Self-crosslinking silicone pressure sensitive adhesive compositions, process for making and articles made thereof
View Patent ↗Disclosed herein are self-crosslinking compositions containing a hydrosilation catalyst and the reaction product of a mixture comprising (i) a resinous copolymer having both silicon-bonded hydrogen and silanol groups, and (ii) one or more vinyl-functional polyorganosiloxanes. These compositions have stable post-cure adhesive properties and are suitable for use in electronic applications.
1. A silicone pressure sensitive adhesive composition comprising
(A) a reaction product of a mixture comprising
(i) a resin comprising R 1 3 SiO 1/2 (“M”) units and SiO 4/2 (“Q”) units,
wherein each R 1 is independently a monovalent hydrocarbon radical having from 1 to 6 carbon atoms;
wherein the resin comprises from about 70 mol % to about 99 mol % of hydroxyl radicals and from about 1 mol % to about 30 mol % of hydride radicals, based on the total moles of the hydroxyl and the hydride radicals of the resin;
wherein the hydroxyl radicals are bonded directly to the silicon atoms of the Q units, and the hydride radicals are bonded to the silicon atoms of the Q units via —OSiHR 5 2 radicals, wherein R 5 is a monovalent hydrocarbon radical having from 1 to 6 carbon atoms; and
(ii) one or more vinyl-functional polyorganosiloxanes; and
(B) a hydrosilation catalyst.
2. The composition of claim 1 wherein the resin (A)(i) comprises from about 75 mol % to about 99 mol % of the hydroxide radicals, based on the total moles of the hydroxyl and the hydride radicals of the resin.
3. The composition of claim 1 wherein the resin (A)(i) comprises from about 5 mol % to about 25 mol % of the hydride radicals based on the total moles of the hydroxyl and the hydride radicals of the resin.
4. The composition of claim 1 wherein the molar ratio of the M units to the Q units in the resin (A)(i) is from about 0.6 to about 1.2 inclusive.
5. The composition of claim 1 wherein R 1 is methyl.
6. The composition of claim 1 wherein the resin (A)(i) is prepared by reacting a MQ resin consisting essentially of R 1 3 SiO 1/2 (“M”) units and SiO 4/2 (“Q”) units with a capping agent selected from the group consisting of silazanes, disilazanes, polysilazanes, organohydrogen chlorosilanes, hydrogen functional siloxanes, and combinations thereof, and
wherein each R 1 is independently a monovalent hydrocarbon radical having from 1 to 6 carbon atoms, the MQ resin comprises from about 1% to about 4% by weight, based on the total weight of the MQ resin, of hydroxyl radicals bonded to the silicon atoms of the Q units, and the MQ resin does not contain hydride radicals.
7. The composition of claim 1 wherein vinyl-functional polyorganosiloxane is represented by the general formula:
R 2 2 R 3 SiO(R 2 2 SiO) x (R 2 2 R 4 SiO) y SiR 3 R 2 2 (I)
wherein each R 2 is independently an alkyl group having from 1 to 10 carbon atoms, a cycloaliphatic group or an aryl group, each R 3 is independently an alkenyl group having from 2 to 10 carbon atoms, and each R 4 is either R 2 or R 3 , and wherein x+y is at least about 520.
8. The composition of claim 1 wherein the composition further comprises a reactive diluent selected from the group consisting of vinyl ethers, vinyl carboxylates, mono-vinyl polysiloxanes, vinyl cycloaliphatics, vinyl cyclic olefinic compounds, and combinations thereof.
9. The composition of claim 1 further comprising at least one additional component selected from the group consisting of organohydrogenpolysiloxanes, MQ resins, vinyl-functional polyorganosiloxanes, and combinations thereof.
10. The composition of claim 9 wherein the organohydrogenpolysiloxane is selected from the group of compounds consisting of:
MD e D H f M,
MD H f M,
MD e D H f M H ,
M H D e D H f M H ,
M H D e M H , and
M H e Q f wherein
M=R 3 SiO 1/2 ,
M H =H g R 3-g SiO 1/2 ,
D=RRSiO 2/2 ,
D H =R H HSiO 2/2 and
Q=SiO 4/2 ,
wherein each R in M, M H , D, and D H is independently a monovalent hydrocarbon having from one to forty carbon atoms, and wherein the subscript g is 1 and subscripts e and f may be zero or positive whereby the sum of e and f ranges from about 10 to about 100 subject to the limitation that the sum off and g is two or greater.
11. The composition of claim 10 wherein R is methyl or phenyl.
12. The composition of claim 9 wherein the MQ resin consists essentially of R 1 3 SiO 1/2 (“M”) units and SiO 4/2 (“Q”) units, wherein each R 1 is independently a monovalent hydrocarbon radical having from 1 to 6 carbon atoms.
