TW202346446A - Heat conductive sheet and heat dissipation device using heat conductive sheet - Google Patents
Heat conductive sheet and heat dissipation device using heat conductive sheet Download PDFInfo
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- TW202346446A TW202346446A TW112130023A TW112130023A TW202346446A TW 202346446 A TW202346446 A TW 202346446A TW 112130023 A TW112130023 A TW 112130023A TW 112130023 A TW112130023 A TW 112130023A TW 202346446 A TW202346446 A TW 202346446A
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Abstract
Description
本發明是有關於一種熱傳導片、及使用熱傳導片的散熱裝置。The present invention relates to a thermal conductive sheet and a heat dissipation device using the thermal conductive sheet.
近年來，伴隨多層配線板的配線的高密度化、相對於半導體封裝的配線的高密度化、電子零件的搭載密度的增大、半導體元件自身的高積體化引起的每單位面積的發熱量的增大等，期望提高自半導體封裝的散熱性。In recent years, the amount of heat generated per unit area has increased with the increase in the density of wiring in multilayer wiring boards, the increase in density of wiring in semiconductor packages, the increase in the mounting density of electronic components, and the increase in integration of semiconductor elements themselves. increase, etc., it is expected to improve the heat dissipation from the semiconductor package.
中央處理裝置（Central Processing Unit，CPU）等一般所使用的半導體封裝具有藉由於半導體晶片等發熱體與鋁、銅等散熱體之間夾持熱傳導片、膏等熱傳導材料並使其密接來散熱的結構。Semiconductor packages commonly used in Central Processing Units (CPUs) and other devices dissipate heat by sandwiching heat conductive materials such as heat conductive sheets and pastes between heat generating bodies such as semiconductor wafers and heat sinks such as aluminum or copper and making them closely connected. structure.
為了提高散熱性，對熱傳導片要求高的熱傳導性。出於提高熱傳導片的熱傳導性的目的，提出將熱傳導性大的石墨粉末調配至基質材料中而成的各種熱傳導性複合材料組成物及其成形加工品。In order to improve heat dissipation, the thermal conductive sheet is required to have high thermal conductivity. For the purpose of improving the thermal conductivity of the thermally conductive sheet, various thermally conductive composite material compositions and their molded products have been proposed in which graphite powder with high thermal conductivity is blended into a matrix material.
例如，於專利文獻1中揭示一種調配有粒徑為1 μm～20 μm的人造石墨的橡膠組成物。於專利文獻2中揭示一種填充有結晶面間隔為0.33 nm～0.34 nm的球狀石墨的矽酮橡膠組成物。For example, Patent Document 1 discloses a rubber composition containing artificial graphite with a particle diameter of 1 μm to 20 μm. Patent Document 2 discloses a silicone rubber composition filled with spherical graphite having a crystal plane spacing of 0.33 nm to 0.34 nm.
進而，於專利文獻3中揭示一種藉由使各向異性（anisotropy）石墨粉於黏合劑成分中配向於一定方向來提昇散熱性的散熱片。另外，於專利文獻4中揭示一種藉由使石墨粒子配向於熱傳導片的厚度方向來提昇熱傳導性的熱傳導片。 [現有技術文獻] [專利文獻] Furthermore, Patent Document 3 discloses a heat sink that improves heat dissipation by arranging anisotropic graphite powder in a certain direction in a binder component. In addition, Patent Document 4 discloses a thermally conductive sheet that improves thermal conductivity by arranging graphite particles in the thickness direction of the thermally conductive sheet. [Prior art documents] [Patent Document]
[專利文獻1]日本專利特開平05-247268號公報 [專利文獻2]日本專利特開平10-298433號公報 [專利文獻3]日本專利第4743344號 [專利文獻4]日本專利第5316254號 [Patent Document 1] Japanese Patent Application Publication No. 05-247268 [Patent Document 2] Japanese Patent Application Laid-Open No. 10-298433 [Patent Document 3] Japanese Patent No. 4743344 [Patent Document 4] Japanese Patent No. 5316254
[發明所欲解決之課題][Problem to be solved by the invention]
另一方面，對於熱傳導片而言，為了保證發熱體的散熱性，亦要求可追隨構件間的熱變形（翹曲）。特別是，近年來伴隨封裝的高性能化，封裝及晶片的大型化不斷發展。藉由該大型化，封裝的翹曲量進一步增大，故於先前的熱傳導片中存在無法追隨翹曲而容易自發熱體及散熱體剝離的問題。另外，例如於在作為發熱體的半導體晶片與作為散熱體的散熱器（heat spreader）之間使用熱傳導片的情況下，為了保證散熱性，要求將晶片及散熱器與熱傳導片充分地密接。On the other hand, in order to ensure the heat dissipation performance of the heating element, the thermal conductive sheet is also required to be able to follow the thermal deformation (warp) between components. In particular, in recent years, as packages have become more high-performance, packages and chips have become larger. Due to this increase in size, the amount of warpage of the package further increases. Therefore, the conventional thermally conductive sheet has a problem that it cannot follow the warpage and easily peels off the heating element and the heat sink. In addition, for example, when a thermal conductive sheet is used between a semiconductor wafer as a heat generator and a heat spreader as a heat sink, in order to ensure heat dissipation, it is required that the wafer, the heat spreader, and the thermal conductive sheet are in sufficient close contact.
例如，於專利文獻3中所記載的散熱片中，藉由使用熱塑性橡膠成分與熱硬化性橡膠成分，與對散熱片所要求的耐熱性、強度等特性一併實現可與被黏體密接的黏性、及柔軟性的提高。另外，於專利文獻4中所記載的熱傳導片中，藉由使用作為基質材料的特定的有機高分子化合物與硬化劑並使有機高分子化合物進行交聯，共同實現強度與柔軟性的提高。然而，就追隨翹曲量增大的半導體封裝中的翹曲的觀點而言，專利文獻3及專利文獻4中所記載的方法存在改善的餘地。For example, in the heat sink described in Patent Document 3, by using a thermoplastic rubber component and a thermosetting rubber component, it is possible to achieve close contact with the adherend in addition to the characteristics required for the heat sink, such as heat resistance and strength. Improved viscosity and softness. In addition, in the thermally conductive sheet described in Patent Document 4, a specific organic polymer compound and a curing agent are used as a matrix material and the organic polymer compound is cross-linked, thereby improving both strength and flexibility. However, the methods described in Patent Document 3 and Patent Document 4 have room for improvement from the viewpoint of following the warpage in a semiconductor package in which the amount of warpage increases.
本發明是鑒於所述問題而成者，其目的在於提供一種穩定地密接於發熱體及散熱體而可確保散熱性的熱傳導片、及使用其的散熱裝置。 [解決課題之手段] The present invention was made in view of the above-mentioned problems, and an object thereof is to provide a thermally conductive sheet that is stably in close contact with a heating element and a heat sink and can ensure heat dissipation, and a heat dissipation device using the same. [Means to solve the problem]
用以解決所述課題的具體手段包含以下態樣。 ＜1＞ 一種熱傳導片，其含有選自由鱗片狀粒子、橢圓體狀粒子及棒狀粒子所組成的群組中的至少一種石墨粒子（A）， 於所述鱗片狀粒子的情況下，面方向配向於厚度方向，於所述橢圓體狀粒子的情況下，長軸方向配向於厚度方向，於所述棒狀粒子的情況下，長軸方向配向於厚度方向， 在150℃下的壓縮應力為0.1 MPa時的彈性係數為1.4 MPa以下， 在25℃下的黏力（tack strength）為5.0 N·mm以上。 ＜2＞ 如＜1＞所述的熱傳導片，其進而含有於25℃下為液狀的成分（B）。 ＜3＞ 如＜1＞或＜2＞所述的熱傳導片，其中所述於25℃下為液狀的成分（B）包含聚丁烯。 ＜4＞ 如＜1＞至＜3＞中任一項所述的熱傳導片，其更含有丙烯酸酯系高分子（C）。 ＜5＞ 如＜4＞所述的熱傳導片，其中所述丙烯酸酯系高分子（C）的玻璃轉移溫度為20℃以下。 ＜6＞ 如＜1＞至＜5＞中任一項所述的熱傳導片，其更含有乙烯-α-烯烴共聚物（D）。 ＜7＞ 如＜1＞至＜6＞中任一項所述的熱傳導片，其更含有熱熔劑（E）。 ＜8＞ 如＜1＞至＜7＞中任一項所述的熱傳導片，其更含有抗氧化劑（F）。 ＜9＞ 如＜1＞至＜8＞中任一項所述的熱傳導片，其中所述石墨粒子（A）包含鱗片狀粒子，所述鱗片狀粒子包含膨脹石墨粒子。 ＜10＞ 如＜1＞至＜9＞中任一項所述的熱傳導片，其中所述石墨粒子（A）的含有率為15體積%～50體積%。 ＜11＞ 一種散熱裝置，其包括發熱體、散熱體、以及配置於所述發熱體及所述散熱體之間的如＜1＞至＜10＞中任一項所述的熱傳導片。 [發明的效果] Specific means for solving the above problems include the following aspects. <1> A thermally conductive sheet containing at least one graphite particle (A) selected from the group consisting of scaly particles, ellipsoidal particles and rod-like particles, In the case of the scaly particles, the plane direction is aligned with the thickness direction, in the case of the ellipsoid-shaped particles, the long axis direction is aligned with the thickness direction, and in the case of the rod-shaped particles, the long axis direction is aligned. in the thickness direction, When the compressive stress at 150°C is 0.1 MPa, the elastic coefficient is 1.4 MPa or less. The tack strength at 25°C is above 5.0 N·mm. <2> The heat conductive sheet according to <1>, further containing a component (B) that is liquid at 25°C. <3> The thermally conductive sheet according to <1> or <2>, wherein the component (B) that is liquid at 25° C. contains polybutene. <4> The heat conductive sheet according to any one of <1> to <3>, further containing an acrylate-based polymer (C). <5> The thermally conductive sheet according to <4>, wherein the glass transition temperature of the acrylic polymer (C) is 20° C. or lower. <6> The heat conductive sheet according to any one of <1> to <5>, further containing an ethylene-α-olefin copolymer (D). <7> The thermal conductive sheet according to any one of <1> to <6>, further containing a hot melt agent (E). <8> The thermal conductive sheet according to any one of <1> to <7>, further containing an antioxidant (F). <9> The thermally conductive sheet according to any one of <1> to <8>, wherein the graphite particles (A) include scaly particles, and the scaly particles include expanded graphite particles. <10> The thermal conductive sheet according to any one of <1> to <9>, wherein the content of the graphite particles (A) is 15% by volume to 50% by volume. <11> A heat dissipation device including a heat generating body, a heat sink, and the thermal conductive sheet according to any one of <1> to <10> arranged between the heat generating body and the heat sink. [Effects of the invention]
根據本揭示，可提供一種穩定地密接於發熱體及散熱體而可確保散熱性的熱傳導片、及使用其的散熱裝置。According to the present disclosure, it is possible to provide a heat conductive sheet that is stably in close contact with a heating element and a heat sink and can ensure heat dissipation, and a heat dissipation device using the same.
以下，對用以實施本發明的形態進行詳細說明。但本發明並不限定於以下的實施形態。於以下的實施形態中，其構成要素（亦包括要素步驟等）除特別明示的情況以外，並非必需。關於數值及其範圍亦同樣，並不限制本發明。 於本揭示中，「步驟」的用語除了獨立於其他步驟的步驟以外，即便於無法與其他步驟明確地區別的情況下，只要達成該步驟的目的，則亦包括該步驟。 於本揭示中，使用「～」來表示的數值範圍中包含「～」的前後所記載的數值分別作為最小值及最大值。 於本揭示中階段性記載的數值範圍中，一個數值範圍所記載的上限值或下限值亦可置換為其他階段性記載的數值範圍的上限值或下限值。另外，於本揭示中所記載的數值範圍中，該數值範圍的上限值或下限值亦可置換為實施例中所示的值。 於本揭示中，各成分亦可包含多種相符的物質。於在組成物中存在多種與各成分相符的物質的情況下，只要無特別說明，則各成分的含有率或含量是指組成物中所存在的該多種物質的合計含有率或含量。 於本揭示中，亦可包含多種與各成分相符的粒子。於在組成物中存在多種與各成分相符的粒子的情況下，只要無特別說明，則各成分的粒徑是指關於組成物中所存在的該多種粒子的混合物的值。 於本揭示中，「層」或「膜」的用語中，當觀察該層或膜所存在的區域時，除了形成於該區域的整體的情況以外，亦包含僅形成於該區域的一部分的情況。 於本揭示中，「積層」的用語表示將層重疊，兩層以上的層可結合，兩層以上的層亦可裝卸。 Hereinafter, the form for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps, etc.) are not essential unless otherwise expressly stated. The same applies to numerical values and their ranges, which do not limit the present invention. In this disclosure, the term "step" includes steps that are independent of other steps, even if they cannot be clearly distinguished from other steps, as long as the purpose of the step is achieved. In this disclosure, the numerical range represented by "～" includes the numerical values described before and after "～" as the minimum value and the maximum value respectively. Among the numerical ranges described in stages in this disclosure, the upper limit or lower limit described in one numerical range may also be replaced with the upper limit or lower limit of another numerical range described in stages. In addition, in the numerical range described in this disclosure, the upper limit value or the lower limit value of the numerical range can also be replaced with the value shown in the embodiment. In this disclosure, each component may also include a variety of consistent substances. When there are multiple substances corresponding to each component in the composition, unless otherwise specified, the content rate or content of each component refers to the total content rate or content of the multiple substances present in the composition. In this disclosure, a variety of particles consistent with each component may also be included. When a plurality of types of particles corresponding to each component are present in the composition, the particle diameter of each component refers to a value for a mixture of the plurality of types of particles present in the composition unless otherwise specified. In this disclosure, the terms "layer" or "film" include when the region in which the layer or film exists is observed, in addition to the case where it is formed in the entire region, it also includes the case where it is formed in only a part of the region. . In this disclosure, the term "lamination" means overlapping layers, two or more layers can be combined, and two or more layers can be attached and detached.
