JP7378284B2 - Powder containing composite particles, method for producing the same, and resin composition containing the powder - Google Patents
Powder containing composite particles, method for producing the same, and resin composition containing the powder Download PDFInfo
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Description
本開示は、複合粒子を含有する粉体及びその製造方法、並びに、該粉体を含有する樹脂組成物に関する。 The present disclosure relates to a powder containing composite particles, a method for producing the same, and a resin composition containing the powder.
パワーデバイス、トランジスタ、サイリスタ、ＣＰＵ等の電子部品においては、使用時に発生する熱を効率的に放熱することが課題となっている。この課題に対して、熱伝導率が高いセラミックス粉末を含有する放熱部材が用いられる。 BACKGROUND ART In electronic components such as power devices, transistors, thyristors, and CPUs, it is a challenge to efficiently dissipate heat generated during use. To solve this problem, a heat dissipation member containing ceramic powder with high thermal conductivity is used.
セラミックス粉末としては、高熱伝導率、高絶縁性、低比誘電率等の特性を有している窒化ホウ素粉末が注目されている。窒化ホウ素粉末は、一般的に、窒化ホウ素の一次粒子が凝集してなる凝集粒子で構成されている。例えば、特許文献１には、凝集粒子の形状を一層球状化して充填性を高めると共に、粉末強度の向上を図り、さらには高純度化により、当該粉末を充填した伝熱シート等の絶縁性の向上および耐電圧の安定化を達成したとされる六方晶窒化ホウ素粉末が開示されている。 As a ceramic powder, boron nitride powder, which has characteristics such as high thermal conductivity, high insulation, and low dielectric constant, is attracting attention. Boron nitride powder is generally composed of agglomerated particles formed by agglomerating primary particles of boron nitride. For example, in Patent Document 1, the shape of the aggregated particles is made more spherical to improve the filling property, and the powder strength is also improved. A hexagonal boron nitride powder is disclosed which is said to have improved and stabilized withstand voltage.
窒化ホウ素粉末が放熱部材に用いられる場合、熱伝導率等の上記特性はもちろん重要であるが、窒化ホウ素の粉体の状態から簡便に放熱部材を作製できることが重要となる。そこで、本発明は、窒化ホウ素を含む粉体から簡便に放熱部材を作製することを目的とする。 When boron nitride powder is used for a heat dissipation member, the above-mentioned properties such as thermal conductivity are of course important, but it is also important that the heat dissipation member can be easily produced from the boron nitride powder state. Therefore, an object of the present invention is to easily produce a heat dissipating member from powder containing boron nitride.
本発明の一側面は、複数の複合粒子を含有する粉体であって、複数の複合粒子のそれぞれは、複数の窒化ホウ素一次粒子が凝集してなる凝集粒子と、樹脂Ａとを含み、樹脂Ａが、凝集粒子内の複数の窒化ホウ素一次粒子同士の隙間に配置されており、凝集粒子の外表面上に樹脂Ａの塊が存在しない、粉体である。 One aspect of the present invention is a powder containing a plurality of composite particles, each of the plurality of composite particles including agglomerated particles formed by aggregation of a plurality of boron nitride primary particles, and a resin A. A is a powder in which resin A is arranged in the gaps between a plurality of boron nitride primary particles within the aggregated particles, and no lump of resin A is present on the outer surface of the aggregated particles.
この粉体に含まれる複合粒子では、窒化ホウ素一次粒子の凝集粒子内の窒化ホウ素一次粒子同士の隙間に樹脂Ａが配置されているため、樹脂が凝集粒子内に存在しない場合に比べて、加圧加熱処理により複合粒子同士を結着させつつ樹脂Ａを更に硬化させることができる。したがって、この粉体のみを用いて簡便に、樹脂Ａ中に凝集粒子が分散された成形体（硬化体）を得ることができる。加えて、この複合粒子では、凝集粒子の外表面上に樹脂Ａの塊が存在しないため、この粉体を含む成形体（硬化体）を作製したときに、窒化ホウ素の凝集粒子同士が接触しやすくなり、より高熱伝導率の成形体（硬化体）を得ることができる。 In the composite particles contained in this powder, resin A is arranged in the gaps between the boron nitride primary particles in the aggregated particles of boron nitride primary particles, so the amount of processing is reduced compared to when the resin is not present in the aggregated particles. Resin A can be further cured while bonding the composite particles to each other by pressure heating treatment. Therefore, a molded body (cured body) in which aggregated particles are dispersed in resin A can be easily obtained using only this powder. In addition, in this composite particle, since there is no lump of resin A on the outer surface of the aggregated particles, when a molded body (cured body) containing this powder is produced, the aggregated particles of boron nitride do not come into contact with each other. This makes it possible to obtain a molded body (cured body) with higher thermal conductivity.
