Curable silicone compositions, electrically conductive silicone adhesives, methods of making and using same, and electrical devices containing same

• US 9,447,308 B2
• Filed: 03/13/2014
• Issued: 09/20/2016
• Est. Priority Date: 03/14/2013
• Status: Active Grant

• Current Assignee: Dow Silicones Corporation (Dow, Inc.)
• Original Assignee: Dow, Inc.
• Inventors: Albaugh, John, Chislea, Brian, Zambova, Adriana
• Primary Examiner(s): Loewe, Robert S
• Application Number:
  US14/775,789
• Publication Number:
  US 20160017185A1
• Time in Patent Office: 922 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: C08K 2003/0806 Silver
• CPC Class Codes: C08K 2003/085 Copper
• CPC Class Codes: C08K 2201/001 Conductive additives
• CPC Class Codes: C08K 3/08 Metals
• CPC Class Codes: C08K 9/02 Ingredients treated with inorganic substances
• CPC Class Codes: C08K 9/10 Encapsulated ingredients
• 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 9/02 Electrically-conducting adhesives
• CPC Class Codes: H01R 4/04 using electrically conductive adhesives

Abstract

A curable silicone composition comprising a curable organosiloxane composition, copper-silver (Cu—Ag) core-shell particles, and hydrocarbon vehicle; the curable silicone composition being characterizable by: a concentration of the Cu—Ag core-shell particles of from 70 to 89 weight percent and a total concentration of silver of from 7.0 to 14 weight percent, all based on weight of the curable silicone composition; wherein the composition remains curable to an electrically conductive silicone adhesive having a volume resistivity of less than 0.020 Ohm-centimeter measured according to Volume Resistivity Test Method.

Claims

1. A curable silicone composition comprising a curable organosiloxane composition, copper-silver (Cu—

Ag) core-shell particles, a mechanical thixotropic filler that is carbon nanotubes, and hydrocarbon vehicle;

the curable silicone composition being characterized by;

a concentration of the Cu—

Ag core-shell particles of from 70 to 89 weight percent and a total concentration of silver of from 7 to 14 weight percent, all based on weight of the curable silicone composition;

wherein the composition remains curable to an electrically conductive silicone adhesive having a volume resistivity of less than 0.020 Ohm-centimeter measured according to Volume Resistivity Test Method; and

wherein the curable silicone composition is characterized by a Thixotropic Index (η

₁/η

₁₀) of from 3 to 10.

2. A curable silicone composition comprising a blend of the following ingredients:

a hydrocarbon vehicle at a concentration of from 4 to 20 weight percent based on weight of the curable silicone composition, wherein the hydrocarbon vehicle is characterized by a boiling point from 100 to 360 degrees Celsius;

a curable organosiloxane composition at a concentration of from 7 to 10 weight percent based on weight of the curable silicone composition;

Cu—

Ag core-shell particles at a concentration of from 70 to 89 weight percent based on weight of the curable silicone composition; and

a mechanical thixotropic filler;

wherein the total concentration of silver is from 7 to 14 weight percent based on weight of the curable silicone composition;

wherein the composition remains curable to an electrically conductive silicone adhesive having a volume resistivity of less than 0.020 Ohm-centimeter measured according to Volume Resistivity Test Method; and

wherein the curable silicone composition is characterized by a Thixotropic Index(η

₁/η

₁₀) of from 3 to 10.

3. The curable silicone composition of claim 2 characterized by a volume resistivity less than 0.0010 Ohm-centimeter measured according to Volume Resistivity Test Method.

4. The curable silicone composition of claim 2 characterized by the following limitations:

wherein the hydrocarbon vehicle is an alkanes mixture of different molecules wherein the lowest boiling molecules have an initial boiling point greater than 150 degrees Celsius and the highest boiling molecules have an end boiling less than 300 degrees Celsius and the hydrocarbon vehicle is at a concentration of from 4 to 15 weight percent based on weight of the curable silicone composition;

wherein the curable organosiloxane composition comprises at least one diorganosiloxane compound, a catalyst, and an adhesion promoter;

wherein the at least one diorganosiloxane compound has on average per molecule at least 1 reactive moiety, wherein each reactive moiety independently is an alkenyl moiety, Si—

H moiety, Si—

OH moiety, Si—

OR moiety, wherein R is (C₁-C₁₀)hydrocarbyl, —

C(O)(C₁-C₁₀)hydrocarbyl, or —

N═

CR¹R², wherein each of R¹ and R² independently is (C₁-C₁₀)hydrocarbyl or R¹ and R² are taken together to form a (C₂-C₁₀)hydrocarbylene; and

wherein the at least one diorganosiloxane compound is at least 50 weight percent of the curable organosiloxane composition;

wherein the Cu—

Ag core-shell particles are unsintered and are at a concentration of from 75 to 89 weight percent based on weight of the curable silicone composition;

wherein n the total concentration of silver is from 7.1 to 12 weight percent based on weight of the curable silicone composition;

wherein the mechanical thixotropic filler is carbon nanotubes, wherein the carbon nanotubes are at a concentration of from 0.1 to 5.0 weight percent based on weight of the curable silicone composition; and

wherein the curable silicone composition is characterized by a volume resistivity less than 0.0010 Ohm-centimeter measured according to Volume Resistivity Test Method.

