KR20110122484A - Silicone polymer composition having an excellent heat-radiating function - Google Patents

Silicone polymer composition having an excellent heat-radiating function Download PDF

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KR20110122484A
KR20110122484A KR1020100042033A KR20100042033A KR20110122484A KR 20110122484 A KR20110122484 A KR 20110122484A KR 1020100042033 A KR1020100042033 A KR 1020100042033A KR 20100042033 A KR20100042033 A KR 20100042033A KR 20110122484 A KR20110122484 A KR 20110122484A
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silicone polymer
polymer composition
heat
weight
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임유승
강형식
이무형
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주식회사 케이씨씨
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/06Preparatory processes
    • C08G77/08Preparatory processes characterised by the catalysts used
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/56Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04Polysiloxanes

Abstract

PURPOSE: A silicone polymer composition for heat protecting is provided to improve the reliability of operational condition due to the high thermal conductivity, good handling property by excellent mobility thereof, excellent heat protection property, and high durability at the high temperature and high humidity condition. CONSTITUTION: A silicone polymer composition for heat protecting comprises an unsaturated silicone polymer, an organohydrogenpolysiloxane, a platinum-based hydrosilyl catalyst, and thermoconductive filler. The unsaturated silicone polymer has a PBW(parts by weight) of 100.0, dynamic viscosity of 100-20,000 mm^2/s at 25°C, 50% relative humidity, molecular weight of 100-20,000, and at least two unsaturated hydrocarbon group. The organohydrogenpolysiloxane has a PBW of 5-10, dynamic viscosity of 0.1-0.4 g/cm·sec at 25°C, 50% relative humidity, molecular weight of 4000-8000, at least two silicon atoms combined with hydrogen atom. The platinum-based hydrosilyl catalyst has a PBW of 0.05-1. The thermoconductive filler has a PBW of 100-1500.

Description

방열 성능이 우수한 실리콘 중합체 조성물{Silicone polymer composition having an excellent heat-radiating function}Silicone polymer composition having an excellent heat-radiating function

본 발명은 방열 성능이 우수한 실리콘 중합체 조성물에 관한 것으로서, 보다 상세하게는 열전도성 충전재를 고함량으로 함유하여 높은 열전도성을 나타내면서도 유동성을 유지하고, 취급성이 양호하며, 고온 고습 조건하에서의 내구성ㆍ신뢰성이 우수한 열전도성 실리콘 중합체 조성물에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone polymer composition having excellent heat dissipation performance. More specifically, the present invention relates to a silicone polymer composition having a high heat dissipation performance. A thermally conductive silicone polymer composition having excellent reliability.

전자 부품의 대부분은 사용 중에 열을 발생시키기 때문에, 그 전자 부품을 적절히 기능시키기 위해서는 전자 부품으로부터 열을 제거하는 것이 필요하다. 특히 퍼스널 컴퓨터에 사용되고 있는 CPU 등의 집적 회로 소자는 동작 주파수의 고속화에 의해 발열량이 증대하고 있어 방열 대책이 중요한 문제가 되고 있다.Since most electronic components generate heat during use, it is necessary to remove heat from the electronic components in order to function properly. In particular, in integrated circuit devices such as CPUs used in personal computers, the amount of heat generated is increased due to the increase in the operating frequency.

이 열을 제거하는 수단으로서 많은 방법이 제안되어 왔다. 특히 발열량이 많은 전자 부품에서는 전자 부품과 히트 싱크 등의 부재 사이에 열전도성 컴파운딩이나 열전도성 시트 등의 열전도성 재료를 개재시켜 열을 밀어내는 방법이 제안되어 왔다. Many methods have been proposed as a means of removing this heat. In particular, in electronic components having a large amount of heat generated, a method of repelling heat by interposing a thermally conductive material such as a thermally conductive compound or a thermally conductive sheet between the electronic component and a member such as a heat sink has been proposed.

이러한 열전도성 재료로는 실리콘 오일을 기재로 하고, 산화아연이나 알루미나 분말을 배합한 방열 컴파운딩이 알려져 있다. 또한, 열전도성을 향상시키기 위해 질화알루미늄 분말을 이용한 열전도성 재료로서 액상 오르가노 실리콘 캐리어, 실리카 섬유, 덴드라이트상 산화아연, 박편상 질화알루미늄 및 박편상 질화붕소로부터 선택되는 1종 이상을 포함하는 요변성 열전도 재료도 알려져 있다. As such a thermally conductive material, heat dissipating compounding based on silicone oil and containing zinc oxide or alumina powder is known. Further, in order to improve thermal conductivity, a thermally conductive material using aluminum nitride powder includes at least one selected from liquid organo silicon carrier, silica fiber, dendrites zinc oxide, flaky aluminum nitride, and flaky boron nitride. Thixotropic thermal conductive materials are also known.

