rare earth metal salt of a fatty acid.

11. A composition according to claim 1, wherein the mixture of step (I) further comprises a solvent having a boiling point of less than 200°

C.

12. A composition according to claim 10, wherein the mixture of step (I) further comprises a solvent having a boiling point of less than 200°

C.

13. A composition according to claim 11, wherein the solvent is selected from benzene, toluene, xylene, alcohols, naphtha, cyclic polysiloxanes, or mineral spirits.

14. A composition according to claim 12, wherein the solvent is selected from benzene, toluene, xylene, alcohols, naphtha, cyclic polysiloxanes, or mineral spirits.

15. A composition according to claim 1, wherein (E) is selected from benzoyl peroxide, dichlorobenzoyl peroxide, azobisisobutyronitrile, or 2,4-dimethyl-4-methoxyvaleronitrile.

16. A composition according to claim 1, wherein step (I) comprises reacting a mixture comprising components (A), (B), and (C), (II) adding component (D) to the product of (I), and optionally (III) heating the product of (II) to form a reaction product.

17. A composition according to claim 1, wherein the reaction product of step (I) has a solids content of at least 60% and a viscosity of up to 200,000 millipascal-seconds (mPa.s).

18. An article of manufacture obtained by a method 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 the steps of

(i) reacting a mixture comprising

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

C.;

(B) at least one soluble silicone resin consisting essentially of at least one R₃ SiO_1/2 unit and at least one SiO_4/2 unit, wherein R is independently 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 wherein the molar ratio of R₃ SiO_1/2 units is from 0.5;

1 to 1.2;

1;

(C) at least one silanol condensation catalyst selected from the group consisting of liquid catalysts having a boiling point of less than 200°

C. and catalysts which are solid at room temperature; and

(D) at least one solvent or plasticizer having a boiling point of at least 200°

C. to form a reaction product; and

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

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

19. An article of manufacture according to claim 18, wherein the article is further obtained by (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.

20. An article of manufacture according to claim 18, wherein step (i) comprises reacting a mixture comprising components (A), (B), and (C), adding component (D), and optionally heating the resulting product to form a reaction product.

21. An article of manufacture according to claim 18, wherein (C) is selected from alkali metal hydroxides, alkali metal alkoxides, alkali metal carbonates, alkali metal silanolates, amines, carboxylic acid salts of amines, quaternary ammonium salts, carboxylic acids, or metal salts of carboxylic acids.

22. An article of manufacture according to claim 18, wherein (D) is selected from the group consisting of aliphatic hydrocarbons, glycol ethers, esters, alcohols, ester alcohols, ketones, kerosenes, naphthas, petrolatums, carboxylic acids having at least six carbon atoms, and amines having at least nine carbon atoms.