JP7402410B2 - Thermally conductive composite material, thermally conductive composite film and method for producing the same - Google Patents
Thermally conductive composite material, thermally conductive composite film and method for producing the same Download PDFInfo
- Publication number
- JP7402410B2 JP7402410B2 JP2018176540A JP2018176540A JP7402410B2 JP 7402410 B2 JP7402410 B2 JP 7402410B2 JP 2018176540 A JP2018176540 A JP 2018176540A JP 2018176540 A JP2018176540 A JP 2018176540A JP 7402410 B2 JP7402410 B2 JP 7402410B2
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- Prior art keywords
- boron nitride
- fine particles
- thermally conductive
- nitride fine
- composite material
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- 239000008096 xylene Substances 0.000 description 1
Description
本発明は、熱伝導性複合材料及びそれを用いた熱伝導性複合材料フィルム、並びにそれらの製造方法に関する。 The present invention relates to a thermally conductive composite material, a thermally conductive composite film using the same, and a method for producing the same.
窒化ホウ素は熱伝導性の高い高絶縁性の材料として知られており、窒化ホウ素粒子を熱伝導性フィラーとしてマトリックス中に分散させた様々な熱伝導性複合材料が開発されている。例えば、特開２０１０－２６０２２５号公報（特許文献１）では、平均粒子径が相違する２種類の窒化ホウ素粉末を熱伝導性フィラーとして含有するシリコーン積層体を積層方向から切断してなる熱伝導性成形体が開示されている。 Boron nitride is known as a highly insulating material with high thermal conductivity, and various thermally conductive composite materials have been developed in which boron nitride particles are dispersed in a matrix as a thermally conductive filler. For example, in JP-A No. 2010-260225 (Patent Document 1), a thermally conductive material obtained by cutting a silicone laminate containing two types of boron nitride powders with different average particle diameters as thermally conductive fillers from the lamination direction. A molded body is disclosed.
また、国際公開２０１３／０３９１０３号公報（特許文献２）では、平板状粒子である窒化ホウ素又はその凝集体である窒化ホウ素の表面に、粒状、繊維状又は平板状ベーマイトが結合又は付着して構成される無機フィラー複合体と樹脂とから構成される熱伝導性樹脂組成物が開示されている。 Furthermore, in International Publication No. 2013/039103 (Patent Document 2), granular, fibrous, or tabular boehmite is bonded or attached to the surface of boron nitride, which is a tabular particle, or boron nitride, which is an aggregate thereof. A thermally conductive resin composition comprising a resin and an inorganic filler composite is disclosed.
さらに、特開２０１５－６９８５号公報（特許文献３）では、窒化ホウ素凝集粒子中の一次粒子同士がカードハウス構造を有している窒化ホウ素凝集粒子よりなるフィラーと樹脂とを含む組成物が開示されている。 Furthermore, JP 2015-6985 A (Patent Document 3) discloses a composition containing a resin and a filler made of boron nitride aggregate particles in which the primary particles in the boron nitride aggregate particles have a card house structure. has been done.
しかしながら、このような従来の熱伝導性複合材料であっても、熱伝導性の向上に限界があり、必ずしも十分な熱伝導性を達成できるものではなかった。また、従来の熱伝導性複合材料においては、フィルム状にスライスしようとするとフィラーとマトリックスとの間の結合が十分でないため脆く、破断が生じ、熱抵抗の低い熱伝導性複合材料フィルムを得ることが困難という問題もあった。 However, even with such conventional thermally conductive composite materials, there is a limit to the improvement in thermal conductivity, and sufficient thermal conductivity cannot always be achieved. In addition, when trying to slice conventional thermally conductive composite materials into a film, the bond between the filler and the matrix is insufficient, resulting in brittleness and breakage, making it difficult to obtain a thermally conductive composite film with low thermal resistance. There was also the problem that it was difficult to
本発明は、上記従来技術の有する課題に鑑みてなされたものであり、優れた熱伝導性を有しており、かつ、破断の発生を十分に抑制しつつフィルム状にスライスすることが可能な熱伝導性複合材料、及びそれを用いた熱抵抗の低い熱伝導性複合材料フィルム、並びにそれらの製造方法を提供することを目的とする。 The present invention has been made in view of the problems of the prior art described above, and has excellent thermal conductivity and can be sliced into a film while sufficiently suppressing the occurrence of breakage. The object of the present invention is to provide a thermally conductive composite material, a thermally conductive composite film with low thermal resistance using the same, and a method for producing the same.
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、板状の窒化ホウ素粒子を含有する流体を高圧でノズルから噴射させて湿式衝突粉砕することにより得られる部分劈開窒化ホウ素微粒子を含有する窒化ホウ素粒子をマトリックスとしてのシリコーン樹脂中に分散させた後、一軸方向に圧縮成形することにより、優れた熱伝導性を有しており、かつ、破断の発生を十分に抑制しつつフィルム状にスライスすることが可能な熱伝導性複合材料が得られることを見出し、本発明を完成するに至った。 As a result of intensive research to achieve the above object, the inventors of the present invention have found that partially cleaved boron nitride fine particles are obtained by injecting a fluid containing plate-shaped boron nitride particles from a nozzle at high pressure and performing wet collision crushing. After dispersing boron nitride particles containing , in a silicone resin as a matrix, compression molding is carried out in a uniaxial direction, resulting in excellent thermal conductivity and sufficient prevention of breakage. The present inventors have discovered that a thermally conductive composite material that can be sliced into a film can be obtained, and have completed the present invention.
すなわち、本発明の熱伝導性複合材料は、窒化ホウ素微粒子のみからなる熱伝導性フィラーをマトリックス中に分散させてなる熱伝導性複合材料であって、
前記熱伝導性フィラーの含有量が、前記複合材料の全量に対して２０～７０体積％であり、
前記窒化ホウ素微粒子が板状の窒化ホウ素微粒子であり、かつ、前記マトリックスがシリコーン樹脂であり、
前記窒化ホウ素微粒子の少なくとも一部が、窒化ホウ素微粒子が部分的に劈開した部分劈開窒化ホウ素微粒子であり、
前記部分劈開窒化ホウ素微粒子の含有量が、前記窒化ホウ素微粒子の全量に対して２０体積％以上であり、
前記部分劈開窒化ホウ素微粒子の劈開空隙中に前記マトリックスが充填されて膨潤した膨潤窒化ホウ素微粒子が前記複合材料に含有されており、
前記複合材料の断面基準で、前記膨潤窒化ホウ素微粒子に相当する領域の合計面積が、前記複合材料の断面面積に対して１０～４０％であり、かつ、
前記窒化ホウ素微粒子の板状面が略一方向に配向している、
ことを特徴とするものである。
That is, the thermally conductive composite material of the present invention is a thermally conductive composite material in which a thermally conductive filler consisting only of boron nitride fine particles is dispersed in a matrix,
The content of the thermally conductive filler is 20 to 70% by volume based on the total amount of the composite material,
The boron nitride fine particles are plate-shaped boron nitride fine particles, and the matrix is a silicone resin,
At least a part of the boron nitride fine particles are partially cleaved boron nitride fine particles obtained by partially cleaving boron nitride fine particles,
The content of the partially cleaved boron nitride fine particles is 20% by volume or more with respect to the total amount of the boron nitride fine particles,
The composite material contains swollen boron nitride fine particles filled with the matrix and swollen in the cleavage voids of the partially cleaved boron nitride fine particles,
Based on the cross-section of the composite material, the total area of the region corresponding to the swollen boron nitride fine particles is 10 to 40% of the cross-sectional area of the composite material, and
The plate-like surfaces of the boron nitride fine particles are oriented in approximately one direction.
It is characterized by this.
また、本発明の熱伝導性複合材料においては、前記窒化ホウ素微粒子が、表面にシランカップリング剤が結合しているシラン化窒化ホウ素微粒子であることが好ましい。 Further, in the thermally conductive composite material of the present invention, it is preferable that the boron nitride fine particles are silanized boron nitride fine particles having a silane coupling agent bonded to the surface.
また、本発明の熱伝導性複合材料フィルムは、前記本発明の熱伝導性複合材料からなるものであり、厚みが５００μｍ以下であり、かつ、前記窒化ホウ素微粒子の板状面が略厚み方向に配向していることを特徴とするものである。 Further, the thermally conductive composite material film of the present invention is made of the thermally conductive composite material of the present invention, has a thickness of 500 μm or less, and has a plate-like surface of the boron nitride fine particles substantially in the thickness direction. It is characterized by being oriented.
さらに、本発明の熱伝導性複合材料の製造方法は、
板状窒化ホウ素粒子を含有する流体を高圧でノズルから噴射させて湿式衝突粉砕することにより、窒化ホウ素微粒子が部分的に劈開した部分劈開窒化ホウ素微粒子を含む窒化ホウ素微粒子を得る工程と、
前記部分劈開窒化ホウ素微粒子を含む窒化ホウ素微粒子のみからなる熱伝導性フィラーをマトリックスとしてのシリコーン樹脂中に分散させて、前記部分劈開窒化ホウ素微粒子の劈開空隙中に前記マトリックスが充填されて膨潤した膨潤窒化ホウ素微粒子を含有する混合物を得る工程と、
前記混合物を１～２０ＭＰａの圧力で一軸圧縮し、前記本発明の熱伝導性複合材料を得る工程と、
を含むことを特徴とする方法である。
Furthermore, the method for manufacturing a thermally conductive composite material of the present invention includes:
A step of obtaining boron nitride fine particles containing partially cleaved boron nitride fine particles in which the boron nitride fine particles are partially cleaved by injecting a fluid containing plate-shaped boron nitride particles from a nozzle at high pressure and performing wet collision crushing;
A thermally conductive filler made only of boron nitride fine particles including the partially cleaved boron nitride fine particles is dispersed in a silicone resin as a matrix, and the cleavage voids of the partially cleaved boron nitride fine particles are filled with the matrix and swell. obtaining a mixture containing boron nitride fine particles;
uniaxially compressing the mixture at a pressure of 1 to 20 MPa to obtain the thermally conductive composite material of the present invention;
The method is characterized in that it includes.
本発明の熱伝導性複合材料の製造方法においては、前記高圧が３０～２５０ＭＰａの圧力であり、前記流体を前記ノズルから噴射させる際の流速が２００～８００ｍ／ｓであることが好ましい。 In the method for producing a thermally conductive composite material of the present invention, it is preferable that the high pressure is a pressure of 30 to 250 MPa, and that the flow velocity when injecting the fluid from the nozzle is 200 to 800 m/s.
また、本発明の熱伝導性複合材料フィルムの製造方法は、前記本発明の熱伝導性複合材料を、前記窒化ホウ素微粒子の板状面の配向方向が略厚み方向となるように５００μｍ以下の厚みでスライスする工程を含むことを特徴とする方法である。 Further, the method for producing a thermally conductive composite material film of the present invention includes preparing the thermally conductive composite material of the present invention to a thickness of 500 μm or less such that the orientation direction of the plate-like surface of the boron nitride fine particles is approximately in the thickness direction. This method is characterized in that it includes a step of slicing.
なお、本発明の熱伝導性複合材料によって優れた熱伝導性が得られる理由は必ずしも定かではないが、本発明者らは以下のように推察する。すなわち、本発明の熱伝導性複合材料においては、熱伝導性フィラーとして用いられる窒化ホウ素微粒子のうちの少なくとも一部が、部分的に劈開して粒子の内部や端部に劈開面を有する部分劈開窒化ホウ素微粒子となっており、このような部分劈開窒化ホウ素微粒子は熱伝導性フィラーとしてマトリックス中に分散させる際に劈開空隙中にマトリックスが入り込んで膨潤した状態となる。そのため、部分的な劈開が形成されていない窒化ホウ素微粒子と比較して、このように膨潤した窒化ホウ素微粒子は見掛けの平均直径が増大するとともに変形しやすくなり、それによって複合材料中で窒化ホウ素微粒子間の接触が生じやすくなるとともに密着性が向上し、窒化ホウ素微粒子間の接触部位を通じて熱が拡散する熱伝導パスのネットワーク構造が効率良く形成されるとともに微粒子間の界面熱抵抗が大幅に低減するため、得られる複合材料の熱伝導性が向上して優れた熱伝導性が達成されるようになると本発明者らは推察する。また、窒化ホウ素微粒子内部の未劈開部分は、劈開前の窒化ホウ素粒子の高熱伝導性構造を保持しているため、粒子内部の熱の伝達も効率良く行うことができ、高熱伝導性の複合材料とした時に有利である。 Although the reason why the thermally conductive composite material of the present invention provides excellent thermal conductivity is not necessarily clear, the present inventors speculate as follows. That is, in the thermally conductive composite material of the present invention, at least some of the boron nitride fine particles used as the thermally conductive filler are partially cleaved and have cleavage planes inside and at the ends of the particles. When these partially cleaved boron nitride fine particles are dispersed in a matrix as a thermally conductive filler, the matrix enters the cleaved voids and becomes swollen. Therefore, compared to boron nitride particles in which no partial cleavage has been formed, the swollen boron nitride particles increase in apparent average diameter and are more easily deformed. Contact between the boron nitride microparticles becomes more likely to occur and adhesion improves, and a network structure of heat conduction paths is efficiently formed in which heat diffuses through the contact areas between the boron nitride microparticles, and the interfacial thermal resistance between the microparticles is significantly reduced. The present inventors conjecture that, as a result, the thermal conductivity of the resulting composite material is improved and excellent thermal conductivity is achieved. In addition, the uncleaved part inside the boron nitride fine particles retains the highly thermally conductive structure of the boron nitride particles before cleavage, so heat can be efficiently transferred inside the particles, making it possible to create highly thermally conductive composite materials. It is advantageous when
さらに、本発明の熱伝導性複合材料においては、板状の窒化ホウ素微粒子の熱伝導率の高い板状面が略一方向に配向しているため、窒化ホウ素微粒子同士が特に配向方向において良好に接触した状態となる。そのため、とりわけ配向方向における微粒子間の界面熱抵抗が大幅に低減すると共に、粒子内部の熱伝達も効率良く発揮されるようになり、特に配向方向における熱伝導性が高い複合材料が得られるようになる。 Furthermore, in the thermally conductive composite material of the present invention, since the plate-like surfaces of the plate-shaped boron nitride fine particles with high thermal conductivity are oriented in approximately one direction, the boron nitride fine particles can be easily bonded to each other, especially in the direction of orientation. They are in contact. Therefore, the interfacial thermal resistance between fine particles, especially in the orientation direction, is significantly reduced, and heat transfer inside the particles is also efficiently achieved, making it possible to obtain a composite material with high thermal conductivity, especially in the orientation direction. Become.
