KR100729412B1 - The composition and production method for self-cohesive heat sink gel - Google Patents
The composition and production method for self-cohesive heat sink gel Download PDFInfo
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Abstract
Description
제 1도는 본 발명에 따른 자기점착형 열전도성 젤 조성물을 이용한 판상구조의 성형체를 도시한 개략도.1 is a schematic view showing a molded body of a plate-like structure using a self-adhesive heat conductive gel composition according to the present invention.
제 2도는 본 발명에 따른 판상구조 성형체를 원형 또는 다각형으로 펀칭가공한 것을 도시한 개략도.Figure 2 is a schematic diagram showing the punching processing of the plate-shaped molded body according to the present invention in a circular or polygonal.
* 도면의 주요부호의 설명 *Explanation of the main symbols in the drawings
10: 판상구조의 성형체 11: 원형 성형체 12: 다각형 성형체DESCRIPTION OF
본 발명은 자기점착형 열전도성 젤 조성물 및 이를 이용한 성형체에 관한 것으로, 더욱 상세하게는 모노비닐기 함유 폴리디메틸실록산과 비닐기 함유 폴리디메틸실록산을 배합한 실리콘 젤과, 열전도성 충진제를 혼합하여 이루어진 것이다.The present invention relates to a self-adhesive heat conductive gel composition and a molded article using the same, and more particularly, a silicone gel containing a monovinyl group-containing polydimethylsiloxane and a vinyl group-containing polydimethylsiloxane, and a thermally conductive filler. will be.
종래 열 방출 기재로는 유체(Fluid)나 그리스 등이 사용되었고 일부 에이치티브이(HTV:high temperature vulcanized silicone) 또는 엘에스알(LSR:liquid silicone rubber)등이 사용되었지만, 유체나 그리스는 온도에 따른 점도 변화로 주변 기기에 대한 오염이 발생되고 실리콘 고무(HTV, LSR) 등은 피착물에 고정시킬 접착 기전 또는 점착 기전이 필요하였고, 이와 관련하여, 플라즈마 표시패널(PDP:Plasma Display Panel) 또는 발광다이오드(LED:light emitting diode)방식을 채용한 엘시디(LCD:liquid crystal display) 등은 빛을 내는 과정 중에 불필요한 열을 발생시키게 되는데, 이 열을 방출시키는 방열기재가 없으면 온도가 점차 상승하여 부품 자체의 열화를 가속화하거나 내장되어 있는 인버터상의 인쇄회로기판(PCB)의 프린팅 라인을 왜곡시키거나 인쇄회로기판(PCB) 굴곡, 트랜지스터, 반도체의 과열 등을 발생시켜 고장 및 열화의 원인이 된다. 이에 일부 그리스나 접착테이프가 붙은 실리콘 쉬트를 사용하거나 방열 실란트를 발열체와 방열기재 사이에 도포 또는 접착시켰다.Conventional heat dissipation substrates include fluid, grease, and some high temperature vulcanized silicone (HTV) or liquid silicone rubber (LSR). The change caused pollution to peripheral devices, and silicone rubber (HTV, LSR), etc. needed an adhesive mechanism or an adhesive mechanism to be fixed to the adherend. In this regard, a plasma display panel (PDP) or a light emitting diode LCD (liquid crystal display), which adopts the LED (light emitting diode) method, generates unnecessary heat during the light emitting process.If there is no heat radiating material that emits this heat, the temperature gradually increases to deteriorate the component itself. Accelerates or distorts the printed lines of printed circuit boards (PCBs) on the built-in inverter, It may cause overheating and cause malfunction and deterioration. Thus, some grease or a silicone sheet with adhesive tape was used, or a heat-dissipating sealant was applied or bonded between the heating element and the heat-radiating base material.
이는 방열성능은 발휘할 수 있었으나 그리스는 온도에 따른 점도의 변화로 주변부품을 오염시키거나 오작동을 발생시키는 사례가 있었으며, 접착테이프방식의 쉬트나 실란트는 유지 보수가 곤란하거나 완벽한 제거가 어렵다는 문제를 갖고 있었다.This could exert heat dissipation performance, but there were cases where grease contaminated the peripheral parts or malfunctioned due to the change of viscosity according to the temperature, and the adhesive tape type sheet or sealant was difficult to maintain or difficult to remove completely. there was.