일본공개특허공보 2005-374486호에는 특정한 오르가노폴리실록산에 일정 입경 범위의 구상 육방정계 질화알루미늄 분말을 배합하여 얻은 실리콘 조성물이 개시되어 있다. 이 일본공개특허에는 입경이 미세한 질화알루미늄 분말과 입경이 거친 질화알루미늄 분말을 조합한 열전도성 실리콘 조성물; 질화알루미늄 분말과 산화아연 분말을 조합한 열전도성 실리콘 조성물; 오르가노실란으로 표면 처리한 질화알루미늄 분말을 이용한 열전도성 compound 조성물; 및 실리콘 수지, 다이아몬드, 산화아연 및 분산제를 포함하는 열전도성 실리콘 조성물이 개시되어 있다. 질화알루미늄의 열전도율은 70 내지 270 W/(mㆍK)이고, 다이아몬드의 열전도성은 이보다 높아 900 내지 2,000 W/(mK)이다. Japanese Laid-Open Patent Publication No. 2005-374486 discloses a silicone composition obtained by mixing spherical hexagonal aluminum nitride powder having a specific particle size range with a specific organopolysiloxane. This Japanese Laid-Open Patent discloses a thermally conductive silicone composition in which aluminum nitride powder having a fine particle diameter and aluminum nitride powder having a rough particle diameter are combined; A thermally conductive silicone composition combining aluminum nitride powder and zinc oxide powder; A thermally conductive compound composition using aluminum nitride powder surface treated with organosilane; And a thermally conductive silicone composition comprising a silicone resin, diamond, zinc oxide, and a dispersant. The thermal conductivity of aluminum nitride is 70 to 270 W / (m · K), and the diamond thermal conductivity is higher than this to 900 to 2,000 W / (mK).

일본공개특허공보 2005-374486호Japanese Laid-Open Patent Publication 2005-374486

본 발명의 목적은 높은 열전도성을 갖고, 우수한 유동성을 유지하기 때문에 작업성이 양호하며, 나아가 미세한 요철을 추종하고, 접촉 열저항을 감소시킴으로써 방열 성능이 우수하며, 고온 고습 조건에서의 내구성이 높아 실장시의 신뢰성을 향상시킬 수 있는 고성능 방열 조성물을 제공하는 것이다.An object of the present invention is to have a high thermal conductivity, good workability because it maintains excellent fluidity, and further excellent in heat dissipation performance by following minute unevenness, reducing contact thermal resistance, high durability at high temperature and high humidity conditions It is to provide a high performance heat dissipating composition which can improve the reliability at the time of mounting.

본 발명에 따르면, (A) 25℃, 50%상대습도에서 동점도가 100 내지 20,000 mm2/s이고, 분자량이 100 내지 20,000이며, 적어도 2개의 불포화 탄화수소기를 갖는 불포화 실리콘 폴리머, (B) 25℃, 50%상대습도에서 점도가 0.1 내지 0.4 g/cmㆍsec 이고, 분자량이 4,000 내지 8,000이며, 적어도 2개의 규소원자-결합된 수소원자를 갖는 오르가노하이드로겐폴리실록산, (C) 백금계 촉매 및 (D) 열전도성 충전재를 포함하는 방열성 실리콘 중합체 조성물이 제공된다.According to the invention, (A) an unsaturated silicone polymer having a kinematic viscosity of 100 to 20,000 mm 2 / s, a molecular weight of 100 to 20,000, at least two unsaturated hydrocarbon groups at 25 ° C. and 50% relative humidity, and (B) 25 ° C. Organohydrogenpolysiloxanes having a viscosity of 0.1 to 0.4 g / cm · sec, a molecular weight of 4,000 to 8,000 at 50% relative humidity and having at least two silicon atom-bonded hydrogen atoms, (C) a platinum-based catalyst and (D) A heat dissipating silicone polymer composition comprising a thermally conductive filler is provided.

본 발명에 따르면, 높은 열전도성을 갖고, 우수한 유동성을 유지하기 때문에 작업성이 양호하며, 나아가 미세한 요철을 추종하고, 접촉 열저항을 감소시킴으로써 방열 성능이 우수하며, 고온 고습 조건에서의 내구성이 높아 실장시의 신뢰성을 향상시킬 수 있 는 방열성 조성물을 얻을 수 있다. 본 발명에 따른 방열성 조성물을, 예를 들면 일반적인 전원; 전원용 파워 트랜지스터, 파워 모듈, 서미스터, 열전대, 온도 센서 등의 전자 기기; LSI, CPU 등의 집적 회로 소자 등의 발열성 전자 부품과 히트 스프레더, 히트 싱크, 히트 파이프, 방열판 등의 방열 부품 사이에 개재시켜 도포하면 상기 발열체로부터 상기 방열체로 효율적으로 열을 전도시킬 수 있기 때문에, 상기 발열체로부터 효과적으로 열을 제거할 수 있다.According to the present invention, it has high thermal conductivity and maintains excellent fluidity, and thus has good workability. Furthermore, it has excellent heat dissipation performance by following minute unevenness and reducing contact thermal resistance, and has high durability at high temperature and high humidity conditions. The heat dissipation composition which can improve the reliability at the time of mounting can be obtained. The heat dissipating composition according to the present invention may be, for example, a general power source; Electronic devices such as power transistors for power sources, power modules, thermistors, thermocouples, and temperature sensors; Since heat is applied between heat generating electronic parts such as integrated circuit elements such as LSI and CPU and heat dissipating parts such as heat spreaders, heat sinks, heat pipes, and heat sinks, heat can be efficiently transferred from the heat generators to the heat sinks. In addition, heat can be effectively removed from the heating element.

이하, 본 발명의 방열성 조성물에 대하여 구성성분별로 보다 상세하게 설명한다.
Hereinafter, the heat dissipating composition of the present invention will be described in detail for each component.