また、本発明の熱伝導性複合材料においては破断の発生を十分に抑制しつつフィルム状にスライスすることが可能となる理由も必ずしも定かではないが、本発明者らは以下のように推察する。すなわち、本発明の熱伝導性複合材料においては、熱伝導性フィラーとして用いられる窒化ホウ素微粒子のうちの少なくとも一部が部分劈開構造を有しているため、マトリックスとしてのシリコーン樹脂とフィラーとの結合がアンカー効果により強固となるため、フィルム状にスライスする際に亀裂の進展が抑制されるようになる。そのため、本発明の熱伝導性複合材料においては、板状窒化ホウ素微粒子の配向方向に対して垂直方向に薄く切り出す場合であっても、破壊や破れを生じることなくフィルム状にスライスすることが可能となるものと本発明者らは推察する。また、本発明の熱伝導性複合材料によれば、窒化ホウ素微粒子の板状面の配向方向が略厚み方向となっている熱伝導性複合材料フィルムを得ることが可能となるため、特に厚み方向における熱伝導性が高い複合材料フィルムが得られるようになる。さらに、このような複合材料フィルム中の板状窒化ホウ素微粒子における部分劈開構造は、単なる板状の構造と比較して、接触する表面に対して形状追従し易く、密着性が良好となるため、本発明の複合材料フィルムによれば界面熱抵抗が十分に低減されるようになるものと本発明者らは推察する。 Furthermore, the reason why the thermally conductive composite material of the present invention can be sliced into a film while sufficiently suppressing the occurrence of breakage is not necessarily clear, but the inventors speculate as follows. . That is, in the thermally conductive composite material of the present invention, at least a part of the boron nitride fine particles used as the thermally conductive filler has a partially cleaved structure, so that the bond between the silicone resin as the matrix and the filler is reduced. is strengthened by the anchor effect, which suppresses the propagation of cracks when slicing into films. Therefore, the thermally conductive composite material of the present invention can be sliced into a film without breaking or tearing, even when thinly sliced in a direction perpendicular to the orientation direction of the plate-shaped boron nitride fine particles. The present inventors conjecture that. Further, according to the thermally conductive composite material of the present invention, it is possible to obtain a thermally conductive composite material film in which the orientation direction of the plate-like surface of the boron nitride fine particles is approximately in the thickness direction. A composite film with high thermal conductivity can be obtained. Furthermore, the partially cleaved structure of the plate-shaped boron nitride fine particles in such a composite material film can easily follow the shape of the contacting surface compared to a simple plate-shaped structure, resulting in better adhesion. The present inventors conjecture that the composite material film of the present invention will sufficiently reduce the interfacial thermal resistance.
本発明によれば、優れた熱伝導性を有しており、かつ、破断の発生を十分に抑制しつつフィルム状にスライスすることが可能な熱伝導性複合材料、及びそれを用いた熱抵抗の低い熱伝導性複合材料フィルム、並びにそれらの製造方法を提供することが可能となる。 According to the present invention, there is provided a thermally conductive composite material that has excellent thermal conductivity and can be sliced into a film while sufficiently suppressing the occurrence of breakage, and a thermally conductive composite material using the same. It becomes possible to provide composite material films with low thermal conductivity and methods for producing them.
以下、本発明をその好適な実施形態に即して詳細に説明する。 Hereinafter, the present invention will be explained in detail based on its preferred embodiments.
先ず、本発明の熱伝導性複合材料について説明する。本発明の熱伝導性複合材料は、窒化ホウ素微粒子からなる熱伝導性フィラーをマトリックス中に分散させてなる熱伝導性複合材料であって、
前記窒化ホウ素微粒子が板状の窒化ホウ素微粒子であり、かつ、前記マトリックスがシリコーン樹脂であり、
前記窒化ホウ素微粒子の少なくとも一部が、窒化ホウ素微粒子が部分的に劈開した部分劈開窒化ホウ素微粒子であり、
前記部分劈開窒化ホウ素微粒子の劈開空隙中に前記マトリックスが充填されて膨潤した膨潤窒化ホウ素微粒子が前記複合材料に含有されており、かつ、
前記窒化ホウ素微粒子の板状面が略一方向に配向している、
ことを特徴とするものである。
First, the thermally conductive composite material of the present invention will be explained. The thermally conductive composite material of the present invention is a thermally conductive composite material in which a thermally conductive filler made of boron nitride fine particles is dispersed in a matrix,
The boron nitride fine particles are plate-shaped boron nitride fine particles, and the matrix is a silicone resin,
At least a part of the boron nitride fine particles are partially cleaved boron nitride fine particles obtained by partially cleaving boron nitride fine particles,
The composite material contains swollen boron nitride fine particles that are swollen by filling the cleavage voids of the partially cleaved boron nitride fine particles with the matrix, and
The plate-like surfaces of the boron nitride fine particles are oriented in approximately one direction.
It is characterized by this.
本発明において用いられる熱伝導性フィラーは、窒化ホウ素（ＢＮ）からなる板状の微粒子であり、窒化ホウ素には六方晶系の常圧相や立方晶系の高圧相等があるが、劈開のしやすさや熱伝導性の観点から板状の窒化ホウ素微粒子であることが必要であり、六方晶系の板状窒化ホウ素微粒子であることが特に好ましい。 The thermally conductive filler used in the present invention is plate-shaped fine particles made of boron nitride (BN), and boron nitride has a hexagonal normal pressure phase, a cubic high pressure phase, etc. From the viewpoint of ease and thermal conductivity, plate-shaped boron nitride fine particles are required, and hexagonal plate-shaped boron nitride fine particles are particularly preferable.
また、前記熱伝導性フィラーを構成する窒化ホウ素微粒子の大きさは特に制限されないが、平均粒子径が１～１００μｍであることが好ましく、２～５０μｍであることがより好ましく、３～３０μｍであることが特に好ましい。窒化ホウ素微粒子の平均粒子径が前記下限未満では、得られる複合材料において窒化ホウ素微粒子間の粒界抵抗及び複合材料中の粒界数が増大するため熱伝導性が低下する傾向にあり、他方、前記上限を超えると、得られる複合材料における熱伝導性フィラーの分散均一性及び充填率が低下して熱伝導性が低下する傾向にある。なお、本明細書において、「平均粒子径」は、原料粒子等に関するカタログ値を除き、走査型電子顕微鏡（ＳＥＭ）観察等により任意に抽出した３００個以上の粒子の粒子径の平均値を意味する。また、粒子の断面が円形状でない場合は、粒子（断面）の外接円を想定し、その外接円の直径を粒子径とする。 Further, the size of the boron nitride fine particles constituting the thermally conductive filler is not particularly limited, but the average particle diameter is preferably 1 to 100 μm, more preferably 2 to 50 μm, and 3 to 30 μm. This is particularly preferred. If the average particle diameter of the boron nitride fine particles is less than the lower limit, the thermal conductivity tends to decrease in the resulting composite material because the grain boundary resistance between the boron nitride fine particles and the number of grain boundaries in the composite material increase. When the above upper limit is exceeded, the dispersion uniformity and filling rate of the thermally conductive filler in the resulting composite material tend to decrease, leading to a decrease in thermal conductivity. In addition, in this specification, "average particle diameter" means the average value of the particle diameter of 300 or more particles arbitrarily extracted by scanning electron microscopy (SEM) observation, etc., excluding catalog values regarding raw material particles, etc. do. Furthermore, when the cross section of the particle is not circular, a circumscribed circle of the particle (cross section) is assumed, and the diameter of the circumscribed circle is defined as the particle diameter.
さらに、前記熱伝導性フィラーを構成する窒化ホウ素微粒子の形状は、いわゆる板状（鱗片状）のものであればよく、特に制限されないが、劈開のしやすさや熱伝導性の観点から、板状形状の粒子の厚みに対する板状面の直径の比（アスペクト比）の平均値が５～１００程度のものが好ましい。 Further, the shape of the boron nitride fine particles constituting the thermally conductive filler is not particularly limited as long as it is so-called plate-like (scale-like). It is preferable that the average ratio of the diameter of the plate-like surface to the thickness of the particle (aspect ratio) is about 5 to 100.
本発明においては、前記窒化ホウ素微粒子のうちの少なくとも一部が、窒化ホウ素微粒子が部分的に劈開した部分劈開窒化ホウ素微粒子となっていることが必要である。このような部分劈開窒化ホウ素微粒子は、窒化ホウ素微粒子が部分的に劈開して粒子の内部や端部に劈開面を有するものであり、熱伝導性フィラーとしてマトリックス中に分散させる際に劈開空隙（対向する劈開面の間の空隙）中にマトリックスが入り込んで膨潤した状態（膨潤窒化ホウ素微粒子）となる。 In the present invention, it is necessary that at least a part of the boron nitride fine particles be partially cleaved boron nitride fine particles, which are partially cleaved boron nitride fine particles. Such partially cleaved boron nitride fine particles are partially cleaved boron nitride fine particles and have cleavage planes inside and at the ends of the particles, and when dispersed in a matrix as a thermally conductive filler, cleavage voids ( The matrix enters the gap between the opposing cleavage planes and becomes swollen (swollen boron nitride fine particles).
なお、このような部分劈開窒化ホウ素微粒子は、得られる複合材料の断面の走査型電子顕微鏡（ＳＥＭ）写真において膨潤窒化ホウ素微粒子として観察され、明度と形状に基づいて、劈開されずに未劈開のまま残っている未劈開窒化ホウ素粒子や、窒化ホウ素粒子が劈開により完全に分割されて得られた内部や端部に劈開面を有していない完全劈開窒化ホウ素微粒子と区別することができる。さらに、ＦＩＢ－ＳＥＭ（集束イオンビーム－走査型電子顕微鏡）による三次元分散構造観察によっても区別が可能である。以下、このような未劈開窒化ホウ素粒子と完全劈開窒化ホウ素微粒子とを合わせて「非膨潤窒化ホウ素微粒子」と総称する。 In addition, such partially cleaved boron nitride fine particles are observed as swollen boron nitride fine particles in a scanning electron microscope (SEM) photograph of the cross section of the resulting composite material, and based on their brightness and shape, they are not cleaved but uncleaved. They can be distinguished from uncleaved boron nitride particles that remain as they are and completely cleaved boron nitride fine particles that do not have cleavage planes in the interior or at the ends, which are obtained by completely dividing boron nitride particles by cleavage. Furthermore, they can be distinguished by observing three-dimensional dispersion structures using FIB-SEM (Focused Ion Beam-Scanning Electron Microscope). Hereinafter, such uncleaved boron nitride particles and completely cleaved boron nitride fine particles will be collectively referred to as "non-swelling boron nitride fine particles."
本発明において用いられる熱伝導性フィラーにおいては、前記部分劈開窒化ホウ素微粒子の含有率が、前記窒化ホウ素微粒子の全量（前記部分劈開窒化ホウ素微粒子と前記未劈開窒化ホウ素粒子と前記完全劈開窒化ホウ素微粒子との総量）に対して５体積％以上となっていることが必要である。前記部分劈開窒化ホウ素微粒子の含有率が５体積％未満では、得られる複合材料中で窒化ホウ素微粒子間の接触部位を通じて熱が拡散する熱伝導パスのネットワーク構造が十分に形成されず、得られる複合材料の熱伝導性が十分に向上しない。また、得られる複合材料の熱伝導性がより向上するという観点から、前記部分劈開窒化ホウ素微粒子の含有率が前記窒化ホウ素微粒子の全量に対して１０体積％以上であることが好ましく、２０体積％以上であることがより好ましい。 In the thermally conductive filler used in the present invention, the content of the partially cleaved boron nitride fine particles is such that the total amount of the boron nitride fine particles (the partially cleaved boron nitride fine particles, the uncleaved boron nitride particles, and the completely cleaved boron nitride fine particles) It is necessary that the amount is 5% by volume or more based on the total amount of If the content of the partially cleaved boron nitride fine particles is less than 5% by volume, a network structure of heat conduction paths in which heat diffuses through contact sites between the boron nitride fine particles will not be formed sufficiently in the resulting composite material, and the resulting composite material will not have a sufficient network structure. The thermal conductivity of the material is not sufficiently improved. Further, from the viewpoint of further improving the thermal conductivity of the resulting composite material, it is preferable that the content of the partially cleaved boron nitride fine particles is 10% by volume or more, and 20% by volume, based on the total amount of the boron nitride fine particles. It is more preferable that it is above.
なお、前記窒化ホウ素微粒子の全量に対する前記部分劈開窒化ホウ素微粒子の含有率は、以下のようにして求められる。すなわち、得られる複合材料の断面の走査型電子顕微鏡写真（ＳＥＭ像）において、明度と形状に基づいて、
（ｉ）前記膨潤窒化ホウ素微粒子（前記部分劈開窒化ホウ素微粒子とその劈開空隙に取り込まれたマトリックス）に相当する領域と、
（ｉｉ）前記非膨潤窒化ホウ素微粒子（前記未劈開窒化ホウ素粒子及び前記完全劈開窒化ホウ素微粒子）に相当する領域と、
（ｉｉｉ）マトリックスのうち前記膨潤窒化ホウ素微粒子中に取り込まれずに存在するマトリックスに相当する領域と、
を区別して認識し、公知の二値化等の画像解析手法によりそれぞれの領域の面積を求めることができる。したがって、得られる複合材料の断面について、例えば、横６０μｍ以上、縦４０μｍ以上の測定領域を任意に１０箇所以上抽出し、それぞれの測定領域のＳＥＭ像において（ｉｉ）前記非膨潤窒化ホウ素微粒子に相当する領域の合計面積を求め、当該測定領域における全ての窒化ホウ素が未劈開窒化ホウ素粒子である場合の全窒化ホウ素粒子に相当する領域の合計面積との関係から当該領域における窒化ホウ素微粒子の全量に対する部分劈開窒化ホウ素微粒子の含有率を求めることができる。そして、全ての測定領域の平均値を算出することにより、用いた熱伝導性フィラーにおける前記窒化ホウ素微粒子の全量に対する前記部分劈開窒化ホウ素微粒子の含有率（平均値）が求められる。
The content of the partially cleaved boron nitride fine particles with respect to the total amount of the boron nitride fine particles is determined as follows. That is, in the scanning electron micrograph (SEM image) of the cross section of the composite material obtained, based on the brightness and shape,
(i) a region corresponding to the swollen boron nitride fine particles (the partially cleaved boron nitride fine particles and the matrix incorporated into the cleavage voids);
(ii) a region corresponding to the non-swelled boron nitride fine particles (the uncleaved boron nitride particles and the completely cleaved boron nitride fine particles);
(iii) a region of the matrix corresponding to the matrix existing without being incorporated into the swollen boron nitride fine particles;
It is possible to distinguish and recognize the areas, and calculate the area of each area using known image analysis techniques such as binarization. Therefore, for the cross section of the obtained composite material, arbitrarily extract 10 or more measurement regions of, for example, 60 μm or more in width and 40 μm or more in length, and in the SEM image of each measurement region, (ii) correspond to the non-swelling boron nitride fine particles. Calculate the total area of the regions to be measured, and calculate the total amount of boron nitride fine particles in the region from the relationship with the total area of the regions corresponding to all boron nitride particles when all boron nitride in the measurement region is uncleaved boron nitride particles. The content of partially cleaved boron nitride fine particles can be determined. Then, by calculating the average value of all measurement regions, the content rate (average value) of the partially cleaved boron nitride fine particles with respect to the total amount of the boron nitride fine particles in the thermally conductive filler used is determined.
