Conducive, silicone-based compositions with improved initial adhesion reduced microvoiding

1. A curable conductive composition of comprising:

(a) a reactive polyorganosiloxane component;

(b) a silicone resin formed as a hydrolysis and condensation product of at least one silane within the formula R 1 m R 2 p Si(X) 4-(m+p) , wherein R 1 and R 2 may be the same or different and may be selected from the group consisting of monovalent ethylenically unsaturated radicals, C 1-12 alkoxy, C 6-12 aryloxy, (meth)acrylate, hydrogen, C 1-12 alkyl, C 6-12 aryl, C 7-18 arylalkyl, and C 7-18 alkylaryl, X is a hydrolyzable functionality, m is an integer from 1 to 3, and m+p is an integer from 1 to 3 provided at least one of R 1 and R 2 is a member selected from the group consisting of monovalent ethylenlcally unsaturated radicals, C 1-12 alkoxy, C 6-12 aryloxy, (meth)acrylate hydrogen; and

(c) a conductive filler component, wherein the composition demonstrates an improved initial adhesion to a substrate with which it is to be used of at least about 7%; and wherein the conductive filler component comprises:

(i) a first conductive filler and

(ii) a second conductive filler, wherein the first conductivc filler is relatively harder than the second conductive filler using a Mohs hardness test, wherein the composition is subjected to shear mixing forces which shearingly disperse the first and second conductive fillers throughout the composition so as to provide a volume fraction of conductive filler throughout the resinous material in the range of about 30 to about 65% by volume of the composition.

2. The composition of claim 1 , wherein the reactive polyorganosiloxane is within

wherein R 1 , R 2 , R 3 , R 4 and R 5 may be the same or different and are each independently selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, alkoxy, alkenyloxy, and aryloxy, provided that at least two of R 1 , R 2 , R 3 , R 4 and R 5 are each reactive functionality selected from the group consisting of alkenyl, alkoxy, and alkenoxy, having up to 12 carbon atoms, with or without substitution by halo- or cyano-groups; and n is an integer between about 100 and 1,200.

3. The composition of claim 1 , wherein the silicone resin is formed as a reaction product of the at least one silane and at least one other silane within the formula, R n Si(X) 4-n , wherein R may be the same or different and selected from the group consisting of hydrogen, C 1-12 alkyl, C 6-12 aryl, C 7-18 arylalkyl, C 7-18 alkylaryl, haloalkyl, and haloaryl, X is a hydrolyzable functionality, and n is an integer of from 0 to 3.

4. A curable conductive composition comprising:

(a) a reactive polyorganosiloxane component;

(b) a silicone resin formed as a hydrolysis and condensation product of at least one silane within the formula R 1 m R 2 p Si(X) 4-(m+p) , wherein R 1 and R 2 may be the same or different and may be selected from the group consisting of monovalent ethylenically unsaturated radicals, C 1-12 alkoxy, C 6-12 aryloxy, (meth) acrylate, hydrogen, C 1-12 alkyl, C 6-12 aryl, C 7-18 arylalkyl, and C 7-18 alkylaryl, X is a hydrolyzable functionality, m is an integer from 1 to 3, and m+p is an integer from 1 to 3 provided at least one of R 1 and R 2 is a member selected from the group consisting of monovalent ethylenically unsaturated radicals, C 1-12 alkoxy, C 6-12 aryloxy, (meth)acrylate hydrogen; and

(c) a conductive filler component, wherein the composition demonstrates an improved initial adhesion to a substrate with which it is to be used of at least about 7%; and wherein at least one of the polyorganosiloxane component and the silicone resin component is moisture curable.

5. The composition of claim 4 , wherein the conductive filler component comprises the combination of at least two conductive fillers.

6. The composition according to claim 1 , wherein the composition is thermally conductive.

7. The composition according to claim 1 , wherein the composition is electrically conductive.

8. The composition according to claim 1 , wherein at least one of the polyorganosiloxane component and the silicone resin component is heat curable.