(A) 불포화 실리콘 폴리머
(A) unsaturated silicone polymer

본 발명의 조성물에는 25℃, 50%상대습도에서 동점도가 100 내지 20,000 mm2/s이고, 분자량이 100 내지 20,000이며, 적어도 2개의 불포화 탄화수소기를 갖는 불포화 실리콘 폴리머가 포함된다. 이 불포화 실리콘 폴리머에 있어서 25℃, 50%상대습도에서 동점도가 100 mm2/s 미만이면 열전도성 충진이 충분치 못한 문제가 있고, 20,000 mm2/s를 초과하면 장기 저장시 충분한 반응을 못하여 층 분리를 유발하는 문제가 있다. 또한 그 분자량이 100 미만이면 반응이 너무 빨리 일어나거나 저장시 층분리를 일으키며, 20,000을초과하면 충진제의 충분한 분산이 어려워진다.The composition of the present invention includes an unsaturated silicone polymer having a kinematic viscosity of 100 to 20,000 mm 2 / s, a molecular weight of 100 to 20,000, and at least two unsaturated hydrocarbon groups at 25 ° C. and 50% relative humidity. The 25 ℃ in the unsaturated silicone polymer, when the kinematic viscosity is less than 100 mm 2 / s at 50% relative humidity, and a problem that the thermally conductive filling is insufficient, when it is more than 20,000 mm 2 / s separation layer mothayeo sufficient response during long-term storage There is a problem that causes. In addition, if the molecular weight is less than 100, the reaction may occur too quickly or cause delamination upon storage, and if it exceeds 20,000, sufficient dispersion of the filler becomes difficult.

본 발명에 있어서, 상기 (A) 불포화 실리콘 폴리머는 적어도 2개의 불포화 탄화수소기를, 바람직하게는 비닐기를 가진다. 또한 바람직하게는, 측쇄에 1 이상의 탄소원자를 갖는 기로서 메틸, 에틸, 프로필기 등의 C1-C6알킬기, 페닐기 등의 C6-C10아릴기, 또는 C2-C6알케닐기를 추가로 가질 수 있고, 그러한 기들의 95% 이상이 메틸기일 수 있다. 히드록시기를 또한 가질 수도 있다.In the present invention, the (A) unsaturated silicone polymer has at least two unsaturated hydrocarbon groups, preferably vinyl groups. Also preferably, the group may further have a C 1 -C 6 alkyl group such as methyl, ethyl or propyl group, a C 6 -C 10 aryl group such as phenyl group, or a C 2 -C 6 alkenyl group as a group having at least one carbon atom. At least 95% of the groups may be methyl groups. It may also have a hydroxyl group.

본 발명의 비람직한 일 구체예에 따르면, 성분 (A)의 불포화 실리콘 폴리머는 비닐기와 같은 알케닐 그룹으로 말단화되고 사슬 측쇄에 규소원자-결합된 탄소함유 치환기를 갖는 직쇄상 폴리실록산이다. 그 예로는 하기 평균식의 비닐 말단 폴리실록산을 들 수 있다.According to one preferred embodiment of the invention, the unsaturated silicone polymer of component (A) is a straight chain polysiloxane terminated with alkenyl groups such as vinyl groups and having a silicon atom-bonded carbon-containing substituent on the chain side chain. As an example, the vinyl terminal polysiloxane of the following average formula is mentioned.

Figure pat00001
Figure pat00001

(R1은 예컨대 메틸, 페닐, 히드록실, m은 0보다 큰 정수)
(R 1 is for example methyl, phenyl, hydroxyl, m is an integer greater than 0)

(B) 오르가노하이드로겐폴리실록산
(B) organohydrogenpolysiloxane

본 발명의 조성물에는 25℃, 50%상대습도에서 점도가 0.1 내지 0.4 g/cmㆍsec 이고, 분자량이 4,000 내지 8,000이며, 적어도 2개의 규소원자-결합된 수소원자를 갖는 오르가노하이드로겐폴리실록산이 포함된다. 이 오르가노하이드로겐폴리실록산에 있어서 25℃, 50%상대습도에서 점도가 0.1 g/cmㆍsec 미만이면 제품 미경화 문제를 유발하고, 0.4 g/cmㆍsec를 초과하면 과경화되어 제품이 고상화되는 문제가 있다. 또한 그 분자량(중량평균분자량)이 4,000 미만이면 반응 제어가 어렵고, 8,000을 초과하면 비닐기와 충분한 반응이 느려 제품 제조가 어려워진다.The composition of the present invention has an organohydrogenpolysiloxane having a viscosity of 0.1 to 0.4 g / cm · sec, a molecular weight of 4,000 to 8,000, and at least two silicon atom-bonded hydrogen atoms at 25 ° C. and 50% relative humidity. Included. In this organohydrogenpolysiloxane, if the viscosity is less than 0.1 g / cm · sec at 25 ° C and 50% relative humidity, the product is not cured, and if it exceeds 0.4 g / cm · sec, the product is hardened to solidify the product. There is a problem. In addition, if the molecular weight (weight average molecular weight) is less than 4,000, reaction control is difficult. If the molecular weight (weight average molecular weight) is more than 8,000, a sufficient reaction with the vinyl group is slow, making the product difficult.