このように本発明において用いられる熱伝導性フィラーは、前記部分劈開窒化ホウ素微粒子を所定量以上含有する前記窒化ホウ素微粒子からなるものであるが、マトリックスへの分散性をより向上させる観点から、窒化ホウ素微粒子の表面に水酸基、カルボキシル基、エステル基、アミド基、アミノ基等の官能基が結合していてもよい。 As described above, the thermally conductive filler used in the present invention is made of the boron nitride fine particles containing a predetermined amount or more of the partially cleaved boron nitride fine particles. A functional group such as a hydroxyl group, a carboxyl group, an ester group, an amide group, or an amino group may be bonded to the surface of the boron fine particles.
さらに、本発明の熱伝導性複合材料においては、マトリックスとしてのシリコーン樹脂と熱伝導性フィラーとの結合がより強固となり、薄くスライスする際の破壊や破れの発生をより確実に防止できるようになるという観点から、前記窒化ホウ素微粒子の表面にシランカップリング剤が結合してシラン化窒化ホウ素微粒子となっていることが好ましく、前記窒化ホウ素微粒子の表面に水酸基を介してシランカップリング剤が結合していることがより好ましい。ここで用いられるシランカップリング剤としては、特に制限されるものではなく、例えば、ビニルトリメトキシシラン、メチルトリメトキシシラン、フェニルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－メタクリロキシトリメトキシシラン、ｐ－スチリルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－イソシアネートトリエトキシシラン、メルカプトプロピルトリメトキシシランが挙げられる。 Furthermore, in the thermally conductive composite material of the present invention, the bond between the silicone resin as a matrix and the thermally conductive filler becomes stronger, making it possible to more reliably prevent breakage or tearing during thin slicing. From this viewpoint, it is preferable that a silane coupling agent is bonded to the surface of the boron nitride fine particles to form silanized boron nitride fine particles, and the silane coupling agent is bonded to the surface of the boron nitride fine particles via a hydroxyl group. It is more preferable that The silane coupling agent used here is not particularly limited, and examples thereof include vinyltrimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxysilane, Examples include trimethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-isocyanatetriethoxysilane, and mercaptopropyltrimethoxysilane.
また、本発明において用いられる熱伝導性フィラーは、前記部分劈開窒化ホウ素微粒子を所定量以上含有する前記窒化ホウ素微粒子のみからなるものであってもよいが、前記板状窒化ホウ素微粒子に加えて、例えば、板状グラファイト、板状窒化アルミニウム、板状アルミナ、アルミフレーク、銅フレーク、ダイヤモンド、窒化ケイ素等の他の熱伝導性粒子や、ＳｉＣ繊維、炭素繊維、カーボンナノチューブ、金属めっきを施した繊維、金属繊維等の他の熱伝導性繊維を更に含有していてもよい。 Further, the thermally conductive filler used in the present invention may consist only of the boron nitride fine particles containing a predetermined amount or more of the partially cleaved boron nitride fine particles, but in addition to the plate-shaped boron nitride fine particles, For example, other thermally conductive particles such as plate graphite, plate aluminum nitride, plate alumina, aluminum flakes, copper flakes, diamond, silicon nitride, SiC fibers, carbon fibers, carbon nanotubes, metal-plated fibers, etc. , may further contain other thermally conductive fibers such as metal fibers.
このように前記熱伝導性フィラーとして、前記窒化ホウ素微粒子に加えて他の熱伝導性材料が含有されている場合、他の熱伝導性材料として熱伝導率が２０Ｗ／ｍＫ以上である高熱伝導性微粒子が含有されていることが好ましく、そのような高熱伝導性微粒子としては等方的に高熱伝導性を有するものがより好ましい。このように前記板状窒化ホウ素微粒子に加えて前記高熱伝導性微粒子が含有されることにより、得られる熱伝導性複合材料における熱伝導性がより向上する傾向にある。 In this way, when the thermally conductive filler contains another thermally conductive material in addition to the boron nitride fine particles, the other thermally conductive material has a high thermal conductivity with a thermal conductivity of 20 W/mK or more. It is preferable that fine particles are contained, and as such high thermal conductive fine particles, those having high thermal conductivity isotropically are more preferable. By thus containing the high thermal conductivity fine particles in addition to the plate-shaped boron nitride fine particles, the thermal conductivity of the obtained thermally conductive composite material tends to be further improved.
また、このように前記高熱伝導性微粒子が含有されている場合は、前記窒化ホウ素微粒子が六方晶系の板状窒化ホウ素微粒子であり、かつ、前記高熱伝導性微粒子が、立方晶窒化ホウ素（熱伝導率：１０００～２０００Ｗ／ｍＫ）、ダイヤモンド（熱伝導率：２０００～３０００Ｗ／ｍＫ）、窒化アルミニウム（熱伝導率：１５０～３５０Ｗ／ｍＫ）、酸化アルミニウム（熱伝導率：２０～３５Ｗ／ｍＫ）、酸化マグネシウム（熱伝導率：４５～６０Ｗ／ｍＫ）、酸化亜鉛（熱伝導率：２０～３０Ｗ／ｍＫ）、窒化ケイ素（熱伝導率：８０～１００Ｗ／ｍＫ）及び炭化ケイ素（熱伝導率：１５０～１７０Ｗ／ｍＫ）からなる群から選択される少なくとも一種の微粒子であることが好ましい。なお、本明細書中における熱伝導率とは、室温（２０℃）における熱伝導率である。 In addition, when the high thermal conductive fine particles are contained in this way, the boron nitride fine particles are hexagonal plate-shaped boron nitride fine particles, and the high thermal conductive fine particles are cubic boron nitride (thermal conductivity: 1000-2000W/mK), diamond (thermal conductivity: 2000-3000W/mK), aluminum nitride (thermal conductivity: 150-350W/mK), aluminum oxide (thermal conductivity: 20-35W/mK) , magnesium oxide (thermal conductivity: 45 to 60 W/mK), zinc oxide (thermal conductivity: 20 to 30 W/mK), silicon nitride (thermal conductivity: 80 to 100 W/mK), and silicon carbide (thermal conductivity: 150 to 170 W/mK). In addition, the thermal conductivity in this specification is the thermal conductivity at room temperature (20 degreeC).
前記高熱伝導性微粒子の大きさは特に制限されないが、平均粒子径が０．１～１００μｍであることが好ましく、０．３～５０μｍであることがより好ましく、０．５～３０μｍであることが特に好ましい。前記高熱伝導性微粒子の平均粒子径が前記下限未満では、得られる複合材料において熱伝導性フィラー間の粒界抵抗及び複合材料中の粒界数が増大するため熱伝導性が低下する傾向にあり、他方、前記上限を超えると、得られる複合材料における熱伝導性フィラーの分散均一性及び充填率が低下して熱伝導性が低下する傾向にある。 The size of the highly thermally conductive fine particles is not particularly limited, but the average particle size is preferably 0.1 to 100 μm, more preferably 0.3 to 50 μm, and preferably 0.5 to 30 μm. Particularly preferred. If the average particle diameter of the highly thermally conductive fine particles is less than the lower limit, the thermal conductivity tends to decrease in the resulting composite material because the grain boundary resistance between the thermally conductive fillers and the number of grain boundaries in the composite material increase. On the other hand, when the above upper limit is exceeded, the dispersion uniformity and filling rate of the thermally conductive filler in the resulting composite material tend to decrease, leading to a decrease in thermal conductivity.
このように他の熱伝導性材料が含有される場合、本発明の熱伝導性フィラーの全量に対する前記窒化ホウ素微粒子の含有率は５体積％以上であることが好ましく、２０体積％以上であることがより好ましく、６０体積％以上であることが特に好ましい。 When other thermally conductive materials are contained in this way, the content of the boron nitride fine particles relative to the total amount of the thermally conductive filler of the present invention is preferably 5% by volume or more, and preferably 20% by volume or more. is more preferable, and particularly preferably 60% by volume or more.
本発明の熱伝導性複合材料においては、前記部分劈開窒化ホウ素微粒子を含有する板状窒化ホウ素微粒子からなる熱伝導性フィラーが、マトリックスとしてのシリコーン樹脂中に、前記窒化ホウ素微粒子の板状面が略一方向に配向するように分散して含有されており、前記部分劈開窒化ホウ素微粒子はその劈開空隙中に前記マトリックスが充填されて膨潤した膨潤窒化ホウ素微粒子となっている。 In the thermally conductive composite material of the present invention, a thermally conductive filler made of plate-like boron nitride fine particles containing the partially cleaved boron nitride fine particles is contained in a silicone resin as a matrix, and the plate-like surface of the boron nitride fine particles is disposed in a silicone resin as a matrix. The partially cleaved boron nitride fine particles are swollen boron nitride fine particles whose cleaved voids are filled with the matrix and swelled.
このような本発明の熱伝導性複合材料におけるマトリックスとしては、高～低温域における柔軟性、耐久性（熱的耐久性及び化学的耐久性）及び電気絶縁性に優れているという観点から、シリコーン樹脂であることが必要である。なお、本発明において用いられるシリコーン樹脂としては、特に制限されるものではなく、いわゆる付加型熱硬化シリコーン樹脂、縮合型熱硬化シリコーン樹脂、過酸化物硬化シリコーン樹脂、カチオン型ＵＶ硬化シリコーン樹脂のいずれであってもよく、また、いわゆるシリコーンゴムであってもよい。このようなシリコーン樹脂としては、成形の利便性、硬化制御性、シリコーン樹脂の物性及び異材接着性に優れているという観点から、メチルシリコーン樹脂、メチルフェニルシリコーン樹脂、フェニルシリコーン樹脂、及びそれらの変性体等が好ましい。 As the matrix in such a thermally conductive composite material of the present invention, silicone is used because it has excellent flexibility, durability (thermal durability and chemical durability), and electrical insulation in a high to low temperature range. It needs to be resin. The silicone resin used in the present invention is not particularly limited, and may be any of the so-called addition-type thermosetting silicone resins, condensation-type thermosetting silicone resins, peroxide-curing silicone resins, and cationic UV-curing silicone resins. It may also be a so-called silicone rubber. As such silicone resins, methyl silicone resins, methylphenyl silicone resins, phenyl silicone resins, and modified versions thereof are used from the viewpoint of convenience in molding, curing controllability, physical properties of silicone resins, and excellent adhesion to different materials. The body etc. are preferable.
本発明の熱伝導性複合材料においては、その断面基準で、前記膨潤窒化ホウ素微粒子に相当する領域の合計面積が、前記複合材料の断面面積に対して１～５０％となっていることが好ましい。前記膨潤窒化ホウ素微粒子に相当する領域の合計面積の比率が１％未満では、複合材料中で窒化ホウ素微粒子間の接触部位を通じて熱が拡散する熱伝導パスのネットワーク構造が十分に形成されず、得られる複合材料の熱伝導性が十分に向上しない傾向にある。一方、前記膨潤窒化ホウ素微粒子に相当する領域の合計面積の比率が５０％を超えると、複合材料にする際にフィラーがかさ高くなって取り扱いが困難となる傾向にある。また、複合材料の熱伝導性がより向上するという観点から、前記膨潤窒化ホウ素微粒子に相当する領域の合計面積の比率が、前記複合材料の断面面積に対して５～４５％であることがより好ましく、１０～４０％であることがさらにより好ましく、１５～３５％であることが特に好ましい。 In the thermally conductive composite material of the present invention, it is preferable that the total area of the region corresponding to the swollen boron nitride fine particles is 1 to 50% of the cross-sectional area of the composite material, based on its cross section. . If the ratio of the total area of the region corresponding to the swollen boron nitride fine particles is less than 1%, a network structure of thermal conduction paths in which heat diffuses through the contact sites between the boron nitride fine particles in the composite material will not be sufficiently formed, resulting in poor yield. Thermal conductivity of composite materials tends to be insufficiently improved. On the other hand, if the ratio of the total area of the region corresponding to the swollen boron nitride fine particles exceeds 50%, the filler tends to become bulky and difficult to handle when it is made into a composite material. Further, from the viewpoint of further improving the thermal conductivity of the composite material, it is preferable that the ratio of the total area of the region corresponding to the swollen boron nitride fine particles is 5 to 45% with respect to the cross-sectional area of the composite material. It is preferably 10 to 40%, even more preferably 15 to 35%.
