WO2009054567A1 - Thermal conductive polymer composite and article using the same - Google Patents

Thermal conductive polymer composite and article using the same Download PDF

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Publication number
WO2009054567A1
WO2009054567A1 PCT/KR2007/007010 KR2007007010W WO2009054567A1 WO 2009054567 A1 WO2009054567 A1 WO 2009054567A1 KR 2007007010 W KR2007007010 W KR 2007007010W WO 2009054567 A1 WO2009054567 A1 WO 2009054567A1
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WO
WIPO (PCT)
Prior art keywords
polymer composite
metal
thermal conductive
fillers
volume
Prior art date
Application number
PCT/KR2007/007010
Other languages
French (fr)
Inventor
Sung Jun Kim
Chang Min Hong
Original Assignee
Cheil Industries Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cheil Industries Inc. filed Critical Cheil Industries Inc.
Priority to EP07860787A priority Critical patent/EP2203524A4/en
Priority to CN200780101161A priority patent/CN101827894A/en
Priority to JP2010530911A priority patent/JP5296085B2/en
Publication of WO2009054567A1 publication Critical patent/WO2009054567A1/en
Priority to US12/764,305 priority patent/US20100204380A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/041—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with metal fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H01L23/3737—Organic materials with or without a thermoconductive filler
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/04—Polysulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to a polymer composite having excellent thermal conductivity and mechanical strength, and more particularly to a thermal conductive polymer composite having excellent thermal conductivity and mechanical strength by including mixed metal fillers and a low-melting- point metal .
  • thermal conductive material used tend to increase with increased power consumption of electric/electronic parts or products.
  • Metals have been mainly used as a conventional thermal conductive material. However, metals have low moldability, productivity and parts designability. Because of these limitations, there have been many efforts to develop a substitute material for metals.
  • Thermal conductive polymers have been proposed as a substitute material. This material has the advantages of high productivity in injection molding methods and allowing precise design. However, the thermal conductive polymer material that can substitute for metal has a thermal conductivity of about 10
  • thermal conductive polymer materials are progressing towards obtaining an optimal thermal conductivity with a minimum content of thermal conductive fillers so as to ensure fluidity for injection molding and an appropriate level of physical properties.
  • Japanese Patent Application Laid-Open Publication No. 2006- 22130 discloses a composite including a crystalline polymer, an inorganic powder having a poor compatibility with a low- melting-point metal and metal powder, and a fibrous reinforcing material.
  • the thermal conductor therein is composed of the inorganic powder having a poor compatibility with a low- melting-point metal and metal powder, and thus takes a different approach as compared to the present invention, in which the thermal conductivity is increased by maximizing the contact efficiency between all thermal conductive fillers.
  • the matrix i.e., the crystalline polymer
  • Japanese Patent Application Laid-Open Publication No. 2006-257174 discloses a thermal conductive polymer composite using expandable graphite and general graphite in a ratio of 1/9 to 5/5, respectively m this order.
  • This invention relates to a composite which increases thermal conductivity by increasing the contact probability between graphite by adjusting the ratio of the expandable graphite and general graphite.
  • the invention uses graphite, there are disadvantages in that the viscosity of the material itself is high and the material may easily break.
  • US Patent No. 6048919 discloses a composite including a thermally conductive filler having an aspect ratio of at least 10:1 and a thermally conductive filler having an aspect ratio of less than 5:1 m a volume ratio of 30 to 60% and 25 to 60%, respectively.
  • the contact probability between the thermally conductive fillers is lower than the optimized contact probability between fibrous and sheet fillers and low-melting-point metal of the present invention.
  • this invention lacks consideration of the physical properties.
  • the present invention has been made in view of the above problems, and it is an object of the present invention to provide a thermal conductive polymer composite having excellent thermal conductivity with a low content of a metal filler and capable of reinforcing mechanical strength by effectively compositing a thermal conductive filler.
  • a thermal conductive polymer composite comprising 30 to 85% by volume of a crystalline polymer resin, 5 to 69% by volume of mixed metal fillers, and 1 to 10% by volume of a low-melting-point metal having a solidus temperature lower than a melting point temperature of the crystalline polymer resin.
  • Thermal conductive polymer materials have been developed mainly by compositing a polymer/thermal conductive filler, and to date, other methods for significantly increasing the thermal conductivity of a polymer material other than the polymer/thermal conductive filler composite have much to be desired.