본 발명에 있어서, 상기 (B) 오르가노하이드로겐폴리실록산은 적어도 2개의 규소원자-결합된 수소원자를 갖는다. 수소원자는 오르가노하이드로겐폴리실록산의 말단 또는 측쇄에 위치하거나 말단 및 측쇄 둘 다에 위치할 수도 있다 또한 바람직하게, 상기 (B) 오르가노하이드로겐폴리실록산은 1 이상의 탄소원자를 갖는 기로서 메틸, 에틸, 프로필기 등의 C1-C6알킬기, 페닐기 등의 C6-C10아릴기, 또는 C2-C6알케닐기를 추가로 가질 수 있다. 또한 바람직하게는, 사슬의 측쇄에 규소원자-결합된 이러한 기들을 2개 갖는 단위와 규소원자-결합된 수소를 1개 이상 갖는 단위의 몰비가 50 : 50일 수 있다.In the present invention, the (B) organohydrogenpolysiloxane has at least two silicon atom-bonded hydrogen atoms. The hydrogen atom may be located at the terminal or side chain of the organohydrogenpolysiloxane, or may be located at both the terminal and side chains. Also, the (B) organohydrogenpolysiloxane may be a group having one or more carbon atoms as methyl, ethyl, It may further have a C1-C6 alkyl group such as a propyl group, a C6-C10 aryl group such as a phenyl group, or a C2-C6 alkenyl group. Also preferably, the molar ratio of the unit having two silicon atom-bonded groups in the side chain of the chain and the unit having at least one silicon atom-bonded hydrogen may be 50:50.

본 발명의 조성물에 있어서, 상기 (B) 오르가노하이드로겐폴리실록산의 함량은 상기 (A) 불포화 실리콘 폴리머 100 중량부당 5 내지 10 중량부인 것이 바람직하다. (B) 성분의 함량이 (A) 성분 100 중량부당 5 중량부에 못 미치면 경화후 장기 저장 물성 저하의 문제점이 있을 수 있고, 10 중량부를 초과하면 경화후 고상화되는 문제점이 있을 수 있다.
In the composition of the present invention, the content of the (B) organohydrogenpolysiloxane is preferably 5 to 10 parts by weight per 100 parts by weight of the (A) unsaturated silicone polymer. If the content of component (B) is less than 5 parts by weight per 100 parts by weight of component (A) there may be a problem of long-term storage properties deterioration after curing, if more than 10 parts by weight may have a problem of solidifying after curing.

(C) 백금계 촉매
(C) platinum-based catalyst

본 발명의 조성물에는 가교 촉진제로서 촉매량의 백금계 화합물이 포함된다. 이 성분 (C)는 성분 (A)와 성분 (B)의 부가반응을 촉진하는 하이드로실릴화촉매이다. 이러한 백금 촉매로는 백금족 금속, 백금족 금속을 함유하는 화합물, 또는 미세캡슐화 백금족 금속 또는 이를 함유하는 화합물이 사용가능하다. 백금족 금속은 백금, 로듐, 루테늄, 팔라듐 및 이리듐을 포함한다. 백금계 촉매로서 바람직하게는 백금족 유기금속계 착화합물이 사용되며, 그 예로는 금속백금과 {(CH2CH)CH3SiO4}m (여기서, m = 4, 또는 6) 간의 착화합물을 들 수 있다. The composition of the present invention contains a catalytic amount of a platinum compound as a crosslinking accelerator. This component (C) is a hydrosilylation catalyst which accelerates the addition reaction between component (A) and component (B). As such a platinum catalyst, a platinum group metal, a compound containing a platinum group metal, or a microencapsulated platinum group metal or a compound containing the same can be used. Platinum group metals include platinum, rhodium, ruthenium, palladium and iridium. As the platinum-based catalyst, a platinum group organometallic complex compound is preferably used, and examples thereof include a complex compound between metal platinum and {(CH 2 CH) CH 3 SiO 4 } m (here, m = 4 or 6).

본 발명의 조성물에 있어서, 상기 (C) 백금계 촉매의 함량은 상기 (A) 불포화 실리콘 폴리머 100 중량부당 0.05 내지 1 중량부인 것이 바람직하다. (C) 성분의 함량이 (A) 성분 100 중량부당 0.05 중량부에 못 미치면 촉매로서의 역할을 충분히 수행 하지 못하는 문제점이 있을 수 있고, 1 중량부를 초과하면 저장시 지속적인 활성으로 초기와 상이한 제품 물성을 나타내는 문제점이 있을 수 있다.
In the composition of the present invention, the content of the platinum catalyst (C) is preferably 0.05 to 1 parts by weight per 100 parts by weight of the (A) unsaturated silicone polymer. If the content of component (C) is less than 0.05 part by weight per 100 parts by weight of component (A), there may be a problem in that it does not fully function as a catalyst. There may be a problem that is indicated.

(D) 열전도성 충전재
(D) thermally conductive filler

본 발명의 조성물에는 방열효과를 위하여 열전도성 충전재가 포함된다. (D) 성분의 구체예로는 알루미늄, 은, 구리, 니켈, 산화아연, 알루미나, 산화마그네슘, 질화알루미늄, 질화붕소, 질화규소, 다이아몬드, 흑연, 탄소 나노튜브, 금속 규소, 탄소 섬유, 플라렌 또는 이들의 2종 이상의 조합을 들 수 있다. 이들 성분은 1종을 단독으로 사용할 수도 있고, 2종 이상을 병용할 수도 있다.The composition of the present invention includes a thermally conductive filler for the heat dissipation effect. Specific examples of component (D) include aluminum, silver, copper, nickel, zinc oxide, alumina, magnesium oxide, aluminum nitride, boron nitride, silicon nitride, diamond, graphite, carbon nanotubes, metal silicon, carbon fiber, flaren or And combinations of two or more thereof. These components may be used individually by 1 type, and may use 2 or more types together.