なお、複合材料の断面基準で、前記膨潤窒化ホウ素微粒子に相当する領域の合計面積の比率（前記複合材料の断面面積に対する比率）は、以下のようにして求められる。すなわち、前述のとおり、複合材料の断面の走査型電子顕微鏡写真（ＳＥＭ像）において、明度と形状に基づいて、
（ｉ）前記膨潤窒化ホウ素微粒子（前記部分劈開窒化ホウ素微粒子とその劈開空隙に取り込まれたマトリックス）に相当する領域と、
（ｉｉ）前記非膨潤窒化ホウ素微粒子（前記未劈開窒化ホウ素粒子及び前記完全劈開窒化ホウ素微粒子）に相当する領域と、
（ｉｉｉ）マトリックスのうち前記膨潤窒化ホウ素微粒子中に取り込まれずに存在するマトリックスに相当する領域と、
を区別して認識し、公知の二値化等の画像解析手法によりそれぞれの領域の面積を求めることができる。したがって、複合材料の断面について、例えば、横６０μｍ以上、縦４０μｍ以上の測定領域を任意に１０箇所以上抽出し、それぞれの測定領域のＳＥＭ像において（ｉ）前記膨潤窒化ホウ素微粒子に相当する領域の合計面積を求め、当該測定領域の面積に対する比率として当該領域における前記膨潤窒化ホウ素微粒子に相当する領域の合計面積の比率を求めることができる。そして、全ての測定領域の平均値を算出することにより、測定対象の熱伝導性複合材料について、その断面基準で、前記膨潤窒化ホウ素微粒子に相当する領域の合計面積の比率（前記複合材料の断面面積に対する比率、平均値）が求められる。
Note that, based on the cross-section of the composite material, the ratio of the total area of the region corresponding to the swollen boron nitride fine particles (ratio to the cross-sectional area of the composite material) is determined as follows. That is, as mentioned above, in a scanning electron micrograph (SEM image) of a cross section of a composite material, based on the brightness and shape,
(i) a region corresponding to the swollen boron nitride fine particles (the partially cleaved boron nitride fine particles and the matrix incorporated into the cleavage voids);
(ii) a region corresponding to the non-swelled boron nitride fine particles (the uncleaved boron nitride particles and the completely cleaved boron nitride fine particles);
(iii) a region of the matrix corresponding to the matrix existing without being incorporated into the swollen boron nitride fine particles;
It is possible to distinguish and recognize the areas, and calculate the area of each area using known image analysis techniques such as binarization. Therefore, on the cross section of the composite material, for example, arbitrarily extract 10 or more measurement regions of 60 μm or more in width and 40 μm or more in length, and in the SEM image of each measurement region (i) The total area is determined, and the ratio of the total area of the region corresponding to the swollen boron nitride fine particles in the region can be determined as a ratio to the area of the measurement region. Then, by calculating the average value of all measurement regions, the ratio of the total area of the region corresponding to the swollen boron nitride fine particles (cross section of the composite material) is calculated based on the cross section of the thermally conductive composite material to be measured. (ratio to area, average value) is calculated.
本発明の熱伝導性複合材料においては、前記熱伝導性フィラーの含有率が前記複合材料の全量に対して１０～９０体積％であることが好ましく、１５～８０体積％であることがより好ましく、２０～７０体積％であることが特に好ましい。前記熱伝導性フィラーの含有率が前記下限未満では、複合材料中で窒化ホウ素微粒子（前記高熱伝導性微粒子を含有する場合は前記窒化ホウ素微粒子及び前記高熱伝導性微粒子）間の接触部位を通じて熱が拡散する熱伝導パスのネットワーク構造が十分に形成されず、得られる複合材料の熱伝導性が十分に向上しない傾向にある。一方、前記熱伝導性フィラーの含有率が前記上限を超えると、膨潤窒化ホウ素微粒子領域にマトリックスが十分に浸透せず、空隙が生じやすくなり、フィラーの部分劈開による高熱伝導化の効果が相殺されてしまい、また、粒子同士の立体的な干渉により充填率が低下してしまう傾向にある。 In the thermally conductive composite material of the present invention, the content of the thermally conductive filler is preferably 10 to 90% by volume, more preferably 15 to 80% by volume, based on the total amount of the composite material. , 20 to 70% by volume is particularly preferred. When the content of the thermally conductive filler is less than the lower limit, heat is transmitted through the contact area between the boron nitride fine particles (or the boron nitride fine particles and the high thermal conductive fine particles when the high thermal conductive fine particles are included) in the composite material. A network structure of diffusing heat conduction paths is not sufficiently formed, and the thermal conductivity of the resulting composite material tends not to be sufficiently improved. On the other hand, if the content of the thermally conductive filler exceeds the upper limit, the matrix will not sufficiently penetrate into the region of the swollen boron nitride fine particles, and voids will likely occur, canceling out the effect of increasing thermal conductivity due to partial cleavage of the filler. Furthermore, the filling rate tends to decrease due to steric interference between particles.
また、本発明の熱伝導性複合材料においては、前記部分劈開窒化ホウ素微粒子を含有する板状窒化ホウ素微粒子が、その板状面が略一方向に配向するように、マトリックスとしてのシリコーン樹脂中に分散して含有されている。このように板状の窒化ホウ素微粒子の板状面が略一方向に配向していることにより、窒化ホウ素微粒子同士が特に配向方向において良好に接触した状態となるため、とりわけ配向方向における微粒子間の界面熱抵抗が大幅に低減すると共に、粒子内部の熱伝達も効率良く発揮されるようになる。そのため、本発明の熱伝導性複合材料においては、特に配向方向において高い熱伝導性が達成されるようになる。 Further, in the thermally conductive composite material of the present invention, the plate-shaped boron nitride fine particles containing the partially cleaved boron nitride fine particles are placed in a silicone resin as a matrix such that the plate-like surface thereof is oriented in approximately one direction. Contained in a dispersed manner. Since the plate-like surfaces of the plate-shaped boron nitride fine particles are oriented in approximately one direction, the boron nitride fine particles are in good contact with each other, especially in the orientation direction. The interfacial thermal resistance is significantly reduced, and heat transfer inside the particles becomes more efficient. Therefore, in the thermally conductive composite material of the present invention, high thermal conductivity is achieved particularly in the orientation direction.
このように板状窒化ホウ素微粒子の板状面が略一方向に配向した状態は、後述する本発明の熱伝導性複合材料の製造方法において、熱伝導性フィラーとしての板状窒化ホウ素微粒子とマトリックスとしてのシリコーン樹脂との混合物を一軸方向に圧縮成形することによって得られるものであり、基本的に板状窒化ホウ素微粒子の板状面が、圧縮方向に対して垂直方向の平面（図１におけるｘ軸とｙ軸を含む平面）に対して略平行となる方向に配向した状態となる。なお、「板状面が略一方向に配向した状態」とは、全ての粒子の板状面が完全に一定方向に平行に配向した状態（一方向に理想的に配向した状態）のみならず、大半の粒子の板状面が概ね一定方向に配向していると認められる状態を含む趣旨であり、例えば、全粒子のうちの５０％以上（個数基準）の粒子の板状面の長手軸が、基準となる平面（例えば、図１におけるｘ軸とｙ軸を含む平面）に対する傾斜角が３０°以内となるように配向している状態が挙げられる。 This state in which the plate-like surfaces of the plate-shaped boron nitride fine particles are oriented in approximately one direction is the state in which the plate-shaped boron nitride fine particles as a thermally conductive filler and the matrix It is obtained by uniaxially compression molding a mixture with a silicone resin, and basically the plate-like surface of the plate-shaped boron nitride fine particles is a plane perpendicular to the compression direction (x in Fig. 1). The plane is oriented in a direction substantially parallel to the plane including the axis and the y-axis. Note that "a state in which the plate-like surfaces are oriented in approximately one direction" refers to not only a state in which the plate-like surfaces of all particles are completely oriented in parallel to a certain direction (a state in which they are ideally oriented in one direction). , includes a state in which the plate-like surfaces of most of the particles are recognized to be oriented in a generally constant direction, for example, the longitudinal axis of the plate-like surfaces of 50% or more (based on number) of all particles. is oriented such that the angle of inclination with respect to a reference plane (for example, a plane including the x-axis and y-axis in FIG. 1) is within 30°.
次に、本発明の熱伝導性複合材料の製造方法について説明する。 Next, a method for manufacturing the thermally conductive composite material of the present invention will be explained.
本発明の熱伝導性複合材料の製造方法は、
板状窒化ホウ素粒子を含有する流体を高圧でノズルから噴射させて湿式衝突粉砕することにより、窒化ホウ素微粒子が部分的に劈開した部分劈開窒化ホウ素微粒子を含む窒化ホウ素微粒子を得る工程（湿式粉砕工程）と、
前記部分劈開窒化ホウ素微粒子を含む窒化ホウ素微粒子からなる熱伝導性フィラーをマトリックスとしてのシリコーン樹脂中に分散させて、前記部分劈開窒化ホウ素微粒子の劈開空隙中に前記マトリックスが充填されて膨潤した膨潤窒化ホウ素微粒子を含有する混合物を得る工程（混合工程）と、
前記混合物を１～２０ＭＰａの圧力で一軸圧縮し、前記本発明の熱伝導性複合材料を得る工程（圧縮成形工程）と、
を含むことを特徴とする方法である。
The method for producing a thermally conductive composite material of the present invention includes:
A process of obtaining boron nitride fine particles containing partially cleaved boron nitride fine particles in which boron nitride fine particles are partially cleaved by injecting a fluid containing plate-shaped boron nitride particles from a nozzle at high pressure and performing wet collision crushing (wet crushing process) )and,
A thermally conductive filler made of boron nitride fine particles containing the partially cleaved boron nitride fine particles is dispersed in a silicone resin as a matrix, and the cleavage voids of the partially cleaved boron nitride fine particles are filled with the matrix and swelled. A step of obtaining a mixture containing boron fine particles (mixing step);
uniaxially compressing the mixture at a pressure of 1 to 20 MPa to obtain the thermally conductive composite material of the present invention (compression molding step);
The method is characterized in that it includes.
このような本発明にかかる湿式粉砕工程においては、原料粒子としての板状窒化ホウ素粒子を含有する流体を高圧でノズルから噴射させることにより、粒子同士が衝突あるいはせん断流動により微細化することによって結晶構造の破壊や過度の微細化を抑制しつつ湿式粉砕されるとともに、粒子が流体中で高圧でせん断流動圧縮させた状態から急激に圧力を低下させることにより、粒子に対して加わっていた圧力が急激に消失することで粒子内部から外部に向かって膨張する力が働き、それに伴って粒子が外側に引っ張られることによって粒子の内部や端部に部分的な劈開が生じて前述の部分劈開窒化ホウ素微粒子が得られるようになる。 In such a wet grinding process according to the present invention, a fluid containing plate-shaped boron nitride particles as raw material particles is injected from a nozzle at high pressure, so that the particles collide with each other or become fine due to shear flow, thereby forming crystals. In addition to wet crushing while suppressing structure destruction and excessive atomization, the pressure applied to the particles is reduced by rapidly reducing the pressure from the state in which the particles are sheared and compressed in a fluid at high pressure. The sudden disappearance causes a force to expand from the inside of the particle to the outside, which pulls the particle outward, causing partial cleavage at the inside and edges of the particle, resulting in the aforementioned partially cleaved boron nitride. Fine particles can now be obtained.
このような湿式粉砕工程に用いる装置としては、特に制限されず、原料粒子を含有する流体を高圧でノズルから噴射させて湿式衝突粉砕させて微細化する原理に基づく市販の湿式粉砕装置（湿式微細化装置）を用いることができる。また、窒化ホウ素粒子の結晶構造の破壊や過度の微細化を抑制しつつ湿式粉砕するという観点から、ストレート型のノズルを備える湿式粉砕装置を用いることが好ましい。 The equipment used in such a wet pulverization process is not particularly limited, and commercially available wet pulverization equipment (wet pulverization equipment) based on the principle of wet impact pulverization by injecting fluid containing raw material particles from a nozzle at high pressure to make it finer. oxidation equipment) can be used. Further, from the viewpoint of performing wet pulverization while suppressing destruction of the crystal structure of boron nitride particles and excessive miniaturization, it is preferable to use a wet pulverization apparatus equipped with a straight nozzle.
また、原料粒子として用いる板状窒化ホウ素粒子も特に制限されず、目的とする窒化ホウ素微粒子の平均粒子径等に応じて、平均粒子径が２～２００μｍ（より好ましくは１０～６０μｍ）程度の市販の板状窒化ホウ素粉末（好ましくは六方晶系の板状窒化ホウ素粉末）を用いることができる。 In addition, the plate-shaped boron nitride particles used as raw material particles are not particularly limited, and depending on the average particle size of the intended boron nitride fine particles, commercially available particles with an average particle size of about 2 to 200 μm (more preferably 10 to 60 μm) are used. A plate-shaped boron nitride powder (preferably a hexagonal plate-shaped boron nitride powder) can be used.
また、前記窒化ホウ素粒子とともにノズルから噴射させる流体の分散媒も特に制限されず、例えば、水；Ｎ－メチル－２－ピロリドン、クロロホルム、ジクロロメタン、四塩化炭素、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトン、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、酢酸イソブチル、酢酸ペンチル、酢酸イソペンチル、酢酸アミル、テトラヒドロフラン、ジメチルホルムアルデヒド、ジメチルアセトアミド、ジメチルスルホキシド、アセトニトリル、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、ヘキサノール、オクタノール、ヘキサフルオロイソプロパノール、エチレングリコール、プロピレングリコール、テトラメチレングリコール、テトラエチレングリコール、ヘキサメチレングリコール、ジエチレングリコール、ベンゼン、トルエン、キシレン、クロロベンゼン、ジクロロベンゼン、トリクロロベンゼン、クロロフェノール、フェノール、テトラヒドロフラン、スルホラン、１，３－ジメチル－２－イミダゾリジノン、γ－ブチロラクトン、Ｎ－ジメチルピロリドン、ペンタン、ヘキサン、ネオペンタン、シクロヘキサン、ヘプタン、オクタン、イソオクタン、ノナン、デカン、ジエチルエーテル等の有機溶媒；シリコーンオイル、流動パラフィン等のオイル類が挙げられる。 Further, the dispersion medium of the fluid injected from the nozzle together with the boron nitride particles is not particularly limited, and examples include water; N-methyl-2-pyrrolidone, chloroform, dichloromethane, carbon tetrachloride, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl Ketones, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, tetrahydrofuran, dimethyl formaldehyde, dimethyl acetamide, dimethyl sulfoxide, acetonitrile, methanol, ethanol, propanol, isopropanol, Butanol, hexanol, octanol, hexafluoroisopropanol, ethylene glycol, propylene glycol, tetramethylene glycol, tetraethylene glycol, hexamethylene glycol, diethylene glycol, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, chlorophenol, phenol, tetrahydrofuran , sulfolane, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, N-dimethylpyrrolidone, pentane, hexane, neopentane, cyclohexane, heptane, octane, isooctane, nonane, decane, diethyl ether, and other organic solvents; silicone Examples include oils such as oil and liquid paraffin.