〔熱傳導片〕 本揭示的熱傳導片含有選自由鱗片狀粒子、橢圓體狀粒子及棒狀粒子所組成的群組中的至少一種石墨粒子（A）（以下，亦簡稱為「石墨粒子（A）」），於所述鱗片狀粒子的情況下，面方向配向於厚度方向，於所述橢圓體狀粒子的情況下，長軸方向配向於厚度方向，於所述棒狀粒子的情況下，長軸方向配向於厚度方向，在150℃下的壓縮應力為0.1 MPa時的彈性係數（以下，亦將施加規定的壓縮應力時的彈性係數稱為「壓縮彈性係數」）為1.4 MPa以下，在25℃下的黏力為5.0 N·mm以上。 認為本揭示的熱傳導片的石墨粒子（A）配向於厚度方向，藉此厚度方向的熱傳導性優異，顯示出低的熱阻（heat resistance）。進而，認為本揭示的熱傳導片在150℃下的壓縮應力為0.1 MPa時的彈性係數為1.4 MPa以下，在25℃下的黏力為5.0 N·mm以上，藉此即便用於翹曲量大的封裝，亦可追隨翹曲而確保密接。 [Thermal conductive sheet] The thermally conductive sheet of the present disclosure contains at least one type of graphite particles (A) selected from the group consisting of scaly particles, ellipsoid particles, and rod-like particles (hereinafter, also referred to as "graphite particles (A)"). In the case of the scaly particles, the plane direction is aligned with the thickness direction, in the case of the ellipsoid-shaped particles, the long axis direction is aligned with the thickness direction, and in the case of the rod-shaped particles, the long axis direction is aligned with the thickness direction. In the thickness direction, the elastic coefficient when the compressive stress at 150°C is 0.1 MPa (hereinafter, the elastic coefficient when a specified compressive stress is applied is also referred to as the "compressive elastic coefficient") is 1.4 MPa or less, and the viscosity at 25°C The force is 5.0 N·mm or more. It is considered that the thermally conductive sheet of the present disclosure has graphite particles (A) aligned in the thickness direction, thereby having excellent thermal conductivity in the thickness direction and exhibiting low heat resistance. Furthermore, it is considered that the thermal conductive sheet of the present disclosure has an elastic coefficient of 1.4 MPa or less when the compressive stress at 150°C is 0.1 MPa, and an adhesive force of 5.0 N·mm or more at 25°C, so that it can be used even when the amount of warpage is large. The packaging can also follow warpage to ensure tight contact.
熱傳導片亦可進而含有於25℃下為液狀的成分（B）、丙烯酸酯系高分子（C）、乙烯-α-烯烴共聚物（D）、熱熔劑（E）、抗氧化劑（F）等，亦可含有其他成分。以下，對本揭示的熱傳導片中所使用的材料進行說明。The thermally conductive sheet may further contain a component (B) that is liquid at 25°C, an acrylic polymer (C), an ethylene-α-olefin copolymer (D), a hot melt agent (E), and an antioxidant (F). etc., may also contain other ingredients. Hereinafter, materials used in the thermally conductive sheet of the present disclosure will be described.
＜石墨粒子（A）＞ 熱傳導片含有石墨粒子（A）。認為石墨粒子（A）主要作為高熱傳導性填料發揮功能。石墨粒子（A）為選自由鱗片狀粒子、橢圓體狀粒子及棒狀粒子所組成的群組中的至少一種。另外，石墨粒子（A）於鱗片狀粒子的情況下，面方向配向於厚度方向，於橢圓體狀粒子的情況下，長軸方向配向於厚度方向，及於棒狀粒子的情況下，長軸方向配向於厚度方向。所謂鱗片狀粒子的面方向配向於厚度方向，是指鱗片狀粒子的沿著主面的任一方向配向於熱傳導片的厚度方向，面的長軸方向可進行配向，面的短軸方向亦可進行配向，抑或可面的其他的軸方向配向於厚度方向。另外，石墨粒子（A）較佳為於鱗片狀粒子的情況下，結晶中的六員環面配向於面方向，於橢圓體狀粒子的情況下，結晶中的六員環面配向於長軸方向，及於棒狀粒子的情況下，結晶中的六員環面配向於長軸方向。所謂六員環面，為六方晶系中形成有六員環的面，且是指（0001）結晶面。 ＜Graphite particles (A)＞ The thermally conductive sheet contains graphite particles (A). It is thought that the graphite particles (A) mainly function as a highly thermally conductive filler. The graphite particles (A) are at least one selected from the group consisting of flake-shaped particles, ellipsoid-shaped particles, and rod-shaped particles. In addition, in the case of scaly particles, the plane direction of the graphite particles (A) is aligned with the thickness direction, in the case of ellipsoid-shaped particles, the long axis direction is aligned with the thickness direction, and in the case of rod-shaped particles, the long axis direction is aligned The direction is aligned with the thickness direction. The so-called scaly particles are aligned in the thickness direction, which means that the scaly particles are aligned in the thickness direction of the thermal conductive sheet in any direction along the main surface. The long axis direction of the surface can be aligned, and the short axis direction of the surface can also be aligned. Alignment can be performed, or other axis directions can be aligned in the thickness direction. In addition, the graphite particles (A) are preferably such that, in the case of scaly particles, the six-membered torus in the crystal is aligned with the plane direction, and in the case of ellipsoidal particles, the six-membered torus in the crystal is aligned with the long axis. direction, and in the case of rod-shaped particles, the six-membered torus in the crystal is aligned in the direction of the long axis. The so-called six-membered ring surface is a surface formed with a six-membered ring in the hexagonal crystal system, and refers to the (0001) crystal surface.
石墨粒子（A）的形狀更佳為鱗片狀。藉由選擇鱗片狀的石墨粒子，有熱傳導性進一步提昇的傾向。可認為這是因為例如鱗片狀的石墨粒子於熱傳導片中更容易朝規定的方向配向。The shape of the graphite particles (A) is preferably flake-like. By selecting scaly graphite particles, thermal conductivity tends to be further improved. This is considered to be because, for example, scaly graphite particles are more easily aligned in a predetermined direction in the thermally conductive sheet.
可藉由X射線繞射測定來確認石墨粒子（A）的結晶中的六員環面是否配向於鱗片狀粒子的面方向、橢圓體狀粒子的長軸方向或棒狀粒子的長軸方向。石墨粒子（A）的結晶中的六員環面的配向方向具體是利用以下的方法來確認。X-ray diffraction measurement can be used to confirm whether the six-membered torus in the crystal of graphite particles (A) is aligned with the plane direction of the scaly particles, the long axis direction of the ellipsoidal particles, or the long axis direction of the rod-shaped particles. The alignment direction of the six-membered torus in the crystal of graphite particles (A) is specifically confirmed by the following method.
首先，製作石墨粒子（A）的鱗片狀粒子的面方向、橢圓體狀粒子的長軸方向或棒狀粒子的長軸方向沿片（sheet）的面方向配向的測定用樣品片。作為測定用樣品片的具體的製作方法，例如可列舉以下的方法。First, a measurement sample piece is prepared in which the plane direction of the scaly particles, the major axis direction of the ellipsoidal particles, or the major axis direction of the rod-shaped particles of the graphite particles (A) are aligned in the plane direction of the sheet. As a specific method of producing a sample piece for measurement, the following method can be cited, for example.
對樹脂、與相對於樹脂而為10體積%以上的量的石墨粒子（A）的混合物進行片化。此處使用的「樹脂」，只要為不顯現妨礙X射線繞射的峰值且可形成片狀物的材料，則並無特別限制。具體可使用丙烯酸橡膠、丙烯腈丁二烯橡膠（acrylonitrile butadiene rubber，NBR）、苯乙烯-異丁烯-苯乙烯共聚物（styrene-isobutylene-styrene，SIBS）等具有作為黏合劑的凝聚力的非晶質樹脂。A mixture of resin and graphite particles (A) in an amount of 10% by volume or more based on the resin is formed into sheets. The "resin" used here is not particularly limited as long as it is a material that does not exhibit peaks that interfere with X-ray diffraction and can be formed into a sheet. Specifically, acrylic rubber, acrylonitrile butadiene rubber (NBR), styrene-isobutylene-styrene copolymer (styrene-isobutylene-styrene, SIBS), and other amorphous resins that have cohesion as a binder can be used. .
以成為原來厚度的1/10以下的方式按壓（press）該混合物的片，將按壓後的片的多枚積層而形成積層體。重覆三次以上進而將該積層體壓扁至1/10以下為止的操作而獲得測定用樣品片。藉由該操作，於測定用樣品片中，石墨粒子（A）於鱗片狀粒子的情況下，成為面方向沿測定用樣品片的面方向配向的狀態，於橢圓體狀粒子的情況下，成為長軸方向沿測定用樣品片的面方向配向的狀態，及於棒狀粒子的情況下，成為長軸方向沿測定用樣品片的面方向配向的狀態。The sheet of the mixture is pressed so that the thickness becomes 1/10 or less of the original thickness, and a plurality of the pressed sheets are laminated to form a laminated body. The operation of flattening the laminated body to 1/10 or less was repeated three or more times to obtain a sample piece for measurement. By this operation, in the sample piece for measurement, the graphite particles (A) are aligned in the plane direction of the sample piece for measurement in the case of scaly particles, and in the case of ellipsoid-shaped particles. The long axis direction is aligned along the plane direction of the sample piece for measurement, and in the case of rod-shaped particles, the long axis direction is aligned along the plane direction of the sample piece for measurement.
對以所述方式製作的測定用樣品片的表面進行X射線繞射測定。測定於2θ=77°附近顯現的與石墨的（110）面相對應的峰值的高度H 1、及於2θ=27°附近顯現的與石墨的（002）面相對應的峰值的高度H 2。於如此般製作的測定用樣品片中，H 1除以H 2而得的值成為0～0.02。 The surface of the measurement sample piece produced in the above manner was subjected to X-ray diffraction measurement. The height H 1 of the peak corresponding to the (110) plane of graphite appearing near 2θ = 77° and the height H 2 of the peak corresponding to the (002) plane of graphite appearing near 2θ = 27° were measured. In the measurement sample piece produced in this way, the value obtained by dividing H 1 by H 2 is 0 to 0.02.
由此，所謂「石墨粒子（A）的結晶中的六員環面於鱗片狀粒子的情況下配向於面方向，於橢圓體狀粒子的情況下配向於長軸方向，及於棒狀粒子的情況下配向於長軸方向」，是指對含有石墨粒子（A）的片的表面進行X射線繞射測定而於2θ=77°附近顯現的與石墨粒子（A）的（110）面相對應的峰值的高度除以於2θ=27°附近顯現的與石墨粒子（A）的（002）面相對應的峰值的高度而得的值成為0～0.02的狀態。From this, the six-membered torus in the crystal of so-called graphite particles (A) is aligned in the plane direction in the case of scaly particles, in the long axis direction in the case of ellipsoidal particles, and in the long axis direction of rod-shaped particles. "Aligned in the long axis direction" means that the surface of the sheet containing graphite particles (A) is measured by X-ray diffraction and appears near 2θ=77° corresponding to the (110) plane of the graphite particles (A). The value obtained by dividing the height of the peak by the height of the peak corresponding to the (002) plane of the graphite particle (A) appearing near 2θ=27° is in a state of 0 to 0.02.
於本揭示中，X射線繞射測定是利用以下的條件進行。 裝置：例如布魯克AXS（Bruker AXS）股份有限公司的「D8DISCOVER」 X射線源：波長1.5406 nm的CuKα、40 kV、40 mA 步幅（測定步寬）：0.01° 步進時間（step time）：720 sec In the present disclosure, X-ray diffraction measurement is performed using the following conditions. Device: For example, "D8DISCOVER" from Bruker AXS Co., Ltd. X-ray source: CuKα with wavelength 1.5406 nm, 40 kV, 40 mA Stride length (measured step width): 0.01° Step time: 720 sec
此處，所謂「石墨粒子於鱗片狀粒子的情況下，面方向配向於熱傳導片的厚度方向，於橢圓體狀粒子的情況下，長軸方向配向於熱傳導片的厚度方向，及於棒狀粒子的情況下，長軸方向配向於熱傳導片的厚度方向」，是指於鱗片狀粒子的情況下，面方向與熱傳導片的表面（主表面）所形成的角度（以下，亦稱為「配向角度」）為60°以上，於橢圓體狀粒子的情況下，長軸方向與熱傳導片的表面（主表面）所形成的角度（以下，亦稱為「配向角度」）為60°以上，及於棒狀粒子的情況下，長軸方向與熱傳導片的表面（主表面）所形成的角度（以下，亦稱為「配向角度」）為60°以上。配向角度較佳為80°以上，更佳為85°以上，進而佳為88°以上。Here, the term “graphite particles” means that in the case of scaly particles, the planar direction is aligned with the thickness direction of the heat conductive sheet, in the case of ellipsoidal particles, the long axis direction is aligned with the thickness direction of the heat conductive sheet, and in the case of rod-shaped particles In the case of ", the long axis direction is aligned with the thickness direction of the thermally conductive sheet" refers to the angle (hereinafter, also referred to as "alignment angle") formed by the plane direction and the surface (main surface) of the thermally conductive sheet in the case of scaly particles. ”) is 60° or more, in the case of ellipsoid-shaped particles, the angle formed by the long axis direction and the surface (main surface) of the thermal conductive sheet (hereinafter, also referred to as the “alignment angle”) is 60° or more, and In the case of rod-shaped particles, the angle formed by the long axis direction and the surface (main surface) of the thermally conductive sheet (hereinafter also referred to as "alignment angle") is 60° or more. The alignment angle is preferably 80° or more, more preferably 85° or more, and further preferably 88° or more.