  • a general polymer material is a thermal insulator having a thermal conductivity of 0.1 to 0.4 [W/mK] .
  • the maximum thermal conductivity that can obtained is 10 [W/mK] .
  • the viscosity of the polymer composite is rapidly increased and the mechanical property is rapidly reduced. Thus, it becomes difficult to realize the actual benefits of the thermal conductive polymer material.
  • the theoretical thermal conductivity of the polymer composite calculated according to Fourier's Law is significantly different from the actual thermal conductivity of the polymer composite. That is, the maximum value of the thermal conductivity of the polymer composite calculated according to Fourier' s Law is much higher than the actual thermal conductivity of the polymer composite, in which the actual physical property of the composite is generally set between the maximum and the minimum value of the theoretically calculated values. That is, for some reason, the actual thermal conductivity of the polymer composite is far from reaching the thermal conductivity of the thermal conductive filler to be added.
  • the present inventors have conducted many experiments. As a result, they have suggested that the interfacial Phonon scattering of the thermal conductive filler/polymer may cause the significant difference for a polymer composite with a low content (filler content in the range that does not generate filler/filler contact) .
  • the interfacial Phonon scattering of the thermal conductive filler/polymer is not a major cause of reducing thermal conductivity in the case of a polymer composite with a high content (filler content in the range of generating filler/filler contact) to obtain high thermal conductivity.
  • the inventors assumed that the Phonon scattering at the interface of the thermal conductive filler/thermal conductive filler is the major cause of reducing thermal conductivity .
  • the Phonon scattering at the interface of the thermal conductive filler/thermal conductive filler causes significant reduction of the conductivity of the thermal conductive filler itself.
  • the filler/filler interface is a characteristic of a material rather than a factor that can be controlled.
  • maximizing the contact probability of the filler/filler can be the major factor for developing the thermal conductive polymer composite.
  • the present inventors have searched for a material composition for maximizing the contact probability between the fillers.
  • a thermal conductive polymer composite having excellent thermal conductivity and mechanical strength, which comprises 30 to 85% by volume of a crystalline polymer resin, 5 to 69% by volume of mixed metal fillers, and 1 to 10% by volume of a low- melting-point metal having a solidus temperature lower than a melting point temperature of the crystalline polymer resin.
  • the polymer resin used as a constituent component of the thermal conductive polymer composite of the present invention is a crystalline polymer resin. This is because the crystalline resin has higher conductivity than a non-crystalline resin. Thus, the final thermal conductivity of the polymer composite varies depending on the thermal conductivity of the polymer resin to be used.
  • crystalline polymer resin examples include but are not limited to polyphenylene sulfide (PPS), liquid crystal polymer (LCP) , polyamide (PA) , syndiotactic polystyrene (sPS) , polyetheretherketone (PEEK) , polyethylene terephthalate (PET) , polybutylene terephthalate (PBT) , polyoxymethylene (POM) , polypropylene (PP) or polyethylene (PE) , alone or in combination of two or more.
  • PPS polyphenylene sulfide
  • LCP liquid crystal polymer
  • PA polyamide
  • sPS syndiotactic polystyrene
  • PEEK polyetheretherketone
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • POM polyoxymethylene
  • PE polypropylene
  • PE polyethylene
  • the crystalline polymer resin of the present invention is present m an amount of 30 to 85% by volume, and more preferably 50 to 79% by volume based on the final content of the thermal conductive polymer composite.
  • the amount of the crystalline polymer resin exceeds 85% by volume, it is difficult to ensure a certain level or more of thermal conductivity suitable for practical use m the environment requiring thermal conductivity.
  • the amount is less than 30% by volume, it is difficult to prepare the polymer composite.
  • Another constituent component of the thermal conductive polymer composite of the present invention is mixed metal fillers, in which metals having two or more shapes are mixed.
  • the mixed metal fillers are used to maximize contact between the thermal conductive fillers .
  • fibrous metal fillers in a shape capable of reinforcing physical properties and sheet metal fillers having high contact probability between fillers are mixed in a volume ratio of 9:1 to 1:9. It is more preferable that the volume ratio of the fibrous fillers and sheet fillers is 4:6 to 6:4 in the point of contact efficiency between the thermal conductive fillers .