5. The curable silicone composition of claim 4, characterized by the following limitations:

wherein the hydrocarbon vehicle is an alkanes mixture;

wherein the curable organosiloxane composition comprises at least one diorganosiloxane compound, at least one organohydrogensilicon compound, a hydrosilylation catalyst, and an epoxy-functional adhesion promoter;

wherein the at least one diorganosiloxane compound has on average per molecule at least 1 alkenyl moiety and the organohydrogensilicon compound has on average per molecule at least 1 Si—

H moiety; and

wherein the at least one diorganosiloxane compound is from 60 to 80 wt % of the curable organosiloxane composition;

wherein the Cu—

Ag core-shell particles are at a concentration of from 79.5 to 86.4 weight percent based on weight of the curable silicone composition;

wherein the total concentration of silver is from 7.5 to 12 weight percent based on weight of the curable silicone composition; and

wherein the carbon nanotubes are single-walled carbon nanotubes, multi-walled carbon nanotubes, derivatized carbon nanotubes or a combination of any two or more of the single-walled carbon nanotubes, multi-walled carbon nanotubes, and derivatized carbon nanotubes; and

the concentration of carbon nanotubes is from 0.2 to 2 weight percent based on weight of the curable silicone composition.

6. The curable silicone composition of claim 5, characterized by the following limitations:

wherein the alkanes mixture is an isoalkanes mixture comprising at least two of (C₉-C₁₂)isoalkanes, at least two of (C₁₂-C₁₆)isoalkanes or at least two of (C₁₆-C₂₂)isoalkanes and the hydrocarbon vehicle is at a concentration of from 4.5 to 15 weight percent based on weight of the curable silicone composition;

wherein the curable organosiloxane composition is hydrosilylation curable and comprises the at least one diorganosiloxane compound, the at least one trimethylsiloxy-terminated dimethyl organohydrogensilicon compound, a microencapsulated hydrosilylation catalyst, and a bis(alpha,omega-glycidoxyalkyl)-dialkyl/(alkyl,alkenyl)siloxane;

wherein the alkenyl of the diorganosiloxane is vinyl and the at least one diorganosiloxane compound has on average per molecule at least 1.1 vinyl moieties, the at least one trimethylsiloxy-terminated dimethyl organohydrogensilicon compound is and has on average per molecule at least 1.1 Si—

H moieties, or the least one diorganosiloxane compound has on average per molecule at least 1.1 vinyl moieties and the at least one organohydrogensilicon compound has on average per molecule at least 1.1 Si—

H moieties;

wherein the at least one diorganosiloxane compound having vinyl moieties is from 70 to 75 wt % of the curable organosiloxane composition;

wherein the at least one trimethylsiloxy-terminated dimethyl organohydrogensilicon compound is from 1 to 5 weight percent, the microencapsulated hydrosilylation catalyst is from 10 to 15 weight percent, and the bis(alpha,omega-glycidoxyalkyl)-dialkyl/(alkyl,alkenyl)siloxane is from 5 to 10 weight percent, and together the organohydrogensilicon compound, microencapsulated hydrosilylation catalyst, and the bis(alpha,omega-glycidoxyalkyl-D3 to D6 alkyl,hydrogencyclosiloxane are from 20 to 30 wt % of the curable organosiloxane composition;

wherein the Cu—

Ag core-shell particles are at a concentration of from 79.9 to 86 weight percent based on weight of the curable silicone composition;

wherein the total concentration of silver is from 7.5 to 12 weight percent based on weight of the curable silicone composition; and

wherein the carbon nanotubes are multi-walled carbon nanotubes at a concentration of from 0.50 to 1.5 weight percent based on weight of the curable silicone composition; and

wherein the curable silicone composition is characterized by a volume resistivity less than 0.00090 Ohm-centimeter measured according to Volume Resistivity Test Method.