本発明の他の一側面は、樹脂Ｂと、上記の粉体と、を含有する樹脂組成物である。樹脂Ｂは、樹脂Ａと異なる樹脂であってよい。 Another aspect of the present invention is a resin composition containing resin B and the above powder. Resin B may be a different resin from resin A.
本発明の他の一側面は、複数の窒化ホウ素一次粒子が凝集してなる凝集粒子と樹脂Ａとを混合して組成物を用意する工程ａと、組成物を粉砕する工程ｂと、を備え、工程ａにおいて、凝集粒子内の複数の窒化ホウ素一次粒子同士の隙間の体積に対して、０．７～２．０倍の体積の樹脂Ａを混合する、粉体の製造方法である。 Another aspect of the present invention includes a step a of preparing a composition by mixing agglomerated particles formed by aggregating a plurality of boron nitride primary particles with resin A, and a step b of pulverizing the composition. , is a powder manufacturing method in which, in step a, resin A is mixed in an amount of 0.7 to 2.0 times the volume of the gap between a plurality of boron nitride primary particles in the aggregated particles.
本発明によれば、窒化ホウ素を含む粉体から簡便に放熱部材を作製することができる。 According to the present invention, a heat radiating member can be easily manufactured from powder containing boron nitride.
以下、本発明の実施形態について詳細に説明する。 Embodiments of the present invention will be described in detail below.
一実施形態に係る粉体は、複数の複合粒子を含有する。当該粉体は、複数の複合粒子の集合体ということもできる。なお、粉体とは、複数の複合粒子が別個独立に存在している状態を意味し、例えば、複数の複合粒子の略全部がバインダー（例えば樹脂）によって互いに結合しているような状態とは区別される。粉体は、それ自体が流動性を示し、任意の安息角を有するものということもできる。 The powder according to one embodiment contains a plurality of composite particles. The powder can also be said to be an aggregate of a plurality of composite particles. Powder means a state in which a plurality of composite particles exist separately and independently, and for example, a state in which almost all of a plurality of composite particles are bound to each other by a binder (for example, a resin) is a state in which a plurality of composite particles exist separately and independently. distinguished. The powder itself exhibits fluidity and can also be said to have an arbitrary angle of repose.
複合粒子は、窒化ホウ素の粒子と樹脂との複合体である。より具体的には、複合粒子のそれぞれは、複数の窒化ホウ素一次粒子が凝集してなる凝集粒子と、樹脂Ａとを含んでいる。 The composite particles are a composite of boron nitride particles and resin. More specifically, each of the composite particles includes resin A and aggregate particles formed by aggregating a plurality of boron nitride primary particles.
窒化ホウ素一次粒子は、例えば鱗片状の六方晶窒化ホウ素粒子であってよい。この場合、窒化ホウ素一次粒子の長手方向の長さは、例えば、１μｍ以上であってよく、１０μｍ以下であってよい。 The primary boron nitride particles may be, for example, scale-shaped hexagonal boron nitride particles. In this case, the length in the longitudinal direction of the boron nitride primary particles may be, for example, 1 μm or more and 10 μm or less.
凝集粒子の平均径（平均粒子径）は、例えば、２０μｍ以上、４０μｍ以上、又は５０μｍ以上であってよく、１５０μｍ以下、１２０μｍ以下、又は１００μｍ以下であってよい。凝集粒子の平均径は、レーザー回折散乱法により測定される体積平均径を意味する。 The average diameter (average particle diameter) of the aggregated particles may be, for example, 20 μm or more, 40 μm or more, or 50 μm or more, and 150 μm or less, 120 μm or less, or 100 μm or less. The average diameter of aggregated particles means the volume average diameter measured by laser diffraction scattering method.