  • the fibrous or sheet metal fillers are made of metals with excellent thermal conductivity such as aluminum, copper, zinc, magnesium, nickel, silver, chromium, iron, molybdenum or stainless steel, or a mixture thereof, which are made into fibrous or sheet shape using a method such as cutting, milling, melt dispersing, electrolyzing, grinding or chemical reduction.
  • the fibrous metal fillers have an aspect ratio
  • the sheet metal fillers have an aspect ratio ( (length/thickness) of 10 to 100,000, and preferably 50 to 500. When the aspect ratio exceeds 100,000, the packing factor in the resin is reduced greatly such that there may be a problem of impregnation in the resin. When the aspect ratio is less than 10, the contact probability between the fillers is inefficient.
  • the mixed metal fillers of the present invention are contained in an amount of 5 to 69% by volume, and preferably 20 to 45% by volume based on the thermal conductive polymer composite.
  • the content exceeds 69% by volume, it is difficult to process the polymer composite preparation. Even if the composite is prepared, it is difficult to process using typical injection molding since its viscosity is considerably high.
  • the content is less than 5% by volume, it is difficult to ensure a certain level or more of thermal conductivity for its adaptation to an applicable field requiring thermal conductivity.
  • C Low-melting-point metal
  • a low-melting-point metal, as another constituent component of the thermal conductive polymer composite of the present invention is a solid solution composed of two or more metal elements. It is particularly preferable that the low- melting-point metal is a metal solid solution whose solidus temperature is lower than the melting point temperature of the above-mentioned crystalline polymer.
  • the low-melting-point metal whose solidus temperature is 20 0 C or more lower than the melting point temperature of the crystalline polymer allows effective networking between the fillers and is good for the convenience of the preparation process. It is preferable that the solidus temperature is 100 0 C or more higher than the environment in which the polymer composite is used for product stability.
  • the low-melting-point metal is made mainly of tin, bismuth, or lead.
  • a metal element such as copper, aluminum, nickel, or silver
  • the physical properties such as solidus temperature, liquidus temperature, or mechanical strength can be controlled.
  • the low-melting-point metal include low-melting-point metals containing tin, bismuth, lead, or a mixture thereof in an amount of 89% by weight or more and less than 100% by weight and copper, aluminum, nickel, silver, or a mixture thereof in an amount exceeding 0% by weight and 11% by weight or less.
  • the low-melting-point metal is not limited to the low-melting-point metal having the above-mentioned constituent components and constitution ratio of the components .
  • aluminum when using aluminum as a metal filler, it is preferable to include aluminum in the components of the solid solution.
  • copper when using copper as a metal filler, it is preferable to include copper in the components of the solid solution.
  • the low-melting-point metal is mainly made of tin instead of bismuth or lead in view of its more eco-friendly nature.
  • the low-melting-point metal of the present invention is contained in an amount of 1 to 10% by volume, and more preferably 1 to 5% by volume of the final thermal conductive polymer composite.
  • the content exceeds 10% by volume, the low-melting-point metal has high interfacial energy with the resin causing difficulties in impregnation/dispersion.
  • the content is less than 1% by volume, the function of allowing networking between the fillers is insignificant, thereby reducing the effect of improving the contact probability between the fillers.
  • the thermal conductive polymer composite of the present invention may contain additives such as talc, silica, mica, alumina, or glass fibers. By adding these inorganic fillers, physical properties such as mechanical strength and heat deflection temperature can be improved.
  • the resin composition of the present invention may further contain a UV absorbent, a heat stabilizer, an antioxidant, a flame retardant, a lubricant, a dye and/or a pigment. The amounts and methods of using these additives are widely known to those skilled m this field of art.
  • the parts produced from the thermal conductive polymer composite of the present invention have high thermal conductivity so that heat generated from general exothermic parts can be effectively radiated. For example, when the polymer composite is used in heat radiation of general power or electric/electronic equipment, or heat radiation of integrated circuits such as LSI or CPU used in electronic equipment such as personal computers or digital video disc drive, it may give the products very good credibility.
  • the polymer composite having excellent thermal conductivity and mechanical strength can be obtained even when the content of the thermal conductive filler has relatively low thermal conductivity.
  • the polymer composite is efficiently used as a material for heat radiation parts of electric/electronic parts. Therefore, using the thermal conductive polymer composite of the present invention can improve the stability or lifespan of the exothermic electric/electronic parts or the electric/electronic equipment including the same.
  • PPS polyphenylene sulfide
  • This PPS resin was Ryton PR-35 available from Cheveron Phillips Chemical Company LLC.