(D) 성분의 평균 입경은 바람직하게는 0.1 ㎛ 내지 100 ㎛의 범위, 보다 바람직하게는 1 내지 50 ㎛의 범위, 보다 더 바람직하게는 1 내지 20 ㎛의 범위이다. (D) 성분의 평균 입경이 상기 범위 내에 있으면, (D) 성분의 부피 밀도가 커지기 쉽고, 비표면적은 작아지기 쉽기 때문에, 본 발명의 조성물 중에 (D) 성분을 고충전하기 쉽다. 반면, 평균 입경이 지나치게 크면, 오일 성분이 분리될 가능성이 있다. 상기 평균 입경은 예를 들면 Horsfield’s Packing Model에 의해 부피 기준의 누적 평균 직경으로서 구할 수 있다.The average particle diameter of the component (D) is preferably in the range of 0.1 µm to 100 µm, more preferably in the range of 1 to 50 µm, even more preferably in the range of 1 to 20 µm. When the average particle diameter of (D) component exists in the said range, since the bulk density of (D) component tends to become large and a specific surface area tends to become small, it is easy to high-fill (D) component in the composition of this invention. On the other hand, when the average particle diameter is too large, there is a possibility that the oil component is separated. The said average particle diameter can be calculated | required as a cumulative average diameter by volume based, for example by Horsfield's Packing Model.

(D) 성분의 형상으로는, 예를 들면 구상, 막대상, 침상, 원반상, 부정형상을 들 수 있지만, 특별히 한정되지 않는다.Examples of the shape of the component (D) include spherical shape, rod shape, needle shape, disk shape, and indefinite shape, but are not particularly limited.

본 발명의 조성물에 있어서, (D) 성분의 함량은, (A) 성분 100 중량부에 대하여 바람직하게는 100 내지 1500 중량부, 더 바람직하게는 100 내지 1000 중량부이다. (D) 성분의 함량이 (A) 성분 100 중량부에 대하여 100 중량부보다 작으면, 얻어지는 방열 부재의 열전도율이 저하되기 쉽다. 한편, 그 함량이 (A) 성분 100 중량부에 대하여 1500 중량부보다 크면, 결과 조성물의 점도가 지나치게 높아져 유동성, 취급성이 불량해지는 경향이 있다.
In the composition of the present invention, the content of component (D) is preferably 100 to 1500 parts by weight, more preferably 100 to 1000 parts by weight based on 100 parts by weight of component (A). When content of (D) component is less than 100 weight part with respect to 100 weight part of (A) component, the thermal conductivity of the heat radiation member obtained will fall easily. On the other hand, when the content is larger than 1500 parts by weight with respect to 100 parts by weight of the component (A), the resulting composition tends to have too high a viscosity, resulting in poor fluidity and handleability.

본 발명의 조성물은 상기한 성분들 외에도, 조성물의 점도를 저하시키고 제조 및 취급과 도포의 용이성을 위해 적당량의 유기 용제를 포함할 수도 있다. 하지만 최근 환경 문제가 부각되고 또한, 인체에 적용될 가능성이 있을 경우 유기 용제 대신, 희석제로서 저점도 메틸 실리콘 오일이나, 옥타메틸사이클로테트라실록산, 헥사메틸사이클로트리실록산 등을 사용할 수도 있다.
In addition to the above components, the composition of the present invention may contain an appropriate amount of an organic solvent for lowering the viscosity of the composition and for ease of preparation, handling and application. However, in recent years, when environmental problems are highlighted and possibly applied to the human body, low viscosity methyl silicone oil, octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, etc. may be used as a diluent instead of an organic solvent.

그 밖에도, 본 발명의 조성물에는, 본 발명의 목적을 손상시키지 않는 범위에서, 임의 성분으로서 통상적으로 사용되는 첨가제 또는 충전제 등을 더 첨가할 수 있다. 구체적으로는 불소 변성 실리콘 계면활성제; 착색제로서 카본 블랙, 이산화티탄, 적산화철 등; 난연성 부여제로서 백금 촉매, 산화철, 산화티탄, 산화세륨 등의 금속 산화물, 또는 금속 수산화물 등을 첨가할 수도 있다. 또한, 열전도성 충전재의 고온시에서의 침강 방지제로서 침강성 실리카 또는 소성 실리카 등의 미분말 실리카, 요변성 향상제 등을 임의로 첨가할 수 있다.
In addition, to the composition of the present invention, additives or fillers commonly used as optional components may be further added to the composition that does not impair the object of the present invention. Specifically, fluorine-modified silicone surfactant; As the colorant, carbon black, titanium dioxide, red iron oxide and the like; As the flame retardant imparting agent, a metal oxide such as platinum catalyst, iron oxide, titanium oxide, cerium oxide, or metal hydroxide may be added. Further, fine powder silica such as precipitated silica or calcined silica, thixotropy enhancer, or the like can be optionally added as an anti-settling agent at a high temperature of the thermally conductive filler.

