CN1990816A - Composition for heat interfacial material - Google Patents
Composition for heat interfacial material Download PDFInfo
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- CN1990816A CN1990816A CN 200510135414 CN200510135414A CN1990816A CN 1990816 A CN1990816 A CN 1990816A CN 200510135414 CN200510135414 CN 200510135414 CN 200510135414 A CN200510135414 A CN 200510135414A CN 1990816 A CN1990816 A CN 1990816A
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Abstract
The invention provides a thermal interface material, which can improve the low thermal conductive coefficient and high resistant value in current thermal interface material. It produces CNT-LC thermal conductive composite structure by using the high thermal conductive property of carbon nano- tube and high regularization of liquid crystal polymer to make the thermal interface material possesses high thermal conductive coefficient. The adding amount of carbon nano- tube is far less than that of traditional metal or ceramic powder, so it is convenient to carry out separate process. The CNT- LC structure is compatible to phase- changing resin, and the phase changing temperature of formed thermal interface material is 45- 75 Deg. C. The holes, caves or depressions can be filled under normal operation temperature, and thus the thermal resistant value of the whole element can be recduced.
Description
Technical field
The present invention relates to a kind of thermal management materials of electronic component, and be particularly related to a kind of composition for heat interfacial material.
Background technology
Along with weeding out the old and bring forth the new of various electronic products, various electronic products need that also electronic product is possessed and have high function, high-transmission, characteristics such as operation expeditiously except needs satisfy basic demand such as light, thin, short, little.(for example CPU etc.) will produce a large amount of heat and make temperature relatively significantly improve under operation because each element, and then causes component failure, therefore needs to improve the heat-sinking capability of integral product or element, to keep the usefulness of integral product or element.
For used heat is shifted out, normally on element, single power supply or logical integrated circuit, radiator element is set.And radiator element normally is fixed on element, single power supply or the logical integrated circuit by heat interfacial material.Therefore, heat interfacial material is played the part of a very crucial role in the heat management design rule.How increasing heat transfer efficiencies between element and radiator element, the heat conduction of heat interfacial material and thermal impedance characteristic are very important.
Known heat interfacial material be with siliceous be phase change resin materials such as resin, aliphatics polymer, low molecular weight polycaprolactone lipid, acrylic resin, paraffin class or Resins, epoxy, add metal again or ceramic powder is used as thermally conductive material, for example aluminium nitride (AlN), boron nitride (BN), aluminum oxide (Al
2O
3), zinc oxide (ZnO) and artificial diamond etc.
For the phase change resin material, have the phase change characteristic in order to make heat interfacial material, its resin partly is mainly lower molecular weight and has the low melting point characteristic.Therefore but these resins repeatedly come to be easy under the back operations volatilization and lose at element, and its thermostability is not good, cause real contact area to reduce gradually and integral heat sink efficient is significantly reduced.
For thermally conductive material, though these metals or ceramic heat conduction powder itself have good thermal conductivity coefficient, the thermal conductivity coefficient of formed heat interfacial material can significantly reduce after thermally conductive material and resin collocation.When increasing the thermal conductivity coefficient of material, must add a large amount of metals or ceramic heat conduction powder (accounting for about 50～90wt%), will cause the interface resistance value of heat interfacial material significantly to increase, relatively reduce the radiating efficiency of overall package element.And also cause cost to improve easily.Therefore known heat interfacial material can have shortcomings such as low thermal conductance coefficient and high impedance value.
Summary of the invention
In view of the foregoing, purpose of the present invention just provides a kind of composition for heat interfacial material, has the regularization structure of high thermal conductivity coefficient and phase change.
A further object of the present invention provides a kind of composition for heat interfacial material, can apply to use for electronic products radiating gaskets such as consumer 3C, industry, automobile, medical treatment, space flight and communication.
The present invention proposes a kind of composition for heat interfacial material, comprises thermoplastic resin, liquid crystal polymer and the CNT (carbon nano-tube) of tool phase change.The content of the thermoplastic resin of tool phase change in constituent is 30～89wt%.The content of liquid crystal polymer in constituent is 10～50wt%.The content of CNT (carbon nano-tube) in constituent is 1～25wt%.
In above-mentioned composition for heat interfacial material, the fusing point of the thermoplastic resin of tool phase change is smaller or equal to 100 ℃.The thermoplastic resin of tool phase change can be ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, polyvinyl chloride, Gum Rosin, polypropylene random copolymer, polyformal multipolymer, polyolefine, polymeric amide, polycarbonate, polyester, ethylene-vinyl acetate copolymer, polyvinyl acetate (PVA), polyimide or these materials mixture in a kind of.
