JP2007277406A - Highly heat-conductive resin compound, highly heat-conductive resin molded article, compounding particle for heat-releasing sheet, highly heat-conductive resin compound, highly heat-conductive resin molded article, heat-releasing sheet, and method for producing the same - Google Patents
Highly heat-conductive resin compound, highly heat-conductive resin molded article, compounding particle for heat-releasing sheet, highly heat-conductive resin compound, highly heat-conductive resin molded article, heat-releasing sheet, and method for producing the same Download PDFInfo
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本発明は、例えば電子機器内の発熱部品と放熱部品の間に設置され放熱に用いられる高熱伝導性樹脂コンパウンド・高熱伝導性樹脂成形体・放熱シート用配合粒子、高熱伝導性樹脂コンパウンド・高熱伝導性樹脂成形体・放熱シート、および、その製造方法に関する。 The present invention is, for example, a high heat conductive resin compound / high heat conductive resin molding / mixed particle for a heat radiating sheet that is installed between a heat generating component and a heat radiating component in an electronic device and used for heat dissipation, a high heat conductive resin compound / high heat conductive The present invention relates to a conductive resin molded body / heat dissipation sheet and a method for producing the same.
最近、エレクトロニクスの進展に伴い、パワーデバイス等電子機器内において発熱する部品が多く使用されてきている。電子回路を制御するに当り、これらの発熱部品からの熱を放散させて系全体を冷却することが重要となってきた。放熱シートは、発熱部品と放熱フィンや金属板との間に設置され、圧着により隙間のないように密着し、熱伝導性を発揮して発熱部品から発生した熱を放熱フィン等に伝えて、系全体の抜熱をすることができる。熱伝導性接着剤等も存在するが、放熱シートは取り扱いの容易さ等により最近普及してきた部材である。 Recently, with the progress of electronics, many components that generate heat have been used in electronic devices such as power devices. In controlling an electronic circuit, it has become important to dissipate heat from these heat generating components to cool the entire system. The heat-dissipating sheet is installed between the heat-generating component and the heat-dissipating fin or metal plate, and is closely attached so that there is no gap by crimping, and exhibits heat conductivity to transmit the heat generated from the heat-generating component to the heat-dissipating fin, etc. It is possible to remove heat from the entire system. Although heat conductive adhesives and the like exist, the heat dissipation sheet is a member that has recently become popular due to its ease of handling.
一般に、放熱シートに代表される高熱伝導性樹脂成形体は、熱伝導性の無機フィラーと樹脂との組成物で構成されている。無機フィラーとしては、安価な水酸化アルミニウムや酸化アルミニウム（以下、アルミナ）、高熱伝導を期待した炭化珪素や窒化硼素、窒化アルミニウムといった材料が用いられている。また、樹脂としては、シリコーン樹脂が一般的であるが、シリコーン樹脂に含まれるシロキサンによる接点不良の問題を解決すべくアクリル系ゴム等の適用も検討されてきている。 In general, a highly thermally conductive resin molded body represented by a heat dissipation sheet is composed of a composition of a thermally conductive inorganic filler and a resin. As the inorganic filler, inexpensive materials such as aluminum hydroxide and aluminum oxide (hereinafter referred to as alumina), silicon carbide, boron nitride and aluminum nitride which are expected to have high thermal conductivity are used. In addition, as a resin, a silicone resin is generally used, but application of acrylic rubber or the like has been studied in order to solve the problem of contact failure due to siloxane contained in the silicone resin.
放熱シートとして、安価な無機フィラーを用いた熱伝導率が1〜3W/mKのものと、高熱伝導性フィラーを用いた3〜5W/mKのものが市販されている。安価で高熱伝導率を有するシートが求められることから、アルミナを用いてできるだけ熱伝導率を向上させるための研究開発が進められてきている。
樹脂に加えるアルミナの充填率を上げることで高熱伝導率化を目指す方法が多く研究されており、フィラーの充填・分散を容易にするものとして、下記の特許文献１に記載されているように角を落とした丸味状アルミナを用いるものや、下記の特許文献２に記載されているように球状アルミナを用いる等のアルミナ形状を変える研究が行なわれた。
As the heat radiating sheet, those having a thermal conductivity of 1 to 3 W / mK using an inexpensive inorganic filler and those having a thermal conductivity of 3 to 5 W / mK using a high thermal conductive filler are commercially available. Since an inexpensive sheet having a high thermal conductivity is required, research and development for improving the thermal conductivity as much as possible using alumina has been underway.
Many methods for increasing the thermal conductivity by increasing the filling rate of alumina added to the resin have been studied, and as described in Patent Document 1 below, it is easy to fill and disperse the filler. Research has been conducted on changing the shape of alumina, such as using rounded alumina with a reduced diameter, or using spherical alumina as described in Patent Document 2 below.
また下記の特許文献３には、熱伝導フィラー（実施例として炭化珪素）を樹脂に充填するに当り、大きな粒子とその間隙に入る小さな粒子を組合せて、熱伝導フィラーの充填率を上げて、シートの熱伝導を向上させ、実施例にて3.5W/mKの放熱シートが得られることが記載されている。フィラーはアルミナではないものの、フィラーの充填率を上げるべく、大小の粒径の異なる粒子を配合することを開示したものである。
さらに、下記の特許文献４には、大きな粒子として50〜80μmの球状アルミナ、小さな粒子として5μｍ以下の非球状アルミナを用いて、配合率を調整し、充填量に見合う熱伝導率を発揮させ、実施例にて5.5W/mKの放熱シートが得られることが記載されている。
In addition, in Patent Document 3 below, in filling a resin with a heat conductive filler (silicon carbide as an example), a combination of large particles and small particles entering the gap, the filling rate of the heat conductive filler is increased, It is described that the heat conduction of the sheet is improved and a heat radiating sheet of 3.5 W / mK can be obtained in the examples. Although the filler is not alumina, in order to increase the filling rate of the filler, it is disclosed that particles having different sizes are mixed.
Furthermore, in Patent Document 4 below, 50-80 μm spherical alumina as large particles and non-spherical alumina of 5 μm or less as small particles are used to adjust the blending ratio and exhibit thermal conductivity commensurate with the filling amount, It is described that a heat dissipation sheet of 5.5 W / mK can be obtained in the examples.
以上のように、放熱シートの熱伝導率を向上させることを目的として、アルミナ粒子の充填率を増加させるため、アルミナ粒子の形状の検討、粒径の検討、配合の検討が行われてきている。
大小の粒径の異なる粒子の配合として、大径の球状粒子とその隙間を埋める小径粒子が用いられている。特許文献３では球状の大径粒子と球状の小径粒子を組合せた配合を用いており、特許文献４では大径の球状粒子と非球状の小径粒子を組合せた配合を用いている。
As a combination of large and small particles having different particle sizes, large spherical particles and small particles filling the gaps are used. Patent Document 3 uses a combination of spherical large diameter particles and spherical small diameter particles, and Patent Document 4 uses a combination of large spherical particles and non-spherical small diameter particles.