본 발명의 조성물의 25 ℃에서의 점도는, 바람직하게는 500 Paㆍs 이하(1 내지 500 Paㆍs)이고, 더 바람직하게는 200 Paㆍs 이하(1 내지 200 Paㆍs)이며, 보다 더 바람직하게는 100 Paㆍs 이하(10 내지 100 Paㆍs)이다. 상기 점도가 상기 범위 내에 있으면, 얻어지는 조성물은 유동성이 양호해지기 쉽기 때문에 디스펜스성, 스크린 인쇄성 등의 작업성이 향상되기 쉽고, 상기 조성물을 기재에 얇게 도포하는 것이 용이해진다.The viscosity at 25 ° C. of the composition of the present invention is preferably 500 Pa · s or less (1 to 500 Pa · s), more preferably 200 Pa · s or less (1 to 200 Pa · s), and more More preferably, it is 100 Pa.s or less (10-100 Pa.s). When the said viscosity is in the said range, since the fluidity | liquidity tends to become favorable in the composition obtained, workability, such as a dispensing property and screen printing property, will improve easily, and it becomes easy to apply | coat a thin composition to a base material.

또한, 본 발명의 조성물은 25 ℃에서의 열저항이 바람직하게는 1.0 ℃/W 이하, 더 바람직하게는 0.5 ℃/W 이하, 보다 더 바람직하게는 0.1 ℃/W 이하이다. 열저항이 상기 범위 내에 있으면, 본 발명의 조성물은 발열량이 큰 발열체에 적용한 경우라도, 상기 발열체로부터 발생하는 열을 효율적으로 방열 부품으로 방산시킬 수 있다Further, the composition of the present invention preferably has a thermal resistance at 25 ° C of 1.0 ° C / W or less, more preferably 0.5 ° C / W or less, even more preferably 0.1 ° C / W or less. If the heat resistance is within the above range, the composition of the present invention can efficiently dissipate heat generated from the heat generating element into the heat dissipation component even when the heat generating amount is applied to the heat generating element.

본 발명의 조성물은, 상술한 성분들을 도우 믹서(니이더), 게이트 믹서, 유선형 믹서, planetary mixer 등의 혼합 기기를 이용하여 혼합함으로써 제조될 수 있다. 이와 같이 하여 얻어진 상기 조성물은, 대폭적인 열전도율의 향상과 양호한 작업성, 내구성, 신뢰성을 갖는다.
The composition of the present invention can be prepared by mixing the above components using a mixing device such as dough mixer (kneader), gate mixer, streamlined mixer, planetary mixer and the like. The composition thus obtained has a significant improvement in thermal conductivity and good workability, durability and reliability.

이하, 실시예 및 비교예를 들어 본 발명을 더 상술하지만, 본 발명은 이들 실시예로 한정되는 것이 아니다.
Hereinafter, although an Example and a comparative example are given and this invention is further explained, this invention is not limited to these Examples.

<실시예><Examples>

이하의 각 성분을 사용하여 실시예 및 비교예 조성물을 제조하였다.Each of the following components was used to prepare an Example and a comparative example composition.

(A) 25℃, 50%상대습도에서 동점도가 약 5,000 mm2/s이고, 분자량이 약 10,000 이며, 적어도 2개의 불포화 탄화수소기를 갖는 불포화 실리콘 폴리머 (A) Unsaturated silicone polymer having a kinematic viscosity of about 5,000 mm 2 / s, a molecular weight of about 10,000, and at least two unsaturated hydrocarbon groups at 25 ° C. and 50% relative humidity.

(B) 25℃, 50%상대습도에서 점도가 약 0.25 g/cmㆍsec 이고, 분자량이 약 6,000 이며, 적어도 2개의 규소원자-결합된 수소원자를 갖는 오르가노하이드로겐폴리실록산 (B) an organohydrogenpolysiloxane having a viscosity of about 0.25 g / cm.sec, a molecular weight of about 6,000 and at least two silicon atom-bonded hydrogen atoms at 25 ° C. and 50% relative humidity.

(C) 하이드로실릴 촉매 (C) hydrosilyl catalyst

: 금속백금과 {(CH2CH)CH3SiO4}m (여기서, m = 4) 간의 착화합물: A complex between metal platinum and {(CH 2 CH) CH 3 SiO 4 } m (where m = 4)

(D) 열전도성 충전재 (D) thermally conductive filler

Z-1: 산화아연(평균 입경 1.0 ㎛)Z-1: zinc oxide (average particle diameter 1.0 mu m)

Z-2: 산화아연(평균 입경 2.0 ㎛)Z-2: zinc oxide (average particle diameter 2.0 mu m)

Z-3: 산화아연(평균 입경 5.0 ㎛)Z-3: Zinc oxide (average particle diameter 5.0 micrometers)

A-1: 알루미나 분말(평균 입경 1.0 ㎛)A-1: alumina powder (average particle diameter 1.0 mu m)

A-2: 알루미늄 분말(평균 입경 5.0 ㎛)A-2: Aluminum powder (average particle diameter 5.0 micrometers)

A-3: 산화아연 분말(평균 입경 10.0 ㎛)A-3: Zinc Oxide Powder (Average Grain Size 10.0 µm)