13. The composition of claim 9 wherein the MQ resin is a M vi MQ or MD vi Q resin, wherein M is R 7 3 SiO 1/2 , M vi is R 8 3 SiO 1/2 , D vi is R 8 2 SiO 2/2 , and Q is SiO 4/2 , wherein each R 7 is independently a monovalent hydrocarbon radical having from 1 to 6 carbon atoms, and each R 8 is independently R 7 , an alkenyl radical having from 2 to 6 carbon atoms or an alkenylhydrocarbonoxy radical having from 2 to 6 carbon atoms, with the proviso that at least one R 8 is an alkenyl radical having from 2 to 6 carbon atoms or an alkenylhydrocarbonoxy radical having from 2 to 6 carbon atoms.
14. The composition of claim 9 wherein the vinyl-functional polyorganosiloxane is represented by the general formula:
R 2 2 R 3 SiO(R 2 2 SiO) x (R 2 2 R 4 SiO) y SiR 3 R 2 2 (I)
wherein each R 2 is independently an alkyl group having from 1 to 10 carbon atoms, a cycloaliphatic group or an aryl group, each R 3 is independently an alkenyl group having from 2 to 10 carbon atoms, and each R 4 is either R 2 or R 3 , and wherein x+y is at least about 520.
15. A process for preparing the silicone pressure sensitive adhesive composition of claim 1 comprising the steps of:
(i) reacting a MQ resin with a capping agent selected from the group consisting of silazanes, disilazanes, polysilazanes, organohydrogen chlorosilanes, hydrogen functional siloxanes, and combinations thereof, to provide a partially end-capped MQ resin,
wherein the MQ resin consists essentially of R 1 3 SiO 1/2 (“M”) units and SiO 4/2 (“Q”) units, each R 1 is independently a monovalent hydrocarbon radical having from 1 to 6 carbon atoms, the MQ resin comprises from about 1% to about 4% by weight, based on the total weight of the MQ resin, of hydroxyl radicals bonded to the silicon atoms of the Q units, and the MQ resin does not contain hydride radicals;
wherein the partially end-capped MQ resin contains from about 70 mol % to about 99 mol % of hydroxyl radicals and from about 1 mol % to about 30 mol % of hydride radicals based on the total moles of the hydroxyl and the hydride radicals of the partially end-capped MQ resin;
(ii) reacting the partially-end capped MQ resin from step (i) with one or more vinyl-functional polyorganosiloxanes in the presence of an organic amine catalyst to provide an intermediate product; and
(iii) contacting the intermediate product from step (ii) with a hydrosilation catalyst thus preparing the silicone pressure sensitive adhesive composition of claim 1 .
16. A process for preparing the silicone pressure sensitive adhesive composition of claim 1 comprising the steps of:
(a) reacting a mixture comprising
(i) a MQ resin consisting essentially of R 1 3 SiO 1/2 (“M”) units and SiO 4/2 (“Q”) units, wherein each R 1 is independently a monovalent hydrocarbon radical having from 1 to 6 carbon atoms, the MQ resin comprises from about 1% to about 4% by weight, based on the total weight of the MQ resin, of hydroxyl radicals bonded to the silicon atoms of the Q units, and the MQ resin does not contain hydride radicals;
(ii) a capping agent selected from the group consisting of silazanes, disilazanes, polysilazanes, organohydrogen chlorosilanes, hydrogen functional siloxanes, and combinations thereof; and
(iii) one or more vinyl-functional polyorganosiloxanes to provide an intermediate product; and
(b) contacting the intermediate product from step (a) with a hydrosilation catalyst thus preparing the silicone pressure sensitive adhesive composition of claim 1 .
17. The process of claim 16 wherein the reaction mixture of step (a) optionally comprises a coupling agent, and wherein the MQ resin is present in an amount of from about 48.0 wt % to about 75.8 wt %, the silanol capping agent is present in an amount of from about 0.56 wt % to about 0.81 wt %, the coupling agent is present in an amount of from 0% to about 0.08 wt %, and the vinyl-functional polyorganosiloxane is present in an amount of from about 22.3 wt % to about 51.1 wt %, based on the total weight of the MQ resin, the silanol capping agent, the coupling agent and the vinyl-functional polyorganoxiloxane.
18. A cured composition of claim 1 .
19. An article containing a substrate having the composition of claim 1 adhered thereto.
20. The article of claim 19 wherein the composition is cured.
21. The article of claim 19 wherein the substrate is selected from the group consisting of glass, metals, porous materials, leather, fabrics, organic polymeric materials, silicone elastomers, silicone resins, painted surfaces and siliceous materials.
22. The article of claim 21 wherein the organic polymeric material is selected from the group consisting of fluorocarbon polymers, polystyrene, polyamides, polyesters and acrylic polymers.
23. The article of claim 19 wherein the article is selected from the group consisting of pressure sensitive tapes, labels, transfer films and electronic devices.
24. The article of claim 20 wherein the article is an electronic device selected from the group consisting of cell phones, GPS navigation displays, television displays, and electronic components.