従来の技術である球状の大径粒子と球状の小径粒子の組合せでは、高い熱伝導率が得られない。また、球状の大径粒子と非球状の小径粒子の組合せでは、高い熱伝導率は得られるが、放熱シートが硬くなり、シートの柔軟性を低下させるという問題があり、高熱伝導率と低シート硬度を両立することは困難であった。
そこで本発明は、高熱伝導率と柔軟性に優れた低シート硬度を両立した放熱シートを製造することができる高熱伝導性樹脂コンパウンド・高熱伝導性樹脂成形体・放熱シート用配合粒子、高熱伝導性樹脂コンパウンド・高熱伝導性樹脂成形体・放熱シート、および、その製造方法を提供することを課題とする。
High thermal conductivity cannot be obtained with the conventional combination of spherical large-diameter particles and spherical small-diameter particles. In addition, a combination of spherical large-diameter particles and non-spherical small-diameter particles can provide high thermal conductivity, but there is a problem that the heat-dissipating sheet becomes hard and the flexibility of the sheet is lowered, and high thermal conductivity and low sheet It was difficult to achieve both hardness.
Accordingly, the present invention provides a high heat conductive resin compound, a high heat conductive resin molding, a compounded particle for a heat radiating sheet, and a high heat conductivity, which can produce a heat radiating sheet having both high thermal conductivity and excellent flexibility and low sheet hardness. It is an object of the present invention to provide a resin compound, a high thermal conductive resin molded body, a heat radiating sheet, and a manufacturing method thereof.
本発明は、前述の課題を解決するため鋭意検討の結果なされたものであり、その要旨とするところは特許請求の範囲に記載した通りの下記内容である。
（１）平均粒径50〜100μmの球状アルミナ粒子が60〜80vol%、平均粒径0.5〜7μmの球状アルミナ粒子が5〜30vol%、平均粒径0.5〜7μmの非球状アルミナ粒子が10〜35vol%の配合で含まれることを特徴とする、高熱伝導性樹脂コンパウンド用配合粒子。
（２）（１）に記載の高熱伝導性樹脂コンパウンド用配合粒子を樹脂成形体に用いることを特徴とする高熱伝導性樹脂成形体用配合粒子。
（３）（２）に記載の高熱伝導性樹脂成形体用配合粒子を放熱シートに用いることを特徴とする放熱シート用配合粒子。
（４）平均粒径50〜100μmの球状アルミナ粒子が60〜80vol%、平均粒径0.5〜7μmの球状アルミナ粒子が5〜30vol%、平均粒径0.5〜7μmの非球状アルミナ粒子が10〜35vol%の配合で含まれる配合粒子を、体積比で60〜90vol%含むことを特徴とする、高熱伝導性樹脂コンパウンド。
（５）（４）に記載の高熱伝導性樹脂コンパウンドを用いて成形したことを特徴とする高熱伝導性樹脂成形体。
The present invention has been made as a result of intensive studies in order to solve the above-mentioned problems, and the gist of the present invention is the following contents as described in the claims.
(1) Spherical alumina particles having an average particle diameter of 50 to 100 μm are 60 to 80 vol%, spherical alumina particles having an average particle diameter of 0.5 to 7 μm are 5 to 30 vol%, and non-spherical alumina particles having an average particle diameter of 0.5 to 7 μm are 10 to 35 vol. Compounded particles for high thermal conductive resin compounds, characterized in that they are contained in a composition of%.
(2) A compounded particle for a high heat conductive resin molding, wherein the compounded particle for a high heat conductive resin compound according to (1) is used for a resin molded product.
(3) A compounded particle for a heat radiating sheet, wherein the compounded particle for a high thermal conductive resin molding according to (2) is used for a heat radiating sheet.
(4) 60-80 vol% of spherical alumina particles with an average particle size of 50-100 μm, 5-30 vol% of spherical alumina particles with an average particle size of 0.5-7 μm, and 10-35 vol of non-spherical alumina particles with an average particle size of 0.5-7 μm A high thermal conductive resin compound characterized in that it contains 60 to 90 vol% of compounded particles contained in a% composition.
(5) A high thermal conductive resin molded product, which is molded using the high thermal conductive resin compound according to (4).
（６）（５）に記載の高熱伝導性樹脂成形体を用いて作製したことを特徴とする放熱シート。
（７）前記放熱シートの熱伝導率が5.6W/mK以上であることを特徴とする、（６）に記載の放熱シート。
（８）前記放熱シートのアスカーC硬度が60以下であることを特徴とする、（６）または（７）に記載の放熱シート。
（９）平均粒径0.5〜7μmの球状及び非球状のアルミナ粒子と樹脂との混合物からなるマトリックスに、平均粒径50〜100μmの球状アルミナ粒子が均一に分散していることを特徴とする、（６）乃至（８）のいずれか１項に記載の放熱シート。
（１０）前記マトリックスのうち樹脂の占める体積が23〜65vol%であることを特徴とする、（９）に記載の放熱シート。
（１１）平均粒径0.5〜7μmの球状及び非球状のアルミナ粒子と樹脂とを予め混合してマトリックスを形成した後、該マトリックスに平均粒径50〜100μmの球状アルミナ粒子を混合して成形することを特徴とする、高熱伝導性樹脂コンパウンドの製造方法。
（１２）（１１）に記載の高熱伝導性樹脂コンパウンドを用いて成形することを特徴とする高熱伝導性樹脂成形体の製造方法。
（１３）（１２）１２に記載の高熱伝導性樹脂成形体を用いて作製することを特徴とする放熱シートの製造方法。
ここに、球状粒子とは、粒子の円形度（相当円の周囲長／粒子投影像の周囲長）の平均値が０．８以上の粒子をいう。
また、非球状粒子とは、粒子の円形度（相当円の周囲長／粒子投影像の周囲長）の平均値が０．８未満の粒子をいう。
(6) A heat-dissipating sheet produced using the high thermal conductive resin molded article according to (5).
(7) The heat dissipation sheet according to (6), wherein the heat dissipation sheet has a thermal conductivity of 5.6 W / mK or more.
(8) The heat dissipation sheet according to (6) or (7), wherein the heat dissipation sheet has an Asker C hardness of 60 or less.
(9) The spherical alumina particles having an average particle size of 50 to 100 μm are uniformly dispersed in a matrix composed of a mixture of spherical and non-spherical alumina particles having an average particle size of 0.5 to 7 μm and a resin. (6) thru | or the heat dissipation sheet | seat of any one of (8).
(10) The heat dissipation sheet according to (9), wherein the volume occupied by the resin in the matrix is 23 to 65 vol%.
(11) A spherical and non-spherical alumina particle having an average particle diameter of 0.5 to 7 μm and a resin are previously mixed to form a matrix, and then the spherical alumina particle having an average particle diameter of 50 to 100 μm is mixed and molded into the matrix. A method for producing a high thermal conductive resin compound.
(12) A method for producing a highly thermally conductive resin molded article, characterized by molding using the highly thermally conductive resin compound according to (11).
(13) A method for producing a heat-dissipating sheet, characterized by being produced using the high thermal conductive resin molded article according to (12) 12.
Here, the spherical particles refer to particles having an average value of circularity of the particles (peripheral length of equivalent circle / perimeter of the projected particle image) of 0.8 or more.
