KR101374818B1 - Thermoplastic resin composition - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition comprising a thermoplastic resin and a polysilicon compound having an average particle size of 1 μm to 10,000 μm, and a heat generating material manufactured using the same, and thus, tensile strength, flexural modulus or impact strength, and the like. A thermoplastic resin composition having excellent mechanical properties and exhibiting high thermal conductivity and heat dissipation properties and a heat dissipation material using the same may be provided.

Description

[0001] THERMOPLASTIC RESIN COMPOSITION [0002]

The present invention relates to a thermoplastic resin composition, and relates to a thermoplastic resin composition having excellent mechanical properties such as tensile strength, flexural modulus or impact strength, and exhibiting high thermal conductivity and heat dissipation characteristics.

Recently, light emitting devices such as LEDs have been applied to various fields such as lighting devices, display devices, automobile head lamps, and the like. In order to commercialize these light emitting devices, light emitting devices or light emitting devices that can be changed into high luminance surface light sources can be used. A heat dissipation sheet or the like for dissipating heat is required.

Conventionally, heat conductive sheets such as alumina, graphite, glass fiber, carbon-fiber, talc, nonferrous metal powder, and ferrous metal powder were mixed with a polymer resin to produce a heat dissipation sheet. However, when excessively adding these thermal conductive materials to electrical conductivity, Problems such as breakage, price increase, specific gravity increase, productivity decrease, and moldability deterioration occurred.

Specifically, when the inorganic thermal conductive material and the thermoplastic resin are mixed, there is a problem that the appearance and surface state of the final product is poor or the impact strength is lowered.

In addition, in the case of mixing a silica-based thermal conductive material, such as silicon carbide with a thermoplastic resin, the production cost is greatly increased due to the high exchange rate of the production equipment, and the dispersion during the manufacture of the product because the compatibility of the silicon carbide and thermoplastic resin is not high And the mixing is not easy, and the thermal conductivity of the final product was also not enough to be applied to commercial products.

In addition, in the case of carbon-based compounds known to have high thermal conductivity, there is a certain limit to increase the amount of additives due to compatibility with thermoplastic resins or deterioration of physical properties and quality generated when used in excess, and the production cost is high because the material itself is expensive. Higher practically not easy for commercial application.

In addition, in the case of a compound such as a non-ferrous metal or a metal, the thermal conductivity when mixed with the thermoplastic resin can be greatly increased, but the moldability is not good, there is a problem that the specific gravity of the final product is increased.

On the other hand, the temperature between the LED PCB substrate and the existing aluminum die-casting heat sink in LED lighting is about 80 ℃ or less (within 1 hour after lighting), so that the thermal conductivity of the heat dissipating resin should be at least 0.5 W / mk to meet this condition. The difference in heat dissipation performance is large depending on the orientation of the thermally conductive material in the resin according to the molding method.

Accordingly, while addressing the limitations of conventionally known methods, development of a heat dissipation material exhibiting high thermal conductivity and heat dissipation characteristics with high mechanical properties is required.

The present invention is to provide a thermoplastic resin composition excellent in mechanical properties such as tensile strength, flexural modulus or impact strength and exhibiting high thermal conductivity and heat dissipation characteristics.

Moreover, this invention is providing the heat radiating material manufactured from the said thermoplastic resin composition.

The present invention is a thermoplastic resin; And it provides a thermoplastic resin composition comprising a polysilicon compound having an average particle size of 1㎛ to 10,000㎛.

Moreover, this invention provides the heat radiation material containing the molded object of the said thermoplastic resin composition.

Hereinafter, the thermoplastic resin composition and the heat dissipating material including the thermoplastic resin composition according to specific embodiments of the present invention will be described in more detail.

According to one embodiment of the invention, a thermoplastic resin; And a polysilicon compound having an average particle size of 1 μm to 10,000 μm.

The inventors have tested that thermoplastic resin compositions prepared by mixing certain polysilicon compounds with thermoplastic resins exhibit high thermal conductivity and heat dissipation properties along with mechanical properties such as excellent tensile strength, flexural modulus or impact strength. Confirmed through and completed the invention. In particular, the thermoplastic resin composition is secured enough to commercialize the appearance characteristics, moldability, and insulation properties can be ensured excellent quality without applying additional processes such as coating or insulation treatment in the final product application.