配向角度為利用掃描式電子顯微鏡（SEM）觀察熱傳導片的剖面，並對任意的50個石墨粒子（A）於鱗片狀粒子的情況下測定面方向與熱傳導片表面（主表面）所形成的角度（配向角度）時的平均值，於橢圓體狀粒子的情況下測定長軸方向與熱傳導片表面（主表面）所形成的角度（配向角度）時的平均值，及於棒狀粒子的情況下測定長軸方向與熱傳導片表面（主表面）所形成的角度（配向角度）時的平均值。The alignment angle is determined by observing the cross-section of the thermally conductive sheet with a scanning electron microscope (SEM) and measuring the angle between the plane direction and the surface (main surface) of the thermally conductive sheet for any 50 graphite particles (A) in the case of scaly particles. (Alignment angle), the average value when measuring the angle (alignment angle) formed by the long axis direction and the surface (main surface) of the thermal conductive sheet in the case of ellipsoid-shaped particles, and the average value in the case of rod-shaped particles The average value is measured when the angle (alignment angle) formed by the long axis direction and the surface (main surface) of the thermal conductive sheet is measured.
石墨粒子（A）的粒徑並無特別限制。石墨粒子（A）的平均粒徑以質量平均粒徑計而較佳為熱傳導片的平均厚度的1/2以上且平均厚度以下。若石墨粒子（A）的質量平均粒徑為熱傳導片的平均厚度的1/2以上，則於熱傳導片中形成有效的熱傳導通路，有熱傳導率提昇的傾向。若石墨粒子（A）的質量平均粒徑為熱傳導片的平均厚度以下，則可抑制石墨粒子（A）自熱傳導片的表面突出，有熱傳導片的表面的密接性優異的傾向。The particle size of the graphite particles (A) is not particularly limited. The average particle diameter of the graphite particles (A) is preferably not less than 1/2 and not more than the average thickness of the average thickness of the thermally conductive sheet in terms of mass average particle diameter. If the mass average particle diameter of the graphite particles (A) is 1/2 or more of the average thickness of the thermal conductive sheet, an effective thermal conductive path is formed in the thermal conductive sheet, and the thermal conductivity tends to increase. When the mass average particle diameter of the graphite particles (A) is equal to or less than the average thickness of the thermally conductive sheet, protrusion of the graphite particles (A) from the surface of the thermally conductive sheet is suppressed, and the adhesion to the surface of the thermally conductive sheet tends to be excellent.
於鱗片狀粒子的情況下，以面方向配向於厚度方向的方式製作熱傳導片的方法並無特別限制，於橢圓體狀粒子的情況下，以長軸方向配向於厚度方向的方式製作熱傳導片的方法並無特別限制，及於棒狀粒子的情況下，以長軸方向配向於厚度方向的方式製作熱傳導片的方法並無特別限制，例如可使用日本專利特開2008-280496號公報中所記載的方法。具體而言，可利用使用組成物製作片，將該片積層來製作積層體，從而對該積層體的側端面（例如，以相對於自積層體的主面而出的法線而為0°～30°的角度）進行切片的方法（以下，亦稱為「積層切片法」）。In the case of scaly particles, the method of producing the thermally conductive sheet is not particularly limited so that the plane direction is aligned with the thickness direction. In the case of ellipsoidal particles, the method of producing the thermally conductive sheet is such that the long axis direction is aligned with the thickness direction. The method is not particularly limited. In the case of rod-shaped particles, there is no particular limitation on the method of producing the thermally conductive sheet so that the long axis direction is aligned with the thickness direction. For example, the method described in Japanese Patent Laid-Open No. 2008-280496 can be used. Methods. Specifically, a sheet is produced using the composition, and the sheets are laminated to produce a laminated body, so that the side end surface of the laminated body (for example, with respect to the normal line from the main surface of the laminated body) is 0°. ~30° angle) (hereinafter also referred to as "laminated sectioning method").
再者，於使用所述積層切片法的情況下，用作原料的石墨粒子（A）的粒徑以質量平均粒徑計而較佳為熱傳導片的平均厚度的1/2倍以上，亦可超過平均厚度。關於用作原料的石墨粒子（A）的粒徑亦可超過熱傳導片的平均厚度的理由，其原因在於：例如即便包含超過熱傳導片的平均厚度的粒徑的石墨粒子（A），連同石墨粒子（A）一起也進行切片而形成熱傳導片，因此，結果石墨粒子（A）不自熱傳導片的表面突出。另外，若如此連同石墨粒子（A）一起進行切片，則產生許多於熱傳導片的厚度方向貫通的石墨粒子（A），形成極其有效的熱傳導通路，有熱傳導性進一步提昇的傾向。Furthermore, when the laminated slicing method is used, the particle diameter of the graphite particles (A) used as the raw material is preferably 1/2 times or more of the average thickness of the thermally conductive sheet in terms of mass average particle diameter, or it may be More than average thickness. The reason why the particle diameter of the graphite particles (A) used as the raw material may exceed the average thickness of the thermally conductive sheet is because, for example, even if graphite particles (A) with a particle diameter exceeding the average thickness of the thermally conductive sheet are included, together with the graphite particles (A) is also sliced together to form a thermally conductive sheet. Therefore, the graphite particles (A) do not protrude from the surface of the thermally conductive sheet. In addition, if the graphite particles (A) are sliced together in this way, a large number of graphite particles (A) penetrating in the thickness direction of the thermal conductive sheet will be generated, forming an extremely effective thermal conduction path, and the thermal conductivity will tend to be further improved.
於使用積層切片法的情況下，用作原料的石墨粒子（A）的粒徑以質量平均粒徑計而更佳為熱傳導片的平均厚度的1倍～5倍，進而佳為2倍～4倍。若石墨粒子（A）的質量平均粒徑為熱傳導片的平均厚度的1倍以上，則形成進而有效的熱傳導通路，熱傳導性進一步提昇。若為熱傳導片的平均厚度的5倍以下，則可抑制石墨粒子（A）於熱傳導片的表面部佔據的面積過大，從而可抑制密接性的降低。When the laminated slicing method is used, the particle diameter of the graphite particles (A) used as the raw material is more preferably 1 to 5 times the average thickness of the thermally conductive sheet in terms of mass average particle diameter, and further preferably 2 to 4 times. times. If the mass average particle diameter of the graphite particles (A) is more than one time the average thickness of the thermal conductive sheet, a more effective thermal conduction path will be formed, and the thermal conductivity will be further improved. If it is 5 times or less the average thickness of the thermally conductive sheet, it is possible to prevent the graphite particles (A) from occupying an excessively large area on the surface of the thermally conductive sheet, thereby suppressing deterioration in adhesion.
石墨粒子（A）的質量平均粒徑（D50）於使用適應雷射繞射．散射法的雷射繞射式粒度分佈裝置（例如，日機裝股份有限公司的「Microtrac Series MT3300」）測定並自小粒徑側描繪重量累積粒度分佈曲線的情況下，與重量累積成為50%的粒徑相對應。The mass average particle diameter (D50) of graphite particles (A) is adapted to laser diffraction. When the scattering method is measured with a laser diffraction particle size distribution device (for example, Nikkiso Co., Ltd.'s "Microtrac Series MT3300") and a weight-cumulative particle size distribution curve is drawn from the small particle size side, the weight-cumulative ratio becomes 50% corresponding to the particle size.
熱傳導片亦可包含鱗片狀粒子、橢圓體狀粒子及棒狀粒子以外的石墨粒子，亦可包含球狀石墨粒子、人造石墨粒子、薄片化石墨粒子、酸處理石墨粒子、膨脹石墨粒子、碳纖維片（flake）等。 石墨粒子（A）較佳為鱗片狀粒子，就結晶度高且容易獲得大粒徑的鱗片的觀點而言，較佳為將經片化的膨脹石墨粉粹而獲得的鱗片狀的膨脹石墨粒子。 The thermally conductive sheet may also contain graphite particles other than scaly particles, ellipsoidal particles, and rod-shaped particles, and may also contain spherical graphite particles, artificial graphite particles, flaked graphite particles, acid-treated graphite particles, expanded graphite particles, and carbon fiber sheets. (flake) etc. The graphite particles (A) are preferably flaky particles, and from the viewpoint of high crystallinity and easy acquisition of large-diameter flakes, flaky expanded graphite particles obtained by pulverizing flaked expanded graphite are preferred. .
例如，就熱傳導性與密接性的平衡的觀點而言，熱傳導片中的石墨粒子（A）的含有率較佳為15體積%～50體積%，更佳為20體積%～45體積%，進而佳為25體積%～40體積%。 若石墨粒子（A）的含有率為15體積%以上，則有熱傳導性提昇的傾向。另外，若石墨粒子（A）的含有率為50體積%以下，則有可抑制黏著性及密接性的降低的傾向。 再者，於熱傳導片含有鱗片狀粒子、橢圓體狀粒子及棒狀粒子以外的石墨粒子的情況下，石墨粒子整體的含有率較佳為所述範圍。 For example, from the viewpoint of the balance between thermal conductivity and adhesion, the content rate of graphite particles (A) in the thermal conductive sheet is preferably 15% to 50% by volume, more preferably 20% to 45% by volume, and further Preferably, it is 25% by volume to 40% by volume. When the content of graphite particles (A) is 15% by volume or more, thermal conductivity tends to increase. In addition, when the content of graphite particles (A) is 50 volume % or less, there is a tendency to suppress decreases in adhesiveness and adhesion. Furthermore, when the thermally conductive sheet contains graphite particles other than scaly particles, ellipsoidal particles, and rod-like particles, the content rate of the entire graphite particles is preferably within the above range.
石墨粒子（A）的含有率（體積%）為利用下式而求出的值。 石墨粒子（A）的含有率（體積%）=[（Aw/Ad）/｛（Aw/Ad）＋（Xw/Xd）｝]×100 Aw：石墨粒子（A）的質量組成（質量%） Xw：其他任意成分的質量組成（質量%） Ad：石墨粒子（A）的密度（本揭示中Ad以2.1進行計算） Xd：其他任意成分的密度 The content rate (volume %) of graphite particles (A) is a value calculated using the following formula. Content rate of graphite particles (A) (volume %) = [(Aw/Ad)/{(Aw/Ad) + (Xw/Xd)}] × 100 Aw: Mass composition of graphite particles (A) (mass %) Xw: Mass composition of other arbitrary components (mass %) Ad: Density of graphite particles (A) (Ad is calculated as 2.1 in this disclosure) Xd: Density of other arbitrary components
＜於25℃下為液狀的成分（B）＞ 本揭示的熱傳導片亦可含有於25℃下為液狀的成分（以下，亦稱為「液狀成分（B）」）。於本揭示中所謂「於25℃下為液狀」，是指於25℃下顯示流動性與黏性、且作為顯示黏性的尺度的黏度於25℃下為0.0001 Pa·s～1000 Pa·s的物質。於本揭示中所謂「黏度」，定義為於25℃下使用流變儀以5.0 s -1的剪切速度測定時的值。詳細而言，「黏度」是作為剪切黏度，使用安裝有錐板（直徑為40 mm、圓錐角為0°）的旋轉式剪切黏度計，於溫度25℃下測定。 <Component (B) that is liquid at 25° C.> The heat conductive sheet of the present disclosure may contain a component that is liquid at 25° C. (hereinafter, also referred to as “liquid component (B)”). In this disclosure, "liquid at 25°C" means that it exhibits fluidity and viscosity at 25°C, and the viscosity as a measure of viscosity is 0.0001 Pa·s to 1000 Pa· at 25°C. s substance. The so-called "viscosity" in this disclosure is defined as the value measured using a rheometer at a shear rate of 5.0 s -1 at 25°C. Specifically, "viscosity" is measured as shear viscosity at a temperature of 25°C using a rotational shear viscometer equipped with a cone and plate (diameter: 40 mm, cone angle: 0°).
液狀成分（B）的25℃下的黏度較佳為0.001 Pa·s～100 Pa·s，更佳為0.01 Pa·s～10 Pa·s。The viscosity of the liquid component (B) at 25°C is preferably 0.001 Pa·s to 100 Pa·s, more preferably 0.01 Pa·s to 10 Pa·s.
液狀成分（B）只要於25℃下為液狀，則並無特別限制，較佳為高分子化合物（聚合物）。作為液狀成分（B），可列舉：聚丁烯、聚異戊二烯、聚硫醚、丙烯腈橡膠、矽酮橡膠、烴樹脂、萜烯樹脂、丙烯酸樹脂等。其中，就耐熱性的觀點而言，液狀成分（B）較佳為包含聚丁烯。液狀成分（B）可單獨使用一種，亦可併用兩種以上。The liquid component (B) is not particularly limited as long as it is liquid at 25° C., but is preferably a high molecular compound (polymer). Examples of the liquid component (B) include polybutene, polyisoprene, polysulfide, acrylonitrile rubber, silicone rubber, hydrocarbon resin, terpene resin, acrylic resin, and the like. Among them, from the viewpoint of heat resistance, the liquid component (B) preferably contains polybutene. One type of liquid component (B) may be used alone, or two or more types may be used in combination.