凝集粒子内には、複数の窒化ホウ素一次粒子同士の隙間（空隙）が存在している。樹脂Ａは、この凝集粒子内の複数の窒化ホウ素一次粒子同士の隙間に配置されている。樹脂Ａは、窒化ホウ素一次粒子同士の隙間の一部に配置されていてよく、隙間の全部に配置されていてもよい。窒化ホウ素一次粒子同士の隙間のできる限り多くに樹脂Ａが配置されていることが好ましい。複合粒子の断面における隙間の面積割合は、好ましくは、３０％以下、２０％以下、１０％以下、又は５％以下であってよい。当該面積割合は、複合粒子の断面を観察したＳＥＭ像（例えば図２のようなＳＥＭ像）において、複合粒子の断面積に対する隙間の断面積の割合（隙間の断面積／複合粒子の断面積）として測定され、任意の１００個の複合粒子について当該測定を行った面積割合の平均値として定義される。 Gaps (voids) between a plurality of boron nitride primary particles exist within the aggregated particles. Resin A is arranged in the gaps between the plurality of boron nitride primary particles within the aggregated particles. Resin A may be placed in some of the gaps between the boron nitride primary particles, or may be placed in all of the gaps. It is preferable that the resin A is placed in as many of the gaps between the boron nitride primary particles as possible. The area ratio of gaps in the cross section of the composite particle may preferably be 30% or less, 20% or less, 10% or less, or 5% or less. The area ratio is the ratio of the cross-sectional area of the gap to the cross-sectional area of the composite particle (cross-sectional area of the gap/cross-sectional area of the composite particle) in a SEM image of the cross-section of the composite particle (for example, a SEM image as shown in FIG. 2). It is defined as the average value of the area ratio of 100 arbitrary composite particles.
樹脂Ａは、凝集粒子内の隙間に加えて、凝集粒子の外表面上の一部又は全部にも配置されていてよい。ただし、凝集粒子の外表面上に、樹脂Ａの塊は存在しない。ここで、樹脂Ａの塊とは、凝集粒子の外表面からの高さが３μｍ以上である塊状の樹脂Ａを意味する。樹脂Ａの塊の有無は、複合粒子の断面を観察したＳＥＭ像に基づいて判断される。 In addition to the gaps within the aggregated particles, the resin A may also be placed on part or all of the outer surface of the aggregated particles. However, no lumps of resin A are present on the outer surface of the aggregated particles. Here, the lump of resin A means a lump of resin A in which the height of the aggregated particles from the outer surface is 3 μm or more. The presence or absence of lumps of resin A is determined based on an SEM image obtained by observing the cross section of the composite particle.
樹脂Ａは、熱硬化性樹脂であってよく、熱可塑性樹脂であってもよい。樹脂Ａが熱硬化性樹脂である場合、樹脂Ａは、半硬化した状態であってよく、完全硬化した状態であってもよい。半硬化した状態の樹脂Ａは、硬化した樹脂Ａと未硬化の樹脂Ａとの両方を含んでいる。 Resin A may be a thermosetting resin or a thermoplastic resin. When resin A is a thermosetting resin, resin A may be in a semi-cured state or may be in a completely cured state. Resin A in a semi-cured state includes both cured resin A and uncured resin A.
樹脂Ａとしては、例えば、エポキシ樹脂、シリコーン樹脂、シリコーンゴム、アクリル樹脂、フェノール樹脂、メラミン樹脂、ユリア樹脂、不飽和ポリエステル、フッ素樹脂、ポリイミド、ポリアミドイミド、ポリエーテルイミド、ポリブチレンテレフタレート、ポリエチレンテレフタレート、ポリフェニレンエーテル、ポリフェニレンスルフィド、全芳香族ポリエステル、ポリスルホン、液晶ポリマー、ポリエーテルスルホン、ポリカーボネート、マレイミド変性樹脂、ＡＢＳ（アクリロニトリル－ブタジエン－スチレン）樹脂、ＡＡＳ（アクリロニトリル－アクリルゴム・スチレン）樹脂、及びＡＥＳ（アクリロニトリル・エチレン・プロピレン・ジエンゴム－スチレン）樹脂が挙げられる。 Examples of resin A include epoxy resin, silicone resin, silicone rubber, acrylic resin, phenol resin, melamine resin, urea resin, unsaturated polyester, fluororesin, polyimide, polyamideimide, polyetherimide, polybutylene terephthalate, and polyethylene terephthalate. , polyphenylene ether, polyphenylene sulfide, fully aromatic polyester, polysulfone, liquid crystal polymer, polyether sulfone, polycarbonate, maleimide modified resin, ABS (acrylonitrile-butadiene-styrene) resin, AAS (acrylonitrile-acrylic rubber/styrene) resin, and AES (acrylonitrile, ethylene, propylene, diene rubber - styrene) resins.