[상기 (D) 성분의 평균 입경은 니끼소 가부시끼가이샤 제조의 입도 분석계인 마이크로 트랙 MT3300EX에 의해 측정한 부피 기준의 누적 평균 직경이다.]
[The average particle diameter of the said (D) component is the cumulative average diameter of the volume reference | measured by the micro track MT3300EX which is a particle size analyzer manufactured by Nikiso Corporation. "

하기 표 1 및 표 2에 나타낸 조성비(중량부)로 1 리터 planetary mixer에 (A) 내지 (D) 성분을 칭량하여 투입한 후 25 ℃에서 3 시간 혼합하여, 실시예 1 내지 6 및 비교예 1 내지 6의 조성물을 얻었다. The components (A) to (D) were weighed and added to a 1 liter planetary mixer at the composition ratios (parts by weight) shown in Tables 1 and 2, followed by mixing at 25 ° C. for 3 hours, Examples 1 to 6 and Comparative Example 1 To 6 compositions were obtained.

얻어진 조성물의 물성을 하기의 시험 방법으로 측정하였고, 그 결과를 표 1 및 2에 나타내었다.The physical properties of the obtained composition were measured by the following test methods, and the results are shown in Tables 1 and 2.

[점도][Viscosity]

얻어진 조성물을 25 ℃의 항온실에 24 시간 방치한 후, 점도계(상품명: 나선형 점도계)를 이용하여 회전수 10 rpm에서의 점도를 측정하였다.After leaving the obtained composition for 24 hours at 25 degreeC constant temperature room, the viscosity in rotation speed of 10 rpm was measured using the viscometer (brand name: spiral viscometer).

[열전도율][Thermal conductivity]

얻어진 조성물을 3 cm 두께의 형틀에 유입시키고, 그 위에 키친용 랩을 씌워 교또 덴시 고교 가부시끼가이샤 제조의 열전도율계(상품명: QTM-500)로 조성물의 열전도율을 측정하였다.The obtained composition was poured into a 3 cm-thick mold, and a kitchen wrap was placed thereon, and the thermal conductivity of the composition was measured by a thermal conductivity meter (trade name: QTM-500) manufactured by Kyoto Denshi Kogyo Co., Ltd.

[열저항][Thermal resistance]

얻어진 조성물을 실제 적용 되는 CPU에 도포하고, 써모랩 TLS-M 열저항 측정기(규격-Modified ASTM5470-06)에 의해 25 ℃에서 열저항을 측정하였다.The obtained composition was applied to a CPU actually applied, and the thermal resistance was measured at 25 ° C. by a thermolab TLS-M thermal resistance measuring instrument (Standard-Modified ASTM5470-06).

[고온 고습하 방치 후의 열저항][Heat Resistance after High Temperature, High Humidity]

얻어진 조성물을 130 ℃/85 %RH 분위기하에서 96 시간 방치한 후, 다시 상기와 동일한 열저항 측정기에 의해 측정하였다.
After leaving the obtained composition for 96 hours in 130 degreeC / 85% RH atmosphere, it measured again with the same thermal resistance measuring instrument as the above.

[표1]Table 1

Figure pat00002
Figure pat00002

[표2][Table 2]

Figure pat00003
Figure pat00003

상기 표 1 및 표 2로부터 알 수 있듯이, 본 발명의 실시예에서는 기존 제품에서 사용하는 실리콘 폴리머와 열전도성 충진제의 단순 분산을 통한 제품에서 발생하는 폴리머와 충진제의 층분리 현상을 극복하기 위하여 폴리머간의 결합을 하였고, 그 결과 열전도율이 우수하면서도(높을수록 우수) 초기 열저항(낮을수록 우수)과 항온항습 방치후 안정성이 우수한 제품을 얻을 수 있었다.
As can be seen from Table 1 and Table 2, in the embodiment of the present invention between the polymer to overcome the delamination phenomenon of the polymer and the filler in the product through the simple dispersion of the silicone polymer and the thermal conductive filler used in the existing product As a result, it was possible to obtain a product having excellent thermal conductivity (higher the better) and excellent initial thermal resistance (lower the better) and stability after constant temperature and humidity.

Claims (7)