Non-spherical particles mean particles having an average value of circularity of particles (peripheral length of equivalent circle / perimeter of particle projection image) of less than 0.8.
本発明によれば、大径アルミナ球状粒子と小径アルミナ非球状粒子に加え、さらに小径アルミナ球状粒子を配合することで、5.6W/mK以上という高い熱伝導率を有するとともに、アスカー硬度が60以下という柔軟性に優れたシートを製造することができる高熱伝導性樹脂コンパウンド・高熱伝導性樹脂成形体・放熱シート用配合粒子、高熱伝導性樹脂コンパウンド・高熱伝導性樹脂成形体・放熱シート、および、その製造方法を提供することができる。 According to the present invention, in addition to the large-diameter alumina spherical particles and small-diameter alumina non-spherical particles, the addition of the small-diameter alumina spherical particles has a high thermal conductivity of 5.6 W / mK or more and an Asker hardness of 60 or less. High thermal conductivity resin compound, high thermal conductivity resin molding, compounded particles for heat dissipation sheet, high thermal conductivity resin compound, high thermal conductivity resin molding, heat dissipation sheet, and A manufacturing method thereof can be provided.
我々は、アルミナフィラーを高充填させる放熱シートにおいて、大径アルミナ球状粒子間の隙間を埋めるマトリックス部に熱伝導に寄与する小径アルミナ粒子を配合させ、かつマトリックス部に流動性を持たせることでシートの柔軟性を得られないか、を鋭意検討した。その結果、１）予め所定量の小径アルミナ球状粒子と所定量の小径アルミナ非球状粒子と樹脂の混合物からなるマトリックスを作製する、２）そのマトリックスに大径アルミナ球状粒子を混合する、３）全ての混合物を成形加工して放熱シートを作製する、という工程を取ることで、高熱伝導かつ柔軟な高熱伝導性樹脂成形体を得ることができた。
本発明の樹脂コンパウンドは、樹脂成形体 として用いる場合には、放熱シートやプリント配線板に用いられる一方、非成形体としては、放熱グリースや接着剤などに用いられる。
以下の説明は、樹脂コンパウンドを成形体の放熱シートとして用いる場合の実施形態を示す。
We are a heat-dissipating sheet that is highly filled with alumina filler. By mixing small-diameter alumina particles that contribute to heat conduction into the matrix part that fills the gaps between the large-diameter spherical spherical particles, and making the matrix part fluid, We have eagerly studied whether or not we can get the flexibility. As a result, 1) a matrix made of a mixture of a predetermined amount of small-diameter alumina spherical particles, a predetermined amount of small-diameter non-spherical alumina particles, and a resin is prepared in advance. 2) Large-diameter alumina spherical particles are mixed in the matrix. It was possible to obtain a highly heat-conductive and flexible highly heat-conductive resin molded article by taking a step of forming a heat-dissipating sheet by molding the mixture.
When the resin compound of the present invention is used as a resin molded body, it is used for a heat radiating sheet or a printed wiring board, while the non-molded body is used for a heat radiating grease or an adhesive.
The following description shows an embodiment in which a resin compound is used as a heat dissipation sheet for a molded body.
マトリックス内の小径アルミナ非球状粒子は、大径粒子の隙間を埋める場合に、球状粒子に比べ大径アルミナ球状粒子との接触面積が大きくなるため、熱伝導率の向上に寄与する。しかし、小径アルミナ粒子として非球状粒子だけを用いた場合、マトリックスの柔軟性が損なわれ、シート硬度が増加してしまう。
そこで、マトリックス内の小径アルミナ非球状粒子の一部を所定量の小径アルミナ球状粒子とすることにより、マトリックスに球状粒子の流動性を加味することができ、全体のアルミナ粒子を高充填した配合においても、シートの高熱伝導性を維持したまま放熱シートの柔軟性を得ることに成功した。小径アルミナ非球状粒子の接触面積が大きいことによる高い熱伝導性と小径アルミナ球状粒子の流動性との両者を兼ね備えることができ、熱伝導を維持したまま、シートの変形が起こる際に大径アルミナ球状粒子の動きを阻害することなくマトリックスが動くことができ、シートの柔軟性が確保できるのである。
ここに、球状粒子とは、粒子の円形度（相当円の周囲長／粒子投影像の周囲長）の平均値が０．８以上の粒子をいう。
また、非球状粒子とは、粒子の円形度（相当円の周囲長／粒子投影像の周囲長）の平均値が０．８未満の粒子をいう。
粒子の円形度は、電子顕微鏡と画像解析装置を用い、例えば、シスメックス社製ＦＰＩＡを用いて測定することができる。
円形度の測定は、粒子個数１００個以上をカウントし、その平均値をその粉末の円形度とする。
The small-diameter alumina non-spherical particles in the matrix contribute to the improvement of thermal conductivity because the contact area with the large-diameter alumina spherical particles is larger than the spherical particles when filling the gaps between the large-diameter particles. However, when only non-spherical particles are used as the small-diameter alumina particles, the flexibility of the matrix is impaired and the sheet hardness increases.
Therefore, by making a part of the small-diameter non-spherical particles in the matrix into a predetermined amount of small-diameter alumina spherical particles, the flowability of the spherical particles can be added to the matrix, However, it succeeded in obtaining the flexibility of the heat dissipation sheet while maintaining the high thermal conductivity of the sheet. Both high thermal conductivity due to the large contact area of small-diameter non-spherical particles and fluidity of small-diameter alumina spherical particles can be combined, and large-diameter alumina can be used when sheet deformation occurs while maintaining thermal conductivity. The matrix can move without hindering the movement of the spherical particles, and the flexibility of the sheet can be secured.
Here, the spherical particles refer to particles having an average value of circularity of the particles (peripheral length of equivalent circle / perimeter of the projected particle image) of 0.8 or more.
Non-spherical particles mean particles having an average value of circularity of particles (peripheral length of equivalent circle / perimeter of particle projection image) of less than 0.8.
The degree of circularity of the particles can be measured using an electron microscope and an image analyzer, for example, using FPIA manufactured by Sysmex Corporation.
In the measurement of the circularity, the number of particles of 100 or more is counted, and the average value is defined as the circularity of the powder.
＜大径粒子の粒径・配合量＞
大径アルミナ球状粒子はシートの熱伝導率に最も寄与するものである。同一体積に充填することを考えた場合、粒径が大きいほど粒子の数を減らすことができることから、大径粒子の粒径が大きくなると、大径粒子と大径粒子の間の熱抵抗となる隙間の数を減らすことができ、熱伝導率を向上させることができる。そのため、大径アルミナ粒子は大きい方が好ましく、またその充填率が高い方が熱伝導の面からは有利となる。大径アルミナ粒子の平均粒径が50μｍ未満であると、同じ充填率の場合には充填に必要な粒子の数が増えるため、大径アルミナ球状粒子の間の熱抵抗が増加し、熱伝導率が低くなる。そのため、その下限値を50μmとした。また、大径アルミナ球状粒子が80μmを超える大径となると、充填に必要な粒子数がさらに減り、大径アルミナ球状粒子の間の熱抵抗をさらに減らすことができ、熱伝導率がさらに向上し、より好適となる。
<Particle size and blending amount of large particles>
Large diameter alumina spherical particles contribute most to the thermal conductivity of the sheet. When considering filling in the same volume, the larger the particle size, the smaller the number of particles. Therefore, when the particle size of the large particle increases, it becomes a thermal resistance between the large particle and the large particle. The number of gaps can be reduced and the thermal conductivity can be improved. For this reason, the larger-diameter alumina particles are preferably larger, and a higher filling rate is advantageous from the viewpoint of heat conduction. If the average particle size of the large-diameter alumina particles is less than 50 μm, the number of particles required for filling increases at the same filling rate, so the thermal resistance between the large-diameter alumina spherical particles increases and the thermal conductivity. Becomes lower. Therefore, the lower limit is set to 50 μm. In addition, when the large-diameter alumina spherical particles have a large diameter exceeding 80 μm, the number of particles necessary for filling is further reduced, the thermal resistance between the large-diameter alumina spherical particles can be further reduced, and the thermal conductivity is further improved. It becomes more suitable.