7. An electrically conductive silicone adhesive that is a product of curing the curable silicone composition of claim 2, wherein the electrically conductive silicone adhesive is characterized by a volume resistivity of less than 0.0010 Ohm-centimeter measured according to Volume Resistivity Test Method, wherein some of the hydrocarbon vehicle remains in the electrically conductive silicone adhesive after curing such that the electrically conductive silicone adhesive has less than 5 weight percent of the hydrocarbon vehicle.

8. An electrical device comprising first and second electrical components having opposing surfaces and the electrically conductive silicone adhesive of claim 7 disposed between and in adhering operative contact with the opposing surfaces of the first and second electrical components, wherein the first and second electrical components are disposed for electrical operative communication with each other via the electrically conductive silicone adhesive, wherein the electrically conductive silicone adhesive is characterized by a volume resistivity of less than 0.0010 Ohm-centimeter measured according to Volume Resistivity Test Method.

9. A method of manufacturing an electrical device comprising first and second electrical components having surfaces and an electrically conductive silicone adhesive, the method comprising depositing the curable silicone composition of claim 2 onto one or both surfaces of the first and second electrical components, and orienting the first and second electrical components so that their surfaces are opposing each other to give a preassembly comprising the curable silicone composition disposed between and in physical contact with the opposing surfaces of the first and second electrical components;

and curing the curable silicone composition between the opposing surfaces of the first and second electrical components to give an electrical device comprising the first and second electrical components and an electrically conductive silicone adhesive disposed between and in adhering operative contact with the opposing surfaces of the first and second electrical components such that the first and second electrical components are disposed for electrical operative communication with each other via the electrically conductive silicone adhesive, wherein the electrically conductive silicone adhesive is characterized by a volume resistivity of less than 0.020 Ohm-centimeter measured according to Volume Resistivity Test Method and wherein some of the hydrocarbon vehicle remains in the electrically conductive silicone adhesive after curing such that the electrically conductive silicone adhesive has less than 5 weight percent of the hydrocarbon vehicle.

10. A curable silicone composition comprising a blend of the following ingredients:

an isoalkanes mixture comprising at least three of (C₁₂-C₁₆)isoalkanes of different molecules wherein the lowest boiling molecules have an initial boiling point of greater than 210 degrees Celsius and the highest boiling molecules have an end boiling point of less than 270 degrees Celsius and the hydrocarbon vehicle is at a concentration of from 4.5 to 12 weight percent based on weight of the curable silicone composition;

a hydrosilylation-curable polydimethylsiloxane composition comprising at least one vinyl-functional polydimethylsiloxane compound having on average per molecule at least 1 vinyl moieties, at least one trimethylsiloxy-terminated dimethyl methylhydrogensilicon compound having on average per molecule at least 1.1 Si—

H moieties, a microencapsulated platinum hydrosilylation catalyst, and bis(alpha,omega-glycidoxyalkyl)-dialkyl/(alkyl,alkenyl)siloxane, and bis(alpha,omega-glycidoxyalkyl-D3 to D6 alkyl,hydrogencyclosiloxane; and

wherein the vinyl-functional polydimethylsiloxane compound is from 70 to 75 weight percent, the trimethylsiloxy-terminated dimethyl methylhydrogensilicon compound is from 1 to 5 weight percent, the microencapsulated hydrosilylation catalyst is from 10 to 15 weight percent, the bis(alpha,omega-glycidoxyalkyl)-dialkyl/(alkyl,alkenyl)siloxane is from 1 to 10 weight percent, and the bis(alpha,omega-glycidoxyalkyl-D3 to D6 alkyl,hydrogencyclosiloxane is from 0 to 7 weight percent, all of the curable polydimethylsiloxane composition; and

wherein together the trimethylsiloxy-terminated dimethyl methylhydrogensilicon compound, microencapsulated hydrosilylation catalyst, and the bis(alpha,omega-glycidoxyalkyl)-dialkyl/(alkyl,alkenyl)siloxane, and bis(alpha,omega-glycidoxyalkyl-D3 to D6 alkyl,hydrogencyclosiloxane are from 20 to 30 wt % of the curable organosiloxane composition;

Cu—

Ag core-shell particles are at a concentration of from 79.9 to 86.0 weight percent based on weight of the curable silicone composition;

wherein the total concentration of silver is from 7.5 to 12 weight percent based on weight of the curable silicone composition; and

Carbon nanotubes at a concentration of from 0.50 to 1.2 weight percent based on weight of the curable silicone composition; and

wherein the curable silicone composition is characterized by a volume resistivity less than 0.00090 Ohm-centimeter measured according to Volume Resistivity Test Method.

11. The curable silicone composition of claim 10, wherein the curable silicone composition is characterized by a Thixotropic Index(η

₁/η

₁₀) of from 3 to 10.