此處，聚丁烯是指將異丁烯或正丁烯聚合而獲得的聚合體。亦包含將異丁烯與正丁烯共聚而獲得的聚合體。作為結構，是指具有「-CH 2-C(CH 3) 2-」或「-CH 2-CH(CH 2CH 3)-」所表示的結構單元的聚合體。有時亦稱為聚異丁烯。聚丁烯只要包含所述結構即可，關於其他結構並無特別限制。 Here, polybutene refers to a polymer obtained by polymerizing isobutylene or n-butene. Also included are polymers obtained by copolymerizing isobutylene and n-butylene. The structure refers to a polymer having a structural unit represented by "-CH 2 -C(CH 3 ) 2 -" or "-CH 2 -CH(CH 2 CH 3 )-". Sometimes also called polyisobutylene. As long as the polybutene contains the above-mentioned structure, other structures are not particularly limited.
作為聚丁烯，可列舉丁烯的均聚物、及丁烯與其他單體成分的共聚物。作為與其他單體成分的共聚物的例子，例如可列舉異丁烯與苯乙烯或異丁烯與乙烯的至少一者的共聚物。共聚物亦可為無規共聚物、嵌段共聚物及接枝共聚物的任一種。Examples of polybutene include homopolymers of butene and copolymers of butene and other monomer components. Examples of copolymers with other monomer components include at least one copolymer of isobutylene and styrene or isobutylene and ethylene. The copolymer may be any of a random copolymer, a block copolymer, and a graft copolymer.
作為聚丁烯，例如可列舉日油股份有限公司的「日油聚丁烯 TM·EMAWET（註冊商標）」、JXTG能源股份有限公司的「日石聚丁烯」、JXTG能源股份有限公司的「Tetrax」、JXTG能源股份有限公司的「Himol」、及巴工業股份有限公司的「聚異丁烯」。 Examples of the polybutene include NOF Co., Ltd.'s "NOF PolybuteneTM EMAWET (registered trademark)", JXTG Energy Co., Ltd.'s "Nissan Polybutene", JXTG Energy Co., Ltd.'s "Tetrax","Himol" of JXTG Energy Co., Ltd., and "Polyisobutylene" of Pakistan Industrial Co., Ltd.
認為液狀成分（B）例如主要兼具耐熱性及耐濕度性優異的應力緩和劑與黏著性賦予劑來發揮功能。另外，藉由與後述的熱熔劑（E）併用，有可進一步提高凝聚力及加熱時的流動性的傾向。It is thought that the liquid component (B) mainly functions as a stress relieving agent and a tackifier that is excellent in heat resistance and humidity resistance, for example. In addition, by using it in combination with a hot melt agent (E) described below, the cohesion force and the fluidity during heating tend to be further improved.
就進一步提高黏著力、密接性、片強度、耐水解性等的觀點而言，熱傳導片中的液狀成分（B）的含有率較佳為10體積%～55體積%，更佳為15體積%～50體積%，進而佳為20體積%～50體積%。 若液狀成分（B）的含有率為10體積%以上，則有黏著性及密接性進一步提昇的傾向。若液狀成分（B）的含有率為55體積%以下，則有可更有效地抑制片強度及熱傳導性的下降的傾向。 From the viewpoint of further improving the adhesion, adhesion, sheet strength, hydrolysis resistance, etc., the content rate of the liquid component (B) in the thermal conductive sheet is preferably 10% to 55% by volume, more preferably 15% by volume. % to 50 volume %, more preferably 20 volume % to 50 volume %. If the content of the liquid component (B) is 10% by volume or more, the adhesiveness and adhesion tend to be further improved. When the content rate of the liquid component (B) is 55% by volume or less, the decrease in sheet strength and thermal conductivity tends to be more effectively suppressed.
＜丙烯酸酯系高分子（C）＞ 熱傳導片亦可含有丙烯酸酯系高分子（C）。認為丙烯酸酯系高分子（C）例如主要兼具黏著性賦予劑與如厚度恢復以追隨翹曲的彈性賦予劑來發揮功能。 ＜Acrylic polymer (C)＞ The thermally conductive sheet may contain an acrylic polymer (C). The acrylic polymer (C) is considered to function mainly as a tackifier and an elasticity-imparting agent that follows warpage such as thickness recovery.
丙烯酸酯系高分子（C）例如可較佳地使用將丙烯酸丁酯、丙烯酸乙酯、丙烯腈、丙烯酸、甲基丙烯酸縮水甘油酯、丙烯酸-2-乙基己酯等作為主要的原料成分，視需要使丙烯酸甲酯等進行共聚而成的丙烯酸酯系高分子（所謂丙烯酸橡膠）。丙烯酸酯系高分子（C）可單獨使用一種，亦可併用兩種以上。The acrylate polymer (C) preferably uses butyl acrylate, ethyl acrylate, acrylonitrile, acrylic acid, glycidyl methacrylate, 2-ethylhexyl acrylate, etc. as the main raw material component. An acrylate-based polymer (so-called acrylic rubber) obtained by copolymerizing methyl acrylate or the like if necessary. One type of acrylic polymer (C) may be used alone, or two or more types may be used in combination.
丙烯酸酯系高分子（C）的重量平均分子量較佳為100,000～1,000,000，更佳為250,000～700,000，進而佳為400,000～600,000。若重量平均分子量為100,000以上，則有膜強度優異的傾向，若為1,000,000以下，則有柔軟性優異的傾向。 重量平均分子量可藉由凝膠滲透層析法並使用標準聚苯乙烯的校準曲線來測定。 The weight average molecular weight of the acrylic polymer (C) is preferably from 100,000 to 1,000,000, more preferably from 250,000 to 700,000, even more preferably from 400,000 to 600,000. When the weight average molecular weight is 100,000 or more, film strength tends to be excellent, and when it is 1,000,000 or less, flexibility tends to be excellent. The weight average molecular weight can be determined by gel permeation chromatography using a calibration curve of standard polystyrene.
丙烯酸酯系高分子（C）的玻璃轉移溫度（Tg）較佳為20℃以下，更佳為-70℃～0℃，進而佳為-50℃～-20℃。若玻璃轉移溫度為20℃以下，則有柔軟性及黏著性優異的傾向。 玻璃轉移溫度（Tg）可進行動態黏彈性測定（拉伸），並根據由此導出的tanδ來算出。 The glass transition temperature (Tg) of the acrylic polymer (C) is preferably 20°C or lower, more preferably -70°C to 0°C, and even more preferably -50°C to -20°C. If the glass transition temperature is 20°C or lower, flexibility and adhesion tend to be excellent. The glass transition temperature (Tg) can be calculated from tan δ derived from dynamic viscoelasticity measurement (tensile).
丙烯酸酯系高分子（C）可藉由內部添加而存在於熱傳導片整體，亦可藉由塗佈或含浸於表面而局部存在於表面。特別是若塗佈於單面或含浸於單面，則可僅對單面賦予強的黏性，因此就獲得操作性佳的片的方面而言較佳。The acrylic polymer (C) can be present in the entire thermally conductive sheet by internal addition, or can be partially present on the surface by coating or impregnation on the surface. In particular, coating or impregnation on one side is preferable in terms of obtaining a sheet with good handleability because strong adhesiveness can be imparted to only one side.
＜乙烯-α-烯烴共聚物（D）＞ 熱傳導片亦可含有乙烯-α-烯烴共聚物（D）。認為乙烯-α-烯烴共聚物（D）例如作為如厚度恢復以追隨翹曲的彈性賦予劑來發揮功能。 <Ethylene-α-olefin copolymer (D)> The thermally conductive sheet may also contain ethylene-α-olefin copolymer (D). The ethylene-α-olefin copolymer (D) is considered to function as an elasticity-imparting agent that follows warpage such as thickness recovery.
乙烯-α-烯烴共聚物（D）只要為乙烯與α-烯烴的共聚物即可，乙烯與α-烯烴的共聚比率並無特別限定。作為α-烯烴的種類，可列舉：丙烯、1-丁烯、1-己烯、1-辛烯。乙烯-α-烯烴共聚物（D）可單獨使用一種，亦可併用兩種以上。The ethylene-α-olefin copolymer (D) only needs to be a copolymer of ethylene and α-olefin, and the copolymerization ratio of ethylene and α-olefin is not particularly limited. Examples of α-olefins include propylene, 1-butene, 1-hexene, and 1-octene. One type of ethylene-α-olefin copolymer (D) may be used alone, or two or more types may be used in combination.
乙烯-α-烯烴共聚物（D）的分子量並無特別限制。乙烯-α-烯烴共聚物（D）的熔體質量流動速率（Melt mass flow rate，MFR）較佳為1 g/10 min～50 g/10 min，更佳為5 g/10 min～50 g/10 min，進而佳為20 g/10 min～40 g/10 min。若熔體質量流動速率（MFR）為1 g/10 min以上，則有流動性變良好，熱傳導片的150℃下的壓縮彈性係數不會過高，可良好地維持高溫時的柔軟性的傾向。若熔體質量流動速率（MFR）為50 g/10 min以下，則有流動性不過高，操作性提昇的傾向。再者，於本揭示中，只要無說明，則熔體質量流動速率（MFR）是指溫度190℃、負荷2.16 kg下的熔體質量流動速率（MFR）。熔體質量流動速率（MFR）的含義與熔融指數相同，成為乙烯-α-烯烴共聚物（D）的分子量的指標。將熔體質量流動速率（MFR）的測定方法示於JIS K 7210：1999中。The molecular weight of the ethylene-α-olefin copolymer (D) is not particularly limited. The melt mass flow rate (MFR) of the ethylene-α-olefin copolymer (D) is preferably 1 g/10 min～50 g/10 min, more preferably 5 g/10 min～50 g /10 min, preferably 20 g/10 min～40 g/10 min. If the melt mass flow rate (MFR) is 1 g/10 min or more, the fluidity will become good, the compression elastic coefficient of the thermal conductive sheet at 150°C will not be too high, and the flexibility at high temperatures will tend to be well maintained. . If the melt mass flow rate (MFR) is 50 g/10 min or less, the fluidity will not be too high and the operability will tend to improve. Furthermore, in this disclosure, unless otherwise specified, the melt mass flow rate (MFR) refers to the melt mass flow rate (MFR) at a temperature of 190°C and a load of 2.16 kg. The melt mass flow rate (MFR) has the same meaning as the melt index and becomes an indicator of the molecular weight of the ethylene-α-olefin copolymer (D). The measuring method of melt mass flow rate (MFR) is shown in JIS K 7210:1999.
作為可市售獲取的乙烯-α-烯烴共聚物（D），例如可列舉：陶氏化學（Dow Chemical）公司的聚烯烴·彈性體「Engage」、陶氏化學（Dow Chemical）公司的「EOR8407」、住友化學股份有限公司的「Esprene SPO」、住友化學股份有限公司的「Excellen FX」、住友化學股份有限公司的「Excellen VL」、普瑞曼聚合物（Prime Polymer）股份有限公司的「Neozex」、普瑞曼聚合物（Prime Polymer）股份有限公司的「Evolue」、及三井化學股份有限公司的「Lucant HC-3000X」。Examples of commercially available ethylene-α-olefin copolymers (D) include polyolefin elastomer "Engage" from Dow Chemical Company, "EOR8407" from Dow Chemical Company ", Sumitomo Chemical Co., Ltd.'s "Esprene SPO", Sumitomo Chemical Co., Ltd.'s "Excellen FX", Sumitomo Chemical Co., Ltd.'s "Excellen VL", Prime Polymer Co., Ltd.'s "Neozex" ", Prime Polymer Co., Ltd.'s "Evolue", and Mitsui Chemicals Co., Ltd.'s "Lucant HC-3000X".
例如，就較佳地賦予彈性的觀點而言，熱傳導片中的乙烯-α-烯烴共聚物（D）的含有率較佳為2體積%～20體積%，更佳為3體積%～10體積%。若乙烯-α-烯烴共聚物（D）的含有率為20體積%以下，則熱傳導片不會過硬，有可抑制彈性係數增加的傾向。For example, from the viewpoint of better imparting elasticity, the content rate of the ethylene-α-olefin copolymer (D) in the thermally conductive sheet is preferably 2 to 20 volume %, and more preferably 3 to 10 volume %. %. If the content of the ethylene-α-olefin copolymer (D) is 20% by volume or less, the thermally conductive sheet will not be too hard and the elastic coefficient will tend to be suppressed from increasing.
＜熱熔劑（E）＞ 熱傳導片亦可含有熱熔劑（E）。熱熔劑（E）具有提高熱傳導片的強度、及提高加熱時的流動性的效果。 ＜Hot melt (E)＞ Thermal conductive sheets may also contain hot melt (E). The hot melt agent (E) has the effect of improving the strength of the heat conduction sheet and improving the fluidity during heating.
作為熱熔劑（E），例如可列舉：芳香族系石油樹脂、萜烯酚醛樹脂（terpene-phenol resin）、及環戊二烯系石油樹脂。另外，熱熔劑（E）亦可為氫化芳香族系石油樹脂、或氫化萜烯酚醛樹脂。熱熔劑（E）可單獨使用一種，亦可併用兩種以上。Examples of the hot melt agent (E) include aromatic petroleum resin, terpene-phenol resin, and cyclopentadiene petroleum resin. In addition, the hot melt agent (E) may also be hydrogenated aromatic petroleum resin or hydrogenated terpene phenolic resin. One type of hot melt agent (E) may be used alone, or two or more types may be used in combination.