상기와 같은 문제점을 해결하고자, 본 발명에서는 전자부품 및 전기부품에서 사용되는 의도와는 관계없이 발생되는 열을 공기 중으로 발산케 함으로써 트랜지스터나, 인쇄회로기판(PCB:Print Cerkit Board)의 오작동, 열화를 방지하여 제품의 성능 향상 및 장기 신뢰성을 향상시키도록 하며, 다른 접착 보조제나 점착 보조제를 사용하지 않고도 자체 점착력을 가지는 자기점착형 열 전도성 젤 조성물 및 이를 이용한 성형체의 제공을 그 목적으로 한다.In order to solve the above problems, in the present invention, by dissipating heat generated in the air irrespective of the intention used in the electronic and electrical components, malfunction or deterioration of a transistor or a printed circuit board (PCB). To improve the performance and long-term reliability of the product to prevent, and to provide a self-adhesive thermally conductive gel composition having a self-adhesion without using other adhesive or adhesive aids and a molded article using the same.
상기와 같은 목적을 달성하고자 본 발명에서는,In the present invention to achieve the above object,
주쇄가 Si-O구조를 가지고 측쇄에(R그룹) 모노비닐과 비닐기가 함유된 폴리디메틸실록산을 사용하여 자기 점착성능을 가진 젤을 형성시키고 여기에 백금계 하이드록실화 촉매를 혼합하여 경화기재를 만들고, 방열부재로 금속산화물을 배합하여 자기점착형 방열젤을 그 주요 구성으로 한다. 즉, 모노비닐기 함유 폴리디메틸실록산과 비닐기 함유 폴리디메틸실록산을 배합한 실리콘 젤 20 ~ 50중량%와, 열 전도성 충진제 50 ~ 80중량%를 혼합하여 이루어진 열 전도성 방열 젤 조성물을 그 주요 구성으로 하고, 상기 열 전도성 충진제는 산화알루미늄 85 ~ 95중량%와 수산화알루미늄 3 ~ 25중량%와 실리콘카바이드 2 ~ 14중량%로 이루어진다.The main chain has a Si-O structure and a polydimethylsiloxane containing monovinyl and vinyl groups in the side chain (R group) is used to form a gel having self-adhesive performance, and a platinum-based hydroxylation catalyst is mixed therein to form a hardened substrate. The self-adhesive heat dissipating gel is made into a main component by mixing a metal oxide with the heat dissipating member. That is, the main composition is a thermally conductive heat-dissipating gel composition formed by mixing 20 to 50% by weight of a silicone gel containing a monovinyl group-containing polydimethylsiloxane and a vinyl group-containing polydimethylsiloxane and 50 to 80% by weight of a thermally conductive filler. In addition, the thermally conductive filler is composed of 85 to 95% by weight of aluminum oxide, 3 to 25% by weight of aluminum hydroxide and 2 to 14% by weight of silicon carbide.
또한, 상기와 같은 자기점착형 열전도성 방열 젤 조성물을 방열도가 1 ~ 3W/(m.K)인 판상 구조 성형물로 제조하고, 그 성형물을 통상의 펀칭 방법을 통해 제조되는 것을 특징으로 하는 자기점착형 열전도성 방열 젤 조성물을 이용한 성형체를 그 주요 구성으로 한다.In addition, the self-adhesive thermally conductive heat-dissipating gel composition as described above is made of a plate-shaped molding having a heat dissipation of 1 to 3 W / (mK), and the molded product is manufactured by a conventional punching method. A molded article using the thermally conductive heat-dissipating gel composition is the main configuration.
이하, 상기한 구성을 더욱 상세히 살펴보도록 한다.Hereinafter, the above configuration will be described in more detail.