また、従来技術では80μｍ以上の粒径の大径アルミナ球状粒子を用いると、シート成形の際にシートの面の平坦度が悪くなり、切断時には大径アルミナ球状粒子がシートの切断面から脱落してしまうという問題があったが、本発明による柔軟性を有するマトリックスを用いることで解決できる。即ち、シートの面出しの際には、従来の樹脂マトリックスを用いた場合にはアルミナ粒子部と樹脂部との段差が生じてしまうが、本発明の混合物よりなるマトリックスを用いると小径アルミナ粒子を含んでいるため段差が付きにくくなり、平坦度に優れるシートが得られる。また、切断の際には、従来の樹脂マトリックスではマトリックスの強度が低く、樹脂マトリックスに亀裂が伝わり大径粒子を包み込んでいたマトリックスごと大径粒子の脱落が起きていたが、本発明の混合物からなるマトリックスとすることで大径アルミナ球状粒子を覆うマトリックス部の強度が向上し、粒子の脱落が起こり難くなった。本発明によって、従来技術では前述のように使用に問題があった80μｍ以上の大径アルミナ球状粒子も使用を可能となった。なお、大径アルミナ球状粒子の平均粒径の上限を100μmとしているが、これは入手できたアルミナ球状粒子がこの平均粒径であったためであり、それ以上の粒径の場合にもこれらの効果が得られることは十分考えられる。
また、アルミナ粒子の総和を100vol%とした場合、大径アルミナ球状粒子の量は60vol%未満であると熱伝導に寄与する粒子が不足して熱伝導率が小さくなるため、その下限値を60vol%とした。また、大径アルミナ球状粒子の量が80vol%を超えると、相対的にマトリックスに含まれる小径アルミナ粒子の量が少なくなるため、大径アルミナ球状粒子の隙間を埋める小径粒子が不足し、熱伝導率が低下してしまうため、その上限値を80vol%とした。
In addition, in the prior art, when large-diameter spherical alumina particles having a particle diameter of 80 μm or more are used, the flatness of the sheet surface deteriorates during sheet forming, and the large-diameter spherical alumina particles fall off from the cut surface of the sheet during cutting. However, this problem can be solved by using the flexible matrix according to the present invention. That is, when the sheet is surfaced, if a conventional resin matrix is used, a step between the alumina particle portion and the resin portion will occur, but if a matrix made of the mixture of the present invention is used, small-diameter alumina particles will be formed. Since it contains, a level | step difference becomes difficult to attach and the sheet | seat which is excellent in flatness is obtained. Further, when cutting, the matrix strength of the conventional resin matrix was low, and cracks were transmitted to the resin matrix, and the large-diameter particles dropped out together with the matrix encapsulating the large-diameter particles. By using this matrix, the strength of the matrix portion covering the large-diameter spherical spherical particles was improved, and the particles were less likely to fall off. According to the present invention, it is possible to use large-sized alumina spherical particles having a diameter of 80 μm or more, which had problems in use in the prior art as described above. The upper limit of the average particle size of the large alumina spherical particles is set to 100 μm. This is because the alumina spherical particles that were available had this average particle size. It is conceivable that is obtained.
In addition, when the total amount of alumina particles is 100 vol%, the amount of large-diameter spherical spherical particles is less than 60 vol%. %. If the amount of large-diameter alumina spherical particles exceeds 80 vol%, the amount of small-diameter alumina particles contained in the matrix is relatively small. Since the rate decreases, the upper limit is set to 80 vol%.
＜小径球状粒子の粒径と配合量＞
小径アルミナ球状粒子の粒径が7μmを超えると、大径アルミナ球状粒子の隙間の大きな部分にしか充填することができず、マトリックスに柔軟性を与えることが困難となり、シート硬度が上昇してしまう。そのため、小径アルミナ球状粒子の粒径の上限値を7μｍとした。また、小径アルミナ球状粒子が0.5μｍより小さくなると、マトリックス内で熱伝導に寄与する粒子数が多くなりマトリックスの粒子間の熱抵抗が増加してマトリックスの熱伝導率が低下し、シートの熱伝導も低下してしまう。そのため、小径アルミナ球状粒子の粒径の下限値を0.5μｍとした。
<Particle size and blending amount of small spherical particles>
If the particle diameter of the small-diameter alumina spherical particles exceeds 7 μm, it can be filled only in the large gaps of the large-diameter alumina spherical particles, making it difficult to give flexibility to the matrix and increasing the sheet hardness. . Therefore, the upper limit of the particle diameter of the small-diameter spherical spherical particles is set to 7 μm. In addition, when the small-diameter alumina spherical particles are smaller than 0.5 μm, the number of particles contributing to heat conduction in the matrix increases, the thermal resistance between the matrix particles increases, the matrix thermal conductivity decreases, and the sheet thermal conductivity decreases. Will also decline. Therefore, the lower limit of the particle diameter of the small-diameter spherical spherical particles is set to 0.5 μm.
小径アルミナ球状粒子が全アルミナ粒子の合計を100vol%とした場合に5vol%より少ないとマトリックスの流動性が不足してシートが硬くなってしまう。そのため、小径アルミナ球状粒子の配合比の下限値を5vol%とした。また、小径アルミナ球状粒子が30vol%より多くなると流動性は得られるものの、マトリックスを構成するアルミナ粒子同士の接触面積が小さくなり、マトリックスの熱伝導を悪化させ、シート全体の熱伝導率が低くなる。そのため、小径アルミナ球状粒子の配合比の上限値を30vol%とした。 When the small-diameter alumina spherical particles are less than 5 vol% when the total of all alumina particles is 100 vol%, the fluidity of the matrix is insufficient and the sheet becomes hard. Therefore, the lower limit value of the mixing ratio of the small-diameter alumina spherical particles is set to 5 vol%. In addition, when small alumina spherical particles exceed 30 vol%, fluidity is obtained, but the contact area between the alumina particles constituting the matrix is reduced, the thermal conductivity of the matrix is deteriorated, and the thermal conductivity of the entire sheet is lowered. . Therefore, the upper limit value of the mixing ratio of the small-diameter alumina spherical particles is set to 30 vol%.