凝集粒子内の隙間、及び、凝集粒子の外表面上には、樹脂Ａに加えてその他の成分が存在していてもよい。すなわち、複合粒子は、凝集粒子及び樹脂Ａに加えて、その他の成分を更に含んでいてもよい。その他の成分としては、例えば、硬化剤、硬化促進剤（硬化触媒）、カップリング剤、湿潤分散剤、及び表面調整剤が挙げられる。 In addition to resin A, other components may be present in the gaps within the aggregated particles and on the outer surfaces of the aggregated particles. That is, in addition to the aggregated particles and resin A, the composite particles may further contain other components. Other components include, for example, a curing agent, a curing accelerator (curing catalyst), a coupling agent, a wetting and dispersing agent, and a surface conditioner.
硬化剤は、樹脂Ａの種類によって適宜選択される。例えば、樹脂Ａがエポキシ樹脂である場合、硬化剤としては、フェノールノボラック化合物、酸無水物、アミノ化合物、及びイミダゾール化合物が挙げられる。硬化剤の含有量は、樹脂Ａ １００質量部に対して、例えば、０．５質量部以上又は１．０質量部以上であってよく、１５質量部以下又は１０質量部以下であってよい。 The curing agent is appropriately selected depending on the type of resin A. For example, when resin A is an epoxy resin, examples of the curing agent include phenol novolac compounds, acid anhydrides, amino compounds, and imidazole compounds. The content of the curing agent may be, for example, 0.5 parts by mass or more or 1.0 parts by mass or more, and 15 parts by mass or less or 10 parts by mass or less, based on 100 parts by mass of the resin A.
硬化促進剤（硬化触媒）としては、例えば、テトラフェニルホスホニウムテトラフェニルボレート、トリフェニルフォスフェイト等のリン系硬化促進剤、２－フェニル－４，５－ジヒドロキシメチルイミダゾール等のイミダゾール系硬化促進剤、及び、三フッ化ホウ素モノエチルアミン等のアミン系硬化促進剤が挙げられる。 Examples of the curing accelerator (curing catalyst) include phosphorus curing accelerators such as tetraphenylphosphonium tetraphenylborate and triphenyl phosphate, imidazole curing accelerators such as 2-phenyl-4,5-dihydroxymethylimidazole, and amine curing accelerators such as boron trifluoride monoethylamine.
カップリング剤としては、例えば、シラン系カップリング剤、チタネート系カップリング剤、及びアルミネート系カップリング剤が挙げられる。これらのカップリング剤に含まれる化学結合基としては、例えば、ビニル基、エポキシ基、アミノ基、メタクリル基、及びメルカプト基が挙げられる。 Examples of the coupling agent include silane coupling agents, titanate coupling agents, and aluminate coupling agents. Examples of the chemical bonding groups contained in these coupling agents include vinyl groups, epoxy groups, amino groups, methacrylic groups, and mercapto groups.
湿潤分散剤としては、例えば、リン酸エステル塩、カルボン酸エステル、ポリエステル、アクリル共重合物、及びブロック共重合物が挙げられる。 Examples of wetting and dispersing agents include phosphoric acid ester salts, carboxylic acid esters, polyesters, acrylic copolymers, and block copolymers.
表面調整剤としては、例えば、アクリル系表面調整剤、シリコーン系表面調整剤、ビニル系調整剤、及びフッ素系表面調整剤が挙げられる。 Examples of the surface conditioner include acrylic surface conditioners, silicone surface conditioners, vinyl surface conditioners, and fluorine surface conditioners.