In above-mentioned composition for heat interfacial material, the thermoplastic resin of tool phase change is an ethylene-vinyl acetate copolymer.The melt flow index of ethylene-vinyl acetate copolymer is 2～100g/10min.In ethylene-vinyl acetate copolymer, the content of vinyl acetate is 30～50wt%.
In above-mentioned composition for heat interfacial material, liquid crystal polymer comprises a kind of among nematic liquid crystal polymer, smectic liquid crystal polymer or the cholesterol liquid crystal polymer.The monomer of liquid crystal polymer comprises cholesterol benzoate.The molecular weight of liquid crystal polymer is 3000～50000.
In above-mentioned composition for heat interfacial material, CNT (carbon nano-tube) can be a kind of among single wall nano carbon or the many walls nano-sized carbon.The median size of CNT (carbon nano-tube) is 1～100nm.The long-width ratio of CNT (carbon nano-tube) is 5～10000.
In above-mentioned composition for heat interfacial material, also comprise solvent.Solvent comprises toluene, dimethylbenzene or methyl ethyl ketone.
In above-mentioned composition for heat interfacial material, the content of the thermoplastic resin of tool phase change is 30～84wt%; The content of liquid crystal polymer is 15～50wt%; The content of CNT (carbon nano-tube) is 1～20wt%.
The present invention's composition for heat interfacial material utilizes the high thermal conduction characteristic of CNT (carbon nano-tube) to reduce the addition of thermally conductive material, and then reduces the thermal contact resistance value of heat interfacial material.
And, utilize the high regularization microstructure of liquid crystal polymer to impel CNT (carbon nano-tube) to disperse and arrangement, and then improve the thermal conductivity coefficient of heat interfacial material along specific direction.
In addition, in composition for heat interfacial material, add the viscosity that liquid crystal polymer can significantly reduce whole resin, therefore can effectively improve the dispersion processing of CNT (carbon nano-tube), prevent the CNT (carbon nano-tube) gathering and the thermal conductivity coefficient and the mechanical properties of reduction material.
In addition, because the thermoplastic resin of CNT (carbon nano-tube)-liquid crystal polymer composite structure and tool phase change can compatibility and can not be separated, and the heat interfacial material that is formed has phase change temperature (phasechange temperature, PCT) be 45～75 ℃, so under normal operation, can fill and lead up hole, space or the depression of element surface, and then therefore the thermal resistance value that can reduce integral member significantly can improve the low thermal conductance coefficient and the high impedance value shortcoming of existing heat interfacial material effectively to original 1/10th.
State with other purpose, feature and advantage and can become apparent on the present invention for allowing, preferred embodiment cited below particularly, and conjunction with figs. are described in detail below.
Embodiment
The present invention's composition for heat interfacial material mainly is the thermoplastic resin that comprises the tool phase change, liquid crystal polymer and as the CNT (carbon nano-tube) of thermally conductive material.
In the present invention, so-called " thermoplastic resin of tool phase change " is meant that this material is under normal room temperature, that is about 25 ℃ the time, with solid-state, semi-solid state is glassy or state such as crystalloid exists, but when high temperature or high temperature range, exist with states such as liquid, semi liquid state or viscous fluids.The phase inversion temperature of the thermoplastic resin of tool phase change is preferably in the operating temperature range that drops on element, for example is between 40-75 ℃.And the fusing point of the thermoplastic resin of tool phase change is preferably smaller or equal to 100 ℃.
For instance, the thermoplastic resin of tool phase change comprises ethylene-vinyl acetate copolymer (ethylene vinyl acetate), ethylene-vinyl acetate copolymer (Ethylene-vinyl acetatecopolymer), polyvinyl chloride (PVC), Gum Rosin (rosin ester), polypropylene random copolymer (polypropylene random copolymer), polyformal multipolymer (polyoxymethylene copolymers), polyolefine (polyolefin), polymeric amide (polyamide), polycarbonate (polycarbonate), polyester (polyester), ethylene-vinyl acetate copolymer (ethylene vinyl acetate), polyvinyl acetate (PVA) (polyvinyl acetate), a kind of in the mixture of polyimide (polyimide) or these materials.
CNT (carbon nano-tube) as thermally conductive material for example is single wall (single-walled) nano-sized carbon or many walls (multi-walled) nano-sized carbon.The median size of CNT (carbon nano-tube) for example is 1～100nm.And, the Aspect Ratio of CNT (carbon nano-tube) in this way 5～10000.