(A) 25℃, 50%상대습도에서 동점도가 100 내지 20,000 mm2/s이고, 분자량이 100 내지 20,000이며, 적어도 2개의 불포화 탄화수소기를 갖는 불포화 실리콘 폴리머 100 중량부,
(B) 25℃, 50%상대습도에서 점도가 0.1 내지 0.4 g/cmㆍsec 이고, 분자량이 4,000 내지 8,000이며, 적어도 2개의 규소원자-결합된 수소원자를 갖는 오르가노하이드로겐폴리실록산 5 내지 10 중량부,
(C) 백금계 하이드로실릴 촉매 0.05 내지 1 중량부, 및
(D) 열전도성 충전재 100 내지 1500 중량부
를 포함하는 방열성 실리콘 중합체 조성물.
(A) 100 parts by weight of an unsaturated silicone polymer having a kinematic viscosity of 100 to 20,000 mm 2 / s, a molecular weight of 100 to 20,000, and at least two unsaturated hydrocarbon groups at 25 ° C. and 50% relative humidity,
(B) 5 to 10 organohydrogenpolysiloxanes having a viscosity of 0.1 to 0.4 g / cm · sec, a molecular weight of 4,000 to 8,000, and at least two silicon atom-bonded hydrogen atoms at 25 ° C. and 50% relative humidity; Weight,
(C) 0.05 to 1 parts by weight of a platinum hydrosilyl catalyst, and
(D) 100 to 1500 parts by weight of the thermally conductive filler
Heat dissipating silicone polymer composition comprising a.
제1항에 있어서, 성분 (A)가, 비닐 그룹으로 말단화되고 사슬 측쇄에 규소원자-결합된 탄소함유 치환기를 갖는 직쇄상 폴리실록산인 것을 특징으로 하는 방열성 실리콘 중합체 조성물.The heat dissipating silicone polymer composition according to claim 1, wherein component (A) is a linear polysiloxane which is terminated with a vinyl group and has a silicon atom-bonded carbon-containing substituent in the chain side chain. 제1항에 있어서, 성분 (C)가 백금족 유기금속계 착화합물인 것을 특징으로 하는 방열성 실리콘 중합체 조성물.The heat dissipating silicone polymer composition according to claim 1, wherein component (C) is a platinum group organometallic complex. 제1항에 있어서, 성분 (D)가 알루미늄, 은, 구리, 니켈, 산화아연, 알루미나, 산화마그네슘, 질화알루미늄, 질화붕소, 질화규소, 다이아몬드, 흑연, 탄소 나노튜브, 금속 규소, 탄소 섬유, 플라렌 또는 이들의 2종 이상의 조합인 것을 특징으로 하는 방열성 실리콘 중합체 조성물.The method of claim 1, wherein component (D) comprises aluminum, silver, copper, nickel, zinc oxide, alumina, magnesium oxide, aluminum nitride, boron nitride, silicon nitride, diamond, graphite, carbon nanotubes, metal silicon, carbon fiber, plastic A heat-dissipating silicone polymer composition, characterized in that the ene or a combination of two or more thereof. 제1항에 있어서, 성분 (D)의 평균 입경이 1 내지 20 ㎛의 범위인 것을 특징으로 하는 방열성 실리콘 중합체 조성물.The heat dissipating silicone polymer composition according to claim 1, wherein the average particle diameter of the component (D) is in the range of 1 to 20 mu m. 제1항 내지 제5항 중 어느 한 항에 있어서, 25 ℃에서의 점도가 500 Paㆍs 이하인 것을 특징으로 하는 방열성 실리콘 중합체 조성물.The heat-dissipative silicone polymer composition according to any one of claims 1 to 5, wherein the viscosity at 25 ° C is 500 Pa · s or less. 제1항 내지 제5항 중 어느 한 항에 있어서, 25 ℃에서의 열저항이 0.5 ℃/W 이하인 것을 특징으로 하는 방열성 실리콘 중합체 조성물.The heat resistant silicone polymer composition according to any one of claims 1 to 5, wherein the heat resistance at 25 ° C is 0.5 ° C / W or less.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100273011A1 (en) * 1996-12-20 2010-10-28 Bianxiao Zhong Silicone Composition, Silicone Adhesive, Coated and Laminated Substrates
WO2013137517A1 (en) * 2012-03-12 2013-09-19 (주)사람과나눔 Insulating heat-dissipation solution filled in housing of led lighting device and led lighting device using same
WO2015076432A1 (en) * 2013-11-21 2015-05-28 주식회사 지앤씨 Light-emitting diode lighting apparatus using heat-dissipating solution
KR20170012919A (en) 2015-07-27 2017-02-06 (주)이월리서치 A method for implementing multi vision in software through multicast
CN113785003A (en) * 2019-05-06 2021-12-10 瓦克化学股份公司 Polyorganosiloxane, and thermally conductive silicone composition containing the same
WO2021256818A1 (en) * 2020-06-18 2021-12-23 재경전광산업 주식회사 Incandescent light bulb-type led lamp having heat-dissipation function
US11486567B2 (en) 2020-06-18 2022-11-01 JK Lighting Co., Ltd Incandescent bulb-type LED lamp having heat dissipation function

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100273011A1 (en) * 1996-12-20 2010-10-28 Bianxiao Zhong Silicone Composition, Silicone Adhesive, Coated and Laminated Substrates
WO2013137517A1 (en) * 2012-03-12 2013-09-19 (주)사람과나눔 Insulating heat-dissipation solution filled in housing of led lighting device and led lighting device using same
KR101318288B1 (en) * 2012-03-12 2013-11-13 고정호 Heat radient insulating liquid filled in led lighting device and led lighting device using the same
WO2015076432A1 (en) * 2013-11-21 2015-05-28 주식회사 지앤씨 Light-emitting diode lighting apparatus using heat-dissipating solution
KR20170012919A (en) 2015-07-27 2017-02-06 (주)이월리서치 A method for implementing multi vision in software through multicast
CN113785003A (en) * 2019-05-06 2021-12-10 瓦克化学股份公司 Polyorganosiloxane, and thermally conductive silicone composition containing the same
CN113785003B (en) * 2019-05-06 2023-04-25 瓦克化学股份公司 Polyorganosiloxane, and thermally conductive silicone composition containing same
WO2021256818A1 (en) * 2020-06-18 2021-12-23 재경전광산업 주식회사 Incandescent light bulb-type led lamp having heat-dissipation function
US11486567B2 (en) 2020-06-18 2022-11-01 JK Lighting Co., Ltd Incandescent bulb-type LED lamp having heat dissipation function

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