The polysilicon compound having an average particle size of 1 μm to 10,000 μm may have a thermal conductivity of 100 W / mk or more. The thermal conductivity is not significantly different from conventionally known thermal conductive materials, but is tensile when mixed with the thermoplastic resin. Strength, flexural strength, flexural modulus, impact strength, heat deflection temperature, etc. can be greatly improved, and are not limited to the molding method or molding conditions, and the like, and the heat dissipation performance and heat conduction performance can be greatly improved.

Specifically, the polysilicon compound may have an average particle size of 1 ㎛ to 10,000 ㎛, preferably 10 ㎛ to 300 ㎛. The average particle size of the polysilicon compound may be measured by electron microscope in the cross section of the specimen.

The polysilicon compound may include monocrystalline polysilicon, polycrystalline polysilicon, amorphous polysilicon, two or more copolymers thereof, and a mixture of two or more of these polymers.

In addition, the polysilicon compound may include plate-like or granular particles having a thermal conductivity of 100 W / mk or more. Such a polysilicon compound is present in the final resin without dissolving during the production of the heat dissipating resin, and can faithfully perform a function as a heat transfer material.

Meanwhile, the thermoplastic resin may be any thermoplastic resin known to be usable in a heat dissipating material, and the like, but may be used without limitation. Preferably, the thermoplastic resin may include a thermoplastic resin having a glass transition temperature (Tg) of -30 ° C to 315 ° C. .

Specific examples of such thermoplastic resins include polycarbonate (PC), polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polystyrene (PS), acrylate resin (MMA or PMMA), polyamide, Acrylonitrile-butadiene-styrene resin (ABS), polyamideimide (PAI), polybenzomidazole (PBI), polyetheramide (PEI), polyphenylene sulfide (PPS), thermoplastic urethane (TPU), polytech Lafluoroethylene (PTFE), Polyvinylidene Floride (PVDF), Polyethylene Terephthalate (PET), Polyoxymethylene (POM), Polyacer Iketone (PEEK), Polyaryl Iseketone (PAEK), Liquid Crystal Polymer (LCP), polyimide (PI), self-prene polyphenylene (SPR), or a mixture of two or more thereof.

In the thermoplastic resin composition, the content of the thermoplastic resin and the polysilicon compound having an average particle size of 1 μm to 10,000 μm is not particularly limited, and may include 1 to 99 wt% of each of only two components. have.

On the other hand, the thermoplastic resin composition may further include a heat conduction aid. As such thermally conductive aids, various previously known compounds, for example, inorganic thermal conductivity aids, silicone thermal conductivity aids, carbon-based thermal conductivity aids, nonferrous metals or ferrous metal thermal conductivity aids may be used.

Preferred examples of such thermal conductivity aids include platelet graphite having an average particle size of 50 μm to 150 μm, spherical graphite having an average particle size of 50 μm to 150 μm, or mixtures thereof. Specifically, the thermal conductivity aid may include a plate-like graphite having an average particle size of 50 μm to 150 μm and a spherical graphite having an average particle size of 50 μm to 150 μm in a ratio of 1: 0.5 to 1: 2. .

On the other hand, when the thermoplastic resin further comprises a thermal conductivity aid, their content range is 20 to 97% by weight of the thermoplastic resin; 1 to 75% by weight of a polysilicon compound having an average particle size of 1 μm to 10,000 μm; And 0.1 to 70% by weight of heat conduction aid.

On the other hand, the thermoplastic resin may further include at least one additive selected from the group consisting of UV stabilizers, long-term heat stabilizers, short-term heat stabilizers, plasticizers, release agents, colorants, antistatic agents, flame retardants, fluorescent brighteners and impact modifiers.

The manufacturing method of the thermoplastic resin composition according to the embodiment of the present invention is not particularly limited, and may be prepared according to conventional methods known in the art.

For example, the thermoplastic resin composition may be premixed with the thermoplastic resin, a polysilicon compound having an average particle size of 1 μm to 10,000 μm, and optionally the heat conduction aid or other additives, and then pre-mixed to a single screw or twin screw extruder. Can be prepared by blending by melt kneading. There is no particular limitation on the mixing apparatus that can be used, but a Hansel mixer, a tumbler, a ribbon blender, a high speed mixer, or the like can be used.

In addition, the method of processing the thermoplastic resin composition is also not particularly limited, and commonly known molding methods of the thermoplastic resin composition may be used. For example, injection molding and extrusion molding of the thermoplastic resin composition prepared as described above may be performed. It can shape | mold to plastic shape by blow molding, press molding, etc.