さらに、前記窒化ホウ素粒子を含有する流体（分散液）の濃度も特に制限されないが、前記窒化ホウ素粒子の含有率が０．１～２０体積％が好ましく、０．５～１０体積％がより好ましい。前記分散液の濃度が前記下限未満では劈開窒化ホウ素微粒子の収率が小さくなる傾向にあり、他方、前記上限を超えると分散液の粘度が高くなり粉砕処理が困難となる傾向にある。 Further, the concentration of the fluid (dispersion liquid) containing the boron nitride particles is not particularly limited, but the content of the boron nitride particles is preferably 0.1 to 20% by volume, more preferably 0.5 to 10% by volume. . If the concentration of the dispersion liquid is less than the lower limit, the yield of cleaved boron nitride fine particles tends to be low, while if it exceeds the upper limit, the viscosity of the dispersion liquid tends to increase, making pulverization difficult.
また、前記湿式粉砕処理の際の諸条件としては、特に制限されるものではないが、前記部分劈開窒化ホウ素微粒子が効率良く得られるという観点から、以下の諸条件が好ましい。
噴射前圧力：３０～２５０ＭＰａ（より好ましくは５０～２００ＭＰａ）
噴射後圧力：常圧
ノズル径：０．１～０．５ｍｍ
流量：０．１～７．０Ｌ／ｍｉｎ（より好ましくは０．５～１．１Ｌ／ｍｉｎ）
ノズル噴射流速：２００～８００ｍ／ｓ（より好ましくは３００～７００ｍ／ｓ）。
Further, the conditions for the wet pulverization treatment are not particularly limited, but the following conditions are preferred from the viewpoint of efficiently obtaining the partially cleaved boron nitride fine particles.
Pre-injection pressure: 30 to 250 MPa (more preferably 50 to 200 MPa)
Pressure after injection: normal pressure Nozzle diameter: 0.1-0.5mm
Flow rate: 0.1 to 7.0 L/min (more preferably 0.5 to 1.1 L/min)
Nozzle jet flow velocity: 200 to 800 m/s (more preferably 300 to 700 m/s).
前記湿式粉砕処理における噴射前圧力や流量やノズル噴射流速が前記下限未満では、前記窒化ホウ素粒子の劈開が進行しにくくなり、前記部分劈開窒化ホウ素微粒子が十分に得られなくなる傾向にある。他方、前記湿式粉砕処理における噴射前圧力や流量やノズル噴射流速が前記上限を超えると、前記窒化ホウ素粒子の劈開が進行し過ぎてしまい、大半の窒化ホウ素粒子が劈開により完全に分割されて前記完全劈開窒化ホウ素微粒子となり、前記部分劈開窒化ホウ素微粒子が十分に得られなくなる傾向にある。 If the pre-injection pressure, flow rate, or nozzle injection flow rate in the wet pulverization treatment is less than the lower limit, cleavage of the boron nitride particles becomes difficult to proceed, and the partially cleaved boron nitride fine particles tend to be insufficient. On the other hand, if the pre-injection pressure, flow rate, or nozzle injection velocity in the wet pulverization process exceeds the upper limit, the cleavage of the boron nitride particles will proceed too much, and most of the boron nitride particles will be completely divided by the cleavage, resulting in the Completely cleaved boron nitride fine particles result, and there is a tendency that the partially cleaved boron nitride fine particles cannot be obtained sufficiently.
さらに、前記窒化ホウ素粒子に前記湿式粉砕処理を施す回数は１回でもよいが、前記窒化ホウ素粒子に前記湿式粉砕処理を繰り返し施して所望量の前記部分劈開窒化ホウ素微粒子を含む窒化ホウ素微粒子を得るようにしてもよい。このように前記湿式粉砕処理を繰り返し施す場合、その繰り返す回数（パス数）は２～２０回（より好ましくは２～１０回）程度が好ましい。湿式粉砕処理を繰り返す回数（パス数）が前記上限を超えると、前記窒化ホウ素粒子の劈開が進行し過ぎてしまい、大半の窒化ホウ素粒子が劈開により完全に分割されて前記完全劈開窒化ホウ素微粒子となり、前記部分劈開窒化ホウ素微粒子が十分に得られなくなる傾向にある。 Furthermore, the boron nitride particles may be subjected to the wet pulverization treatment once, but the boron nitride particles may be repeatedly subjected to the wet pulverization treatment to obtain boron nitride fine particles containing a desired amount of the partially cleaved boron nitride fine particles. You can do it like this. When the wet pulverization treatment is repeated in this manner, the number of repetitions (pass number) is preferably about 2 to 20 times (more preferably 2 to 10 times). If the number of times the wet pulverization process is repeated (number of passes) exceeds the upper limit, the cleavage of the boron nitride particles will progress too much, and most of the boron nitride particles will be completely divided by the cleavage to become the completely cleaved boron nitride fine particles. , there is a tendency that the partially cleaved boron nitride fine particles cannot be obtained sufficiently.
前記湿式粉砕工程においては、前記湿式粉砕処理の後に、必要に応じてろ過、洗浄、及び乾燥処理を施して前記部分劈開窒化ホウ素微粒子を含む前記窒化ホウ素微粒子を得るが、かかるろ過、洗浄、及び乾燥処理としてはいずれも特に制限されず、公知の方法を適宜採用することができる。 In the wet pulverization step, after the wet pulverization treatment, filtration, washing, and drying are performed as necessary to obtain the boron nitride fine particles containing the partially cleaved boron nitride fine particles. The drying process is not particularly limited, and any known method can be used as appropriate.
次に、本発明の熱伝導性複合材料の製造方法においては、前記部分劈開窒化ホウ素微粒子を含む窒化ホウ素微粒子からなる熱伝導性フィラーをマトリックスとしてのシリコーン樹脂中に分散させて、前記部分劈開窒化ホウ素微粒子の劈開空隙中に前記マトリックスが充填されて膨潤した膨潤窒化ホウ素微粒子を含有する混合物を得る工程（混合工程）と、その後に、前記混合物を１～２０ＭＰａの圧力で一軸圧縮し、前記本発明の熱伝導性複合材料を得る工程（圧縮成形工程）とが実施される、
このような本発明にかかる混合工程においては、先ず、前記部分劈開窒化ホウ素微粒子を含む板状窒化ホウ素微粒子からなる熱伝導性フィラーとマトリックスとしてのシリコーン樹脂とを混合する。その際、得られる複合材料中の熱伝導性フィラーの含有率が目的の含有率となるように熱伝導性フィラーとマトリックスとの混合割合を定める。また、熱伝導性フィラーとマトリックスとを混合する方法は特に制限されず、公知の混合方法が適宜用いられる。
Next, in the method for producing a thermally conductive composite material of the present invention, a thermally conductive filler made of boron nitride fine particles containing the partially cleaved boron nitride fine particles is dispersed in a silicone resin as a matrix, and the partially cleaved nitride A step (mixing step) of obtaining a mixture containing swollen boron nitride fine particles filled with the matrix in the cleavage voids of the boron fine particles, and then uniaxially compressing the mixture at a pressure of 1 to 20 MPa, A step (compression molding step) of obtaining a thermally conductive composite material of the invention is carried out,
In such a mixing step according to the present invention, first, a thermally conductive filler made of plate-shaped boron nitride fine particles containing the partially cleaved boron nitride fine particles and a silicone resin as a matrix are mixed. At that time, the mixing ratio of the thermally conductive filler and the matrix is determined so that the content of the thermally conductive filler in the resulting composite material becomes the desired content. Further, the method of mixing the thermally conductive filler and the matrix is not particularly limited, and any known mixing method may be used as appropriate.
なお、このようなマトリックスとして硬化前のシリコーン樹脂を用いる場合、前記熱伝導性フィラーと前記樹脂とを混合して均一混合物とし、得られた混合物を後述する圧縮成形することにより前記熱伝導性複合材料を得ることができる。すなわち、このように前記熱伝導性フィラーと前記樹脂とを混合及び成形する過程において、前記部分劈開窒化ホウ素微粒子の劈開空隙中に前記樹脂が入り込んで膨潤窒化ホウ素微粒子となり、前記膨潤窒化ホウ素微粒子を含有する熱伝導性複合材料が得られる。 In addition, when using a silicone resin before curing as such a matrix, the thermally conductive filler and the resin are mixed to form a homogeneous mixture, and the resulting mixture is compression molded as described below to form the thermally conductive composite. materials can be obtained. That is, in the process of mixing and molding the thermally conductive filler and the resin in this manner, the resin enters the cleavage voids of the partially cleaved boron nitride fine particles to become swollen boron nitride fine particles, and the swollen boron nitride fine particles are formed. A thermally conductive composite material is obtained.
このように前記熱伝導性フィラーと前記シリコーン樹脂とを混合して均一混合物とする際に、分散媒を更に加えて均一スラリーとしてもよく、その場合は真空乾燥等の公知の方法で分散媒を除去した後に成形することが好ましい。このような分散媒としては特に制限されず、前記窒化ホウ素粒子とともにノズルから噴射させる流体の分散媒として挙げた有機溶媒と同様の有機溶媒を適宜用いてもよい。 In this way, when mixing the thermally conductive filler and the silicone resin to form a uniform mixture, a dispersion medium may be further added to form a uniform slurry. In that case, the dispersion medium may be removed by a known method such as vacuum drying. It is preferable to mold it after removing it. Such a dispersion medium is not particularly limited, and organic solvents similar to those mentioned above as the dispersion medium of the fluid injected from the nozzle together with the boron nitride particles may be used as appropriate.
また、本発明にかかる圧縮成形工程における圧縮方法としては、一軸圧縮であればよく、具体的な圧縮方法は特に制限されない。また、圧縮時の圧力は、１～２０ＭＰａであることが必要であり、３～１０ＭＰａであることがより好ましい。圧縮時の圧力が前記下限未満になると、得られる複合材料に空隙が残存しやすくなるとともに、板状窒化ホウ素微粒子の板状面が圧縮方向に対して略垂直な方向に十分に配向した状態とすることが困難となる。他方、圧縮時の圧力が前記上限を超えると、得られる複合材料内のフィラーの配向制御が困難となり、残留ひずみが発生する傾向にある。また、圧縮成形する際の温度と時間も特に制限されないが、室温～１５０℃程度で１０～１０００分程度が一般的である。 Moreover, the compression method in the compression molding process according to the present invention may be any uniaxial compression, and the specific compression method is not particularly limited. Further, the pressure during compression needs to be 1 to 20 MPa, more preferably 3 to 10 MPa. When the pressure during compression is less than the lower limit, voids tend to remain in the resulting composite material, and the plate-shaped surfaces of the plate-shaped boron nitride particles are sufficiently oriented in a direction substantially perpendicular to the compression direction. It becomes difficult to do so. On the other hand, if the pressure during compression exceeds the upper limit, it becomes difficult to control the orientation of the filler in the resulting composite material, and residual strain tends to occur. Further, the temperature and time for compression molding are not particularly limited, but are generally about 10 to 1000 minutes at room temperature to about 150°C.
さらに、前記混合物を成形する際に樹脂を硬化させる方法としては特に制限はなく、用いるシリコーン樹脂に応じて公知の硬化方法を適宜採用することができる。また、このような硬化は、成形時又は成形後のいずれにおいて実施してもよいが、圧縮成形後に硬化させることが好ましい。 Further, there is no particular restriction on the method of curing the resin when molding the mixture, and any known curing method can be appropriately employed depending on the silicone resin used. Further, such curing may be performed either during molding or after molding, but it is preferable to perform curing after compression molding.
次に、本発明の熱伝導性複合材料フィルム及びその製造方法について説明する。 Next, the thermally conductive composite material film of the present invention and its manufacturing method will be explained.
本発明の熱伝導性複合材料フィルムは、前記本発明の熱伝導性複合材料からなるものであり、厚みが５００μｍ以下であり、かつ、前記窒化ホウ素微粒子の板状面が略厚み方向に配向していることを特徴とするものである。また、本発明の熱伝導性複合材料フィルムの製造方法は、前記本発明の熱伝導性複合材料を、前記窒化ホウ素微粒子の板状面の配向方向が略厚み方向となるように５００μｍ以下の厚みでスライスする工程を含むことを特徴とする方法である。 The thermally conductive composite material film of the present invention is made of the thermally conductive composite material of the present invention, has a thickness of 500 μm or less, and has a plate-like surface of the boron nitride fine particles oriented substantially in the thickness direction. It is characterized by the fact that Further, the method for producing a thermally conductive composite material film of the present invention includes preparing the thermally conductive composite material of the present invention to a thickness of 500 μm or less such that the orientation direction of the plate-like surface of the boron nitride fine particles is approximately in the thickness direction. This method is characterized in that it includes a step of slicing.
前述のとおり、本発明の熱伝導性複合材料においては、熱伝導性フィラーとして用いられる窒化ホウ素微粒子のうちの少なくとも一部が部分劈開構造を有しているため、マトリックスとしてのシリコーン樹脂とフィラーとの結合がアンカー効果により強固となるため、フィルム状にスライスする際に亀裂の進展が抑制されるようになる。そのため、本発明の熱伝導性複合材料においては、板状窒化ホウ素微粒子の配向方向に対して垂直方向に薄く切り出す場合であっても、破壊や破れを生じることなくフィルム状にスライスすることが可能となる。 As mentioned above, in the thermally conductive composite material of the present invention, at least a part of the boron nitride fine particles used as the thermally conductive filler has a partially cleaved structure, so that the silicone resin as the matrix and the filler are Since the bond between the two becomes stronger due to the anchor effect, the propagation of cracks is suppressed when slicing into a film. Therefore, the thermally conductive composite material of the present invention can be sliced into a film without breaking or tearing, even when thinly sliced in a direction perpendicular to the orientation direction of the plate-shaped boron nitride fine particles. becomes.
したがって、本発明の熱伝導性複合材料フィルムのように、窒化ホウ素微粒子の板状面の配向方向が略厚み方向となっている熱伝導性複合材料フィルムを得ることが可能となるため、特に厚み方向における熱伝導性が高い複合材料フィルムが得られるようになる。 Therefore, like the thermally conductive composite film of the present invention, it is possible to obtain a thermally conductive composite film in which the orientation direction of the plate-like surface of the boron nitride fine particles is approximately in the thickness direction. A composite film with high thermal conductivity in the direction can now be obtained.