其中，於使用聚丁烯作為液狀成分（B）的情況下，熱熔劑（E）較佳為包含選自由氫化芳香族系石油樹脂、及氫化萜烯酚醛樹脂所組成的群組中的至少一種。該些熱熔劑（E）的穩定性高，且與聚丁烯的相容性優異，因此於構成熱傳導片的情況下，有可達成更優異的熱傳導性、柔軟性、及操作性的傾向。Among them, when polybutene is used as the liquid component (B), the hot melt agent (E) preferably contains at least one selected from the group consisting of hydrogenated aromatic petroleum resin and hydrogenated terpene phenolic resin. One kind. These hot melt agents (E) have high stability and excellent compatibility with polybutene, and therefore tend to achieve better thermal conductivity, flexibility, and handleability when constituting a thermally conductive sheet.
作為可市售獲取的氫化芳香族系石油樹脂，例如可列舉荒川化學工業股份有限公司的「alcon」、及出光興產股份有限公司的「imarv」。另外，作為可市售獲取的氫化萜烯酚醛樹脂，例如可列舉安原化工（Yasuhara chemical）股份有限公司的「Clearon」。另外，作為可市售獲取的環戊二烯系石油樹脂，例如可列舉日本瑞翁（zeon）股份有限公司的「Quinton」、及丸善石油化學股份有限公司的「Marukarez」。Examples of commercially available hydrogenated aromatic petroleum resins include "alcon" from Arakawa Chemical Industry Co., Ltd. and "imarv" from Idemitsu Kosan Co., Ltd. Examples of commercially available hydrogenated terpene phenolic resins include "Clearon" from Yasuhara Chemical Co., Ltd. Examples of commercially available cyclopentadiene-based petroleum resins include "Quinton" from Zeon Co., Ltd. and "Marukarez" from Maruzen Petrochemical Co., Ltd.
熱熔劑（E）較佳為於25℃下為固形，軟化溫度為40℃～150℃。若使用熱塑性樹脂作為熱熔劑（E），則熱壓接時的軟化流動性提昇，結果有密接性提昇的傾向。另外，若軟化溫度為40℃以上，則可保持室溫附近的凝聚力，結果有容易獲得所需的片強度且操作性優異的傾向。若軟化溫度為150℃以下，則熱壓接時的軟化流動性變高，結果有密接性提昇的傾向。軟化溫度更佳為60℃～120℃。再者，軟化溫度可藉由環球法（JIS K 2207：1996）來測定。The hot melt agent (E) is preferably solid at 25°C and has a softening temperature of 40°C to 150°C. If a thermoplastic resin is used as the hot melt agent (E), the softening fluidity during thermocompression bonding is improved, and as a result, the adhesiveness tends to be improved. In addition, if the softening temperature is 40° C. or higher, the cohesion force near room temperature can be maintained, and as a result, the required sheet strength tends to be easily obtained and the workability is excellent. When the softening temperature is 150° C. or lower, the softening fluidity during thermocompression bonding becomes high, and as a result, the adhesiveness tends to be improved. The softening temperature is preferably 60°C to 120°C. Furthermore, the softening temperature can be measured by the ring and ball method (JIS K 2207: 1996).
就提高黏著力、密接性、片強度等的觀點而言，熱傳導片中的熱熔劑（E）的含有率較佳為3體積%～25體積%，更佳為5體積%～20體積%，進而佳為5體積%～15體積%。 若熱熔劑（E）的含有率為3體積%以上，則有黏著力、加熱流動性、片強度等變充分的傾向，若為25體積%以下，則有柔軟性變充分且操作性及耐熱循環性優異的傾向。 From the viewpoint of improving adhesion, adhesion, sheet strength, etc., the content rate of the hot melt agent (E) in the thermally conductive sheet is preferably 3% to 25% by volume, more preferably 5% to 20% by volume. More preferably, it is 5% by volume to 15% by volume. If the content rate of the hot melt agent (E) is 3% by volume or more, the adhesive force, heating fluidity, sheet strength, etc. tend to become sufficient. If it is 25% by volume or less, the flexibility becomes sufficient and the workability and heat resistance are likely to be sufficient. Tend to have excellent cyclic properties.
＜抗氧化劑（F）＞ 熱傳導片例如亦可出於賦予高溫時的熱穩定性的目的而含有抗氧化劑（F）。作為抗氧化劑（F），可列舉：酚系抗氧化劑、磷系抗氧化劑、胺系抗氧化劑、硫系抗氧化劑、肼系抗氧化劑、醯胺系抗氧化劑等。抗氧化劑（F）可根據所使用的溫度條件等來適宜選擇，更佳為酚系抗氧化劑。抗氧化劑（F）可單獨使用一種，亦可併用兩種以上。 ＜Antioxidant (F)＞ The thermally conductive sheet may contain an antioxidant (F) for the purpose of providing thermal stability at high temperatures, for example. Examples of antioxidants (F) include phenolic antioxidants, phosphorus antioxidants, amine antioxidants, sulfur antioxidants, hydrazine antioxidants, amide antioxidants, and the like. The antioxidant (F) can be appropriately selected according to the temperature conditions used, etc., and a phenolic antioxidant is more preferred. One type of antioxidant (F) may be used alone, or two or more types may be used in combination.
作為可市售獲取的酚系抗氧化劑，例如可列舉艾迪科（ADEKA）股份有限公司的adekastab AO-50、adekastab AO-60、及adekastab AO-80。Examples of commercially available phenolic antioxidants include adekastab AO-50, adekastab AO-60, and adekastab AO-80 from ADEKA Co., Ltd.
熱傳導片中的抗氧化劑（F）的含有率並無特別限制，較佳為0.1體積%～5體積%，更佳為0.2體積%～3體積%以下，進而佳為0.3體積%～1體積%以下。若抗氧化劑（F）的含有率為0.1體積%以上，則有可充分獲得抗氧化效果的傾向。若抗氧化劑（F）的含有率為5體積%以下，則有可抑制熱傳導片的強度降低的傾向。The content rate of the antioxidant (F) in the thermally conductive sheet is not particularly limited, but is preferably 0.1% to 5% by volume, more preferably 0.2% to 3% by volume, and even more preferably 0.3% to 1% by volume. the following. When the content rate of the antioxidant (F) is 0.1% by volume or more, the antioxidant effect tends to be sufficiently obtained. When the content of the antioxidant (F) is 5% by volume or less, the strength of the thermally conductive sheet tends to be suppressed from decreasing.
＜其他成分＞ 熱傳導片亦可根據目的而含有石墨粒子（A）、液狀成分（B）、丙烯酸酯系高分子（C）、乙烯-α-烯烴共聚物（D）、熱熔劑（E）、及抗氧化劑（F）以外的其他成分。例如，熱傳導片亦可出於賦予阻燃性的目的而含有阻燃劑。阻燃劑並無特別限定，可自通常所使用的阻燃劑中適宜選擇。例如可列舉紅磷系阻燃劑及磷酸酯系阻燃劑。其中，就安全性優異、藉由塑化效果而密接性提昇的觀點而言，較佳為磷酸酯系阻燃劑。 ＜Other ingredients＞ The thermal conductive sheet may also contain graphite particles (A), liquid component (B), acrylic polymer (C), ethylene-α-olefin copolymer (D), hot melt agent (E), and antioxidant depending on the purpose. Ingredients other than (F). For example, the thermally conductive sheet may contain a flame retardant for the purpose of imparting flame retardancy. The flame retardant is not particularly limited and can be appropriately selected from commonly used flame retardants. Examples include red phosphorus flame retardants and phosphate ester flame retardants. Among them, phosphate ester flame retardants are preferred from the viewpoint of excellent safety and improved adhesion due to the plasticizing effect.
作為紅磷系阻燃劑，除純粹的紅磷粒子以外，亦可出於提高安全性或穩定性的目的來使用施加各種塗佈者、進行母料化而成者等。具體可列舉磷化學工業股份有限公司的novared、novaexcel、novakuel、novaperet（均為商品名）等。As the red phosphorus-based flame retardant, in addition to pure red phosphorus particles, those coated with various coatings or masterbatch-formed for the purpose of improving safety or stability can also be used. Specific examples include novared, novaexcel, novakuel, and novaperet (all are trade names) of Phosphorus Chemical Industry Co., Ltd.
作為磷酸酯系阻燃劑，可列舉：磷酸三甲酯、磷酸三乙酯、磷酸三丁酯等脂肪族磷酸酯；磷酸三苯酯、磷酸三甲苯酯、磷酸甲苯二苯酯、磷酸三（二甲苯）酯（trixylenyl phosphate）、磷酸甲苯二（2,6-二甲苯）酯（cresyl di 2,6-xylenyl phospahte）、磷酸三（第三丁基化苯基）酯、磷酸三（異丙基化苯基）酯、磷酸三芳基異丙基化物等芳香族磷酸酯；磷酸間苯二酚雙二苯酯（resorcinol bisdiphenyl phosphate）、雙酚A雙（磷酸二苯酯） （bisphenol-A bis(diphenyl phosphate)）、磷酸間苯二酚雙二（二甲苯）酯（resorcinol bis(dixylenyl phosphate)）等芳香族縮合磷酸酯等。 該些中就耐水解性優異、且藉由塑化效果而提昇密接性的效果優異的觀點而言，較佳為雙酚A雙（磷酸二苯酯）。 Examples of phosphate-based flame retardants include aliphatic phosphates such as trimethyl phosphate, triethyl phosphate, and tributyl phosphate; triphenyl phosphate, tricresyl phosphate, diphenyl toluene phosphate, and tris(phosphate). trixylenyl phosphate, cresyl di 2,6-xylenyl phospahte, tris(tert-butylated phenyl) phosphate, tris(isopropyl phosphate) Aromatic phosphates such as phenyl esters and triarylisopropyl phosphates; resorcinol bisdiphenyl phosphate, bisphenol-A bis (diphenyl phosphate)), resorcinol bis(dixylenyl phosphate) and other aromatic condensed phosphates. Among these, bisphenol A bis(diphenyl phosphate) is preferable from the viewpoint of being excellent in hydrolysis resistance and having an excellent effect of improving adhesion through a plasticizing effect.
熱傳導片中的阻燃劑的含有率並無限制，可以使阻燃性發揮的量使用，較佳為設為30體積%以下程度，就抑制由阻燃劑成分於熱傳導片的表面滲出而引起的熱阻的惡化的觀點而言，較佳為設為20體積%以下。The content rate of the flame retardant in the thermally conductive sheet is not limited. It can be used in an amount that exerts flame retardancy. It is preferably about 30% by volume or less to suppress the flame retardant component from seeping out on the surface of the thermally conductive sheet. From the viewpoint of deterioration of thermal resistance, it is preferable to set it to 20 volume % or less.
熱傳導片的平均厚度並無特別限制，可根據目的而適宜選擇。熱傳導片的厚度可根據所使用的半導體封裝等的規格來適宜選擇。厚度越小則有熱阻越降低的傾向，厚度越大則有翹曲追隨性越提昇的傾向。熱傳導片的平均厚度可為50 μm～3000 μm，就熱傳導性及密接性的觀點而言，較佳為100 μm～500 μm，更佳為200 μm～400 μm。熱傳導片的平均厚度是使用測微計來測定3個部位的厚度，並以其算術平均值的形式來提供。The average thickness of the thermally conductive sheet is not particularly limited and can be appropriately selected depending on the purpose. The thickness of the thermally conductive sheet can be appropriately selected according to the specifications of the semiconductor package to be used. Thermal resistance tends to decrease as the thickness becomes smaller, and the warp followability tends to improve as the thickness increases. The average thickness of the thermally conductive sheet can be 50 μm to 3000 μm. From the viewpoint of thermal conductivity and adhesion, it is preferably 100 μm to 500 μm, and more preferably 200 μm to 400 μm. The average thickness of the thermally conductive sheet is measured at three locations using a micrometer and is provided as the arithmetic mean.
熱傳導片亦可於至少其中一面具有保護膜，較佳為於兩面具有保護膜。藉此可保護熱傳導片的黏著面。The thermally conductive sheet may also have a protective film on at least one side, and preferably has protective films on both sides. This protects the adhesive surface of the thermally conductive sheet.
保護膜例如可使用聚乙烯、聚酯、聚丙烯、聚對苯二甲酸乙二酯、聚醯亞胺、聚醚醯亞胺、聚醚萘二甲酸酯、甲基戊烯等樹脂膜，塗料紙、塗料布、及鋁等金屬箔。該些保護膜可單獨使用一種，亦可組合兩種以上而製成多層膜。保護膜較佳為以矽酮系、二氧化矽系等的脫模劑等進行表面處理。For example, resin films such as polyethylene, polyester, polypropylene, polyethylene terephthalate, polyimide, polyetherimide, polyether naphthalate, and methylpentene can be used as the protective film. Coated paper, coated cloth, and aluminum and other metal foils. One type of these protective films may be used alone, or two or more types may be combined to form a multilayer film. The protective film is preferably surface-treated with a silicone-based, silicon dioxide-based release agent, or the like.
本揭示的熱傳導片在150℃下的壓縮應力為0.1 MPa時的彈性係數為1.4 MPa以下，且在25℃下的黏力為5.0 N·mm以上。認為藉由彈性係數及黏力滿足所述範圍，於翹曲量增大的半導體封裝中可相對於發熱體及散熱體維持密接，從而可維持接著面積。The thermally conductive sheet disclosed in this disclosure has an elastic coefficient of 1.4 MPa or less when the compressive stress at 150°C is 0.1 MPa, and an adhesive force of 5.0 N·mm or more at 25°C. It is considered that when the elastic coefficient and adhesive force satisfy the above range, close contact with the heating element and the heat sink can be maintained in a semiconductor package with an increased amount of warpage, thereby maintaining the contact area.