실리콘이란 명칭은 산업분야에 일반적으로 채택되었으며, 이때에 말하는 실리콘은 대부분 골격인 실록산 쇄에 메틸기가 결합된 폴리디메틸실록산을 의미하는 것으로, 상기 폴리디메틸실록산(poly(dimethylsiloxane))은 과량의 물 존재하에서 디메틸디염화실란의 가수분해에 의해 얻어지는 것으로, 관련한 반응식은 다음과 같다.The name of silicone is generally adopted in the industrial field, and in this case, silicon refers to polydimethylsiloxane having a methyl group bonded to a siloxane chain, which is mostly a skeleton, and the polydimethylsiloxane (poly (dimethylsiloxane)) is present in excess of water. It is obtained by hydrolysis of dimethyldichloride silane under the following reaction scheme.
상기한 바와 같이, 본 발명은 실리콘 젤을 구성하기 위해 모노비닐기 함유 폴리디메틸실록산과 비닐기 함유 폴리디메틸실록산을 배합하고, 열전도성 젤 전체중량에 대해 20 ~ 50중량%의 배합비율로 사용된다. 20중량% 이하로 사용할 경우에는 자기점착성이 떨어지고, 50중량% 이상으로 사용할 경우에는 물성이 떨어지므로, 20 ~ 50중량%의 배합비율로 사용하는 것이 바람직하다.As described above, the present invention mixes monovinyl group-containing polydimethylsiloxane and vinyl group-containing polydimethylsiloxane to form a silicone gel, and is used in a blending ratio of 20 to 50% by weight based on the total weight of the thermal conductive gel. . When used at 20% by weight or less, the self-adhesiveness is inferior, and when used at 50% by weight or more, the physical properties are inferior, so it is preferable to use the compounding ratio of 20 to 50% by weight.
상기 충진제는 주제나 경화제에 배합하여 경화수지의 기계적 특성을 향상시키는 것이 주목적이며, 일반적으로 첨가량이 증가하면 기계적 특성은 향상된다. 충진제의 종류 및 기타 부자재의 영향은 있으나 배합량의 증가에 따라 일정한 점까지 향상되다가 오히려 떨어지게 되므로 그 양을 적절히 정해주어야 한다.The filler is mainly incorporated in a main material or a curing agent to improve the mechanical properties of the cured resin, and in general, the mechanical properties are improved when the amount of the additive is increased. The type of filler and other subsidiary materials may be affected, but the amount of the filler should be appropriately determined since the amount of the filler is improved and then dropped.
이와 같은 충진제의 사용은, 원가절감, 열팽창율의 감소, 경화수축률의 감소, 경화시의 발열을 제어, 접착성의 개선 등이 주목적이며, 그 외에 칙소성을 수 지조성에 부여하는 것, 경화물에 난연성 부여, 내 약품성을 강하게 하는 것, 열전도성의 향상, 경화 중의 가사시간 연장, 충진재에 따라 기계적 강도의 증대, 경화물의 전기적 성질의 개선, 경량 충진재의 사용으로 주형물의 경량화, 내 마모성의 향상 등의 역할을 하게 되는 것으로, 본 발명의 충진제는 산화알루미늄 85 ~ 95중량%와 수산화알루미늄 3 ~ 25중량%와 실리콘카바이드 2 ~ 14중량%으로 혼합된 것을 사용한다. 상기 산화알루미늄와, 수산화알루미늄과, 실리콘카바이드가 일정비율로 충진재는 열전도성 젤 전체중량에 대해 50 ~ 80중량%의 배합비율로 사용되는 것으로, 50중량%이하로 사용할 경우에는 열전도성 및 물성이 떨어지고, 80중량%이상으로 사용할 경우에는 자기점착성 및 물성이 떨어지므로 50 ~ 80중량%의 배합비율로 사용하는 것이 바람직하다.The use of such fillers is mainly aimed at cost reduction, reduction of thermal expansion rate, reduction of curing shrinkage rate, control of heat generation during curing, improvement of adhesiveness, etc. In addition to providing thixotropy to resin composition, cured product Impart flame retardancy, strengthen chemical resistance, improve thermal conductivity, increase pot life during curing, increase mechanical strength with fillers, improve electrical properties of hardened products, reduce weight of moldings by using lightweight fillers, improve wear resistance, etc. The filler of the present invention uses a mixture of 85 to 95% by weight of aluminum oxide, 3 to 25% by weight of aluminum hydroxide and 2 to 14% by weight of silicon carbide. The aluminum oxide, aluminum hydroxide, and silicon carbide at a constant ratio of the filler is used in a blending ratio of 50 to 80% by weight relative to the total weight of the thermal conductive gel, when used below 50% by weight, the thermal conductivity and physical properties are inferior When used in more than 80% by weight, self-adhesiveness and physical properties are inferior, so it is preferable to use it in the blending ratio of 50 to 80% by weight.