このようにして得られる本発明の熱伝導性複合材料フィルムの厚みは５００μｍ以下であることが必要であり、３０～２００μｍであることがより好ましい。熱伝導性複合材料フィルムの厚みが前記上限を超えると、熱伝導性複合材料フィルムを当接せしめる対象となる基材の表面に対して形状が追従しにくくなり、熱伝導性複合材料フィルムと基材との間の界面熱抵抗の低減が達成されにくくなる。 The thickness of the thermally conductive composite material film of the present invention obtained in this manner must be 500 μm or less, and more preferably 30 to 200 μm. If the thickness of the thermally conductive composite material film exceeds the above upper limit, it becomes difficult for the thermally conductive composite material film to follow the surface of the base material against which it is brought into contact, and the thermally conductive composite material film and the base material become difficult to follow. It becomes difficult to achieve a reduction in the interfacial thermal resistance between the material and the material.
また、本発明の熱伝導性複合材料を薄く切り出す（スライス）方法は、特に制限されず、例えば、熱伝導性複合材料からフィルムを切り出す側の面を粘着剥離材で固定した後、切削機や切断機を用いてフィルム状にスライスして所望の膜厚の熱伝導性複合材料フィルムを切り出し、その後に粘着剥離材から熱伝導性複合材料フィルムを剥離する方法が挙げられる。 Furthermore, the method of slicing the thermally conductive composite material of the present invention is not particularly limited. An example of this method is to cut out a thermally conductive composite material film of a desired thickness by slicing it into a film using a cutting machine, and then peel the thermally conductive composite material film from an adhesive release material.
以下、実施例および比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.
（実施例１）
原料粒子としての窒化ホウ素粒子としてモメンティブ社製「窒化ホウ素（ＢＮ）パウダー ＰＴ１１０」（平均粒子径：４０μｍ、六方晶板状窒化ホウ素（ＢＮ）粒子）を用い、Ｎ－メチル－２－ピロリドン（ＮＭＰ）を分散媒とする５体積％分散液を得た。次いで、市販のストレート型ノズルを備えた湿式粉砕装置を用い、噴射前のチャンバー内圧力を１００ＭＰａとし、前記窒化ホウ素粒子を含有する分散液をノズル（ノズル径：０．２ｍｍ）から流量０．７５６Ｌ／ｍｉｎ、流速４４７ｍ／ｓで噴射させ、高圧でせん断流動圧縮された状態から常圧まで急激に圧力を低下させることにより、１回目の湿式粉砕処理が施された分散液を得た。さらに、得られた分散液を再び同じ条件でノズルから噴射させる湿式粉砕処理を計２回繰り返し（パス数：２回）、湿式粉砕された窒化ホウ素微粒子を含有する分散液を得た。そして、得られた分散液から窒化ホウ素微粒子をろ過し、メタノールで洗浄した後に真空乾燥して、湿式粉砕された窒化ホウ素微粒子（粉砕ＢＮ）を得た。得られた窒化ホウ素微粒子の平均粒子径は１７μｍであった。
(Example 1)
"Boron nitride (BN) powder PT110" manufactured by Momentive (average particle size: 40 μm, hexagonal plate-shaped boron nitride (BN) particles) was used as boron nitride particles as raw material particles, and N-methyl-2-pyrrolidone (NMP) was used. ) was used as a dispersion medium to obtain a 5% by volume dispersion. Next, using a commercially available wet grinding device equipped with a straight nozzle, the chamber pressure before injection was set to 100 MPa, and the dispersion containing the boron nitride particles was passed through the nozzle (nozzle diameter: 0.2 mm) at a flow rate of 0.756 L. /min, at a flow rate of 447 m/s, and the pressure was rapidly lowered from a high pressure shear flow compressed state to normal pressure, to obtain a dispersion that had been subjected to the first wet pulverization treatment. Furthermore, the wet pulverization treatment in which the obtained dispersion was again injected from a nozzle under the same conditions was repeated twice (number of passes: 2 times) to obtain a dispersion containing wet-pulverized boron nitride fine particles. Then, boron nitride fine particles were filtered from the obtained dispersion, washed with methanol, and then vacuum dried to obtain wet-pulverized boron nitride fine particles (pulverized BN). The average particle diameter of the obtained boron nitride fine particles was 17 μm.
次いで、得られた窒化ホウ素微粒子（粉砕ＢＮ）を熱伝導性フィラーとし、二液型シリコーン樹脂（信越シリコーン社製「二液型シリコーン樹脂 ＫＥ１０６」、シリコーン樹脂Ａ）をマトリックスとして、以下のようにして複合材料を得た。すなわち、先ず、得られる複合材料中のフィラー（窒化ホウ素微粒子）含有率が４０体積％となるように、前記窒化ホウ素微粒子２．７２ｇと二液混合したシリコーン樹脂１．８４ｇを秤量し、ジエチルエーテル２０ｇを加えて混合して均一スラリーとした後、得られたスラリーを撹拌しながらジエチルエーテルを揮発させた後に約１５分真空乾燥してジエチルエーテルを完全に除去して、前記窒化ホウ素微粒子が前記シリコーン樹脂中に分散した混合物を得た。次いで、得られた混合物を、ステンレス製の直方体金型（内面の寸法は２０×２０×５ｍｍ）に充填し、図１に示すように２０×５ｍｍの面の方向（ｚ軸方向）から１０ＭＰａの型締め圧力で圧縮した状態で１６０℃に３０分維持してシリコーン樹脂を硬化せしめて直方体の熱伝導性複合材料１を得た。得られた複合材料の空隙率は０％であった。 Next, the obtained boron nitride fine particles (pulverized BN) were used as a thermally conductive filler, and a two-component silicone resin ("Two-component silicone resin KE106" manufactured by Shin-Etsu Silicone Co., Ltd., silicone resin A) was used as a matrix, as follows. A composite material was obtained. That is, first, 2.72 g of the boron nitride fine particles and 1.84 g of silicone resin mixed in two parts were weighed, and diethyl ether After adding and mixing 20 g to make a uniform slurry, the resulting slurry was stirred to volatilize the diethyl ether, and then vacuum-dried for about 15 minutes to completely remove the diethyl ether. A mixture dispersed in silicone resin was obtained. Next, the obtained mixture was filled into a rectangular stainless steel mold (inner dimensions: 20 x 20 x 5 mm), and as shown in Figure 1, the mixture was heated to 10 MPa from the direction of the 20 x 5 mm surface (z-axis direction). The silicone resin was cured by maintaining the compressed state at 160° C. for 30 minutes under mold clamping pressure to obtain a rectangular parallelepiped thermally conductive composite material 1. The porosity of the obtained composite material was 0%.
＜熱伝導率測定＞
熱伝導性複合材料１の表面を黒体スプレーで黒化し、熱伝導率測定用試料とした。前記試料の厚さ方向（ｘ軸方向）又は圧縮方向に平行な方向（ｚ軸方向）を熱流方向としてキセノンフラッシュアナライザー（ＮＥＴＺＳＣＨ社製「ＬＦＡ ４４７ ＮａｎｏＦｌａｓｈ」）を用いて圧縮方向に垂直な方向（ｘ軸方向）及び圧縮方向に平行な方向（ｚ軸方向）の熱拡散率を測定した。
<Thermal conductivity measurement>
The surface of the thermally conductive composite material 1 was blackened with blackbody spray, and used as a sample for thermal conductivity measurement. The direction perpendicular to the compression direction ( Thermal diffusivity was measured in the direction parallel to the compression direction (x-axis direction) and the direction parallel to the compression direction (z-axis direction).
また、前記試料の比熱を熱振動型示差走査熱量測定装置（ティー・エイ・インスツル社製）を用いてＤＳＣ法により測定した。さらに、前記試料の密度を水中置換法（アルキメデス法）により求めた。これらの結果から次式：
熱伝導率（Ｗ／（ｍ・Ｋ））＝比熱（Ｊ／（ｋｇ・Ｋ））×密度（ｋｇ／ｍ３）×熱拡散率（ｍ２／秒）
により、圧縮方向に垂直な方向（ｘ軸方向）及び圧縮方向に平行な方向（ｚ軸方向）の熱伝導率を求めた。得られた結果を表１に示す。
Further, the specific heat of the sample was measured by the DSC method using a thermal vibration type differential scanning calorimeter (manufactured by TA Instruments). Furthermore, the density of the sample was determined by an underwater displacement method (Archimedes method). From these results, the following formula:
Thermal conductivity (W/(m・K)) = Specific heat (J/(kg・K)) x Density (kg/m 3 ) x Thermal diffusivity (m 2 /sec)
The thermal conductivity in the direction perpendicular to the compression direction (x-axis direction) and in the direction parallel to the compression direction (z-axis direction) was determined. The results obtained are shown in Table 1.
＜断面の電子顕微鏡観察及び構造解析１＞
直方体の複合材料の断面の構造観察のため、２０×２０ｍｍの面の表面を研磨機（ビューラー社製「ミニメットＴＭ１０００」）を用いて機械研磨した後、オスミウムコートを施し、ＥＤＸ付き走査型電子顕微鏡（（株）日立ハイテクノロジーズ製「ＮＢ－５０００」）を用いて断面の電子顕微鏡観察を行い、元素マッピング処理を施した。図３に、得られたＳＥＭ像及び元素マッピング像（「Ｂ」はホウ素マッピング、「Ｃ」は炭素マッピング、「Ｎ」は窒素マッピング、「Ｏ」は酸素マッピング、「Ｓｉ」はケイ素マッピング）のそれぞれ一例を示す。
<Cross-sectional electron microscope observation and structural analysis 1>
In order to observe the structure of the cross section of the rectangular parallelepiped composite material, the surface of the 20 x 20 mm surface was mechanically polished using a polishing machine ("Minimet TM 1000" manufactured by Buehler), then coated with osmium, and then polished using a scanning electronics with EDX. The cross section was observed with an electron microscope using a microscope ("NB-5000" manufactured by Hitachi High-Technologies Corporation), and elemental mapping processing was performed. Figure 3 shows the obtained SEM image and elemental mapping image (“B” is boron mapping, “C” is carbon mapping, “N” is nitrogen mapping, “O” is oxygen mapping, and “Si” is silicon mapping). An example is shown for each.
図３に示したＳＥＭ像及び元素マッピング像から、実施例１において得られた熱伝導性複合材料においては、部分劈開構造を有する板状窒化ホウ素微粒子の板状面が、圧縮方向に対して垂直方向の平面（図１におけるｘ軸とｙ軸を含む平面）に対して略平行となる方向に配向した状態となっており、微粒子の板状面同士が良好に接触しており、圧縮方向に垂直な方向（ｘ軸方向）に高い熱伝導率を有している構造となっていることが確認された。 From the SEM image and elemental mapping image shown in FIG. 3, in the thermally conductive composite material obtained in Example 1, the plate-like surfaces of the plate-like boron nitride fine particles having a partially cleaved structure are perpendicular to the compression direction. The particles are oriented in a direction approximately parallel to the plane of the direction (the plane including the x-axis and y-axis in Figure 1), and the plate-like surfaces of the particles are in good contact with each other, and the particles are oriented in the compression direction. It was confirmed that the structure had high thermal conductivity in the vertical direction (x-axis direction).
＜断面の電子顕微鏡観察及び構造解析２＞
直方体の複合材料から断面の電子顕微鏡観察用の試料を切り出し、任意の１０箇所の断面測定領域（実施例１においては縦６０ミクロン、横４０ミクロンの領域）について研磨機（ビューラー社製「ミニメットＴＭ１０００」）を用いて機械研磨を施した後に走査型電子顕微鏡（（株）日立ハイテクノロジーズ製「ＮＢ－５０００」）を用いて断面の電子顕微鏡観察を行った。
<Cross-sectional electron microscope observation and structural analysis 2>
A sample for cross-sectional electron microscopy observation is cut out from a rectangular parallelepiped composite material, and the cross-sectional measurement area of 10 arbitrary locations (in Example 1, an area of 60 microns in length and 40 microns in width) is polished using a polishing machine (Buehler's "Minimet TM" ). After performing mechanical polishing using a 1000"), the cross section was observed with an electron microscope using a scanning electron microscope ("NB-5000" manufactured by Hitachi High-Technologies Corporation).
次いで、得られた各測定領域のＳＥＭ像において、明度と形状に基づいて、
（ｉ）膨潤窒化ホウ素微粒子（部分劈開窒化ホウ素微粒子とその劈開空隙に取り込まれたマトリックス）に相当する領域と、
（ｉｉ）非膨潤窒化ホウ素微粒子（未劈開窒化ホウ素粒子及び完全劈開窒化ホウ素微粒子）に相当する領域と、
（ｉｉｉ）マトリックスのうち前記膨潤窒化ホウ素微粒子中に取り込まれずに存在するマトリックスに相当する領域と、
を区別して認識し、二値化により（ｉ）膨潤窒化ホウ素微粒子に相当する領域の合計面積を求め、当該測定領域の面積に対する比率として当該領域における膨潤窒化ホウ素微粒子に相当する領域の合計面積の比率を求めた。そして、全ての測定領域の平均値を算出することにより、得られた複合材料における膨潤窒化ホウ素微粒子に相当する領域の合計面積の比率（前記複合材料の断面面積に対する比率、平均値）を求めた。得られた結果を表２に示す。
Next, in the SEM image of each measurement area obtained, based on the brightness and shape,
(i) a region corresponding to swollen boron nitride fine particles (partially cleaved boron nitride fine particles and matrix incorporated into the cleavage voids);
(ii) a region corresponding to non-swelled boron nitride fine particles (uncleaved boron nitride particles and completely cleaved boron nitride fine particles);
(iii) a region of the matrix corresponding to the matrix existing without being incorporated into the swollen boron nitride fine particles;
(i) Calculate the total area of the region corresponding to the swollen boron nitride fine particles and calculate the total area of the region corresponding to the swollen boron nitride fine particles in the area as a ratio to the area of the measurement area. The ratio was calculated. Then, by calculating the average value of all measurement areas, the ratio of the total area of the area corresponding to the swollen boron nitride fine particles in the obtained composite material (ratio to the cross-sectional area of the composite material, average value) was determined. . The results obtained are shown in Table 2.