若在150℃下的壓縮應力為0.1 MPa時的彈性係數為1.4 MPa以下，則柔軟性優異，於密接於發熱體與散熱體時的高溫按壓條件下熱傳導片容易壓潰（crush），更容易密接於發熱體與散熱體。進而，即便於在高溫按壓後封裝恢復至常溫時產生的翹曲增大的半導體封裝中，熱傳導片亦可穩定地密接於發熱體及散熱體，抑制接著面積的降低。If the elastic coefficient when the compressive stress at 150°C is 0.1 MPa is 1.4 MPa or less, the flexibility will be excellent, and the thermal conductive sheet will be easily crushed under the high-temperature pressing conditions when in close contact with the heating element and the radiator, making it easier to Closely connected to the heating element and radiator. Furthermore, even in a semiconductor package in which warpage increases when the package returns to normal temperature after high-temperature pressing, the thermally conductive sheet can be stably in close contact with the heating element and the heat sink, thereby suppressing a reduction in the bonding area.
本揭示的熱傳導片在150℃下的壓縮應力為0.1 MPa時的彈性係數較佳為1.4 MPa以下，更佳為1.3 MPa以下，進而佳為1.2 MPa以下。若所述壓縮彈性係數為1.2 MPa以下，則密接性進一步提昇，容易追隨翹曲。在150℃下的壓縮應力為0.1 MPa時的彈性係數的下限並無特別限制。所述壓縮彈性係數可為0.5 MPa以上，亦可為0.7 MPa以上。When the compressive stress of the heat conductive sheet of the present disclosure is 0.1 MPa at 150°C, the elastic coefficient is preferably 1.4 MPa or less, more preferably 1.3 MPa or less, and even more preferably 1.2 MPa or less. If the compression elastic coefficient is 1.2 MPa or less, the adhesion will be further improved and the warpage will be easily followed. The lower limit of the elastic coefficient when the compressive stress at 150°C is 0.1 MPa is not particularly limited. The compression elastic coefficient may be 0.5 MPa or more, or 0.7 MPa or more.
熱傳導片的壓縮彈性係數可使用壓縮試驗裝置（例如，INSTRON 5948 Micro Tester（英斯特朗（INSTRON）公司））來測定。對熱傳導片於厚度方向施加負荷來測定位移（mm）與負荷（N）。於橫軸表示藉由位移（mm）/厚度（mm）而求出的應變（無因次（dimensionless）），於縱軸表示藉由負荷（N）/面積（mm 2）而求出的應力（MPa），將規定應力時的斜度設為壓縮彈性係數（MPa）。具體而言，例如可利用實施例中記載的方法來進行測定。 The compressive elastic coefficient of the thermally conductive sheet can be measured using a compression test device (for example, INSTRON 5948 Micro Tester (INSTRON Corporation)). Apply a load to the thermally conductive sheet in the thickness direction to measure the displacement (mm) and load (N). The horizontal axis represents the strain (dimensionless) calculated by displacement (mm)/thickness (mm), and the vertical axis represents the stress calculated by load (N)/area (mm 2 ). (MPa), and the slope at a specified stress is set as the compression elastic coefficient (MPa). Specifically, for example, the method described in the Examples can be used for measurement.
熱傳導片的25℃下的黏力為5.0 N·mm以上，較佳為6.0 N·mm以上，更佳為7.0 N·mm以上。若黏力為5.0 N·mm以上，則可抑制於產生翹曲而發熱體與散熱體的間隔增大時熱傳導片自發熱體及散熱體剝離。黏力的上限值並無特別限制。所述黏力可為20.0 N·mm以下，亦可為15.0 N·mm以下。The adhesive force of the thermally conductive sheet at 25°C is 5.0 N·mm or more, preferably 6.0 N·mm or more, more preferably 7.0 N·mm or more. If the adhesive force is 5.0 N·mm or more, the thermal conductive sheet can be prevented from peeling off from the heating element and the radiator when warpage occurs and the distance between the heating element and the radiator increases. The upper limit of the adhesive force is not particularly limited. The adhesive force may be 20.0 N·mm or less, or 15.0 N·mm or less.
熱傳導片的25℃下的黏力可使用萬能物性試驗機（例如，物性測定儀（texture analyser），（英弘精機股份有限公司））來測定。於25℃（常溫）下，以負荷40 N將直徑7 mm的探針抵接於熱傳導片並保持10秒鐘後，將提拉探針時的負荷與位移曲線加以積分，將所得的面積設為25℃下的黏力（N·mm）。The viscosity of the thermally conductive sheet at 25°C can be measured using a universal physical testing machine (for example, texture analyzer (Eiko Seiki Co., Ltd.)). At 25°C (normal temperature), a probe with a diameter of 7 mm is brought into contact with the heat conductive sheet with a load of 40 N and held for 10 seconds. The load and displacement curves when the probe is pulled are integrated, and the resulting area is set to is the viscosity at 25°C (N·mm).
獲得在150℃下的壓縮應力為0.1 MPa時的彈性係數為1.4 MPa以下且在25℃下的黏力為5.0 N·mm以上的熱傳導片的方法並無特別限制，例如可藉由調整熱傳導片中所使用的各成分的調配比例來獲得。There is no particular restriction on the method of obtaining a thermal conductive sheet with an elastic coefficient of 1.4 MPa or less when the compressive stress at 150°C is 0.1 MPa and a viscosity of 5.0 N·mm or more at 25°C. For example, the thermal conductive sheet can be adjusted Obtained by the blending ratio of each ingredient used in.
若熱傳導片不自發熱體及散熱體剝離而可維持接著面積，則可抑制接觸熱阻增大，可抑制散熱裝置整體的散熱特性降低。因而，理想的是即便於發熱體發生翹曲，亦可維持熱傳導片與發熱體及散熱體的接著面積。If the thermally conductive sheet can maintain the contact area without peeling off the heating element and the heat sink, the increase in contact thermal resistance can be suppressed, and the decrease in the heat dissipation characteristics of the entire heat dissipation device can be suppressed. Therefore, it is desirable to maintain the contact area between the heat conductive sheet, the heating element, and the heat sink even if the heating element warps.
熱傳導片的用途並無特別限定。本揭示的熱傳導片特別適於作為將半導體晶片設為發熱體並將散熱器設為散熱體時的介隔存在有半導體晶片與散熱器的熱傳導片（TIM1；Thermal Interface Material 1）。特別是本揭示的熱傳導片即便伴隨例如安裝過程的加熱及冷卻而翹曲量發生變動，亦可追隨翹曲而維持與半導體晶片及散熱器的充分的接著面積。藉此，於翹曲量增大的半導體封裝中亦可保證優異的散熱特性。該理由未必明確，但考慮如下。本揭示的熱傳導片在150℃下的壓縮應力為0.1 MPa時的彈性係數為1.4 MPa以下，25℃下的黏力為5.0 N·mm以上。認為根據該些特性，若於半導體晶片上經由熱傳導片而設置散熱器來進行高溫按壓，則熱傳導片充分壓潰，並且熱傳導片充分地接著於半導體晶片及散熱器。因此，認為即便因之後的冷卻而翹曲量發生變化，亦可追隨翹曲而維持接著面積。The use of the thermally conductive sheet is not particularly limited. The thermally conductive sheet of the present disclosure is particularly suitable as a thermally conductive sheet (TIM1; Thermal Interface Material 1) in which a semiconductor wafer is used as a heat generator and a heat sink is used as a heat sink, with the semiconductor chip and the heat sink interposed therebetween. In particular, the thermally conductive sheet disclosed in the present disclosure can follow the warpage and maintain a sufficient contact area with the semiconductor chip and the heat sink even if the amount of warpage changes due to heating and cooling during the mounting process, for example. This ensures excellent heat dissipation characteristics even in semiconductor packages with increased warpage. The reason is not necessarily clear, but consider it as follows. The thermally conductive sheet disclosed in this disclosure has an elastic coefficient of less than 1.4 MPa when the compressive stress is 0.1 MPa at 150°C, and a viscous force of more than 5.0 N·mm at 25°C. It is considered that based on these characteristics, if a heat sink is provided on the semiconductor wafer via a heat conductive sheet and high-temperature pressing is performed, the heat conductive sheet will be fully crushed and the heat conductive sheet will be fully adhered to the semiconductor wafer and the heat sink. Therefore, it is considered that even if the amount of warpage changes due to subsequent cooling, the bonded area can be maintained following the warpage.
〔熱傳導片的製造方法〕 熱傳導片的製造方法只要可獲得具有所述構成者，則並無特別限制。作為熱傳導片的製造方法，例如可列舉以下的方法。 [Method for manufacturing thermal conductive sheet] The manufacturing method of the thermally conductive sheet is not particularly limited as long as one having the above-mentioned structure can be obtained. Examples of methods for manufacturing a thermally conductive sheet include the following methods.
於一實施形態中，熱傳導片的製造方法具有：準備含有石墨粒子（A）與任意的其他成分的組成物的步驟（亦稱為「準備步驟」）、將所述組成物片化而獲得片的步驟（亦稱為「片製作步驟」）、製作所述片的積層體的步驟（亦稱為「積層體製作步驟」）、以及對所述積層體的側端面進行切片的步驟（亦稱為「切片步驟」）。另外，熱傳導片的製造方法亦可進而具有將切片步驟中所獲得的切割片貼附於保護膜而加以層壓的步驟（亦稱為「層壓步驟」）。In one embodiment, a method for manufacturing a thermally conductive sheet includes: preparing a composition containing graphite particles (A) and optional other components (also referred to as a "preparation step"); and converting the composition into sheets to obtain sheets. a step (also called a "sheet making step"), a step of making a laminated body of the sheet (also called a "laminated body making step"), and a step of slicing the side end surface of the laminated body (also called a "laminated body making step") is the "slicing step"). In addition, the manufacturing method of the thermally conductive sheet may further include a step of attaching the cut sheet obtained in the slicing step to a protective film and laminating it (also referred to as a "lamination step").
藉由利用所述方法製造熱傳導片，容易形成有效的熱傳導通路，因此有可獲得高熱傳導性與密接性優異的熱傳導片的傾向。By manufacturing a thermally conductive sheet using the method described above, it is easy to form an effective thermally conductive path, and therefore a thermally conductive sheet with high thermal conductivity and excellent adhesion tends to be obtained.
＜準備步驟＞ 於準備步驟中，準備含有石墨粒子（A）與任意的其他成分（例如，於25℃下為液狀的成分（B）、丙烯酸酯系高分子（C）、乙烯-α-烯烴共聚物（D）、熱熔劑（E）、抗氧化劑（F）、其他成分）的組成物。作為調配各成分的方法，只要可均勻地混合各成分，則可使用任一方法，並無特別限定。另外，組成物亦可獲取市售者來準備。組成物的製備的詳情可參照日本專利特開2008-280496號公報的段落[0033]。 ＜Preparation steps＞ In the preparation step, a material containing graphite particles (A) and optional other components (for example, a component (B) that is liquid at 25° C., an acrylate polymer (C), and an ethylene-α-olefin copolymer ( D), hot melt agent (E), antioxidant (F), other ingredients). As a method of preparing each component, any method can be used and is not particularly limited as long as each component can be mixed uniformly. In addition, the composition can also be obtained from a commercial seller and prepared. For details on preparation of the composition, refer to paragraph [0033] of Japanese Patent Application Laid-Open No. 2008-280496.
＜片製作步驟＞ 片製作步驟只要可將之前的步驟中所獲得的組成物片化，則可利用任一方法進行，並無特別限定。例如，較佳為使用選自由壓延、按壓、擠出、及塗敷所組成的群組中的至少一種成形方法來實施。片製作步驟的詳情可參照日本專利特開2008-280496號公報的段落[0034]。 ＜Steps of film production＞ The sheet preparation step can be performed by any method and is not particularly limited as long as the composition obtained in the previous step can be formed into tablets. For example, it is preferable to use at least one molding method selected from the group consisting of calendering, pressing, extrusion, and coating. For details on the film production steps, please refer to paragraph [0034] of Japanese Patent Application Laid-Open No. 2008-280496.
＜積層體製作步驟＞ 積層體製作步驟是形成之前的步驟中所獲得的片的積層體。積層體例如可依次將獨立的多枚片重合來製作，亦可將一枚片翻折來製作，抑或可使片的一枚捲繞來製作。積層體製作步驟的詳情可參照日本專利特開2008-280496號公報的段落[0035]～段落[0037]。 ＜Laminated body production steps＞ The laminated body production step is to form a laminated body of the sheets obtained in the previous step. For example, the laminated body can be produced by sequentially stacking a plurality of independent sheets, by folding one sheet, or by winding one sheet. For details of the laminate production steps, refer to paragraphs [0035] to [0037] of Japanese Patent Application Laid-Open No. 2008-280496.
＜切片步驟＞ 切片步驟只要可對之前的步驟中所獲得的積層體的側端面進行切片，則亦可為任一方法，並無特別限定。自藉由於熱傳導片的厚度方向貫通的石墨粒子（A）而形成極其有效的熱傳導通路，熱傳導性進一步提昇的觀點而言，較佳為以石墨粒子（A）的質量平均粒徑的2倍以下的厚度進行切片。切片步驟的詳情可參照日本專利特開2008-280496號公報的段落[0038]。 ＜Slicing step＞ The slicing step may be any method and is not particularly limited as long as the side end surface of the laminated body obtained in the previous step can be sliced. From the viewpoint that the graphite particles (A) penetrating through the thickness direction of the thermal conductive sheet form an extremely effective thermal conduction path and the thermal conductivity is further improved, the mass average particle diameter of the graphite particles (A) is preferably 2 times or less. thickness for slicing. For details of the slicing step, refer to paragraph [0038] of Japanese Patent Application Laid-Open No. 2008-280496.