＜小径非球状粒子の粒径と配合量＞
小径アルミナ非球状粒子については、流動性が悪いものの、粒子同士の接触面積は球状粒子の場合に比べ大きくなることから、小径アルミナ非球状粒子を用いることは熱伝導の点で有効である。全アルミナ粒子の合計を100vol%とした場合に、小径アルミナ非球状粒子が10vol%より少ないとシート全体の熱伝導が悪くなる。小径アルミナ非球状粒子が35vol%より多いとマトリックスの流動性が低減し、シートが硬くなってしまう。そのため、小径アルミナ非球状粒子の配合比の下限値を10vol%とし、上限値を35vol%とした。
小径アルミナ非球状粒子の粒径が7μmより大きくなると、大径アルミナ球状粒子の隙間の大きな部分にしか充填することができず、大径アルミナ球状粒子の隙間を高充填することができなくなり、熱伝導率が低下する。さらに、隙間の大きな部分にしか入れない非球状粒子同士が互いの動きを抑制しあって柔軟性が損なわれ、シートの硬度も増加する。そのため、小径アルミナ非球状粒子の粒径の上限値を7μｍとした。
<Particle size and blending amount of non-spherical particles>
Although the fluidity of the small-diameter alumina non-spherical particles is poor, the contact area between the particles is larger than that in the case of spherical particles. Therefore, the use of small-diameter alumina non-spherical particles is effective in terms of heat conduction. When the total of all alumina particles is 100 vol%, if the small-diameter alumina non-spherical particles are less than 10 vol%, the heat conduction of the entire sheet is deteriorated. When the amount of non-spherical alumina non-spherical particles is more than 35 vol%, the fluidity of the matrix is reduced and the sheet becomes hard. Therefore, the lower limit value of the mixing ratio of the small-diameter non-spherical particles is 10 vol%, and the upper limit value is 35 vol%.
When the particle diameter of the small-diameter alumina non-spherical particles is larger than 7 μm, the large-diameter alumina spherical particles can be filled only in a large portion of the gap, and the large-diameter alumina spherical particles cannot be highly filled. Conductivity decreases. Furthermore, non-spherical particles that can only enter a large gap portion suppress the movement of each other, thereby reducing the flexibility and increasing the hardness of the sheet. Therefore, the upper limit of the particle diameter of the small-diameter non-spherical alumina particles is set to 7 μm.
小径アルミナ非球状粒子の粒径が0.5μｍより小さくなるとシートは柔軟にできるものの、大径アルミナ球状粒子の隙間で熱伝導に寄与する粒子数が多くなり粒子の間の接触熱抵抗が増加してしまい熱伝導が低下する。そのため、小径アルミナ球状粒子の粒径の下限値を0.5μｍとした。 Although the sheet can be made flexible when the particle size of the small alumina non-spherical particles is smaller than 0.5 μm, the number of particles contributing to heat conduction increases in the gaps between the large alumina spherical particles and the contact thermal resistance between the particles increases. As a result, heat conduction decreases. Therefore, the lower limit of the particle diameter of the small-diameter spherical spherical particles is set to 0.5 μm.
＜シート内のアルミナ配合粒子の比率＞
本発明の放熱シートでは、前述した大径アルミナ球状粒子と小径アルミナ球状粒子と小径アルミナ非球状粒子から構成されるアルミナ配合粒子とシート全体に含まれる樹脂との合計体積を100vol%とした場合、アルミナ配合粒子の比率（これをシート体積比という）が60vol%より少なくなると、熱伝導率が低い樹脂の比率が多くなるため、シートの熱伝導率が低下する。そのため、シート体積比の下限を60vol%とした。
また、シート体積比が90vol%より多くなると、本発明のマトリックス中の樹脂の相対量が少なくなるため、マトリックスの柔軟性が悪化し、大径アルミナ球状粒子の隙間を十分に埋めることが困難となり、熱伝導率が低下する。そのため、シート体積比の上限を90vol%とした。なお、シート体積比が70〜90vol%の場合には熱伝導率が6.0W/mK以上となり、より好適な範囲となる。
<Ratio of alumina-mixed particles in the sheet>
In the heat dissipation sheet of the present invention, when the total volume of the alumina-containing particles composed of the large-diameter alumina spherical particles, the small-diameter alumina spherical particles, and the small-diameter non-spherical particles and the resin contained in the entire sheet is 100 vol%, When the ratio of the alumina-mixed particles (this is referred to as the sheet volume ratio) is less than 60 vol%, the ratio of the resin having a low thermal conductivity increases, so the thermal conductivity of the sheet decreases. Therefore, the lower limit of the sheet volume ratio is set to 60 vol%.
Further, when the sheet volume ratio is more than 90 vol%, the relative amount of the resin in the matrix of the present invention decreases, so that the flexibility of the matrix deteriorates and it becomes difficult to sufficiently fill the gaps between the large-diameter spherical alumina particles. , Thermal conductivity decreases. Therefore, the upper limit of the sheet volume ratio is 90 vol%. When the sheet volume ratio is 70 to 90 vol%, the thermal conductivity is 6.0 W / mK or more, which is a more preferable range.
＜マトリックス中の樹脂比率＞
大径アルミナ球状粒子の隙間にマトリックスが十分に充填できるかを、マトリックスを形成する樹脂と小径アルミナ粒子の比率を基に評価できることが分かった。樹脂と小径アルミナ球状粒子および小径アルミナ非球状粒子との合計体積を100vol%とした場合、樹脂の比率が23vol%未満であると、樹脂と小径アルミナ球状粒子および小径アルミナ非球状粒子との混合物の粘度が高くなり、マトリックスが大径アルミナ球状粒子の隙間を十分に埋めることが困難となり、熱伝導率が低下する。また、マトリックスの柔軟性が損なわれるためシート硬度も高くなる。そのため、樹脂の比率の下限値を23vol%とした。また、樹脂の比率が65vol%を超えると、熱伝導率に寄与するマトリックス中の小径アルミナ球状粒子および小径アルミナ非球状粒子が相対的に少なくなり、熱伝導率が低下するため、樹脂の比率の上限値を65vol%とした。
<Resin ratio in the matrix>
It was found that whether the matrix can be sufficiently filled in the gaps between the large-diameter spherical spherical particles can be evaluated based on the ratio of the resin forming the matrix and the small-diameter alumina particles. When the total volume of the resin and small-diameter alumina spherical particles and small-diameter alumina non-spherical particles is 100 vol%, if the resin ratio is less than 23 vol%, the mixture of the resin and small-diameter alumina spherical particles and small-diameter alumina non-spherical particles The viscosity increases, it becomes difficult for the matrix to sufficiently fill the gaps between the large-diameter spherical alumina particles, and the thermal conductivity decreases. Further, since the flexibility of the matrix is impaired, the sheet hardness is increased. Therefore, the lower limit value of the resin ratio is set to 23 vol%. In addition, when the resin ratio exceeds 65 vol%, the small-diameter alumina spherical particles and the small-diameter nonspherical particles in the matrix that contribute to the thermal conductivity are relatively reduced, and the thermal conductivity is lowered. The upper limit was 65 vol%.