상기 충진제의 구성요소 중 산화알루미늄(aluminum oxide, Al2O3)은 분자량이 101.96인 것으로, 충진제 전체중량에 대해 85 ~ 95중량%의 배합비율을 가지며, 85중량%이하로 사용할 경우에는 방열도가 크게 저하되는 문제점이 발생되고, 95중량%이상으로 사용할 경우에는 폴리머와의 결합력을 저하시키고 비중이 증가하며 자기점착력을 잃게되는 문제점이 발생되므로 85 ~ 95중량%의 배합비율로 사용되는 것이 바람직하다.Aluminum oxide (aluminum oxide, Al 2 O 3 ) among the components of the filler has a molecular weight of 101.96, has a compounding ratio of 85 to 95% by weight relative to the total weight of the filler, the heat dissipation degree when used below 85% by weight Is a problem that greatly decreases, and when used in more than 95% by weight, it is preferable to use the compounding ratio of 85 to 95% by weight because the problem of lowering the bonding strength with the polymer, increasing the specific gravity and losing the self-adhesion Do.
수산화알루미늄(Al(OH)3)은 비중 2.423인 것으로, 천연으로는 깁사이트·다이아스포어로서 존재하고, 알루미늄염의 수용액에 암모니아수를 가하면 백색의 콜로이드상 침전으로 생기는 것으로, 산화알루미늄(alumium oxide)은 끓는점이 2050 ℃이고, 녹는점이 2990℃이고, 비중이 3.99이고, 용해도가 1mg/l(29℃)인 것을 사용하고, 충진제 전체중량에 대해 3 ~ 25중량%의 배합비율을 가지며, 3중량%이하로 사용할 경우에는 난연성(Flame Retardant)에 큰 효과를 보이지 않는 문제점이 발생되고, 25중량%이상으로 사용할 경우에는 비중의 증가와 폴리머와의 결합력을 저하시키고 자기점착력을 떨어뜨리는 문제점이 발생되므로 3 ~ 25중량%의 배합비율로 사용되는 것이 바람직하다.Aluminum hydroxide (Al (OH) 3 ) has a specific gravity of 2.423, which is naturally present as a gibbsite diaspore. It has a boiling point of 2050 ° C., a melting point of 2990 ° C., a specific gravity of 3.99, a solubility of 1 mg / l (29 ° C.), and a blending ratio of 3 to 25% by weight based on the total weight of the filler, and 3% by weight When used below, there is a problem that does not show a great effect on the flame retardant, and when used at 25% by weight or more, there is a problem of increasing the specific gravity, decreasing the bonding strength with the polymer, and lowering the self-adhesion. It is preferable to use it in the compounding ratio of-25 weight%.