  • the zero viscosity measured at 315.5 0 C under nitrogen atmosphere was 1000 [P].
  • B Mixed metal fillers
  • the fibrous metal fillers were aluminum having an average particle diameter of 40 ⁇ m, an average length of 2.5 mm, and an aspect ratio (length/diameter) of 62.5
  • the sheet metal fillers were aluminum having an average thickness of 350 run, an average length of 40 ⁇ m, and an aspect ratio (diameter/thickness) of 114.
  • C Low-meltmg-pomt metal
  • the low-meltmg-pomt metal used m Examples of the present invention was a tm/alummum low-meltmg-pomt metal having tin as a major component. Specifically, a tm/alummum solid solution whose solidus temperature was 228 0 C, m which the content of tin was 99.7% by weight and the content of aluminum was 0.3% by weight, was used.
  • thermal conductive polymer composites with the formulations shown m Examples 1 to 6 of Table 1 were prepared using a typical process for preparing a polymer composite such as a twin screw extruder and injection machine.
  • the thermal conductivity was measured by guarded heat flow method, and the mechanical properties were measured based on ASTM D790.
  • the results are presented in Table 1. [Table 1] (Unit: vol%)
  • Polymer composites containing carbon fiber, graphite or aluminum powder in addition to the above-mentioned constituent components were prepared using a typical process for preparing a polymer composite such as a twin screw extruder and injection machine. Their specific formulations, thermal conductivity and mechanical properties are presented in Table 2. The thermal conductivity and mechanical properties were measured in the same manner as in Examples 1-6.
  • the present invention has overcome low mechanical strength and resolved problems such as slurping by not using graphite-based thermal conductive filler.

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Abstract

A thermal conductive polymer composite having excellent thermal conductivity with a low content of a metal filler and capable of reinforcing mechanical strength by effectively compositing a thermal conductive filler is provided. The polymer composite includes 30 to 85 % by volume of a crystalline polymer resin, 5 to 69 % by volume of mixed metal fillers, and 1 to 10 % by volume of a low-melting-point metal.

Description

[DESCRIPTION]
[invention Title]
THERMAL CONDUCTIVE POLYMER COMPOSITE AND ARTICLE USING THE SAME
[Technical Field]
The present invention relates to a polymer composite having excellent thermal conductivity and mechanical strength, and more particularly to a thermal conductive polymer composite having excellent thermal conductivity and mechanical strength by including mixed metal fillers and a low-melting- point metal .
[Background Art]
The range and amount of thermal conductive material used tend to increase with increased power consumption of electric/electronic parts or products.
Metals have been mainly used as a conventional thermal conductive material. However, metals have low moldability, productivity and parts designability. Because of these limitations, there have been many efforts to develop a substitute material for metals.
Thermal conductive polymers have been proposed as a substitute material. This material has the advantages of high productivity in injection molding methods and allowing precise design. However, the thermal conductive polymer material that can substitute for metal has a thermal conductivity of about 10
[W/mK] at maximum. Thus, metals are still used where the parts require high thermal conductivity.
Currently, development of thermal conductive polymer materials is progressing towards obtaining an optimal thermal conductivity with a minimum content of thermal conductive fillers so as to ensure fluidity for injection molding and an appropriate level of physical properties.
With regard to the thermal conductive polymer composites, Japanese Patent Application Laid-Open Publication No. 2006- 22130 discloses a composite including a crystalline polymer, an inorganic powder having a poor compatibility with a low- melting-point metal and metal powder, and a fibrous reinforcing material. The thermal conductor therein is composed of the inorganic powder having a poor compatibility with a low- melting-point metal and metal powder, and thus takes a different approach as compared to the present invention, in which the thermal conductivity is increased by maximizing the contact efficiency between all thermal conductive fillers. In addition, the matrix, i.e., the crystalline polymer, contains a high content of materials having poor compatibility with each other, which may have a negative influence on the physical properties, and there is a disadvantage that additional glass fibers must be added to reinforce the properties.
Japanese Patent Application Laid-Open Publication No. 2006-257174 discloses a thermal conductive polymer composite using expandable graphite and general graphite in a ratio of 1/9 to 5/5, respectively m this order. This invention relates to a composite which increases thermal conductivity by increasing the contact probability between graphite by adjusting the ratio of the expandable graphite and general graphite. However, since the invention uses graphite, there are disadvantages in that the viscosity of the material itself is high and the material may easily break. Moreover, there is a problem of slurping causing the graphite to come off from the surface of the material.