平均粒径50〜100μmの大径アルミナ球状粒子が60〜80vol%、平均粒径0.5〜７μmの小径アルミナ球状粒子が5〜30vol%、平均粒径0.5〜７μmの小径アルミナ非球状粒子が10〜35vol%、の配合であるアルミナ配合粒子の比率がシート体積比で60〜90vol%の場合に、5.6W/mK以上の高い熱伝導性とシート硬度60以下の柔軟性の両方の特性を備えた放熱シートが得られることが分かった。
以下、実施例にて詳細に説明する。
60-80 vol% of large-diameter spherical alumina particles with an average particle size of 50-100 μm, 5-30 vol% of small-diameter spherical alumina particles with an average particle size of 0.5-7 μm, and 10-10 small-sized alumina non-spherical particles with an average particle size of 0.5-7 μm When the volume ratio of alumina compounded particles, which is 35 vol%, is 60 to 90 vol% in the sheet volume ratio, it has both high thermal conductivity of 5.6 W / mK or more and flexibility of sheet hardness of 60 or less. It was found that a heat dissipation sheet was obtained.
Hereinafter, the embodiment will be described in detail.
放熱シートの原料は樹脂とアルミナ粒子であるが、樹脂は東レダウコーニングのシリコーンゲルCY52-276を用い、アルミナ粒子は平均粒径が40、50、83、100μmの大径球状粒子と平均粒径が0.3、0.5、7、8μmの小径非球状粒子と平均粒径が0.3、0.5、7、8μｍの小径球状粒子を用いた。
樹脂CY52-276（実際には、CY52-276A液とCY52-276B液を等量）と小径アルミナ非球状粒子と小径アルミナ球状粒子を表１〜3に示す体積量となるように秤量し、ハイブリッドミキサーを用いて混合した。得られた樹脂混合物に、大径アルミナ球状粒子を表1〜3に示す量を加え、ハイブリッドミキサーで発熱が起こらない時間条件で混合した。
The raw material of the heat dissipation sheet is resin and alumina particles, but the resin is Toray Dow Corning silicone gel CY52-276, the alumina particles are large spherical particles with an average particle size of 40, 50, 83, 100 μm and average particle size Were small non-spherical particles having an average particle size of 0.3, 0.5, 7, 8 μm and small spherical particles having an average particle size of 0.3, 0.5, 7, 8 μm.
Resin CY52-276 (actually, CY52-276A solution and CY52-276B solution are equivalent), small-diameter non-spherical alumina particles and small-diameter alumina spherical particles are weighed to the volume shown in Tables 1-3, and hybrid Mix using a mixer. The obtained resin mixture was added with large-diameter spherical spherical particles in the amounts shown in Tables 1 to 3, and mixed with a hybrid mixer under a time condition that does not generate heat.
得られた樹脂組成物を型枠に入れ、熱プレス装置を用いて、70℃で30分間、100kgf/cm2の加圧加熱処理を行ないシート成形した後に、樹脂の硬化反応を確実に行なわせるため、70℃1時間後、120℃で1時間ベーク処理を行ない、放熱シートを作製した。
得られた放熱シートについて、アスカーC硬度計を用いてシート硬度を測定し、50mmφ×2.5mmｔの試料を切り抜き、熱流計法による熱伝導率測定を行なった。
In order to ensure that the resin curing reaction is carried out after placing the obtained resin composition into a mold and performing sheet heating by applying pressure heat treatment of 100 kgf / cm2 at 70 ° C. for 30 minutes using a hot press device After 1 hour at 70 ° C., baking treatment was performed at 120 ° C. for 1 hour to produce a heat dissipation sheet.
About the obtained heat radiating sheet, sheet hardness was measured using an Asker C hardness meter, a sample of 50 mmφ × 2.5 mmt was cut out, and thermal conductivity was measured by a heat flow meter method.
表１の試料No.1〜4は大径アルミナ球状粒子の粒径を変えた場合、試料No.5〜12は小径アルミナ粒子の粒径を変えた場合の特性変化を表した実施例であり、表２の試料No.13〜16は大径アルミナ球状粒子と小径アルミナ粒子の配合を変えた場合、試料No.17〜24は小径アルミナ配合の非球状粒子と球状粒子の配合を変えた場合の特性変化を表した実施例であり、表３の試料No.25〜30はアルミナ配合粒子と樹脂の比率を変えた場合、Ｎｏ．31〜33はマトリックス中の樹脂と小径アルミナ粒子の比率を変えた場合の特性変化を表した実施例である。 Sample Nos. 1 to 4 in Table 1 are examples showing changes in characteristics when the particle diameters of large-diameter alumina spherical particles are changed, and Samples Nos. 5 to 12 are examples showing changes in characteristics when the particle diameters of small-diameter alumina particles are changed. Sample Nos. 13 to 16 in Table 2 have a different mixture of large-diameter alumina spherical particles and small-diameter alumina particles. Sample Nos. 17 to 24 have a different mixture of non-spherical particles and spherical particles mixed with small-diameter alumina. The sample Nos. 25 to 30 in Table 3 are No. 5 when the ratio of the alumina-mixed particles and the resin is changed. 31 to 33 are examples showing changes in characteristics when the ratio of the resin in the matrix and the small-diameter alumina particles is changed.
＜アルミナの粒径＞
試料No.1〜4は、小径アルミナ粒子の粒径と、樹脂とアルミナ配合粒子との体積比を本発明の範囲内の一定値として、大径アルミナ球状粒子の粒径を変化させた例である。試料No.1の大径アルミナ球状粒子の粒径が40μｍの場合、シート硬度は55と低いものの、熱伝導率が5.3W/mKと低い。大径アルミナ球状粒子の粒径が50〜100μｍの範囲において、シート硬度60以下かつ熱伝導率5.6W/mK以上となる。また、大径アルミナ球状粒子の粒径が80〜100μｍの範囲においては、シート硬度60以下かつ熱伝導率6.0W/mK以上となるため、さらに好適となる。
<Alumina particle size>
Samples Nos. 1 to 4 are examples in which the particle diameter of the small-diameter alumina particles and the volume ratio of the resin and alumina-mixed particles are set to a constant value within the scope of the present invention, and the particle diameter of the large-diameter alumina spherical particles is changed. is there. When the particle diameter of the large alumina spherical particles of sample No. 1 is 40 μm, the sheet hardness is as low as 55, but the thermal conductivity is as low as 5.3 W / mK. When the particle diameter of the large alumina spherical particles is in the range of 50 to 100 μm, the sheet hardness is 60 or less and the thermal conductivity is 5.6 W / mK or more. Moreover, when the particle diameter of the large-diameter spherical spherical particles is in the range of 80 to 100 μm, the sheet hardness is 60 or less and the thermal conductivity is 6.0 W / mK or more, which is more preferable.