실리콘카바이트(Si-SiC)는 부피밀도(Bulk density)가 3.1g/㎤이고, 굽힘강도(Flexural strength)가 53kg/㎟이고, 경도(Hardness)가 2800hv이고, 영모듈(Young's Modulus)이 4.2×104kg/㎟이고, 열팽창계수(Coefficient of thermal expansion)가 4×10-6/℃이고, 열전도도(Thermal Conductivity)가 125 w/m·℉인 것으로, 충진제 전체중량에 대해 2 ~ 14중량%의 배합비율을 가지며, 2중량%이하로 사용할 경우에는 방열효과를 크게 기대할 수 없다는 문제점이 발생되고, 14중량%이상으로 사용할 경우에는 열경화시 기포의 제거가 곤란하거나, 경화를 지연시키는 문제점이 발생되므로 2 ~ 14중량%의 배합비율로 사용되는 것이 바람직하다.Si-SiC has a bulk density of 3.1 g / cm3, flexural strength of 53 kg / mm2, hardness of 2800 hv, and Young's Modulus of 4.2 ×. 10 4 kg / mm 2, Coefficient of thermal expansion is 4 × 10 −6 / ° C., Thermal Conductivity is 125 w / m · ° F. It has a compounding ratio of%, and when used at 2% by weight or less, the problem that the heat dissipation effect is not expected to be large, and when used at 14% by weight or more, it is difficult to remove bubbles during thermal curing or to delay curing. It is preferable to use the compounding ratio of 2 to 14% by weight since it is generated.
이하, 상기한 구성을 실시 예를 통해 더욱 구체적으로 살펴보도록 한다.Hereinafter, the above configuration will be described in more detail with reference to the following examples.
실시 예 : Example: 열전도성Thermal conductivity 충진제Filler
실시 예 1Example 1
산화알루미늄 95중량%와 수산화알루미늄 3중량%와 실리콘카바이드 2중량%의 배합비율로 혼합하여 열전도성 충진제를 구성한다.A thermally conductive filler is formed by mixing 95% by weight of aluminum oxide, 3% by weight of aluminum hydroxide, and 2% by weight of silicon carbide.
실시 예 2Example 2
산화알루미늄 90중량%와 수산화알루미늄 6중량%와 실리콘카바이드 4중량%의 배합비율로 혼합하여 열전도성 충진제를 구성한다.A thermally conductive filler is formed by mixing 90% by weight of aluminum oxide, 6% by weight of aluminum hydroxide, and 4% by weight of silicon carbide.
실시 예 3Example 3
산화알루미늄 88중량%와 수산화알루미늄 7중량%와 실리콘카바이드 5중량%의 배합비율로 혼합하여 열전도성 충진제를 구성한다.A thermally conductive filler is formed by mixing 88% by weight of aluminum oxide, 7% by weight of aluminum hydroxide, and 5% by weight of silicon carbide.
실시 예 : Example: 열전도성Thermal conductivity 젤 Gel
실시 예 4Example 4
모노비닐기 함유 폴리디메틸실록산과 비닐기 함유 폴리디메틸실록산을 배합한 실리콘 젤 50중량%에 백금계 하이드록실화 촉매를 첨가하여 경화기재를 이루고, 여기에 실시 예 1에서와 같은 배합비율을 갖는 열전도성 충진제 50중량%를 혼합하여 열전도성 젤을 구성한다.A platinum base hydroxylated catalyst was added to 50% by weight of a silicone gel containing a monovinyl group-containing polydimethylsiloxane and a vinyl group-containing polydimethylsiloxane to form a cured base material, and a thermoelectric having a compounding ratio as in Example 1 was added thereto. 50 wt% of the conductive filler is mixed to form a thermally conductive gel.
실시 예 5Example 5
모노비닐기 함유 폴리디메틸실록산과 비닐기 함유 폴리디메틸실록산을 배합한 실리콘 젤 40중량%에 백금계 하이드록실화 촉매를 첨가하여 경화기재를 이루고, 여기에 실시 예 2에서와 같은 배합비율을 갖는 열전도성 충진제 60중량%를 혼합하여 열전도성 젤을 구성한다.A platinum base hydroxylated catalyst was added to 40% by weight of a silicone gel containing a monovinyl group-containing polydimethylsiloxane and a vinyl group-containing polydimethylsiloxane to form a cured base material, and a thermoelectric having a compounding ratio as in Example 2 was added thereto. 60 wt% of the conductive filler is mixed to form a thermally conductive gel.
