SILICONE FREE THERMAL INTERFACE MATERIAL WITH REACTIVE DILUENT

Abstract

A silicone-free thermal interface for placement along a thermal dissipation pathway is provided for long-term durability. The thermal interface is formed from a multi-part composition and cured in place to obtain a conformable coating with low durometer hardness, which is maintained by a non-crosslinked diluent product formed from a reactive diluent system.

Claims

1. A thermal interface formed from a two-part composition comprising: a first component having a first reactant with a reactive functionality of one or two, the first component exhibiting a viscosity of less than 500,000 cP at 1s.sup.−1 and 20° C.; a second component having a second reactant with a reactive functionality of: (i) one or two if the first reactant functionality is one or two; and (ii) three or more only if the first reactant functionality is one, wherein the second component exhibits a viscosity of less than 500,000 cP at 1 s.sup.−1 and 20° C.; a non-silicone cross-linkable polymer; and thermally conductive filler; wherein the first and second reactants are reactable with one another to form a product having a viscosity of at least 1,000,000 cP at 1 s.sup.−1 and 20° C. and wherein the thermal interface exhibits a thermally conductivity of at least 1 W/m*K.

2. The thermal interface as in claim 1 wherein each of the polymer and the thermally conductive filler are included in one or more of the first and second components.

3. The thermal interface as in claim 2 wherein the composition is curable to a hardness of less than 80 Shore 00.

4. The thermal interface as in claim 3 wherein the composition is curable to a hardness of between 20-70 Shore 00.

5. The thermal interface as in claim 4 wherein neither the first nor second reactants react with the polymer.

6. The thermal interface as in claim 1 wherein the polymer cures at temperatures exceeding 25° C.

7. The thermal interface as in claim 1 wherein the polymer includes a silyl-modified polymer.

8. The thermal interface as in claim 1 wherein the thermally conductive filler is selected from the group consisting of aluminum oxide, aluminum nitride, silicon oxide, zinc oxide, and boron nitride.

9. The thermal interface as in claim 1 wherein the first and second reactants are selected from reactive sets from the group consisting of epoxies, amines, acrylates, thiols, polyols, and isocyanates.

10. The thermal interface as in claim 1 being silicone free.

11. A battery system, comprising; a battery; and the thermal interface of claim 1 thermally coupled to said battery.

12. The battery system as in claim 11 wherein the thermal interface is coated on said battery.

13. A method for forming a thermal interface on a surface, the method comprising: (a) providing: (i) a first component with a first reactive diluent having a viscosity of less than 100 cP; (ii) a second component with a second reactive diluent having a viscosity of less than 100 cP, the first and second diluents being reactive with one another to form a non-crosslinked product with a viscosity of greater than 1000 cP; (iii) a non-silicone curable resin; and (iv) thermally conductive filler; (b) dispensing the first and second components, and the resin and the filler, through at least one orifice onto the surface to cause the first diluent to react with the second diluent; and (c) curing the resin.

14. The method as in claim 13 wherein the thermal interface exhibits a thermal conductivity of at least 1.0 W/m*K.

15. The method as in claim 13 wherein each of the resin and thermally conductive filler are included in one or more of the first and second components.

16. The method as in claim 15, including dispensing the first component as a first liquid through a first orifice, and dispensing the second component as a second liquid through a second liquid orifice.

17. The method as in claim 16 wherein the surface is connected to a battery or is a portion of a battery.

18. The method as in claim 13 wherein the thermal interface exhibits to a hardness of less than 80 Shore 00.

19. The method as in claim 13, including curing the resin at temperatures exceeding 25° C.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0018] FIG. 1 is a schematic illustration of a system for forming a thermal interface on a surface.

[0019] FIG. 2 is a schematic illustration of a system for forming a thermal interface on a surface.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0020] The objects and advantages enumerated above together with other objects, features, and advances represented by the present invention will now be presented in terms of detailed embodiments described with reference to the attached drawing figures. Other embodiments and aspects of the invention are recognized as being within the grasp of those having ordinary skill in the art.

[0021] The thermally conductive interface of the present invention may be formed as a coating on a surface or a self-supporting body for placement along a thermal dissipation pathway, typically to remove excess heat from a heat-generating electronic component. The thermal interface is preferably silicone-free and filled with thermally conductive particles to achieve a desired thermal conductivity, typically at least about 1 W/m*K. The thermal interface is preferably conformable to surface roughness by exhibiting a durometer hardness of less than about 80 Shore 00.

[0022] Generally, the thermally conductive interface is a curable material formed from a composition of a first component having a first reactant, a second component having a second reactant that is reactable with the first reactant, a non-silicone cross-linkable polymer, and a thermally conductive particulate filler. The first and second reactants are preferably diluents which themselves have a relatively low viscosity and are provided to reduce the viscosity of the overall pre-cured composition so that the composition is readably dispensable through liquid dispensing equipment. The first and second reactive diluents may therefore each exhibit a viscosity of less than 500 cP. In another embodiment, each of the first and second reactive diluents may exhibit a viscosity of less than 100 cP. In an example embodiment, each of the first and second reactive diluents exhibit a viscosity of approximately 20 cP. The quantitative viscosity values described herein are considered to be taken at room temperature (20° C.) and a shear rate of 1 s.sup.−1 on a parallel-plate rheometer.