US Patent No. 6048919 discloses a composite including a thermally conductive filler having an aspect ratio of at least 10:1 and a thermally conductive filler having an aspect ratio of less than 5:1 m a volume ratio of 30 to 60% and 25 to 60%, respectively. In this invention, the contact probability between the thermally conductive fillers is lower than the optimized contact probability between fibrous and sheet fillers and low-melting-point metal of the present invention. Moreover, this invention lacks consideration of the physical properties.
[Disclosure] [Technical Problem]
Therefore, the present invention has been made in view of the above problems, and it is an object of the present invention to provide a thermal conductive polymer composite having excellent thermal conductivity with a low content of a metal filler and capable of reinforcing mechanical strength by effectively compositing a thermal conductive filler.
The present invention is not limited to the above- mentioned objects, and other objects will be apparently understood from the following description of the present invention by those skilled in the art to which the present invention pertains.
[Technical Solution]
In accordance with an aspect of the present invention, the above and other objects can be accomplished by the provision of a thermal conductive polymer composite comprising 30 to 85% by volume of a crystalline polymer resin, 5 to 69% by volume of mixed metal fillers, and 1 to 10% by volume of a low-melting-point metal having a solidus temperature lower than a melting point temperature of the crystalline polymer resin. Thermal conductive polymer materials have been developed mainly by compositing a polymer/thermal conductive filler, and to date, other methods for significantly increasing the thermal conductivity of a polymer material other than the polymer/thermal conductive filler composite have much to be desired.
A general polymer material is a thermal insulator having a thermal conductivity of 0.1 to 0.4 [W/mK] . When compositing a general polymer material and a thermal conductive filler, the maximum thermal conductivity that can obtained is 10 [W/mK] . However, when using a high content of the thermal conductive filler to obtain such a high thermal conductivity, the viscosity of the polymer composite is rapidly increased and the mechanical property is rapidly reduced. Thus, it becomes difficult to realize the actual benefits of the thermal conductive polymer material.
In developing the thermal conductive polymer material, the theoretical thermal conductivity of the polymer composite calculated according to Fourier's Law is significantly different from the actual thermal conductivity of the polymer composite. That is, the maximum value of the thermal conductivity of the polymer composite calculated according to Fourier' s Law is much higher than the actual thermal conductivity of the polymer composite, in which the actual physical property of the composite is generally set between the maximum and the minimum value of the theoretically calculated values. That is, for some reason, the actual thermal conductivity of the polymer composite is far from reaching the thermal conductivity of the thermal conductive filler to be added. The main cause of this difference is that in the thermal conductive polymer composite, especially at the interface of the thermal conductive filler and polymer, a considerable amount of Phonon is scattered, thereby interfering with heat transfer. Thus, it is assumed that the function of the thermal conductive filler is significantly limited in the composite.
However, the present inventors have conducted many experiments. As a result, they have suggested that the interfacial Phonon scattering of the thermal conductive filler/polymer may cause the significant difference for a polymer composite with a low content (filler content in the range that does not generate filler/filler contact) . However, the interfacial Phonon scattering of the thermal conductive filler/polymer is not a major cause of reducing thermal conductivity in the case of a polymer composite with a high content (filler content in the range of generating filler/filler contact) to obtain high thermal conductivity. Instead, the inventors assumed that the Phonon scattering at the interface of the thermal conductive filler/thermal conductive filler is the major cause of reducing thermal conductivity .
That is, the Phonon scattering at the interface of the thermal conductive filler/thermal conductive filler causes significant reduction of the conductivity of the thermal conductive filler itself.
Even though the Phonon scattering is generated at the interface of the thermal conductive filler/thermal conductive filler, the thermal conductivity is still higher than in the case where the filler is isolated inside the polymer composite. Thus, an important factor for developing a thermal conductive polymer composite is to increase contact probability between the thermal conductive fillers. That is, since the thermal conductivity of the polymer itself is largely lower than that of the thermal conductive filler, it is thought that the level of Phonon scattering at the interface of thermal conductive filler/polymer will not have a significant effect on the whole polymer composite.