실시 예 6Example 6
모노비닐기 함유 폴리디메틸실록산과 비닐기 함유 폴리디메틸실록산을 배합한 실리콘 젤 30중량%에 백금계 하이드록실화 촉매를 첨가하여 경화기재를 이루고, 여기에 실시 예 3에서와 같은 배합비율을 갖는 열전도성 충진제 70중량%를 혼합하여 열전도성 젤을 구성한다.A platinum base hydroxylated catalyst was added to 30% by weight of a silicone gel containing a monovinyl group-containing polydimethylsiloxane and a vinyl group-containing polydimethylsiloxane to form a cured base material, and a thermoelectric having a compounding ratio as in Example 3 was added thereto. 70 wt% of the conductive filler is mixed to form a thermally conductive gel.
이상에서 살펴본 바와 같이, 열전도성 젤 조성물은 모노비닐기 함유 폴리디메틸실록산과 비닐기 함유 폴리디메틸실록산을 배합한 실리콘 젤 20 ~ 50중량%와, 열전도성 충진제 50 ~ 80중량%와 같이 조성되는 것으로, 이와 같이 조성된 열전도성 젤 조성물에 상온 이상의 열을 가하여 압축성형, 카렌다링 또는 압출성형 중 선택되는 어느 1종의 방법을 통하여 도 1에 도시된 바와 같이, 방열도가 1 ~ 3W/(m.K)인 패드 또는 쉬트류와 같은 판상구조의 성형체(10)로 가공하는 것으로,As described above, the thermally conductive gel composition is composed of 20 to 50% by weight of a silicone gel containing a monovinyl group-containing polydimethylsiloxane and a vinyl group-containing polydimethylsiloxane, and 50 to 80% by weight of a thermally conductive filler. As shown in FIG. 1 through any one method selected from compression molding, calendaring, or extrusion molding by applying heat above room temperature to the thermally conductive gel composition thus prepared, the heat dissipation degree is 1 to 3 W / (mK). By processing into a molded
이와 같이 가공된 판상 구조를 갖는 성형물을 도 2에 도시된 바와 같이, 펀칭 가공하여 원형 성형체(11) 또는 다각형 성형체(12)로 가공되어 사용된다. 이상에서와 같은 성형물은 다른 보조 접착 보조제나 점착 보조제를 사용하지 않고도 자 체 점착력을 갖는 기재를 구성하게 된다.As shown in Fig. 2, the molded article having the plated structure processed as described above is punched and processed into a circular molded
이상에서와 같은 구성을 갖는 본 발명의 열전도성 조성물 및 이를 이용한 성형물은 주쇄가 Si-O 구조를 가지고 측쇄에(R그룹)모노비닐과 비닐기가 함유된 폴리디메틸실록산을 사용하여 자기 점착성능을 가진 젤을 형성시키고 여기에 백금계 하이드록시화 촉매를 혼합하여 경화기재를 만들고 접착방식에서 문제가 된 유지보수 성능을 향상시키고, 온도에 의한 주변 품으로의 오염전이를 방지하므로서 방열기재로서 우수한 성능을 발휘할 수 있으며, 트랜지스터의 방열, 반도체 소자의 방열은 물론 발광다이오드(LED)나 프라즈마 발생 장치에 방열 기재로 적합하며, 유연성과 밀착력이 우수하여 계면 열저항을 낮추게 되어 플랙서블 인쇄회로기판(Flexible PCB:printed circuit board) 등에도 사용이 가능하다는 장점을 갖는다.The thermally conductive composition of the present invention having the configuration as described above and the molded article using the same have a self-adhesive performance using a polydimethylsiloxane in which the main chain has a Si—O structure and contains monovinyl and vinyl groups in the side chain (R group). It forms a gel and mixes platinum-based hydroxylation catalyst with it to make a hard base, improves maintenance performance that is a problem in the adhesion method, and prevents contamination transition to the surrounding products due to temperature, thereby providing excellent performance as a heat radiating base. It is suitable for heat dissipation of transistors, heat dissipation of semiconductor elements, as well as heat dissipation substrates for light emitting diodes (LEDs) or plasma generators, and has excellent flexibility and adhesion to lower interfacial thermal resistance, resulting in flexible PCBs. It has the advantage that it can be used for printed circuit board.
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