複合粒子中の凝集粒子（窒化ホウ素一次粒子）の含有量は、複合粒子の全体積を基準として、例えば、３０体積％以上、４０体積％以上、又は５０体積％以上であってよく、８０体積％以下、７０体積％以下、又は６０体積％以下であってよい。 The content of aggregated particles (boron nitride primary particles) in the composite particles may be, for example, 30 volume% or more, 40 volume% or more, or 50 volume% or more, based on the total volume of the composite particles, and may be 80 volume% or more. % or less, 70 volume % or less, or 60 volume % or less.
複合粒子中の樹脂Ａの含有量は、複合粒子の全体積を基準として、例えば、３０体積％以上、４０体積％以上、又は５０体積％以上であってよく、７０体積％以下、６０体積％以下、又は５５体積％以下であってよい。 The content of resin A in the composite particles may be, for example, 30 volume% or more, 40 volume% or more, or 50 volume% or more, and 70 volume% or less, 60 volume%, based on the total volume of the composite particles. or less, or 55% by volume or less.
複合粒子中のその他の成分の含有量（合計の含有量）は、複合粒子の全体積を基準として、例えば、１０体積％以下、５体積％以下、３体積％以下、又は１体積％以下であってよく、０体積％であってもよい。 The content of other components in the composite particle (total content) is, for example, 10 volume% or less, 5 volume% or less, 3 volume% or less, or 1 volume% or less, based on the total volume of the composite particle. The content may be 0% by volume.
粉体（複合粒子）は、例えば、凝集粒子及び樹脂Ａを混合して組成物を用意する工程ａと、組成物を粉砕する工程ｂとを備える製造方法により製造される。樹脂Ａが熱硬化性樹脂である場合、当該製造方法は、工程ａと工程ｂとの間に、組成物中の樹脂Ａを硬化させる工程ｃを更に備えていてよい。 The powder (composite particles) is manufactured, for example, by a manufacturing method comprising a step a of mixing aggregated particles and resin A to prepare a composition, and a step b of pulverizing the composition. When resin A is a thermosetting resin, the manufacturing method may further include a step c of curing resin A in the composition between step a and step b.
工程ａで用いられる凝集粒子は、公知の方法により製造できる。工程ａでは、凝集粒子及び樹脂Ａに加えて、必要に応じて上述したその他の成分を更に混合してもよく、溶媒（例えば樹脂Ａを溶解させる溶媒）を更に混合してもよい。溶媒としては、例えば、アルコール系溶媒、グリコールエーテル系溶媒、芳香族系溶剤、及びケトン系溶剤が挙げられる。アルコール系溶媒としては、例えば、イソプロピルアルコール及びジアセトンアルコールが挙げられる。グリコールエーテル系溶媒としては、例えば、エチルセロソルブ及びブチルセロソルブが挙げられる。芳香族系溶剤としては、例えば、トルエン及びキシレンが挙げられる。ケトン系溶剤としては、例えば、メチルエチルケトン及びメチルイソブチルケトンが挙げられる。 The aggregated particles used in step a can be produced by a known method. In step a, in addition to the aggregated particles and resin A, other components mentioned above may be further mixed as needed, and a solvent (for example, a solvent for dissolving resin A) may be further mixed. Examples of the solvent include alcohol solvents, glycol ether solvents, aromatic solvents, and ketone solvents. Examples of alcoholic solvents include isopropyl alcohol and diacetone alcohol. Examples of glycol ether solvents include ethyl cellosolve and butyl cellosolve. Examples of aromatic solvents include toluene and xylene. Examples of ketone solvents include methyl ethyl ketone and methyl isobutyl ketone.