[0023] The first and second diluents are preferably reactive with one another to form a non-crosslinked product with a viscosity of more than 1000 cP. In some embodiments, the first and second diluent reactants are reactable with one another to form a product having a viscosity of at least 10,000 cP. By being reactable with one another, the first and second reactive diluents may react to form a diluent product with an increased molecular weight that is less likely to migrate out from the thermal interface than conventional diluent materials. As a result, the diluent product formed from the reaction of the first and second reactive diluents may continue to act as a hardness modifier to the thermal interface over an extended period of time. Such increase in molecular weight, however, occurs only upon reaction between the first and second reactive diluents, which may take place upon mixing of the first and second components of the thermal interface-forming composition subsequent to liquid dispensation.

[0024] An aspect of the present invention is that the reactive diluents do not participate in the polymer cross-linking reaction. Moreover, the diluent reaction itself does not cross-link, whereby the molecular weight of the diluent product is limited to an extent at which the diluent product retains a hardness reducing property to the overall thermal interface. Accordingly, the first and second reactive diluents are selected to be reactive with one another, but not undergo a cross-linking reaction. The first and second reactive diluents may therefore be selected to form only a non-crosslinked product. For the purpose hereof, the term “non-crosslinked” means that no reactant molecule is linked to more than two other reactant molecules unless the other reactant molecules are linked only to a single reactant molecule. Example non-crosslinked diluent products are as follows:

##STR00001##

[0025] wherein:

[0026] x=first reactive diluent

[0027] y=second reactive diluent

[0028] In order to control the reactivity of the first and second reactive diluents, the “functionality” of the reactive diluent should be considered. The term functionality refers to the number of polymerizable groups in the reactant, which affects the formation and degree of cross-linking of polymers. A monofunctional molecule possesses a functionality (f)=1, a difunctional molecule possesses a functionality (f)=2, and a trifunctional possesses a functionality (f)=3. In the case of a functionality (f=2), a linear reaction product may be formed. Reactants with a functionality (f≥3) can lead to a branching point and cross-linked products. Monofunctional reactants (f=1) lead to a chain termination. The following are example diluent reaction products of diluent reactants with noted functionality:

##STR00002##

[0029] wherein:

[0030] x=first reactive diluent

[0031] y=second reactive diluent

[0032] x.sup.1 is f=1

[0033] x.sup.2 is f=2

[0034] x.sup.3 is f=3

[0035] In some embodiments, the first reactant has a reactive functionality of 1 or 2, and the second reactant has a reactive functionality of

[0036] (i) 1 or 2 if the first reactant functionality is 1 or 2; and

[0037] (ii) 3 or more only if the first reactant functionality is 1.

[0038] With such functionality limitations, the first and second reactants are reactive to only form a non-crosslinked product. By preventing a cross-linking of the first and second reactants, the diluent reaction product, albeit with larger molecular weight, is able to soften the thermal interface material.

[0039] The first and second reactive diluents may be added to the composition in an amount suitable to appropriately adjust viscosity for pre-cured dispensability, and post-cured softness. In some embodiments, the reactive diluents may represent between about 5-50 percent by weight of the composition. Example reactive diluent systems representing the first and second reactive diluents include epoxies/amines, amines/acrylates, acrylates/acrylates plus catalysts, thiols/acrylates, polyols/isocyanates, and amines/isocyanates. It is contemplated that those of ordinary skill in the art may select reactive sets of appropriate diluents from one or more of epoxies, amines, acrylates, thiols, polyols, and isocyanates.

[0040] The composition for forming the thermal interface of the present invention preferably includes a non-silicone curable resin, which forms the bulk matrix of the thermal interface. In some embodiments, the composition may include a non-silicone cross-linkable polymer. In preferred embodiments, the thermal interface is silicone-free, wherein no more than trace amounts of silicone are contained in the thermal interface. It is contemplated that a wide variety of non-silicone cross-linkable polymers may be used in the compositions of the present invention to achieve desired physical characteristics. Example cross-linking polymer systems include silyl-modified polymers (SMP), epoxies/amines, epoxies/anhydrides, acrylates, and polyurethanes. Preferably, the cross-linking polymer is any non-silicone polymer that forms a cross-linked network without reacting with the diluents. The applicant has found that SMP materials, such as those described in U.S. Pat. No. 3,632,557 and U.S. Patent Application Publication No. 2004/0127631, the contents of which being incorporated herein their entireties, may be particularly useful in the preparation of thermally conductive interfaces of the present invention. It is to be understood that various combinations of cross-linking polymer and reactive diluent systems may be selected for particular properties. Example combinations of cross-linking polymers and reactive diluents is set forth in the following Table 1:

TABLE-US-00001 TABLE 1 Cross-Linkable Polymer Reactive Diluent System Silyl-modified polymers (SMP) Epoxy/amine Silyl-modified polymers (SMP) Amine/acrylate Silyl-modified polymers (SMP) Acrylate Silyl-modified polymers (SMP) Thiol/acrylate Epoxy/anhydride Acrylate Epoxy/anhydride Polyol/isocyanate

[0041] Systems using epoxy/amine, acrylate, polyurethane, or thiol/ene polymer cross-linking systems could potentially co-react with some of the diluents listed in Table 1 above, but specific combinations of molecules with appropriate catalysts and/or inhibitors may be possible.