Consequently, minimizing the Phonon scattering at the interface of filler/filler and maximizing the contact probability between the fillers at the same time may be important factors for developing the thermal conductive polymer composite. However, the filler/filler interface is a characteristic of a material rather than a factor that can be controlled. Thus, maximizing the contact probability of the filler/filler can be the major factor for developing the thermal conductive polymer composite.
In this regard, the present inventors have searched for a material composition for maximizing the contact probability between the fillers. As a result, they have developed a thermal conductive polymer composite having excellent thermal conductivity and mechanical strength, which comprises 30 to 85% by volume of a crystalline polymer resin, 5 to 69% by volume of mixed metal fillers, and 1 to 10% by volume of a low- melting-point metal having a solidus temperature lower than a melting point temperature of the crystalline polymer resin.
First, constituent components forming the resin composition of the present invention are examined.
(A) Crystalline polymer resin
It is preferable that the polymer resin used as a constituent component of the thermal conductive polymer composite of the present invention is a crystalline polymer resin. This is because the crystalline resin has higher conductivity than a non-crystalline resin. Thus, the final thermal conductivity of the polymer composite varies depending on the thermal conductivity of the polymer resin to be used. Examples of the crystalline polymer resin include but are not limited to polyphenylene sulfide (PPS), liquid crystal polymer (LCP) , polyamide (PA) , syndiotactic polystyrene (sPS) , polyetheretherketone (PEEK) , polyethylene terephthalate (PET) , polybutylene terephthalate (PBT) , polyoxymethylene (POM) , polypropylene (PP) or polyethylene (PE) , alone or in combination of two or more.
It is preferable that the crystalline polymer resin of the present invention is present m an amount of 30 to 85% by volume, and more preferably 50 to 79% by volume based on the final content of the thermal conductive polymer composite. When the amount of the crystalline polymer resin exceeds 85% by volume, it is difficult to ensure a certain level or more of thermal conductivity suitable for practical use m the environment requiring thermal conductivity. When the amount is less than 30% by volume, it is difficult to prepare the polymer composite.
(B) Mixed metal fillers
Another constituent component of the thermal conductive polymer composite of the present invention is mixed metal fillers, in which metals having two or more shapes are mixed. The mixed metal fillers are used to maximize contact between the thermal conductive fillers .
It is particularly preferable that fibrous metal fillers in a shape capable of reinforcing physical properties and sheet metal fillers having high contact probability between fillers are mixed in a volume ratio of 9:1 to 1:9. It is more preferable that the volume ratio of the fibrous fillers and sheet fillers is 4:6 to 6:4 in the point of contact efficiency between the thermal conductive fillers .
The fibrous or sheet metal fillers are made of metals with excellent thermal conductivity such as aluminum, copper, zinc, magnesium, nickel, silver, chromium, iron, molybdenum or stainless steel, or a mixture thereof, which are made into fibrous or sheet shape using a method such as cutting, milling, melt dispersing, electrolyzing, grinding or chemical reduction.
The fibrous metal fillers have an aspect ratio
(length/diameter) of 10 to 10,000, and preferably 50 to 300. When the aspect ratio exceeds 10,000, there is difficulty processing the composite preparation. When the aspect ratio is less than 10, the contact probability between the fillers and physical properties thereof are inefficient.
The sheet metal fillers have an aspect ratio ( (length/thickness) of 10 to 100,000, and preferably 50 to 500. When the aspect ratio exceeds 100,000, the packing factor in the resin is reduced greatly such that there may be a problem of impregnation in the resin. When the aspect ratio is less than 10, the contact probability between the fillers is inefficient.
The mixed metal fillers of the present invention are contained in an amount of 5 to 69% by volume, and preferably 20 to 45% by volume based on the thermal conductive polymer composite. When the content exceeds 69% by volume, it is difficult to process the polymer composite preparation. Even if the composite is prepared, it is difficult to process using typical injection molding since its viscosity is considerably high. Moreover, when the content is less than 5% by volume, it is difficult to ensure a certain level or more of thermal conductivity for its adaptation to an applicable field requiring thermal conductivity. (C) Low-melting-point metal A low-melting-point metal, as another constituent component of the thermal conductive polymer composite of the present invention, is a solid solution composed of two or more metal elements. It is particularly preferable that the low- melting-point metal is a metal solid solution whose solidus temperature is lower than the melting point temperature of the above-mentioned crystalline polymer.
Specifically, the low-melting-point metal whose solidus temperature is 200C or more lower than the melting point temperature of the crystalline polymer allows effective networking between the fillers and is good for the convenience of the preparation process. It is preferable that the solidus temperature is 1000C or more higher than the environment in which the polymer composite is used for product stability.