＜層壓步驟＞ 層壓步驟只要將切片步驟中所獲得的切割片貼附於保護膜，則亦可為任一方法，並無特別限定。 ＜Lamination step＞ The lamination step may be any method and is not particularly limited as long as the cut piece obtained in the slicing step is attached to a protective film.
〔散熱裝置〕 本揭示的散熱裝置是使本揭示的熱傳導片配置於發熱體與散熱體之間而成。作為發熱體，可列舉：半導體晶片、半導體封裝、功率模組等。作為散熱體，可列舉：散熱器、散熱片、水冷管等。 [Heat dissipation device] The heat dissipation device of the present disclosure is configured by disposing the thermal conductive sheet of the present disclosure between a heating element and a heat sink. Examples of heating elements include semiconductor wafers, semiconductor packages, power modules, etc. Examples of heat sinks include radiators, heat sinks, water cooling tubes, etc.
以下，使用圖1來對散熱裝置的一例進行更具體的說明。使熱傳導片1的其中一面密接於半導體晶片2（發熱體），使另一面密接於散熱器3（散熱體）來使用。半導體晶片2（發熱體）是使用填底膠材5而被固定於基板4上，散熱器3（散熱體）是藉由密封材6而固著於基板4上，藉由按壓來提昇熱傳導片1與半導體晶片2及散熱器3的密接性。再者，無須相對於一枚熱傳導片1而發熱體及散熱體分別為一個。例如，可相對於一枚熱傳導片1而設置多個半導體晶片2（發熱體），亦可相對於多枚熱傳導片1而設置一個半導體晶片2（發熱體），抑或可相對於多枚熱傳導片1而設置多個半導體晶片2（發熱體）。Hereinafter, an example of the heat dissipation device will be described in more detail using FIG. 1 . The thermally conductive sheet 1 is used with one side in close contact with the semiconductor wafer 2 (heating body) and the other side in close contact with the heat sink 3 (radiator). The semiconductor chip 2 (heating body) is fixed on the substrate 4 using the underfill material 5. The heat sink 3 (heat sink) is fixed on the substrate 4 through the sealing material 6. The heat conductive sheet is lifted by pressing. 1. Adhesion to semiconductor chip 2 and heat sink 3. Furthermore, there is no need for one heat-generating body and one heat-radiating body for one heat-conducting sheet 1 . For example, a plurality of semiconductor wafers 2 (heating bodies) may be provided with respect to one heat conduction sheet 1 , one semiconductor chip 2 (heating body) may be provided with respect to a plurality of heat conduction sheets 1 , or a plurality of heat conduction sheets 1 may be provided with one semiconductor chip 2 (heating body). 1 and a plurality of semiconductor wafers 2 (heating bodies) are provided.
散熱裝置是使本揭示的熱傳導片配置於發熱體與散熱體之間而成。藉由經由熱傳導片而積層發熱體與散熱體，可效率良好地將來自發熱體的熱傳導至散熱體。若可效率良好地進行熱傳導，則可提供於散熱裝置的使用中壽命得到提昇，於長期使用時亦穩定地發揮功能的散熱裝置。The heat dissipation device is formed by arranging the thermally conductive sheet of the present disclosure between a heating body and a heat sink. By laminating the heating element and the radiating body via the thermally conductive sheet, heat from the heating element can be efficiently conducted to the radiating body. If heat conduction can be performed efficiently, the life of the heat dissipation device can be increased during use, and a heat dissipation device that can function stably even during long-term use can be provided.
可特佳地使用熱傳導片的溫度範圍例如為-10℃～150℃。由此，作為發熱體，可列舉例如半導體封裝、顯示器、發光二極體（light emitting diode，LED）、電燈、汽車用功率模組及產業用功率模組作為較佳的發熱體的例子。The temperature range in which the thermally conductive sheet can be particularly preferably used is, for example, -10°C to 150°C. Therefore, preferred examples of the heat generating body include semiconductor packages, displays, light emitting diodes (LEDs), electric lamps, automotive power modules, and industrial power modules.
作為散熱體，例如可列舉：鋁或銅的鰭片、利用板等的散熱片、連接於熱傳導管的鋁或銅的塊、利用泵使冷卻液體於內部循環的鋁或銅的塊、以及帕耳帖（Peltier）元件及具備其的鋁或銅的塊。Examples of the heat sink include aluminum or copper fins, heat sinks using plates, etc., aluminum or copper blocks connected to heat transfer tubes, aluminum or copper blocks that circulate cooling liquid inside with a pump, and pajamas. Peltier components and aluminum or copper blocks equipped with them.
散熱裝置可藉由使熱傳導片的各個面與發熱體及散熱體接觸來構成。使發熱體與熱傳導片的其中一面接觸的方法、及使散熱體與熱傳導片的另一面接觸的方法只要為可將各個以充分地密接的狀態固定的方法，則並無特別限制。The heat dissipation device can be configured by contacting each surface of the heat conduction sheet with the heating element and the heat dissipation element. The method of bringing the heating element into contact with one side of the thermally conductive sheet and the method of bringing the heat sink into contact with the other side of the thermally conductive sheet are not particularly limited as long as they can be fixed in a sufficiently close contact state.
例如可列舉以下方法：將熱傳導片配置於發熱體與散熱體之間，並利用可加壓至0.05 MPa～1 MPa程度的夾具加以固定，於該狀態下使發熱體發熱，或者利用烘箱等加熱至80℃～180℃程度。另外，可列舉使用可於80℃～180℃、0.05 MPa～1 MPa下進行加熱加壓的按壓機的方法。該方法中較佳的壓力的範圍為0.10 MPa～1 MPa，較佳的溫度的範圍為100℃～170℃。藉由將壓力設為0.10 MPa以上或將加熱溫度設為100℃以上，有可獲得優異的密接性的傾向。另外，藉由壓力為1 MPa以下或加熱溫度為180℃以下，有密接的可靠性進一步提昇的傾向。認為這是因為可抑制熱傳導片被過度壓縮而厚度變薄，或周邊構件的應變或殘留應力變得過大。For example, the following methods can be used: arranging a thermally conductive sheet between a heating element and a radiator, fixing it with a clamp that can be pressurized to about 0.05 MPa to 1 MPa, and causing the heating element to generate heat in this state, or heating with an oven or the like. to about 80℃～180℃. Another example is a method using a press that can heat and press at 80°C to 180°C and 0.05 MPa to 1 MPa. In this method, the preferred pressure range is 0.10 MPa ~ 1 MPa, and the preferred temperature range is 100°C ~ 170°C. By setting the pressure to 0.10 MPa or more or the heating temperature to 100°C or more, excellent adhesion tends to be obtained. In addition, when the pressure is 1 MPa or less or the heating temperature is 180°C or less, the reliability of the close contact tends to be further improved. This is considered to be because the thermally conductive sheet can be prevented from being excessively compressed and thus thinned, or the strain or residual stress of peripheral members from becoming excessively large.
關於熱傳導片，相對於配置於發熱體與散熱體之間進行壓接之前的初期厚度的、於壓接後進一步減少的厚度的比例（壓縮率）亦可為1%～35%。Regarding the thermally conductive sheet, the ratio (compression ratio) of the thickness that is further reduced after the pressure-bonding with respect to the initial thickness before the pressure-bonding is arranged between the heating element and the heat sink may be 1% to 35%.
固定時除夾子以外亦可使用螺絲、彈簧等夾具，就使密接持續的方面而言，較佳為利用接著劑等通常所使用的手段進而進行固定。In addition to clips, clamps such as screws and springs may be used for fixing. In order to maintain close contact, it is preferable to use commonly used means such as adhesives for further fixing.
使用圖2來對將本揭示的熱傳導片用於TIM1用途時的翹曲量進行說明。翹曲量的分析範圍是設為自基板側看到的晶片部分a。測定晶片部分a的基板的位移，將其部分的中央與端部的位移差定義為翹曲量b。本揭示中的設想的翹曲量為60 μm～120 μm，翹曲量越大，則於翹曲產生時越容易自作為發熱體的半導體晶片及作為散熱體的散熱器剝離。本揭示提供一種即便為翹曲量為60 μm以上的半導體封裝，亦不會發生剝離而維持接著面積的熱傳導片。 [實施例] The amount of warpage when the thermally conductive sheet of the present disclosure is used for TIM1 will be described using FIG. 2 . The analysis range of the warpage amount is set to the wafer portion a viewed from the substrate side. The displacement of the substrate in the wafer part a is measured, and the difference in displacement between the center and the end of the part is defined as the warpage amount b. The assumed amount of warpage in this disclosure is 60 μm to 120 μm. The larger the amount of warpage, the easier it is to peel off from the semiconductor chip as the heat generating body and the heat sink as the heat sink when warping occurs. The present disclosure provides a thermally conductive sheet that does not peel off and maintains a contact area even in a semiconductor package with a warpage amount of 60 μm or more. [Example]
以下，藉由實施例來對本發明進行詳細說明，但本發明並不限定於該些實施例。再者，於各實施例中，壓縮彈性係數、黏力、熱阻、及接著面積的評價是利用以下的方法來進行。Hereinafter, the present invention will be described in detail through examples, but the present invention is not limited to these examples. Furthermore, in each embodiment, the compression elastic coefficient, viscosity, thermal resistance, and bonding area were evaluated using the following methods.
（壓縮彈性係數的測定） 測定時使用附有恒溫槽的壓縮試驗裝置（INSTRON 5948 Micro Tester（英斯特朗（INSTRON）公司））。將熱傳導片剪裁成直徑14 mm的圓形而用於試驗。將熱傳導片夾於0.1 mm厚的紙（脫模紙），於恒溫槽的溫度150℃下相對於熱傳導片的厚度方向而以0.1 mm/min的位移速度施加負荷，從而測定位移（mm）與負荷（N）。於橫軸表示藉由位移（mm）/厚度（mm）而求出的應變（無因次），於縱軸表示藉由負荷（N）/面積（mm 2）而求出的應力（MPa），將應力為0.1 MPa時的斜度設為壓縮彈性係數（MPa）。 (Measurement of compression elastic coefficient) A compression testing device equipped with a constant temperature bath (INSTRON 5948 Micro Tester (INSTRON)) was used for the measurement. The thermally conductive sheet was cut into a circle with a diameter of 14 mm and used for testing. The thermally conductive sheet is sandwiched between 0.1 mm thick paper (release paper), and a load is applied at a displacement speed of 0.1 mm/min with respect to the thickness direction of the thermally conductive sheet at a temperature of 150°C in a constant temperature bath, and the displacement (mm) and Load (N). The horizontal axis represents strain (dimensionless) calculated from displacement (mm)/thickness (mm), and the vertical axis represents stress (MPa) calculated from load (N)/area (mm 2 ). , let the slope when the stress is 0.1 MPa be the compression elastic coefficient (MPa).
（黏力的測定） 使用萬能物性試驗機（物性測定儀，（英弘精機股份有限公司）），於25℃（常溫）下，以負荷40 N將直徑7 mm的探針抵接於熱傳導片並保持10秒鐘後，將提拉探針時的負荷與位移曲線加以積分，將所得的面積設為黏力（N·mm）。 (Measurement of viscosity) Using a universal physical property testing machine (physical property tester, (Eihong Seiki Co., Ltd.)), at 25°C (normal temperature), a probe with a diameter of 7 mm is brought into contact with the thermal conductive sheet with a load of 40 N and held for 10 seconds. The load and displacement curves when the probe is pulled are integrated, and the resulting area is defined as the viscous force (N·mm).
（熱阻的測定） 將熱傳導片剪裁成10 mm見方，並夾於作為發熱體的電晶體（2SC2233）與作為散熱體的銅塊之間，以80℃、0.14 MPa的壓力按壓電晶體，並且測定流通有電流時的電晶體的溫度T1（℃）及銅塊的溫度T2（℃），根據測定值與施加電力W1（W）如以下般算出每單位面積（1 cm 2）的熱阻值X（K·cm 2/W）。 X=（T1-T2）×1/W1 (Measurement of thermal resistance) Cut the thermal conductive sheet into a 10 mm square and sandwich it between the transistor (2SC2233) as the heating element and the copper block as the heat sink. Press the transistor at 80°C and 0.14 MPa. Then, measure the temperature T1 (°C) of the transistor and the temperature T2 (°C) of the copper block when current is flowing, and calculate the thermal resistance per unit area (1 cm 2 ) as follows based on the measured values and the applied power W1 (W). Value X (K·cm 2 /W). X=（T1-T2）×1/W1
（接著面積評價試驗） 為了評價對封裝的翹曲的追隨性，製作簡易的封裝而用於接著面積評價試驗。基板是使用MCL-E-700G（R）（0.81 mm，日立化成股份有限公司），填底膠材是使用CEL-C-3730N-2（日立化成股份有限公司），密封材是使用矽酮系接著劑（SE4450，東麗道康寧（Toray Dow Corning）股份有限公司）。另外，散熱器是使用於厚度1 mm的銅板的表面利用鎳進行鍍敷處理而成者。將基板及散熱器的尺寸設為45 mm，將半導體晶片尺寸設為20 mm，使用將封裝組裝後的晶片面積部的基板的翹曲量為60 μm～75 μm的封裝。 翹曲量是使用3D加熱表面形狀測定裝置（TherMoire PS200，AKROMETRIX公司）來進行測定。測定晶片面積部（20 mm×20 mm）的基板的翹曲量。 封裝的組裝是如以下般進行。將厚度0.3 mm的熱傳導片剪裁成30 mm見方，並貼附於散熱器，使用高精度加壓·加熱接合裝置（HTB-MM，阿爾法設計（Alpha design）股份有限公司）於熱板溫度150℃、負荷46 N下加熱加壓3分鐘。之後，於150℃的恒溫槽中進行2小時處理，使密封材完全硬化。 接著面積是如以下般進行評價。使用超音波圖像診斷裝置（Insight-300，Insight股份有限公司），利用反射法於35 MHz的條件下觀察貼附狀態。進而，藉由圖像分析軟體（圖像（Image）J）將所述圖像進行二值化，將20 mm見方的晶片部分中貼附的面積的比例設為接著面積（%）。 (Following the area evaluation test) In order to evaluate the ability to follow package warpage, a simple package was produced and used in a bonding area evaluation test. The substrate is made of MCL-E-700G (R) (0.81 mm, Hitachi Chemical Co., Ltd.), the underfill material is CEL-C-3730N-2 (Hitachi Chemical Co., Ltd.), and the sealing material is silicone-based. Adhesive (SE4450, Toray Dow Corning Co., Ltd.). In addition, the heat sink is made of a copper plate with a thickness of 1 mm, and the surface is plated with nickel. The dimensions of the substrate and heat sink were set to 45 mm, the size of the semiconductor chip was set to 20 mm, and the amount of warpage of the substrate in the chip area after the package was assembled was 60 μm to 75 μm. The amount of warpage was measured using a 3D heating surface shape measuring device (TherMoire PS200, AKROMETRIX Company). The amount of warpage of the substrate in the wafer area (20 mm × 20 mm) was measured. The package is assembled as follows. Cut a thermally conductive sheet with a thickness of 0.3 mm into a 30 mm square and attach it to the heat sink. Use a high-precision pressurizing and heating bonding device (HTB-MM, Alpha Design Co., Ltd.) at a hot plate temperature of 150°C. , heat and pressurize under a load of 46 N for 3 minutes. After that, it is processed in a constant temperature bath at 150° C. for 2 hours to completely harden the sealing material. Next, the area was evaluated as follows. An ultrasonic imaging diagnostic device (Insight-300, Insight Co., Ltd.) was used to observe the adhesion state using the reflection method at 35 MHz. Furthermore, the image was binarized using image analysis software (Image J), and the ratio of the bonded area in the 20 mm square wafer portion was defined as the bonding area (%).