[0042] In order to enhance the thermal conductivity of the thermally conductive interface, the compositions of the present invention may include thermally conductive particles dispersed therein. The particles may be both thermally conductive and electrically conductive. Alternative, the particles may be thermally conductive and electrically insulating. Example thermally conductive particles include aluminum oxide, silicone oxide, aluminum trihydrate, zinc oxide, graphite, magnesium oxide, aluminum nitride, boron nitride, metal particulate, and combinations thereof. The thermally conductive particles may be of various shape and size, and it is contemplated that a particle size distribution may be employed to fit the parameters of any particular application. In some embodiments, the thermally conductive particles may have an average particle size of between about 0.1-100 micrometers, and may be present in the thermally conductive material at a concentration by weight of between about 20-95 percent.

[0043] The thermally conductive particles may be dispersed in at least one of the first and second components at a loading concentration of between about 20-95 percent by weight. It is desirable that sufficient thermally conductive particles are provided so that the thermally conductive interface formed from the component mixture exhibits a thermal conductivity of at least 1 W/m*K. In some embodiments, each of the cross-linkable polymer and the thermally conductive filler may be included in one or more of the first and second components.

[0044] The compositions for forming the thermal interface of the present invention are preferably selected to be curable to a hardness of less than 80 Shore 00, and more preferably to a hardness between 20-70 Shore 00. Such durometer hardness of the cured thermal interface is driven by a combination of the selected reactive diluents, the non-silicone cross-linkable polymer, and the thermally conductive filler, as well as the reactive concentrations of each component.

[0045] Various additional components may be included in the compositions of the present invention to achieve desired reaction rates and physical properties of the reactants and final thermal interface. Example additives include cross-linking catalysts, non-reactive diluents, solvents, anti-oxidants, surfactants, reaction accelerators, reaction inhibitors, stabilizers, fillers, and combinations thereof.

[0046] A system and method for forming a thermal interface of the present invention on a surface is schematically illustrated in FIGS. 1 and 2. Systems 10, 110 include a supply of a first component 12, 112 having a first reactive diluent, and a supply of a second component 14, 114 having a second reactive diluent that is reactive with the first reactive diluent. In the illustrated embodiments, a non-silicone curable resin and a thermally conductive filler is provided in one or more of the first and second components supplies 12, 112 and 14, 114. The first and second components are dispensed through at least one orifice onto a surface 22, 122 to cause the first reactive diluent to react with the second reactive diluent. In system 10 illustrated in FIG. 1, the first and second components are dispensed through a common orifice 16. In system 110 illustrated in FIG. 2, first and second components are dispensed through separate orifices 116A, 116B. Surface 22 may be a surface of or thermally coupled to a battery 20. Following dispensation of the first and second components onto surface 22, 122, the coating may be cured by a curing means 30, 130. Example curing means may include a heating oven, an ultra-violet (UV) radiation lamp, a photo initiator, or the like. In some embodiments, the curable resin maybe cured at temperatures exceeding 25° C. The schematic illustrations of FIGS. 1 and 2 illustrate a conveyor 40, 140 for moving the coated battery 20, 120 into a curing station exposed to the curing means 30, 130. In preferred embodiments, the first and second components may be dispensed through at least one orifice 16, 116 in liquid form.

Examples

[0047] A first example thermal interface was formed from the following two-component composition:

TABLE-US-00002 First Component Second Component Concentration Concentration Material (PHR) Material (PHR) Monoamine 100 Dimethoxy silane 40 terminated terminated polyether polyethers Alumina 1050 O-cresyl glycidyl 60 ether (monoepoxide) Alumina 1050

[0048] The first component exhibited a viscosity of 100,000 cP and the second component exhibited a viscosity of 200,000 cP as measured on a parallel plate rheometer at a shear rate of 1 s.sup.−1.

[0049] Upon mixing of the first and second components, a cured solid with a durometer hardness of 50 Shore 00 and a thermal conductivity of 3.0 W/m*K was produced after 24 hours at 25° C.

[0050] A second example thermal interface was prepared with the following composition:

TABLE-US-00003 Part A Part B Concentration Concentration Material (PHR) Material (PHR) Plasticizer 50-75 Monoamine diluent 40-60 Epoxy resin 25-35 SMP cross-linking 40-55 resin Alumina  600-1000 Alumina  600-1000

[0051] Upon mixing the first and second components, a cured solid with a hardness of 55 Shore 00 was obtained.

[0052] The invention has been described herein in considerable detail in order to comply with the patent statutes, and to provide those skilled in the art with the information needed to apply the novel principles and to construct and use embodiments of the invention as required. However, it is to be understood that various modifications can be accomplished without departing from the scope of the invention itself.