In general, the low-melting-point metal is made mainly of tin, bismuth, or lead. By adjusting the content of these major components and a metal element such as copper, aluminum, nickel, or silver, the physical properties such as solidus temperature, liquidus temperature, or mechanical strength can be controlled. Examples of the low-melting-point metal include low-melting-point metals containing tin, bismuth, lead, or a mixture thereof in an amount of 89% by weight or more and less than 100% by weight and copper, aluminum, nickel, silver, or a mixture thereof in an amount exceeding 0% by weight and 11% by weight or less. However, as long as the solidus temperature is lower than the melting point temperature of the crystalline polymer, the low-melting-point metal is not limited to the low-melting-point metal having the above-mentioned constituent components and constitution ratio of the components . For example, when using aluminum as a metal filler, it is preferable to include aluminum in the components of the solid solution. When using copper as a metal filler, it is preferable to include copper in the components of the solid solution.
Meanwhile, it is preferable that the low-melting-point metal is mainly made of tin instead of bismuth or lead in view of its more eco-friendly nature.
It is preferable that the low-melting-point metal of the present invention is contained in an amount of 1 to 10% by volume, and more preferably 1 to 5% by volume of the final thermal conductive polymer composite. When the content exceeds 10% by volume, the low-melting-point metal has high interfacial energy with the resin causing difficulties in impregnation/dispersion. When the content is less than 1% by volume, the function of allowing networking between the fillers is insignificant, thereby reducing the effect of improving the contact probability between the fillers.
The thermal conductive polymer composite of the present invention may contain additives such as talc, silica, mica, alumina, or glass fibers. By adding these inorganic fillers, physical properties such as mechanical strength and heat deflection temperature can be improved. Moreover, the resin composition of the present invention may further contain a UV absorbent, a heat stabilizer, an antioxidant, a flame retardant, a lubricant, a dye and/or a pigment. The amounts and methods of using these additives are widely known to those skilled m this field of art. The parts produced from the thermal conductive polymer composite of the present invention have high thermal conductivity so that heat generated from general exothermic parts can be effectively radiated. For example, when the polymer composite is used in heat radiation of general power or electric/electronic equipment, or heat radiation of integrated circuits such as LSI or CPU used in electronic equipment such as personal computers or digital video disc drive, it may give the products very good credibility.
[Advantageous Effects]
According to the present invention, the polymer composite having excellent thermal conductivity and mechanical strength can be obtained even when the content of the thermal conductive filler has relatively low thermal conductivity. Thus, the polymer composite is efficiently used as a material for heat radiation parts of electric/electronic parts. Therefore, using the thermal conductive polymer composite of the present invention can improve the stability or lifespan of the exothermic electric/electronic parts or the electric/electronic equipment including the same.
[Best Mode]
Hereinafter, the components and functions of the present invention will be described in greater detail by way of appropriate Examples of the present invention, but these
Examples are not intended to limit the present invention in any way. The contents, which are not described herein, are technically analogized by those skilled in the art to which the present invention pertains without difficulty, and therefore, a description thereof will be omitted.
A detailed description of the constituent components used in the Examples and Comparative Examples of the present invention is as follows. (A) Crystalline polymer
In the Examples of the present invention, PPS (polyphenylene sulfide) was used as a crystalline polymer resin. This PPS resin was Ryton PR-35 available from Cheveron Phillips Chemical Company LLC. The zero viscosity measured at 315.50C under nitrogen atmosphere was 1000 [P]. (B) Mixed metal fillers Among the mixed metal fillers used in the Examples of the present invention, the fibrous metal fillers were aluminum having an average particle diameter of 40 μm, an average length of 2.5 mm, and an aspect ratio (length/diameter) of 62.5, and the sheet metal fillers were aluminum having an average thickness of 350 run, an average length of 40 μm, and an aspect ratio (diameter/thickness) of 114. (C) Low-meltmg-pomt metal
The low-meltmg-pomt metal used m Examples of the present invention was a tm/alummum low-meltmg-pomt metal having tin as a major component. Specifically, a tm/alummum solid solution whose solidus temperature was 2280C, m which the content of tin was 99.7% by weight and the content of aluminum was 0.3% by weight, was used.