The thermoplastic resin composition ensures excellent thermal conductivity, mechanical properties, heat resistance, impact strength, etc., without damaging the properties of the thermoplastic resin and the polysilicon compound even during fixing, such as melting, mixing, or injection, such as a heat sink or a heat dissipation sheet. It can be easily applied as a heat dissipating material.

On the other hand, the thermoplastic resin composition can be easily hygroscopic, it is preferable that the molding is made in a dried state before injection. In addition, it is preferable to adjust the content of the polysilicon-based thermal conductive material and the above-mentioned thermal conductive auxiliary material according to the thickness and calorific value of the thermoplastic heat dissipating resin composition.

On the other hand, according to another embodiment of the invention, it is possible to provide a heat dissipation material comprising a molding of the thermoplastic resin composition.

The molded article may be a heat dissipation sheet, a profile or an injection molded product, and in particular, a molded product in a field where heat dissipation, impact resistance, mechanical strength, and heat resistance characteristics are important, for example, portable mobile communication devices, automotive parts, mechanical parts, and electrical and electronic products. It can be used for office equipment such as computer, or miscellaneous goods.

According to the present invention, a thermoplastic resin composition having excellent mechanical properties such as tensile strength, flexural modulus or impact strength, and exhibiting high thermal conductivity and heat dissipation characteristics, and a heat generating material manufactured using the resin composition can be provided.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[ Example  And Comparative Example : Preparation of Thermoplastic Resin Composition]

The thermoplastic resin compositions of Examples, Reference Examples and Comparative Examples were prepared by mixing the components described in Tables 1 to 3. Details of each component are as described in Table 4.

[ Experimental Example Property evaluation]

The resin composition obtained in the said Example, the reference example, and the comparative example was extruded using the Toshiba TEM-26SS twin screw extruder. In addition, the Ujin Serex 120MT injection machine, a mold having an ASTM specimen shape, and a LED MR16 type heat sink mold were fabricated to measure mechanical properties, thermal conductivity, and heat dissipation characteristics, respectively.

1. Thermal conductivity measurement

The thermal conductivity of the obtained specimen was measured using a C-therm thermal conductivity measuring apparatus manufactured by Tci.

2. Heat dissipation  Measure

With respect to the obtained specimen, the temperature between the PCB substrate and the heat sink was measured for about 1 hour using MR16 lighting of ASP Semiconductor.

3. Release Extrusion Surface

The surface of the molded product was observed when demold extrusion using the die of the aluminum heat sink model for the conventional LED tube light.

Compositions of Examples 1-7 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 ingredient
Polycarbonate resin
(PC-1100S) 80 80 70 70 70 70 70 Single crystal polysilicon 30 10 Polycrystalline polysilicon 20 30 10 Amorphous polysilicon 20 30 Carbon-based graphite
(60% on plate + 40% of thought) 20 20 Properties Thermal Conductivity (W / mk) 0.65 0.65 1.00 1.05 0.71 0.70 1.00 MR16 heat radiation temperature (℃) 77 79 74 73 75 76 75 Tensile Strength-Yield Stress (kgf / cm ² ) 590 590 700 700 600 610 750 Flexural modulus (kgf / cm ² ) 55000 55000 60000 65000 60000 60000 60000 Impact strength
(kg · cm / cm) 14 14 15 15 10 11 14 Release Extrusion Surface Good Good Good Good Good Good Good

Compositions of Examples 8-14 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 ingredient
Polycarbonate resin
(PC-1100S) 70 60 60 60 50 50 50 Single crystal polysilicon 20 30 Polycrystalline polysilicon 20 30 Amorphous polysilicon 10 20 30 Carbon-based graphite
(60% on plate + 40% of thought) 20 20 20 20 20 20 20 Properties Thermal Conductivity (W / mk) 0.70 1.05 1.02 1.00 1.25 1.30 1.27 MR16 heat radiation temperature (℃) 76 73 72 74 71 71 72 Tensile Strength-Yield Stress (kgf / cm ² ) 605 700 690 710 750 725 750 Flexural modulus (kgf / cm ² ) 60000 70000 70000 71000 80000 85000 86000 Impact strength
(kg · cm / cm) 12 11 13 12 12 13 14 Release Extrusion Surface Good Good Good Good Good Good Good