Liquid crystal polymer for example is nematic (nematic type) liquid crystal polymer, stratose type (semectictype) liquid crystal polymer or cholesterol type (cholesteric type) liquid crystal polymer.The monomer of liquid crystal polymer for example is a cholesterol benzoate.The molecular weight of liquid crystal polymer is preferably 3000～50000.Because CNT (carbon nano-tube) has axial thermal conductivity character and the thermal conductive property of laterally not having, therefore the present invention adds liquid crystal polymer in composition for heat interfacial material, impel CNT (carbon nano-tube) to disperse and arrangement with the high regularization microstructure of utilizing liquid crystal polymer, and then improve the thermal conductivity coefficient of heat interfacial material along specific direction.
In the present invention's composition for heat interfacial material, also comprise solvent.Solvent for example is toluene, dimethylbenzene or methyl ethyl ketone.In addition, the present invention's composition for heat interfacial material also can contain general additive commonly used, and additive can comprise wetting agent or interfacial agent, opaque (opacifying) or defoamer (anti-foaming) agent, chain extension agent, tackifier (tackifier), pigment (pigment), lubricant (lubricant), stablizer (Stabilizer), fire retardant (flame retardant) and the antioxidant (antioxidants) of tradition.
In the present invention's composition for heat interfacial material, the content of the thermoplastic resin of tool phase change is 30～89wt%, is preferably 30～84wt%; The content of liquid crystal polymer is 10～50wt%, is preferably 15～50wt%; The content of CNT (carbon nano-tube) is 1～20wt%.
The preparation method of the present invention's composition for heat interfacial material then, is described.Earlier the thermoplastic resin with phase change is dissolved in the solvent, again liquid crystal polymer is added stir after, CNT (carbon nano-tube) is slowly added in the solution, impel even and orderlyization of CNT (carbon nano-tube) to be arranged in the microstructure of liquid crystal polymer.In the whole composition for heat interfacial material, solids content for example is 20～40wt%.
Below enumerate experimental example 1 and the effect of comparative example 1～3, but the present invention is not limited in following experimental example with proof the present invention's composition for heat interfacial material.In following experimental example 1 and comparative example 1～3, the phase change thermoplastic resin is to adopt the ethylene-vinyl acetate copolymer (Ethylene-vinyl acetate copolymer) of selecting low melting point (≤100 ℃), its melt flow index is between 60～800g/10min, in ethylene-vinyl acetate copolymer, vinyl acetate content for example is 25～45wt%.Liquid crystal polymer is to adopt the system MJ05661 (trade(brand)name) of Merck ﹠ Co., Inc. liquid crystal polymer.CNT (carbon nano-tube) is to adopt seedchem corporate system, the CNT (carbon nano-tube) of caliber 40～60nm.Aluminum oxide is to adopt Showa Denko corporate system, the aluminum oxide that diameter is 1.4 microns.
Experimental example 1
Use is provided with 4 mouthfuls of glass reactors of 1 liter of the stirring rod of 3 impellers.After glass reactor adds the 600g toluene solvant, add the thermoplastic resin of 200g tool phase change again: ethylene-vinyl acetate copolymer (Elvax
40W, DuPont), and carry out stirring and dissolving it.Then, add 200g liquid crystal polymer (MJ05661, Merck Ltd., Japan) in solution, stir, and in stirring, slowly add 20g CNT (carbon nano-tube) (MWNT, d=40～60nm, Seedchem Co.), stirred fast 30 minutes, and obtained the composition for heat interfacial material of the regularization structure of tool high thermal conductivity coefficient and phase change after stirring.
Comparative example 1
Use is provided with 4 mouthfuls of glass reactors of 1 liter of the stirring rod of 3 impellers.After glass reactor adds the 600g toluene solvant, add the thermoplastic resin of 200g tool phase change again: ethylene-vinyl acetate copolymer (Elvax
40W, DuPont), and carry out stirring and dissolving it.(MWNT, d=40～60nm SeedchemCo.), stirred 30 minutes fast, obtained the composition for heat interfacial material of tool high thermal conductivity coefficient after stirring slowly to add the 20g CNT (carbon nano-tube) in stirring.
Comparative example 2
Use is provided with 4 mouthfuls of glass reactors of 1 liter of the stirring rod of 3 impellers.After glass reactor adds the 600g toluene solvant, add the thermoplastic resin of 200g tool phase change again: ethylene-vinyl acetate copolymer (Elvax
40W, DuPont), and carry out stirring and dissolving it.After stirring fast 30 minutes, obtain composition for heat interfacial material.