Examples 1 to 6
Using the above-mentioned constituent components, the thermal conductive polymer composites with the formulations shown m Examples 1 to 6 of Table 1 were prepared using a typical process for preparing a polymer composite such as a twin screw extruder and injection machine. The thermal conductivity was measured by guarded heat flow method, and the mechanical properties were measured based on ASTM D790. The results are presented in Table 1. [Table 1] (Unit: vol%)
Figure imgf000018_0001
Comparative Examples 1 to 6
Polymer composites containing carbon fiber, graphite or aluminum powder in addition to the above-mentioned constituent components were prepared using a typical process for preparing a polymer composite such as a twin screw extruder and injection machine. Their specific formulations, thermal conductivity and mechanical properties are presented in Table 2. The thermal conductivity and mechanical properties were measured in the same manner as in Examples 1-6.
[Table 2] (Unit: vol%)
Figure imgf000018_0002
Figure imgf000019_0001
1) : Pitch-based carbon fiber having a diameter of 11 μm and a length of 6 mm
2) : Artificial graphite having an average particle diameter of 80 μm
3) : Aluminum powder having an average particle diameter of 40 μm
From the above results, mechanical properties such as flexural modulus or flexural strength were evaluated to be excellent as more fibrous aluminum was included. By increasing the content of the low-melting-point metal, the contact efficiency between the fillers was maximized, thereby having positive effects on the thermal conductivity. Meanwhile, with regard to thermal conductivity, it was evaluated that the thermal conductivity is most excellent when a volume ratio of the fibrous and sheet aluminum is 5:5.
In the case of carbon fiber, which is preferable as a conventional thermal conductive filler, the results showed that mechanical properties were excellent, but thermal conductivity decreased. In the case of graphite, thermal conductivity was excellent, but mechanical properties deteriorated significantly. It is also well known, m the case of graphite, that the viscosity of the polymer composite is increased, which causes slurping.
Consequently, by maximizing the contact between the thermal conductive fillers by using the mixed metal fillers and the low-melting-pomt metal according to the present invention, a polymer composite having excellent thermal conductivity with relatively small content of the thermal conductive filler can be obtained, to thereby solve the problem of high viscosity of conventional thermal conductive polymers. In addition, by compositing effectively in a form of thermal conductive filler, the present invention has overcome low mechanical strength and resolved problems such as slurping by not using graphite-based thermal conductive filler.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled m the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed m the accompanying claims .

Claims

[CLAIMS]
[Claim l] A thermal conductive polymer composite comprising: 30 to 85% by volume of a crystalline polymer resin; 5 to 69% by volume of mixed metal fillers; and 1 to 10% by volume of a low-melting-point metal having a solidus temperature lower than a melting point temperature of the crystalline polymer resin.
[Claim 2] The polymer composite according to claim 1, wherein the crystalline polymer resin is at least one selected from a group consisting of polyphenylene sulfide (PPS) , liquid crystal polymer (LCP) , polyamide (PA) , syndiotactic polystyrene (sPS) , polyetheretherketone (PEEK) , polyethylene terephthalate (PET) , polybutylene terephthalate (PBT) , polyoxymethylene (POM) , polypropylene (PP) or polyethylene (PE) .
[Claim 3] The polymer composite according to claim 1, wherein the mixed metal filler is composed of fibrous metal fillers and sheet metal fillers.
[Claim 4] The polymer composite according to claim 3, comprising the fibrous metal fillers and sheet metal fillers m a ratio (volume ratio) of 9:1 to 1:9.
[Claim 5] The polymer composite according to claim 1, wherein metals of the mixed metal fillers include aluminum, copper, zinc, magnesium, nickel, silver, chromium, iron, molybdenum, stainless steel, or a mixture thereof.
[Claim 6] The polymer composite according to claim 3, wherein the fibrous metal filler has an aspect ratio (length/diameter) of 10 to 10,000.
[Claim 7] The polymer composite according to claim 3, wherein the sheet metal filler has an aspect ratio (length/thickness) of 10 to 100,000.
[Claim 8] The polymer composite according to claim 1, wherein the low-melting-point metal is a metal solid solution composed of two or more metal elements.
[Claim 9] The polymer composite according to claim 1, wherein the low-melting-point metal is a metal solid solution prepared with two or more metals selected from a group consisting of tin, bismuth, lead, copper, aluminum, nickel or silver . [Claim lθ] A mold produced from a thermal conductive polymer composite of claim 1.
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