試料No.5〜8は大径アルミナ球状粒子の粒径と、小径アルミナ球状粒子の粒径と、樹脂とアルミナ配合粒子との体積比を本発明の範囲内の一定値とし、小径アルミナ非球状粒子の粒径のみを変化させた例である。試料No.5の小径アルミナ非球状粒子の粒径が8μｍの場合、シート硬度が75と高く熱伝導率が5.4と低い。また、試料No.8の小径アルミナ非球状粒子の粒径が0.3μｍの場合、シート硬度は49と低いものの熱伝導率が5.1W/mKと低い。小径アルミナ非球状粒子の粒径が0.5〜7μｍの範囲において、シート硬度60以下かつ熱伝導率5.6W/mK以上となる。 Samples Nos. 5 to 8 have a small particle diameter of non-spherical alumina, with the particle diameter of large-diameter alumina spherical particles, the particle diameter of small-diameter alumina spherical particles, and the volume ratio of the resin and alumina-mixed particles within a range of the present invention. This is an example in which only the particle diameter is changed. When the particle size of the small-diameter non-spherical particles of sample No. 5 is 8 μm, the sheet hardness is as high as 75 and the thermal conductivity is as low as 5.4. Further, when the particle size of the small-diameter non-spherical particles of Sample No. 8 is 0.3 μm, the sheet conductivity is as low as 49, but the thermal conductivity is as low as 5.1 W / mK. When the particle diameter of the small-diameter non-spherical particles is in the range of 0.5 to 7 μm, the sheet hardness is 60 or less and the thermal conductivity is 5.6 W / mK or more.
試料No.9〜12は大径アルミナ球状粒子の粒径と、小径アルミナ非球状粒子の粒径と、樹脂とアルミナ配合粒子との体積比を本発明の範囲内の一定値とし、小径アルミナ球状粒子の粒径を変化させた例である。試料No.9の小径アルミナ球状粒子の粒径が8μｍの場合、シート硬度が68と高く熱伝導率が5.3と低い。また、試料No.12の小径アルミナ球状粒子の粒径が0.3μｍの場合、シート硬度は49と低いものの熱伝導率が5.0W/mKと低い。小径アルミナ球状粒子の粒径が0.5〜7μｍの範囲において、シート硬度60以下かつ熱伝導率5.6W/mK以上となる。 Samples Nos. 9 to 12 have a particle diameter of large-diameter alumina spherical particles, a small-diameter alumina non-spherical particle, and a volume ratio of resin and alumina-mixed particles to a constant value within the scope of the present invention. This is an example in which the particle size of the particles is changed. When the particle diameter of the small-diameter alumina spherical particles of Sample No. 9 is 8 μm, the sheet hardness is as high as 68 and the thermal conductivity is as low as 5.3. When the particle diameter of the small-diameter spherical alumina particles of Sample No. 12 is 0.3 μm, the sheet conductivity is as low as 49, but the thermal conductivity is as low as 5.0 W / mK. When the particle diameter of the small-sized alumina spherical particles is in the range of 0.5 to 7 μm, the sheet hardness is 60 or less and the thermal conductivity is 5.6 W / mK or more.
＜大小の粒子の配合＞
試料No.13〜16は大径アルミナ球状粒子の粒径と、小径アルミナ粒子の粒径と、樹脂とアルミナ配合粒子との体積比を本発明の範囲内の一定値とし、大径アルミナ球状粒子と小径アルミナ粒子の配合比を変化させ、大径粒子の配合比率を検討した例である。大径アルミナ球状粒子と小径アルミナ粒子の合計体積を100vol%とした場合、試料No.13の大径アルミナ球状粒子の配合比率が85vol%の場合、シート硬度は57と低いものの熱伝導率が5.1と低い。また、試料No.16の大径アルミナ球状粒子の配合比率が55vol%ではシート硬度は42と低いものの熱伝導率が5.3W/mKと低い。大径アルミナ球状粒子の配合比率が60〜80vol%の範囲において、シート硬度60以下かつ熱伝導率5.6W/mK以上となる。
<Combination of large and small particles>
Sample Nos. 13 to 16 have a large particle diameter of spherical alumina particles, a particle diameter of large particle alumina particles, a particle diameter of small particle alumina particles, and a volume ratio of resin and alumina compounded particles to a constant value within the scope of the present invention. This is an example in which the mixing ratio of large-diameter particles was examined by changing the mixing ratio of small-diameter alumina particles. When the total volume of large-diameter alumina spherical particles and small-diameter alumina particles is 100 vol%, when the mixing ratio of the large-diameter alumina spherical particles of sample No. 13 is 85 vol%, the sheet conductivity is as low as 57, but the thermal conductivity is 5.1. And low. Further, when the blending ratio of the large-diameter spherical spherical particles of Sample No. 16 is 55 vol%, the sheet conductivity is as low as 42, but the thermal conductivity is as low as 5.3 W / mK. When the blending ratio of the large-diameter spherical spherical particles is in the range of 60 to 80 vol%, the sheet hardness is 60 or less and the thermal conductivity is 5.6 W / mK or more.
＜小径の粒子配合＞
試料No.17〜20は大径アルミナ球状粒子の粒径と、小径アルミナ粒子の粒径と、樹脂とアルミナ配合粒子との体積比を本発明の範囲内の一定値とし、大径アルミナ球状粒子と小径アルミナ粒子の配合比を変化させ、小径アルミナ非球状粒子の配合比率を検討した例である。大径アルミナ球状粒子と小径アルミナ粒子の合計体積を100vol%とした場合、試料No.20の小径アルミナ非球状粒子の配合比率が36vol%の場合、シート硬度が65と高く熱伝導率が5.3と低い。また、試料No.17の小径アルミナ非球状粒子の配合比率が9vol%の場合、シート硬度は60と低いものの熱伝導率が5.5W/mKと低い。小径アルミナ非球状粒子の配合比率が10〜35vol%の範囲において、シート硬度60以下かつ熱伝導率5.6W/mK以上となる。
<Small-diameter particle formulation>
Sample Nos. 17 to 20 have a large particle diameter of spherical alumina particles, a small particle diameter of alumina particles, and a volume ratio of resin and alumina-mixed particles within a range of the present invention. This is an example in which the mixing ratio of small-diameter alumina non-spherical particles was examined by changing the mixing ratio of small-diameter alumina particles. When the total volume of large-diameter alumina spherical particles and small-diameter alumina particles is 100 vol%, when the mixing ratio of the small-diameter nonspherical particles of sample No. 20 is 36 vol%, the sheet hardness is 65 and the thermal conductivity is 5.3. Low. Further, when the blending ratio of the small-diameter non-spherical alumina particles of Sample No. 17 is 9 vol%, the sheet conductivity is as low as 60, but the thermal conductivity is as low as 5.5 W / mK. When the mixing ratio of the small-diameter non-spherical particles is in the range of 10 to 35 vol%, the sheet hardness is 60 or less and the thermal conductivity is 5.6 W / mK or more.