工程ａにおいて、樹脂Ａ（及び必要に応じて用いられるその他の成分）が、凝集粒子内の複数の窒化ホウ素一次粒子同士の隙間に入り込むと共に、凝集粒子の外表面上にも配置される。このとき、樹脂Ａの塊が生じないように、工程ａにおいて凝集粒子に対して混合する樹脂Ａの量を適切に設定する必要がある。具体的には、樹脂Ａの配合量は、凝集粒子内の複数の窒化ホウ素一次粒子同士の隙間の体積に対して、好ましくは０．７倍以上、より好ましくは１．０倍以上、更に好ましくは１．３倍以上、特に好ましくは１．６倍以上の体積であり、好ましくは２．０倍以下、より好ましくは１．９倍以下、更に好ましくは１．８倍以下の体積であり、０．７～２．０倍、０．７～１．９倍、０．７～１．８倍、１．０～２．０倍、１．０～１．９倍、１．０～１．８倍、１．３～２．０倍、１．３～１．９倍、１．３～１．８倍、１．６～２．０倍、１．６～１．９倍、又は１．６～１．８倍の体積であってよい。 In step a, resin A (and other components used as necessary) enters the gaps between the plurality of boron nitride primary particles within the aggregated particles, and is also placed on the outer surface of the aggregated particles. At this time, it is necessary to appropriately set the amount of resin A to be mixed with the aggregated particles in step a so as not to form lumps of resin A. Specifically, the blending amount of resin A is preferably 0.7 times or more, more preferably 1.0 times or more, and even more preferably is 1.3 times or more, particularly preferably 1.6 times or more in volume, preferably 2.0 times or less, more preferably 1.9 times or less, still more preferably 1.8 times or less in volume, 0.7 to 2.0 times, 0.7 to 1.9 times, 0.7 to 1.8 times, 1.0 to 2.0 times, 1.0 to 1.9 times, 1.0 to 1 .8 times, 1.3 to 2.0 times, 1.3 to 1.9 times, 1.3 to 1.8 times, 1.6 to 2.0 times, 1.6 to 1.9 times, or It may be 1.6 to 1.8 times the volume.
工程ｂにおいて、組成物を粉砕する方法は、例えば凍結粉砕であってよい。凍結粉砕は、例えば、組成物を液体窒素で凍結した状態で粉砕する。粉砕する際の条件は、複合粒子同士が分離するように適宜選択される。具体的には、例えば、凍結粉砕機を用いて、１５００～３５００ｒｐｍで１～３０秒間の条件で粉砕する。 In step b, the method of grinding the composition may be, for example, freeze grinding. Freeze pulverization involves, for example, pulverizing a composition in a frozen state using liquid nitrogen. Conditions for pulverization are appropriately selected so that the composite particles are separated from each other. Specifically, for example, it is crushed using a freeze crusher at 1500 to 3500 rpm for 1 to 30 seconds.
工程ｃにおいて樹脂Ａを硬化させる方法は、樹脂Ａ（及び必要に応じて用いられる硬化剤）の種類に応じて適宜選択される。例えば、樹脂Ａがエポキシ樹脂であり、上述した硬化剤が共に用いられる場合、工程ｃでは、加熱により樹脂Ａを硬化させることができる。工程ａにおいて溶媒を用いる場合は、工程ｃにおいて、樹脂Ａを硬化させると共に、当該溶媒を揮発させてもよい。工程ｃでは、樹脂Ａを半硬化させてよく、完全硬化させてもよい。 The method for curing resin A in step c is appropriately selected depending on the type of resin A (and the curing agent used as necessary). For example, when resin A is an epoxy resin and the above-mentioned curing agent is used together, resin A can be cured by heating in step c. When a solvent is used in step a, the resin A may be cured and the solvent may be volatilized in step c. In step c, resin A may be semi-cured or completely cured.
工程ｃでは、樹脂Ａを硬化させる前に、工程ａで用意した組成物をシート状に成形してもよい。具体的には、例えば、フィルムアプリケーターを用いて、当該組成物を基材上に塗工することにより、５０～４００μｍの厚さのシート状に成形してよい。 In step c, before curing resin A, the composition prepared in step a may be molded into a sheet. Specifically, for example, the composition may be applied onto a base material using a film applicator to form a sheet having a thickness of 50 to 400 μm.
以上説明した粉体に含まれる複合粒子では、窒化ホウ素一次粒子の凝集粒子内の窒化ホウ素一次粒子同士の隙間に樹脂Ａが配置されているため、樹脂が凝集粒子内に存在しない場合に比べて、加圧加熱処理により複合粒子同士を結着させつつ樹脂Ａを更に硬化させることができる。したがって、この粉体のみを用いて簡便に、樹脂Ａ中に凝集粒子が分散された成形体（硬化体）を得ることができる。このような成形体（硬化体）は、放熱部材に好適に用いられる。 In the composite particles contained in the powder described above, resin A is arranged in the gaps between the boron nitride primary particles in the aggregated particles of boron nitride primary particles, so compared to the case where the resin does not exist in the aggregated particles. The resin A can be further cured while bonding the composite particles together by the pressure and heat treatment. Therefore, a molded body (cured body) in which aggregated particles are dispersed in resin A can be easily obtained using only this powder. Such a molded body (cured body) is suitably used for a heat dissipation member.