9. The composition according to claim 1 , wherein at least one of the polyorganosiloxane component and the silicone resin component is radical curable.

10. The composition according to claim 1 , wherein the particle size of the first conductive filler is larger relative to the second conductive filler.

11. The composition according to claim 1 , wherein the first and second conductive fillers are selected from at least one of the group consisting of iron, aluminum, zinc, silver, gold, lead, nickel, magnesium, boron, barium, platinum, palladium, copper, zirconium, titanium, uranium, vanadium, niobium, tungsten, silicon and derivatives and combinations thereof.

12. The composition according to claim 1 , wherein the conductive filler component includes as the first conductive filler from about 75% to about 95% by weight aluminum oxide, based on the total weight of the conductive filler component, and as the second conductive filler from about 5% to about 25% by weight zinc oxide based on the total weight of the conductive filler.

13. The composition according to claim 1 , wherein after subjection to shear mixing forces the first and the second conductive fillers are densely packed in a substantially uniform manner within the composition.

14. A process for preparing a conductive composition, said process comprising the steps of:

(a) providing a curable conductive composition comprising:

(i) a reactive polyorganosiloxane component;

(ii) a silicone resin formed as a hydrolysis and condensation product of at least one silane within the formula R 1 m R 2 p Si(X) 4-(m+p) , wherein R 1 and R 2 may be the same or different and may be selected from the group consisting of monovalent ethylenically unsaturated radicals, C 1-12 alkoxy, C 6-12 aryloxy, (meth)acrylate, hydrogen, C 1-12 alkyl, C 6-12 aryl, C 7-18 arylalkyl, and C 7-18 alkylaryl, X is a hydrolyzable functionality, m is an integer from 1 to 3, and m+p is an integer from 1 to 3 provided at least one of R 1 and R 2 is a member selected from the group consisting of monovalent ethylenically unsaturated radicals, C 1-12 alkoxy, C 6-12 aryloxy, (meth)acrylate hydrogen; and

(iii) a conductive filler component, wherein the composition demonstrates an improved initial adhesion to a substrate with which it is to be used of at least about 7%, and

b) shearingly dispersing the components thereof by application of shear mixing forces to form a substantially homogeneous composition in which the conductive filler is densely packed in the composition.

15. A process for using a conductive composition to bond a pair of substrates, said process comprising the steps of:

(a) dispensing a curable conductive composition comprising:

(i) a reactive polyorganosiloxane component;

(ii) a silicone resin formed as a hydrolysis and condensation product of at least one silane within the formula R 1 m R 2 p Si(X) 4-(m+p) , wherein R 1 and P2 may be the same or different and may be selected from the group consisting of monovalent ethylenically unsaturated radicals, C 1-12 alkoxy, C 6-12 aryloxy, (meth)acrylate, hydrogen, C 1-12 alkyl, C 6-12 aryl, C 7-18 arylalkyl, and C 7-18 alkylaryl, X is a hydrolyzable functionality, m is an integer from 1 to 3, and m+p is an integer from 1 to 3 provided at least one of R 1 and R 2 is a member selected from the group consisting of monovalent ethylenically unsaturated radicals C 1-12 alkoxy, C 6-12 aryloxy, (meth)acrylate hydrogen; and

(iii) a conductive filler component, wherein the conductive filler component comprise:

a) a first conductive filler and

b) a second conductive filler wherein the first conductive filler is relatively harder than the second conductive filler using a Mohs hardness test, wherein the composition is subjected to shear mixing forces which shearingly disperse the first and second conductive fillers throughout the composition so as to provide a volume fraction of conductive filler throughout the resinous material in the range of about 30 to about 65% by volume of the composition and wherein the composition demonstrates an improved initial adhesion to a substrate with which it is to be used of at least about 7% onto a surface of at least one of the substrates;

(b) joining the other substrate therewith; and

(c) exposing the joined substrates to conditions favorable to cure the conductive composition.