Compositions of Reference Examples and Comparative Examples 1 to 4 Reference Example Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 ingredient
MR16 aluminum heat sink 100 Polycarbonate resin
(PC-1100S) 100 90 80 70 Single crystal polysilicon Polycrystalline polysilicon Amorphous polysilicon Carbon-based graphite
(60% on plate + 40% of thought) 10 20 30 Properties Thermal Conductivity (W / mk) - 0.2 0.3 0.35 0.4 MR16 heat radiation temperature (℃) 80 95 89 85 83 Tensile Strength - Yield Stress
(kgf / cm ² ) - 500 550 570 605 Flexural modulus (kgf / cm ² ) - 35000 36000 38000 40000 Impact strength
(kg · cm / cm) - 80 5 4 2 Release Extrusion Surface Good Good Bad Bad Bad

Each component used for the Example and the comparative example subject Product Name / Composition Remarks Polycarbonate resin Hopelex PC-1100S (Honam Petrochemical) Glass transition temperature: 145 ℃ Polysilicon Single crystal polysilicon Average particle size: about 100㎛ Polycrystalline polysilicon Average particle size: about 100㎛ Amorphous polysilicon Average particle size: about 100㎛ Graphite 60% of plate Average particle size: about 100㎛ Concept 40% Average particle size: about 100㎛

As shown in Tables 1 to 2, it was confirmed that the resin molded article (sample) obtained using the thermoplastic resin composition of the example had high thermal conductivity, low heat dissipation temperature, high mechanical properties, impact strength, and good release extrusion surface. Can be.

In particular, in Examples 5 to 14, in which a thermoplastic resin, a polysilicon compound, and graphite (plate 60% + spherical 40%) are used, thermal conductivity, low heat dissipation temperature, high mechanical properties, impact strength, It showed good release extrusion surface properties, it was confirmed that the thermoplastic resin composition of the above embodiment exhibits excellent heat dissipation properties required in the application field.

As shown in Table 3, while the aluminum heat sink of the reference example is maintained at 80 ℃ after LED light, Comparative Example 1 containing only polycarbonate or Comparative Examples 2 to 4 containing polycarbonate and graphite has a relatively low thermal conductivity It showed high heat dissipation temperature and was confirmed to have low heat dissipation.

Claims (10)

Thermoplastic resin; And
A thermoplastic resin composition comprising a polysilicon compound having a thermal conductivity of 100 W / mk or more and including plate-shaped or granular particles having an average particle size of 1 μm to 10,000 μm.
The method of claim 1,
The polysilicon compound is a thermoplastic resin composition comprising at least one selected from the group consisting of monocrystalline polysilicon, polycrystalline polysilicon, amorphous polysilicon and two or more copolymers thereof.
delete The method of claim 1,
The thermoplastic resin has a glass transition temperature (Tg) of -30 ℃ to 315 ℃.
The method of claim 1,
The thermoplastic resin is polycarbonate (PC), polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polystyrene (PS), acrylate resin, polyamide, acrylonitrile-butadiene-styrene resin ( ABS), polyamideimide (PAI), polybenzomidazole (PBI), polyetheramide (PEI), polyphenylenesulfide (PPS), thermoplastic urethane (TPU), polytechlafluoroethylene (PTFE), poly Vinylidene fluoride (PVDF), polyethylene terephthalate (PET), polyoxymethylene (POM), polyacer ketone (PEEK), polyaryl isoketone (PAEK), liquid crystal polymer (LCP), polyimide (PI) And one or more selected from the group consisting of self-preserved polyphenylene (SPR) thermoplastic resin composition.
The method of claim 1,
A thermoplastic resin composition further comprising a heat conduction aid.
The method according to claim 6,
The thermal conductive auxiliary agent comprises at least one member selected from the group consisting of plate-like graphite having an average particle size of 50 μm to 150 μm and spherical graphite having an average particle size of 50 μm to 150 μm.
The method according to claim 6,
20 to 97% by weight of thermoplastic resin;
1 to 75% by weight of a polysilicon compound having an average particle size of 1 μm to 10,000 μm; And
A thermoplastic resin composition comprising 0.1 to 70% by weight of the heat conduction aid.
The method of claim 1,
A thermoplastic resin composition further comprising at least one additive selected from the group consisting of UV stabilizers, long-term heat stabilizers, short-term heat stabilizers, plasticizers, mold release agents, colorants, antistatic agents, flame retardants, fluorescent brighteners, and impact modifiers.
A heat radiation material comprising the molded article of the thermoplastic resin composition of claim 1.