（實施例1～實施例4） 以成為表1所示的混合比率（體積%）的方式將下述材料投入至捏合混練機（森山（Moriyama）股份有限公司，DS3-SGHM-E型加壓雙臂型捏合機），於溫度150℃的條件下進行混練，從而獲得組成物。 (Example 1 to Example 4) The following materials were put into a kneading machine (Moriyama Co., Ltd., DS3-SGHM-E pressurized double-arm type kneader) so that the mixing ratio (volume %) shown in Table 1 would be The composition is obtained by kneading at 150°C.
＜石墨粒子（A）＞ （A）-1：鱗片狀的膨脹石墨粒子（日立化成股份有限公司的「HGF-L」，質量平均粒徑：270 μm，藉由使用所述X射線繞射測定的方法來確認結晶中的六員環面配向於鱗片狀粒子的面方向） ＜液狀成分（B）＞ （B）-1：異丁烯·正丁烯共聚物（日油股份有限公司的「日油聚丁烯 TM·EMAWET（註冊商標），grade 3N」） （B）-2：異丁烯·正丁烯共聚物（日油股份有限公司的「日油聚丁烯 TM·EMAWET（註冊商標），grade 30N」） （B）-3：異丁烯的均聚物（新日本石油股份有限公司的「tetrax 6T」） ＜丙烯酸酯系高分子（C）＞ （C）-1：丙烯酸酯共聚樹脂（丙烯酸丁酯/丙烯酸乙酯/丙烯腈/丙烯酸共聚物，重量平均分子量：53萬，Tg=-39℃） ＜乙烯-α-烯烴共聚物（D）＞ （D）-1：乙烯辛烯彈性體（陶氏化學（Dow chemical）公司的「EOR8407」） （D）-2：乙烯丙烯共聚物（三井化學股份有限公司的「Lucant HC-3000X」） ＜熱熔劑（E）＞ （E）-1：氫化石油樹脂（荒川化學工業股份有限公司的「alcon P90」） ＜抗氧化劑（F）＞ （F）-1：受阻酚系抗氧化劑（艾迪科（ADEKA）股份有限公司的「adekastab AO-60」） <Graphite Particles (A)> (A)-1: Scale-like expanded graphite particles ("HGF-L" from Hitachi Chemical Co., Ltd., mass average particle diameter: 270 μm, measured by using the above-mentioned X-ray diffraction method to confirm that the six-membered ring plane in the crystal is aligned with the plane direction of the scaly particles) <Liquid component (B)> (B)-1: Isobutylene·n-butene copolymer ("Nissan Oil Co., Ltd." Oil polybuteneTM EMAWET (registered trademark), grade 3N") (B)-2: Isobutylene n-butene copolymer (NOF Co., Ltd.'s "NOF PolybuteneTM EMAWET (registered trademark), grade 30N") (B)-3: Isobutylene homopolymer (New Nippon Oil Co., Ltd.'s "tetrax 6T") <Acrylate polymer (C)> (C)-1: Acrylate copolymer resin (acrylic acid Butyl ester/ethyl acrylate/acrylonitrile/acrylic acid copolymer, weight average molecular weight: 530,000, Tg=-39℃) <Ethylene-α-olefin copolymer (D)> (D)-1: Ethylene octene elastomer ("EOR8407" from Dow Chemical Co., Ltd.) (D)-2: Ethylene propylene copolymer ("Lucant HC-3000X" from Mitsui Chemicals Co., Ltd.) <Hot melt (E)> (E)-1 : Hydrogenated petroleum resin ("alcon P90" from Arakawa Chemical Industry Co., Ltd.) <Antioxidant (F)> (F)-1: Hindered phenol antioxidant ("adekastab AO-" from ADEKA Co., Ltd. 60")
（熱傳導片的製作） 將混練而獲得的組成物放入至擠出成形機（派克（Parker）股份有限公司，商品名：HKS40-15型擠出機），並以寬20 cm、厚1.5 mm～1.6 mm的平板形狀進行擠出而獲得一次片。使用40 mm×150 mm的模具刀對所獲得的一次片進行按壓衝壓，並積層61枚經衝壓的片，以高度成為80 mm的方式夾持高度80 mm的間隔件而在積層方向以90℃施加30分鐘的壓力，從而獲得40 mm×150 mm×80 mm的積層體。繼而，利用木工用切片機對該積層體的80 mm×150 mm的側端面進行切片來獲得厚0.3 mm的熱傳導片。 (Production of thermal conductive sheets) The kneaded composition was put into an extrusion molding machine (Parker Co., Ltd., trade name: HKS40-15 extruder), and formed into a flat plate shape of 20 cm wide and 1.5 mm to 1.6 mm thick. Extrusion is performed to obtain primary tablets. The obtained primary sheets were pressed and punched using a 40 mm × 150 mm die knife, and 61 stamped sheets were stacked. Spacers with a height of 80 mm were sandwiched so that the height became 80 mm, and the lamination direction was maintained at 90°C. Pressure was applied for 30 minutes to obtain a laminated body of 40 mm×150 mm×80 mm. Next, the 80 mm×150 mm side end surface of the laminated body was sliced using a woodworking slicer to obtain a 0.3 mm thick thermally conductive sheet.
（比較例1～比較例3） 以成為表1的混合比率（體積%）的方式，藉由與實施例1～實施例4相同的步驟對表1所示的各材料進行混練、積層、按壓、及切片，從而製作熱傳導片。 (Comparative Example 1 to Comparative Example 3) Each material shown in Table 1 was kneaded, laminated, pressed, and sliced in the same steps as in Examples 1 to 4 so that the mixing ratio (volume %) in Table 1 was obtained, thereby producing a thermally conductive sheet.
[表1]
（壓縮彈性係數） 如所述壓縮彈性係數的測定般評價厚0.3 mm的熱傳導片，結果在150℃下的壓縮應力為0.1 MPa時的壓縮彈性係數（MPa）如表2般。實施例1～實施例4的壓縮彈性係數為1.4 MPa以下，比較例1～比較例3的壓縮彈性係數大於1.4 MPa。 (Compression elastic coefficient) A thermally conductive sheet with a thickness of 0.3 mm was evaluated as described above for the measurement of the compressive elastic coefficient. The results showed that the compressive elastic coefficient (MPa) when the compressive stress at 150°C was 0.1 MPa is as shown in Table 2. The compressive elastic coefficients of Examples 1 to 4 are 1.4 MPa or less, and the compressive elastic coefficients of Comparative Examples 1 to 3 are greater than 1.4 MPa.
（黏力） 如所述黏力的測定般評價厚0.3 mm的熱傳導片，結果實施例1～實施例4的黏力為5.0 N·mm以上。另外，比較例1的黏力為5.0 N·mm以上，但比較例2及比較例3的黏力低於5.0 N·mm。 (stickiness) The thermally conductive sheet with a thickness of 0.3 mm was evaluated as described above for measuring the adhesive force. As a result, the adhesive force of Examples 1 to 4 was 5.0 N·mm or more. In addition, the adhesive force of Comparative Example 1 is 5.0 N·mm or more, but the adhesive force of Comparative Examples 2 and 3 is less than 5.0 N·mm.
（接著面積） 如所述接著面積評價試驗般評價厚0.3 mm的熱傳導片，結果實施例1～實施例4中接著面積顯示90%以上，確認到可追隨翹曲，可充分地進行接著。特別是實施例2～實施例4中接著面積顯示95%以上，確認到存在更優異的翹曲追隨性。另一方面，比較例1～比較例3的接著面積成為72%～76%，確認到翹曲大的晶片的四個角落未接著而剝離的狀態。 (followed by area) The thermally conductive sheet with a thickness of 0.3 mm was evaluated as in the above-mentioned bonding area evaluation test. As a result, the bonding area showed 90% or more in Examples 1 to 4, and it was confirmed that warpage could be followed and sufficient bonding could be performed. In particular, in Examples 2 to 4, the bonding area showed 95% or more, and it was confirmed that there is more excellent warpage following property. On the other hand, in Comparative Examples 1 to 3, the bonding area was 72% to 76%, and it was confirmed that the four corners of the wafer with large warpage were not bonded but peeled off.
（熱阻） 如所述熱阻的測定般評價厚0.3 mm的熱傳導片，結果實施例1～實施例4、及比較例1～比較例3的熱阻為0.13 K·cm 2/W～0.15 K·cm 2/W，熱阻均小，顯示出熱傳導性優異。 (Thermal resistance) A thermally conductive sheet with a thickness of 0.3 mm was evaluated as in the measurement of thermal resistance. As a result, the thermal resistance of Examples 1 to 4 and Comparative Examples 1 to 3 was 0.13 K·cm 2 /W to 0.15 K·cm 2 /W, the thermal resistance is small, and the thermal conductivity is excellent.
[表2]
根據以上，於作為含有石墨粒子（A）、在150℃下的壓縮應力為0.1 MPa時的壓縮彈性係數為1.4 MPa以下、在25℃下的黏力為5.0 N·mm以上的熱傳導片的實施例1～實施例4中，作為翹曲追隨性的指標的接著面積顯示90%以上，顯示出優異的翹曲追隨性。Based on the above, the implementation of a thermally conductive sheet containing graphite particles (A), a compressive elastic coefficient of 1.4 MPa or less when the compressive stress at 150°C is 0.1 MPa, and an adhesive force of 5.0 N·mm or more at 25°C In Examples 1 to 4, the bonding area, which is an index of warpage following properties, was 90% or more, indicating excellent warping following properties.
本說明書中所記載的所有文獻、專利申請案、及技術規格是與具體且分別記載各文獻、專利申請案、及技術規格藉由參照而併入的情況相同程度地，藉由參照而併入本說明書中。All documents, patent applications, and technical specifications described in this specification are incorporated by reference to the same extent as if each individual document, patent application, or technical specification was specifically and individually stated to be incorporated by reference. in this manual.
1:熱傳導片 2:半導體晶片（發熱體） 3:散熱器（散熱體） 4:基板 5:填底膠材 6:密封材 a:晶片部分 b:翹曲量 1: Thermal conductive sheet 2: Semiconductor chip (heater) 3: Radiator (radiator) 4:Substrate 5: Bottom filling material 6:Sealing material a:wafer part b: warpage amount
圖1表示作為本發明的一實施形態的發熱體為半導體晶片、散熱體為散熱器的散熱裝置的概略剖面圖。 圖2表示於作為本發明的一實施形態的發熱體為半導體晶片、散熱體為散熱器的散熱裝置中對翹曲量進行說明的圖。 FIG. 1 is a schematic cross-sectional view of a heat dissipation device in which the heat generating body is a semiconductor chip and the heat dissipating body is a heat sink as an embodiment of the present invention. FIG. 2 is a diagram illustrating the amount of warpage in a heat dissipation device in which the heat generating element is a semiconductor wafer and the heat dissipating element is a heat sink according to one embodiment of the present invention.
1:熱傳導片 1: Thermal conductive sheet
2:半導體晶片(發熱體) 2: Semiconductor chip (heater)
3:散熱器(散熱體) 3: Radiator (radiator)
4:基板 4:Substrate
5:填底膠材 5: Bottom filling material
6:密封材 6:Sealing material
Claims (13)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW112130023A TWI835694B (en) | 2019-03-05 | Heat conductive sheet and heat dissipation device using heat conductive sheet |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW112130023A TWI835694B (en) | 2019-03-05 | Heat conductive sheet and heat dissipation device using heat conductive sheet |
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| Publication Number | Publication Date |
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| TW202346446A true TW202346446A (en) | 2023-12-01 |
| TWI835694B TWI835694B (en) | 2024-03-11 |
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