また、凝集粒子の表面に樹脂の塊が存在する場合、成形体（硬化体）を作製したときに、凝集粒子間に樹脂が存在しやすくなり、この樹脂によって凝集粒子同士の接触が妨げられるおそれがある。これに対し、上述した複合粒子では、凝集粒子の外表面上に樹脂Ａの塊が存在しないため、この粉体を含む成形体（硬化体）を作製したときに、凝集粒子同士が接触しやすくなり、凝集粒子の表面に樹脂の塊が存在する場合に比べて、より高熱伝導率の成形体（硬化体）を得ることができる。 In addition, if a lump of resin exists on the surface of the aggregated particles, when a molded body (cured body) is produced, resin tends to exist between the aggregated particles, and this resin may prevent contact between the aggregated particles. There is. On the other hand, in the above-mentioned composite particles, since there is no lump of resin A on the outer surface of the aggregated particles, when a molded body (cured body) containing this powder is produced, the aggregated particles easily come into contact with each other. Therefore, a molded body (hardened body) having higher thermal conductivity can be obtained than when a lump of resin is present on the surface of the aggregated particles.
粉体は、複合粒子のみからなっていてよく、複合粒子に加えて、その他の粒子を更に含有していてもよい。その他の粒子は、例えば無機材料で構成されていてよい。無機材料としては、例えば、窒化ホウ素、窒化アルミニウム、窒化珪素、酸化アルミニウム、二酸化ケイ素、酸化マグネシウム、炭化珪素、金属アルミニウム、及び黒鉛が挙げられる。粉体中の複合粒子の含有量は、粉体の全体積を基準として、例えば、４０体積％以上、５０体積％以上、６０体積％以上、７０体積％以上、８０体積％以上、又は９０体積％以上であってよい。 The powder may consist only of composite particles, or may further contain other particles in addition to the composite particles. Other particles may be composed of inorganic materials, for example. Examples of inorganic materials include boron nitride, aluminum nitride, silicon nitride, aluminum oxide, silicon dioxide, magnesium oxide, silicon carbide, metallic aluminum, and graphite. The content of the composite particles in the powder is, for example, 40 volume% or more, 50 volume% or more, 60 volume% or more, 70 volume% or more, 80 volume% or more, or 90 volume% based on the total volume of the powder. % or more.
その他の粒子は、複数の窒化ホウ素一次粒子が凝集してなる凝集粒子と、樹脂とを含み、当該樹脂が、凝集粒子内の複数の窒化ホウ素一次粒子同士の隙間に配置されており、凝集粒子の外表面上に当該樹脂の塊が存在する粒子（すなわち、凝集粒子の外表面上に樹脂の塊が存在すること以外は、上記の複合粒子と同様の構成を有する粒子）であってもよい。この場合、上記の複合粒子の個数割合は、多くの凝集粒子同士が接触することができ、凝集粒子間の樹脂による熱伝導性の低下を抑制できる観点から、上記の複合粒子と樹脂の塊を有する粒子との合計を基準として、好ましくは、７０個数％以上、８０個数％以上、又は９０個数％以上である。当該個数割合は、ＳＥＭにより粒子１００個の断面を観察して樹脂の塊の有無を判断し、樹脂の塊を有さない上記複合粒子の個数から算出される。 The other particles include aggregated particles formed by aggregating a plurality of boron nitride primary particles and a resin, and the resin is arranged in the gaps between the plurality of boron nitride primary particles in the aggregated particles, and the aggregated particles may be particles in which a lump of the resin exists on the outer surface of the aggregated particle (i.e., a particle having the same structure as the above-mentioned composite particle except that the lump of resin exists on the outer surface of the aggregated particle). . In this case, the number ratio of the composite particles described above is determined from the viewpoint that many aggregated particles can come into contact with each other and a decrease in thermal conductivity due to the resin between the aggregated particles can be suppressed. Based on the total number of particles, the proportion is preferably 70% by number or more, 80% by number or more, or 90% by number or more. The number ratio is calculated by observing the cross section of 100 particles using SEM to determine the presence or absence of resin lumps, and from the number of composite particles that do not have resin lumps.