また、得られた各測定領域のＳＥＭ像において、同様に二値化により（ｉｉ）非膨潤窒化ホウ素微粒子（未劈開窒化ホウ素粒子及び完全劈開窒化ホウ素微粒子）に相当する領域の合計面積を求め、当該測定領域における全ての窒化ホウ素が未劈開窒化ホウ素粒子である場合の全窒化ホウ素粒子に相当する領域の合計面積との関係から、当該領域における窒化ホウ素微粒子の全量に対する部分劈開窒化ホウ素微粒子の含有率を求めた。そして、全ての測定領域の平均値を算出することにより、得られた複合材料に用いたフィラーにおける窒化ホウ素微粒子の全量に対する部分劈開窒化ホウ素微粒子の含有率（平均値）を求めた。得られた結果を表２に示す。 In addition, in the SEM image of each measurement area obtained, (ii) the total area of the region corresponding to non-swelled boron nitride particles (uncleaved boron nitride particles and completely cleaved boron nitride particles) is determined by binarization, From the relationship with the total area of the area corresponding to all boron nitride particles when all boron nitride in the measurement area is uncleaved boron nitride particles, the content of partially cleaved boron nitride fine particles with respect to the total amount of boron nitride fine particles in the relevant area. The rate was calculated. Then, by calculating the average value of all measurement regions, the content ratio (average value) of partially cleaved boron nitride fine particles to the total amount of boron nitride fine particles in the filler used in the obtained composite material was determined. The results obtained are shown in Table 2.
（実施例２）
得られる複合材料中のフィラー（窒化ホウ素微粒子）含有率が６０体積％となるように、前記窒化ホウ素微粒子４．０９ｇと二液混合したシリコーン樹脂１．２ｇを用いるようにしたこと以外は実施例１と同様にして熱伝導性複合材料を得た。そして、得られた複合材料について実施例１と同様にして熱伝導率測定を行い、圧縮方向に垂直な方向（ｘ軸方向）の熱伝導率を求めた。得られた結果を表１に示す。
(Example 2)
Example except that 1.2 g of silicone resin mixed in two parts with 4.09 g of boron nitride fine particles was used so that the filler (boron nitride fine particles) content in the resulting composite material was 60% by volume. A thermally conductive composite material was obtained in the same manner as in Example 1. Then, the thermal conductivity of the obtained composite material was measured in the same manner as in Example 1, and the thermal conductivity in the direction perpendicular to the compression direction (x-axis direction) was determined. The results obtained are shown in Table 1.
また、得られた複合材料について、実施例１における＜断面の電子顕微鏡観察及び構造解析１＞と同様にして断面の電子顕微鏡観察を行い、元素マッピング処理を施した。図４に、得られたＳＥＭ像及び元素マッピング像（「Ｂ」はホウ素マッピング、「Ｃ」は炭素マッピング、「Ｎ」は窒素マッピング、「Ｏ」は酸素マッピング、「Ｓｉ」はケイ素マッピング）のそれぞれ一例を示す。 Further, the obtained composite material was subjected to cross-sectional electron microscopic observation in the same manner as <Cross-sectional electron microscopic observation and structural analysis 1> in Example 1, and elemental mapping processing was performed. Figure 4 shows the obtained SEM image and elemental mapping image (“B” is boron mapping, “C” is carbon mapping, “N” is nitrogen mapping, “O” is oxygen mapping, and “Si” is silicon mapping). An example is shown for each.
図４に示したＳＥＭ像及び元素マッピング像から、実施例２において得られた熱伝導性複合材料においては、部分劈開構造を有する板状窒化ホウ素微粒子の板状面が、圧縮方向に対して垂直方向の平面（図１におけるｘ軸とｙ軸を含む平面）に対して略平行となる方向に配向した状態となっており、微粒子の板状面同士が良好に接触しており、圧縮方向に垂直な方向（ｘ軸方向）に高い熱伝導率を有している構造となっていることが確認された。 From the SEM image and elemental mapping image shown in FIG. 4, in the thermally conductive composite material obtained in Example 2, the plate-like surface of the plate-like boron nitride fine particles having a partially cleaved structure is perpendicular to the compression direction. The particles are oriented in a direction approximately parallel to the plane of the direction (the plane including the x-axis and y-axis in Figure 1), and the plate-like surfaces of the particles are in good contact with each other, and the particles are oriented in the compression direction. It was confirmed that the structure had high thermal conductivity in the vertical direction (x-axis direction).
さらに、得られた複合材料について、実施例１における＜断面の電子顕微鏡観察及び構造解析２＞と同様にして断面の電子顕微鏡観察及び構造解析を行い、得られた複合材料における膨潤窒化ホウ素微粒子に相当する領域の合計面積の比率、並びに、用いたフィラーにおける部分劈開窒化ホウ素微粒子の含有率を求めた。得られた結果を表２に示す。 Furthermore, the obtained composite material was subjected to cross-sectional electron microscopic observation and structural analysis in the same manner as <Cross-sectional electron microscopic observation and structural analysis 2> in Example 1. The ratio of the total area of the corresponding regions and the content of partially cleaved boron nitride fine particles in the filler used were determined. The results obtained are shown in Table 2.
（比較例１）
窒化ホウ素粒子（未粉砕ＢＮ）としてデンカ株式会社製「デンカボロンナイトライド粉 ＳＧＰ」（平均粒子径：１８μｍ）を用い、湿式粉砕することなくそのまま熱伝導性フィラーとして用いるようにしたこと以外は実施例１と同様にして熱伝導性複合材料を得た。そして、得られた複合材料について実施例１と同様にして熱伝導率測定を行い、圧縮方向に垂直な方向（ｘ軸方向）の熱伝導率を求めた。得られた結果を表１に示す。
(Comparative example 1)
Except that "Denka Boron Nitride Powder SGP" (average particle size: 18 μm) manufactured by Denka Co., Ltd. was used as the boron nitride particles (unpulverized BN) and used as a thermally conductive filler without wet pulverization. A thermally conductive composite material was obtained in the same manner as in Example 1. Then, the thermal conductivity of the obtained composite material was measured in the same manner as in Example 1, and the thermal conductivity in the direction perpendicular to the compression direction (x-axis direction) was determined. The results obtained are shown in Table 1.
また、得られた複合材料について、実施例１における＜断面の電子顕微鏡観察及び構造解析２＞と同様にして断面の電子顕微鏡観察及び構造解析を行い、得られた複合材料における膨潤窒化ホウ素微粒子に相当する領域の合計面積の比率、並びに、用いたフィラーにおける部分劈開窒化ホウ素微粒子の含有率を求めたところ、いずれも０％であった。 In addition, the obtained composite material was subjected to cross-sectional electron microscopic observation and structural analysis in the same manner as <Cross-sectional electron microscopic observation and structural analysis 2> in Example 1, and the swelling boron nitride fine particles in the obtained composite material were When the ratio of the total area of the corresponding regions and the content of partially cleaved boron nitride fine particles in the filler used were determined, both were 0%.
（比較例２）
窒化ホウ素粒子（未粉砕ＢＮ）としてデンカ株式会社製「デンカボロンナイトライド粉 ＳＧＰ」（平均粒子径：１８μｍ）を用い、湿式粉砕することなくそのまま熱伝導性フィラーとして用いるようにしたこと以外は実施例２と同様にして熱伝導性複合材料を得た。そして、得られた複合材料について実施例１と同様にして熱伝導率測定を行い、圧縮方向に垂直な方向（ｘ軸方向）の熱伝導率を求めた。得られた結果を表１に示す。
(Comparative example 2)
Except that "Denka Boron Nitride Powder SGP" (average particle size: 18 μm) manufactured by Denka Co., Ltd. was used as the boron nitride particles (unpulverized BN) and used as a thermally conductive filler without wet pulverization. A thermally conductive composite material was obtained in the same manner as in Example 2. Then, the thermal conductivity of the obtained composite material was measured in the same manner as in Example 1, and the thermal conductivity in the direction perpendicular to the compression direction (x-axis direction) was determined. The results obtained are shown in Table 1.
また、得られた複合材料について、実施例１における＜断面の電子顕微鏡観察及び構造解析２＞と同様にして断面の電子顕微鏡観察及び構造解析を行い、得られた複合材料における膨潤窒化ホウ素微粒子に相当する領域の合計面積の比率、並びに、用いたフィラーにおける部分劈開窒化ホウ素微粒子の含有率を求めたところ、いずれも０％であった。 In addition, the obtained composite material was subjected to cross-sectional electron microscopic observation and structural analysis in the same manner as <Cross-sectional electron microscopic observation and structural analysis 2> in Example 1, and the swelling boron nitride fine particles in the obtained composite material were When the ratio of the total area of the corresponding regions and the content of partially cleaved boron nitride fine particles in the filler used were determined, both were 0%.
（比較例３）
実施例１において原料粒子として用いた窒化ホウ素粒子（未粉砕ＢＮ）を、湿式粉砕することなくそのまま熱伝導性フィラーとして用いるようにしたこと以外は実施例１と同様にして熱伝導性複合材料を得た。そして、得られた複合材料について実施例１と同様にして熱伝導率測定を行い、圧縮方向に垂直な方向（ｘ軸方向）の熱伝導率を求めた。得られた結果を表１に示す。
(Comparative example 3)
A thermally conductive composite material was produced in the same manner as in Example 1, except that the boron nitride particles (unground BN) used as raw material particles in Example 1 were used as a thermally conductive filler without being wet-pulverized. Obtained. Then, the thermal conductivity of the obtained composite material was measured in the same manner as in Example 1, and the thermal conductivity in the direction perpendicular to the compression direction (x-axis direction) was determined. The results obtained are shown in Table 1.
また、得られた複合材料について、実施例１における＜断面の電子顕微鏡観察及び構造解析２＞と同様にして断面の電子顕微鏡観察及び構造解析を行い、得られた複合材料における膨潤窒化ホウ素微粒子に相当する領域の合計面積の比率、並びに、用いたフィラーにおける部分劈開窒化ホウ素微粒子の含有率を求めたところ、いずれも０％であった。 In addition, the obtained composite material was subjected to cross-sectional electron microscopic observation and structural analysis in the same manner as <Cross-sectional electron microscopic observation and structural analysis 2> in Example 1, and the swelling boron nitride fine particles in the obtained composite material were When the ratio of the total area of the corresponding regions and the content of partially cleaved boron nitride fine particles in the filler used were determined, both were 0%.
（実施例３）
マトリックスとして二液型シリコーン樹脂（信越シリコーン社製「二液型シリコーン樹脂 ＫＥ１２０４」、シリコーン樹脂Ｂ）を用い、得られる複合材料中のフィラー（窒化ホウ素微粒子）含有率が４０体積％となるように、前記窒化ホウ素微粒子２．７２ｇと二液混合したシリコーン樹脂２．７７ｇを用いるようにしたこと以外は実施例１と同様にして熱伝導性複合材料を得た。そして、得られた複合材料について実施例１と同様にして熱伝導率測定を行い、圧縮方向に垂直な方向（ｘ軸方向）及び圧縮方向に平行な方向（ｚ軸方向）の熱伝導率を求めた。得られた結果を表１に示す。
(Example 3)
A two-component silicone resin ("Two-component silicone resin KE1204" manufactured by Shin-Etsu Silicone Co., Ltd., Silicone Resin B) was used as the matrix, and the content of filler (boron nitride fine particles) in the resulting composite material was 40% by volume. A thermally conductive composite material was obtained in the same manner as in Example 1, except that 2.77 g of a silicone resin mixed with 2.72 g of the boron nitride fine particles was used. Then, the thermal conductivity of the obtained composite material was measured in the same manner as in Example 1, and the thermal conductivity in the direction perpendicular to the compression direction (x-axis direction) and in the direction parallel to the compression direction (z-axis direction) was measured. I asked for it. The results obtained are shown in Table 1.
（実施例４）
実施例１で得られた湿式粉砕された窒化ホウ素微粒子（粉砕ＢＮ）１５ｇ及び５Ｍ水酸化ナトリウム水溶液８０ｇをオートクレーブ中で混合し、ペースト状とした。次いで、オートクレーブを密閉し、１１０℃で２０時間加熱した後、攪拌機（シンキー社製「あわとり練太郎」）を用いて１２００ｒｐｍで９０秒撹拌した後、さらに１１０℃で１５時間オートクレーブ中で加熱した。得られた反応物を５００ｍｌのイオン交換水で４回洗浄した後、水に沈降する粒子のみを集め、８０℃で５時間真空乾燥して１２．０２ｇの乾燥物（表面に水酸基が結合している粉砕ＢＮ微粒子）を得た。得られた乾燥物に６５ｇの水を加え、混合してペースト状とした後、ビニルトリメトキシシラン０．３７ｇを１５０ｍｌのイオン交換水と混合し、酢酸を３滴加えて均一とした後に５０℃で３０分撹拌して作製した水溶液を加え、７０℃で１時間撹拌した。得られた反応物をろ過し、４回水洗した後、ろ液のｐＨが中性であることを確認した後に真空乾燥して１１．８ｇのシリル化粉砕ＢＮ微粒子（表面に水酸基を介してシランカップリング剤が結合している粉砕ＢＮ微粒子）を得た。
(Example 4)
15 g of wet-pulverized boron nitride fine particles (pulverized BN) obtained in Example 1 and 80 g of a 5M aqueous sodium hydroxide solution were mixed in an autoclave to form a paste. Next, the autoclave was sealed and heated at 110°C for 20 hours, then stirred at 1200 rpm for 90 seconds using a stirrer ("Awatori Rentaro" manufactured by Shinky), and further heated in the autoclave at 110°C for 15 hours. . After washing the obtained reaction product four times with 500 ml of ion-exchanged water, only the particles that precipitated in the water were collected and vacuum-dried at 80°C for 5 hours to obtain 12.02 g of dried product (with hydroxyl groups bonded to the surface). (pulverized BN fine particles) were obtained. After adding 65 g of water to the obtained dried product and mixing to form a paste, 0.37 g of vinyltrimethoxysilane was mixed with 150 ml of ion-exchanged water, and after adding 3 drops of acetic acid to make it homogeneous, the mixture was heated at 50°C. An aqueous solution prepared by stirring for 30 minutes was added, and the mixture was stirred at 70°C for 1 hour. The obtained reaction product was filtered, washed with water four times, and after confirming that the pH of the filtrate was neutral, it was vacuum-dried to form 11.8 g of silylated crushed BN fine particles (silane via hydroxyl groups on the surface). Pulverized BN fine particles bound with a coupling agent) were obtained.