試料No.21〜24は大径アルミナ球状粒子の粒径と、小径アルミナ粒子の粒径と、樹脂とアルミナ配合粒子との体積比を本発明の範囲内の一定値とし、大径アルミナ球状粒子と小径アルミナ粒子の配合比を変化させ、小径アルミナ球状粒子の配合比率を検討した例である。大径アルミナ球状粒子と小径アルミナ粒子の合計体積を100vol%とした場合、試料No.24の小径アルミナ球状粒子の配合比率が4vol%では熱伝導率が5.8と高いもののシート硬度が66と高い。また、試料No.21の小径アルミナ球状粒子の配合比率が31vol%ではシート硬度は51と低いものの熱伝導率が5.4W/mKと低い。小径アルミナ球状粒子の配合比率が5〜30vol%の範囲において、シート硬度60以下かつ熱伝導率5.6W/mK以上となる。 Sample Nos. 21 to 24 are large-diameter alumina spherical particles having a large particle diameter of spherical alumina particles, a small particle diameter of alumina particles, and a volume ratio of resin and alumina-mixed particles within a range of the present invention. This is an example in which the blending ratio of small-diameter alumina particles is examined by changing the blending ratio of small-diameter alumina particles. When the total volume of the large-diameter alumina spherical particles and the small-diameter alumina particles is 100 vol%, the sheet hardness is as high as 66, although the thermal conductivity is as high as 5.8 when the mixing ratio of the small-diameter alumina spherical particles of sample No. 24 is 4 vol%. Further, when the mixing ratio of the small-diameter spherical alumina particles of Sample No. 21 is 31 vol%, the sheet conductivity is as low as 51, but the thermal conductivity is as low as 5.4 W / mK. When the blending ratio of the small-diameter spherical spherical particles is in the range of 5 to 30 vol%, the sheet hardness is 60 or less and the thermal conductivity is 5.6 W / mK or more.
＜シート内のアルミナ配合粒子の比率＞
試料No25〜30は、大径アルミナ球状粒子の粒径と小径アルミナ粒子の粒径と両者の粒子の比率を本発明の範囲内の一定値として、樹脂の量を変えてアルミナ粒子と樹脂との比率を変化させた例である。アルミナ粒子と樹脂の合計体積を100vol%とした場合、試料No.25や30の場合、アルミナ粒子の配合比率が60vol%未満や90vol%超であると、熱伝導率は5.6W/ｍK未満となり、60〜90vol%の範囲が好適である（これをシート体積比という）。なお、アルミナ粒子の配合比率が70〜90vol%であると、熱伝導率が6.0W/mKを超えてさらに好適な範囲となる。
<Ratio of alumina-mixed particles in the sheet>
Samples Nos. 25 to 30 were prepared by changing the amount of the resin between the alumina particles and the resin by changing the amount of the resin so that the particle size of the large-diameter spherical spherical particles, the particle size of the small-diameter alumina particles, and the ratio of both particles were constant values within the scope of the present invention. This is an example in which the ratio is changed. When the total volume of alumina particles and resin is 100 vol%, in the case of sample No. 25 and 30, if the mixing ratio of alumina particles is less than 60 vol% or more than 90 vol%, the thermal conductivity is less than 5.6 W / mK. The range of 60 to 90 vol% is preferable (this is referred to as the sheet volume ratio). When the mixing ratio of the alumina particles is 70 to 90 vol%, the thermal conductivity exceeds 6.0 W / mK and becomes a more preferable range.
試料No.31〜33は、大径アルミナ球状粒子の粒径と小径アルミナ粒子の粒径と両者の粒子の比率を本発明の範囲内の一定値として、マトリックスとなる樹脂と小径アルミナ粒子との比率を変化させた例である。試料No.31のマトリックス中の樹脂の比率が22vol%の場合、熱伝導率が5.9W/mKであり、試料No.33のマトリックス中の樹脂の比率が66vol%の際には熱伝導率は5.7W/mKの値を示した。マトリックス中の樹脂の比率が23〜65vol%の範囲である熱伝導率が6.0W/mKを超え、さらに好適となる。 Sample Nos. 31 to 33 were prepared by setting the particle diameter of the large-sized alumina spherical particles, the particle diameter of the small-diameter alumina particles, and the ratio of the two particles to a constant value within the scope of the present invention. This is an example in which the ratio is changed. When the ratio of the resin in the matrix of sample No. 31 is 22 vol%, the thermal conductivity is 5.9 W / mK, and when the ratio of the resin in the matrix of sample No. 33 is 66 vol%, the thermal conductivity is A value of 5.7 W / mK was shown. The thermal conductivity in which the ratio of the resin in the matrix is in the range of 23 to 65 vol% exceeds 6.0 W / mK, which is more preferable.
＜製造方法＞
以上の実施例はすべて前述のように、予め樹脂と小径アルミナ粒子を混合する工程と、得られた混合物に大径アルミナ球状粒子を混合する工程と、混合後の樹脂混合物を成形してシート化する工程により行なったものである。
比較例として、熱伝導率7.2W/mKシート硬度58と高特性のシートが得られた試料No.6の配合について、樹脂と大径アルミナ球状粒子と小径アルミナ粒子を同時に混合し、混合後の樹脂混合物を成形してシート化する工程を用い、アルミナ粒子の混合のタイミング以外の条件はすべて同一として放熱シートを作製した。得られたシートの特性は、シート硬度はほぼ同じ59であったが、熱伝導率が4.8W/mKと低かった。SEMにて内部を観察すると、大径アルミナ球状粒子の周りを樹脂のみが覆い、小径粒子と大径粒子の接触が見られず、本発明で必要なマトリックスが部分的にしか形成されてないことを確認した。
In all of the above examples, as described above, a step of previously mixing a resin and small-diameter alumina particles, a step of mixing large-diameter alumina spherical particles with the obtained mixture, and molding the resin mixture after mixing into a sheet The process is performed.
As a comparative example, for the composition of sample No. 6 obtained a sheet with a thermal conductivity of 7.2 W / mK sheet hardness 58 and a high characteristic, resin, large-diameter alumina spherical particles and small-diameter alumina particles were mixed simultaneously, Using the process of forming a resin mixture into a sheet, all the conditions other than the timing of mixing the alumina particles were the same, and a heat radiating sheet was produced. As for the characteristics of the obtained sheet, the sheet hardness was almost the same 59, but the thermal conductivity was as low as 4.8 W / mK. When the inside is observed with SEM, only the resin covers the large-sized alumina spherical particles, the contact between the small-sized particles and the large-sized particles is not seen, and the matrix necessary for the present invention is only partially formed. It was confirmed.
Claims (13)
It produces using the highly heat conductive resin molding of Claim 12, The manufacturing method of the thermal radiation sheet | seat characterized by the above-mentioned.
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| JPWO2019150944A1 (en) * | 2018-01-31 | 2020-04-02 | 積水ポリマテック株式会社 | Heat conductive composition and heat conductive molded article |
| WO2020217634A1 (en) * | 2019-04-24 | 2020-10-29 | 信越化学工業株式会社 | Thermally conductive silicone composition, method for producing same and thermally conductive silicone cured product |
| KR20220101082A (en) | 2019-11-15 | 2022-07-19 | 타츠타 전선 주식회사 | heat dissipation sheet |
| WO2021195204A1 (en) * | 2020-03-26 | 2021-09-30 | Ddp Specialty Electronic Materials Us, Llc | Thermal interface material comprising multimodally distributed spherical fillers |
| CN115135710A (en) * | 2020-03-26 | 2022-09-30 | Ddp特种电子材料美国有限责任公司 | Thermal interface material comprising a multimodal distribution of spherical fillers |
| KR20230156884A (en) | 2021-03-12 | 2023-11-15 | 타츠타 전선 주식회사 | thermal conductive sheet |
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