Comparative example 3
Use is provided with 4 mouthfuls of glass reactors of 1 liter of the stirring rod of 3 impellers.After glass reactor adds the 600g toluene solvant, add the thermoplastic resin of 200g tool phase change again: ethylene-vinyl acetate copolymer (Elvax
40W, DuPont), and carry out stirring and dissolving it.In stirring, slowly add 20g aluminum oxide (Al
2O
3, d=1.4 μ m, Showa Denko Co.), stirred fast 30 minutes, obtain composition for heat interfacial material after stirring.
Behind the composition for heat interfacial material of preparing experimental example 1 and comparative example 1～3, these composition for heat interfacial material are carried out Physical Property Analysis.Physical Property Analysis comprises thermal conductivity coefficient and uses elementary errors scanning calorimeter flow measurement instrument (DSC) to measure the phase change temperature.Experimental example 1 is listed in the table one with the ratio of component and the relevant rerum natura of comparative example 1～3.
Table one
By the result of above-mentioned table one as can be known, in the composition for heat interfacial material of experimental example 1 and comparative example 1～3, the composition for heat interfacial material of experimental example 1 has the highest thermal conductivity coefficient.
And the composition for heat interfacial material of experimental example 1 is compared with the composition for heat interfacial material of comparative example 1, has higher thermal conductivity coefficient.This is because added liquid crystal polymer, can impel CNT (carbon nano-tube) to disperse and arrangement along specific direction, so can improve the thermal conductivity coefficient of heat interfacial material.
On the other hand, compare with the composition for heat interfacial material of comparative example 2～3, have higher thermal conductivity coefficient by the composition for heat interfacial material of comparative example 2.That is, use CNT (carbon nano-tube) as the thermal conductivity material, better than known conventional metals or ceramic powder.And under same amount, the thermal conductivity coefficient of the composition for heat interfacial material of comparative example 1 is 10～40 times of thermal conductivity coefficient of the composition for heat interfacial material of comparative example 2～3.That is the addition of CNT (carbon nano-tube) is few more than some conventional metals or ceramic powder, therefore helps dispersion processing and handles.
In sum, at the present invention's composition for heat interfacial material, utilize the high thermal conduction characteristic of CNT (carbon nano-tube) to reduce the addition of thermally conductive material, and then reduce the thermal contact resistance value of heat interfacial material.But,, therefore utilize the high regularization microstructure of liquid crystal polymer to impel CNT (carbon nano-tube) to disperse and arrangement, and then improve the thermal conductivity coefficient of heat interfacial material along specific direction because CNT (carbon nano-tube) has axial thermal conductivity character and the thermal conductive property of laterally not having.
And, owing in composition for heat interfacial material, add the viscosity that liquid crystal polymer can significantly reduce whole resin, therefore can effectively improve the dispersion processing of CNT (carbon nano-tube), prevent the CNT (carbon nano-tube) gathering and the thermal conductivity coefficient and the mechanical properties of reduction material.Control by microstructure and to prepare novel nano carbon pipe-liquid crystal (CNT-LC) heat conduction composite structure, and the hot interface of this novel C NT-LC composite structure made material composite, to lack more than some conventional metals or ceramic powder than the addition of traditional hot interface, and therefore help dispersion processing and handle with the thermal conductivity coefficient of material composite high 10～40 times and CNT (carbon nano-tube).
In addition, the thermoplastic resin of this novel C NT-LC composite structure and tool phase change can be compatible and can not be separated, and the heat interfacial material that is formed has phase change temperature (phase changetemperature, PCT) be 45～75 ℃, so under normal operation, can fill and lead up hole, space or the depression of element surface, and then therefore the thermal resistance value that can reduce integral member significantly can improve the low thermal conductance coefficient and the high impedance value shortcoming of existing heat interfacial material effectively to original 1/10th.
Though the present invention discloses as above with preferred embodiment; right its is not in order to limit the present invention; any person of ordinary skill in the field; without departing from the spirit and scope of the invention; when can doing a little change and improvement, so the present invention's protection domain is as the criterion when looking the claim person of defining.
Claims (15)
1. composition for heat interfacial material is characterized in that comprising:
The thermoplastic resin of tool phase change, the content in constituent are 30～89wt%;
Liquid crystal polymer, the content in constituent are 10～50wt%; And
CNT (carbon nano-tube), the content in constituent are 1～25wt%.
2. the composition for heat interfacial material according to claim 1, the fusing point of thermoplastic resin that it is characterized in that the tool phase change is smaller or equal to 100 ℃.