次いで、実施例１において用いた粉砕ＢＮ微粒子に代えて前記シリル化粉砕ＢＮ微粒子を用いるようにしたこと以外は実施例１と同様にして熱伝導性複合材料を得た。そして、得られた複合材料について実施例１と同様にして熱伝導率測定を行い、圧縮方向に垂直な方向（ｘ軸方向）の熱伝導率を求めた。得られた結果を表１に示す。 Next, a thermally conductive composite material was obtained in the same manner as in Example 1 except that the silylated crushed BN fine particles were used in place of the crushed BN fine particles used in Example 1. Then, the thermal conductivity of the obtained composite material was measured in the same manner as in Example 1, and the thermal conductivity in the direction perpendicular to the compression direction (x-axis direction) was determined. The results obtained are shown in Table 1.
（実施例５）
実施例２において用いた粉砕ＢＮ微粒子に代えて実施例４で得られた前記シリル化粉砕ＢＮ微粒子を用いるようにしたこと以外は実施例２と同様にして熱伝導性複合材料を得た。そして、得られた複合材料について実施例１と同様にして熱伝導率測定を行い、圧縮方向に垂直な方向（ｘ軸方向）の熱伝導率を求めた。得られた結果を表１に示す。
(Example 5)
A thermally conductive composite material was obtained in the same manner as in Example 2, except that the silylated crushed BN fine particles obtained in Example 4 were used instead of the crushed BN fine particles used in Example 2. Then, the thermal conductivity of the obtained composite material was measured in the same manner as in Example 1, and the thermal conductivity in the direction perpendicular to the compression direction (x-axis direction) was determined. The results obtained are shown in Table 1.
表１及び表２に示した結果から明らかな通り、本発明の熱伝導性複合材料の製造方法により得られた実施例１～２の熱伝導性複合材料においては、いずれも部分劈開窒化ホウ素微粒子の含有率が窒化ホウ素微粒子の全量に対して５体積％以上であり、かつ、複合材料の断面基準で膨潤窒化ホウ素微粒子に相当する領域の合計面積が複合材料の断面面積に対して１～５０％の範囲内にあるものであった。 As is clear from the results shown in Tables 1 and 2, in the thermally conductive composite materials of Examples 1 and 2 obtained by the method for producing a thermally conductive composite material of the present invention, partially cleaved boron nitride fine particles The content of boron nitride fine particles is 5% by volume or more based on the total amount of boron nitride fine particles, and the total area of the region corresponding to the swollen boron nitride fine particles based on the cross-sectional area of the composite material is 1 to 50% by volume based on the cross-sectional area of the composite material. %.
また、表１に示した結果から明らかな通り、本発明の熱伝導性複合材料の製造方法により得られた実施例１～５の熱伝導性複合材料はいずれも、窒化ホウ素粒子を湿式粉砕することなくそのまま熱伝導性フィラーとして用いた比較例１～３の熱伝導性複合材料に比べて、熱伝導率が非常に高いことが確認された。 Further, as is clear from the results shown in Table 1, the thermally conductive composite materials of Examples 1 to 5 obtained by the method for manufacturing a thermally conductive composite material of the present invention were all produced by wet-pulverizing boron nitride particles. It was confirmed that the thermal conductivity was much higher than that of the thermally conductive composite materials of Comparative Examples 1 to 3, which were used as thermally conductive fillers as they were.
＜フィルム切り出し試験＞
実施例１～５及び比較例１～３で得られた熱伝導性複合材料を用いて、以下のようにしてフィルム切り出し試験を実施し、破れの発生の有無を評価した。
<Film cutting test>
Using the thermally conductive composite materials obtained in Examples 1 to 5 and Comparative Examples 1 to 3, a film cutting test was conducted as follows to evaluate the occurrence of tearing.
すなわち、各熱伝導性複合材料のフィルムを切り出す側の面（２０×２０ｍｍの面）を粘着剥離材で固定した後、切削機を用いて図２に示すように２０×２０ｍｍの面に平行にフィルム状にスライスし、膜厚５０μｍの熱伝導性複合材料フィルム２を切り出し、その後に粘着剥離材から熱伝導性複合材料フィルム２を剥離した。そして、このように各熱伝導性複合材料を膜厚５０μｍのフィルムとなるように薄くスライスする際に、フィルムに破れが発生するか否かを評価した。得られた結果を表１に示す。 That is, after fixing the cut side (20 x 20 mm surface) of each thermally conductive composite film with an adhesive release material, use a cutting machine to cut out the film parallel to the 20 x 20 mm surface as shown in Figure 2. A thermally conductive composite material film 2 having a thickness of 50 μm was cut out by slicing into a film shape, and then the thermally conductive composite material film 2 was peeled from the adhesive release material. Then, when each thermally conductive composite material was sliced into a film having a thickness of 50 μm, it was evaluated whether or not the film would break. The results obtained are shown in Table 1.
表１に示した結果から明らかな通り、本発明の熱伝導性複合材料の製造方法により得られた実施例１～５の熱伝導性複合材料はいずれも、膜厚５０μｍという非常に薄いフィルムを、板状窒化ホウ素微粒子の配向方向に対して垂直方向に、破れや破断を発生させることなく切り出すことが可能なものであることが確認された。 As is clear from the results shown in Table 1, the thermally conductive composite materials of Examples 1 to 5 obtained by the method of manufacturing thermally conductive composite materials of the present invention all had very thin films with a film thickness of 50 μm. It was confirmed that the plate-shaped boron nitride fine particles could be cut out in a direction perpendicular to the orientation direction without causing any tearing or breakage.
＜熱伝導性複合材料フィルムの熱抵抗試験＞
実施例２で得られた熱伝導性複合材料を用いて、膜厚１４５μｍのフィルムとなるようにしたこと以外は前記＜フィルム切り出し試験＞と同様にして膜厚１４５μｍの熱伝導性複合材料フィルムを得た。
<Thermal resistance test of thermally conductive composite material film>
Using the thermally conductive composite material obtained in Example 2, a thermally conductive composite material film with a thickness of 145 μm was prepared in the same manner as in the <Film Cutting Test> above, except that the film was made with a thickness of 145 μm. Obtained.
次いで、得られた熱伝導性複合材料フィルムの両面（２０×２０ｍｍの面）を上下から銅製ブロック（直径２０ｍｍの円柱）で挟持し、１ＭＰａ、２ＭＰａ、３ＭＰａで加圧した状態で熱抵抗測定器を用いて常法により熱抵抗を測定した。得られた結果を表３に示す。 Next, both sides (20 x 20 mm sides) of the resulting thermally conductive composite film were sandwiched between copper blocks (cylinders with a diameter of 20 mm) from above and below, and a thermal resistance measuring device was applied under pressure of 1 MPa, 2 MPa, and 3 MPa. Thermal resistance was measured using a conventional method. The results obtained are shown in Table 3.
（比較例４）
前記の膜厚１４５μｍの熱伝導性複合材料フィルムに代えて、酸化亜鉛を含有量が５５体積％となるようにシリコーンオイル（信越シリコーン社製「シリコーンオイル」）に分散させて得たペースト材を膜厚が１４５μｍとなるように用いたこと以外は前記＜熱伝導性複合材料フィルムの熱抵抗試験＞と同様にして熱抵抗を測定した。得られた結果を表３に示す。
(Comparative example 4)
Instead of the thermally conductive composite material film with a thickness of 145 μm, a paste material obtained by dispersing zinc oxide in silicone oil (“Silicone Oil” manufactured by Shin-Etsu Silicone Co., Ltd.) to a content of 55% by volume was used. Thermal resistance was measured in the same manner as in <Thermal resistance test of thermally conductive composite material film> above, except that the film thickness was 145 μm. The results obtained are shown in Table 3.
表３に示した結果から明らかな通り、本発明の熱伝導性複合材料フィルムにおいては、加圧する圧力が高くなるに伴って熱抵抗が顕著に小さくなっていくという特異的な現象が確認された。このような現象は、複合材料フィルム中の板状窒化ホウ素微粒子における部分劈開構造が接触する表面に対して形状追従し易いため、圧力の増加に伴って密着性がより良好となり、界面熱抵抗が小さくなっていくことによるものと本発明者らは推察する。 As is clear from the results shown in Table 3, in the thermally conductive composite film of the present invention, a specific phenomenon was confirmed in which the thermal resistance decreased significantly as the applied pressure increased. . This phenomenon occurs because the partially cleaved structure of the plate-shaped boron nitride microparticles in the composite film easily follows the shape of the contacting surface, so as the pressure increases, the adhesion becomes better and the interfacial thermal resistance increases. The present inventors conjecture that this is due to the decrease in size.
以上説明したように、本発明によれば、優れた熱伝導性を有しており、かつ、破断の発生を十分に抑制しつつフィルム状にスライスすることが可能な熱伝導性複合材料、及びそれを用いた熱抵抗の低い熱伝導性複合材料フィルム、並びにそれらの製造方法を提供することが可能となる。したがって、本発明の複合材料は、熱伝導性に優れていると共に、基材との界面熱抵抗が小さくなるように薄くスライスすることが可能であるため、例えば、自動車用放熱材料、ヒーター材料等として有用である。 As described above, the present invention provides a thermally conductive composite material that has excellent thermal conductivity and can be sliced into a film while sufficiently suppressing the occurrence of breakage; It becomes possible to provide thermally conductive composite films with low thermal resistance using the same, and methods for producing them. Therefore, the composite material of the present invention has excellent thermal conductivity and can be sliced thinly so that the interfacial thermal resistance with the base material is small. It is useful as
また、本発明の複合材料として、高い熱伝導性を有していると共に絶縁性のものが得られることから、電気系部品等と組み合わせて使用する場合に絶縁シート等を用いることなく本発明の複合材料のみによって熱を拡散・伝達することが可能となる。したがって、本発明の複合材料は、インバーター、コンバーター等の電力変換器に用いられるパワーデバイスやＣＰＵ等の発熱性電子部品の熱を放熱部材に伝達する中間部材(熱インターフェース材)等としても非常に有用である。 In addition, since the composite material of the present invention has high thermal conductivity and is insulating, the composite material of the present invention can be used in combination with electrical components etc. without using an insulating sheet. Only composite materials can diffuse and transfer heat. Therefore, the composite material of the present invention is very useful as an intermediate member (thermal interface material) that transfers heat from power devices used in power converters such as inverters and converters, and heat generating electronic components such as CPUs to heat radiating members. Useful.
１：熱伝導性複合材料、２：熱伝導性複合材料フィルム。 1: Thermal conductive composite material, 2: Thermal conductive composite material film.
Claims (6)
前記熱伝導性フィラーの含有量が、前記複合材料の全量に対して２０～７０体積％であり、
前記窒化ホウ素微粒子が板状の窒化ホウ素微粒子であり、かつ、前記マトリックスがシリコーン樹脂であり、
前記窒化ホウ素微粒子の少なくとも一部が、窒化ホウ素微粒子が部分的に劈開した部分劈開窒化ホウ素微粒子であり、
前記部分劈開窒化ホウ素微粒子の含有量が、前記窒化ホウ素微粒子の全量に対して２０体積％以上であり、
前記部分劈開窒化ホウ素微粒子の劈開空隙中に前記マトリックスが充填されて膨潤した膨潤窒化ホウ素微粒子が前記複合材料に含有されており、
前記複合材料の断面基準で、前記膨潤窒化ホウ素微粒子に相当する領域の合計面積が、前記複合材料の断面面積に対して１０～４０％であり、かつ、
前記窒化ホウ素微粒子の板状面が略一方向に配向している、
ことを特徴とする熱伝導性複合材料。 A thermally conductive composite material in which a thermally conductive filler consisting only of boron nitride fine particles is dispersed in a matrix,
The content of the thermally conductive filler is 20 to 70% by volume based on the total amount of the composite material,
The boron nitride fine particles are plate-shaped boron nitride fine particles, and the matrix is a silicone resin,
At least a part of the boron nitride fine particles are partially cleaved boron nitride fine particles obtained by partially cleaving boron nitride fine particles,
The content of the partially cleaved boron nitride fine particles is 20% by volume or more with respect to the total amount of the boron nitride fine particles,
The composite material contains swollen boron nitride fine particles filled with the matrix and swollen in the cleavage voids of the partially cleaved boron nitride fine particles,
Based on the cross-section of the composite material, the total area of the region corresponding to the swollen boron nitride fine particles is 10 to 40% of the cross-sectional area of the composite material, and
The plate-like surfaces of the boron nitride fine particles are oriented in approximately one direction.
A thermally conductive composite material characterized by:
厚みが５００μｍ以下であり、かつ、
前記窒化ホウ素微粒子の板状面が略厚み方向に配向している、
ことを特徴とする熱伝導性複合材料フィルム。 Consisting of the thermally conductive composite material according to claim 1 or 2 ,
The thickness is 500 μm or less, and
The plate-like surfaces of the boron nitride fine particles are oriented substantially in the thickness direction,
A thermally conductive composite material film characterized by:
前記部分劈開窒化ホウ素微粒子を含む窒化ホウ素微粒子のみからなる熱伝導性フィラーをマトリックスとしてのシリコーン樹脂中に分散させて、前記部分劈開窒化ホウ素微粒子の劈開空隙中に前記マトリックスが充填されて膨潤した膨潤窒化ホウ素微粒子を含有する混合物を得る工程と、
前記混合物を１～２０ＭＰａの圧力で一軸圧縮し、請求項１又は２に記載の熱伝導性複合材料を得る工程と、
を含むことを特徴とする熱伝導性複合材料の製造方法。 A step of obtaining boron nitride fine particles containing partially cleaved boron nitride fine particles in which the boron nitride fine particles are partially cleaved by injecting a fluid containing plate-shaped boron nitride particles from a nozzle at high pressure and performing wet collision crushing;
A thermally conductive filler made only of boron nitride fine particles including the partially cleaved boron nitride fine particles is dispersed in a silicone resin as a matrix, and the cleavage voids of the partially cleaved boron nitride fine particles are filled with the matrix and swell. obtaining a mixture containing boron nitride fine particles;
uniaxially compressing the mixture at a pressure of 1 to 20 MPa to obtain the thermally conductive composite material according to claim 1 or 2 ;
A method for producing a thermally conductive composite material, the method comprising:
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