3. the composition for heat interfacial material, the thermoplastic resin that it is characterized in that the tool phase change according to claim 1 comprise ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, polyvinyl chloride, Gum Rosin, polypropylene random copolymer, polyformal multipolymer, polyolefine, polymeric amide, polycarbonate, polyester, ethylene-vinyl acetate copolymer, polyvinyl acetate (PVA), polyimide or these materials mixture in a kind of.
4. the composition for heat interfacial material according to claim 1, the thermoplastic resin that it is characterized in that the tool phase change is an ethylene-vinyl acetate copolymer.
5. the composition for heat interfacial material according to claim 4, the melt flow index that it is characterized in that ethylene-vinyl acetate copolymer is 2～100g/10min.
6. the composition for heat interfacial material according to claim 4 is characterized in that in ethylene-vinyl acetate copolymer, and the content of vinyl acetate is 30～50wt%.
7. the composition for heat interfacial material according to claim 1 is characterized in that liquid crystal polymer comprises a kind of among nematic liquid crystal polymer, smectic liquid crystal polymer or the cholesterol liquid crystal polymer.
8. the composition for heat interfacial material according to claim 1 is characterized in that the monomer of liquid crystal polymer comprises cholesterol benzoate.
9. the composition for heat interfacial material according to claim 1, the molecular weight that it is characterized in that liquid crystal polymer is 3000～50000.
10. the composition for heat interfacial material according to claim 1 is characterized in that CNT (carbon nano-tube) comprises a kind of among single wall or the many walls nano-sized carbon.
11. the composition for heat interfacial material according to claim 1, the median size that it is characterized in that CNT (carbon nano-tube) is 1～100nm.
12. the composition for heat interfacial material according to claim 1, the long-width ratio that it is characterized in that CNT (carbon nano-tube) is 5～10000.
13. the composition for heat interfacial material according to claim 1 is characterized in that also comprising solvent.
14. the composition for heat interfacial material according to claim 13 is characterized in that solvent comprises toluene, dimethylbenzene or methyl ethyl ketone.
15. the composition for heat interfacial material according to claim 1, the content that it is characterized in that the thermoplastic resin of tool phase change is 30～84wt%; The content of liquid crystal polymer is 15～50wt%; The content of CNT (carbon nano-tube) is 1～20wt%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510135414 CN1990816A (en) | 2005-12-28 | 2005-12-28 | Composition for heat interfacial material |
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| CN 200510135414 CN1990816A (en) | 2005-12-28 | 2005-12-28 | Composition for heat interfacial material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980863A (en) * | 2014-05-26 | 2014-08-13 | 湘潭大学 | Side-chain type liquid crystal polymer composite shaping phase change material and preparation method thereof |
| CN104371665A (en) * | 2014-11-04 | 2015-02-25 | 湘潭大学 | Flexible-spacer-free side chain liquid crystal polymer composite shaped phase-change material and preparation method thereof |
| CN105189693A (en) * | 2013-03-18 | 2015-12-23 | 西门子公司 | Composite material for a thermal energy storage means and process for producing a composite material for a thermal energy storage means |
| CN109679198A (en) * | 2018-12-28 | 2019-04-26 | 苏州赛伍应用技术股份有限公司 | A kind of heat conductive phase change material and preparation method thereof |
-
2005
- 2005-12-28 CN CN 200510135414 patent/CN1990816A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105189693A (en) * | 2013-03-18 | 2015-12-23 | 西门子公司 | Composite material for a thermal energy storage means and process for producing a composite material for a thermal energy storage means |
| CN103980863A (en) * | 2014-05-26 | 2014-08-13 | 湘潭大学 | Side-chain type liquid crystal polymer composite shaping phase change material and preparation method thereof |
| CN103980863B (en) * | 2014-05-26 | 2016-08-24 | 湘潭大学 | A kind of side chain liquid crystalline polymer composite shape-setting phase-change material and preparation method thereof |
| CN104371665A (en) * | 2014-11-04 | 2015-02-25 | 湘潭大学 | Flexible-spacer-free side chain liquid crystal polymer composite shaped phase-change material and preparation method thereof |
| CN104371665B (en) * | 2014-11-04 | 2018-02-16 | 湘潭大学 | One kind is without flexible spacer side chain liquid crystalline polymer composite shape-setting phase-change material and preparation method thereof |
| CN109679198A (en) * | 2018-12-28 | 2019-04-26 | 苏州赛伍应用技术股份有限公司 | A kind of heat conductive phase change material and preparation method thereof |
| CN109679198B (en) * | 2018-12-28 | 2022-03-08 | 苏州赛伍应用技术股份有限公司 | Heat-conducting phase-change material and preparation method thereof |
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