本発明の他の一実施形態は、上記の粉体（複合粒子）と、樹脂Ｂと、を含有する樹脂組成物である。このような樹脂組成物も、放熱部材として好適に用いられる。 Another embodiment of the present invention is a resin composition containing the above powder (composite particles) and resin B. Such a resin composition is also suitably used as a heat radiating member.
樹脂Ｂは、上述した樹脂Ａと同一の樹脂であってよく、樹脂Ａと異なる樹脂であってもよく、放熱部材に求められる特性を得やすい観点から、好ましくは樹脂Ａと異なる樹脂である。樹脂Ｂの例は、樹脂Ａの例として説明した樹脂と同じである。 Resin B may be the same resin as resin A described above, or may be a different resin from resin A, and is preferably a different resin from resin A from the viewpoint of easily obtaining the characteristics required for the heat dissipation member. The example of resin B is the same as the resin described as the example of resin A.
樹脂組成物中の複合粒子の含有量は、樹脂組成物の全体積を基準として、樹脂組成物の熱伝導率を向上させ、優れた放熱性能が得られやすい観点から、好ましくは、３０体積％以上、４０体積％以上、５０体積％以上、又は６０体積％以上であってよく、絶縁性及び機械強度の低下を抑制できる観点から、好ましくは、８５体積％以下又は８０体積％以下であってよい。 The content of the composite particles in the resin composition is preferably 30% by volume based on the total volume of the resin composition, from the viewpoint of improving the thermal conductivity of the resin composition and easily obtaining excellent heat dissipation performance. The above content may be 40 volume% or more, 50 volume% or more, or 60 volume% or more, and preferably 85 volume% or less or 80 volume% or less from the viewpoint of suppressing a decrease in insulation properties and mechanical strength. good.
樹脂組成物中の樹脂Ｂの含有量は、樹脂組成物の全体積を基準として、例えば、１５体積％以上、２０体積％以上、３０体積％以上、又は４０体積％以上であってよく、７０体積％以下又は６０体積％以下であってよい。 The content of resin B in the resin composition may be, for example, 15% by volume or more, 20% by volume or more, 30% by volume or more, or 40% by volume or more, based on the total volume of the resin composition. It may be less than or equal to 60% by volume.
樹脂組成物は、複合粒子及び樹脂Ｂ以外のその他の成分を更に含有してもよい。その他の成分は、例えば、樹脂Ｂを硬化させる硬化剤を更に含有してもよい。硬化剤は、樹脂Ｂの種類に応じて適宜選択される。硬化剤の含有量は、樹脂Ｂ １００質量部に対して、例えば、０．５質量部以上又は１．０質量部以上であってよく、１５質量部以下又は１０質量部以下であってよい。 The resin composition may further contain components other than the composite particles and resin B. Other components may further contain a curing agent for curing resin B, for example. The curing agent is appropriately selected depending on the type of resin B. The content of the curing agent may be, for example, 0.5 parts by mass or more or 1.0 parts by mass or more, and 15 parts by mass or less or 10 parts by mass or less, based on 100 parts by mass of the resin B.
樹脂組成物中のその他の成分の含有量（合計の含有量）は、樹脂組成物の全体積を基準として、例えば、１０体積％以下、５体積％以下、３体積％以下、又は１体積％以下であってよく、０体積％であってもよい。 The content of other components in the resin composition (total content) is, for example, 10% by volume or less, 5% by volume or less, 3% by volume or less, or 1% by volume, based on the total volume of the resin composition. It may be less than or equal to 0% by volume.
以下、実施例に基づき本発明を更に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 explained in more detail based on Examples, but the present invention is not limited to the following Examples.
窒化ホウ素一次粒子の凝集粒子（平均粒径：８７μｍ、空隙率：４９％）５０体積部と、エポキシ樹脂（ＤＩＣ社製、製品名：ＨＰ４０３２）４１．５体積部と、硬化剤（ＤＩＣ社製、製品名：ＶＨ４１５０）５．１体積部と、２種の硬化促進剤（硬化触媒）（北興化学社製、製品名：ＴＰＰ）０．３体積部及び（四国化成工業社製、製品名：２ＰＨＺ－ＰＷ）０．５体積部と、カップリング剤（東レ・ダウコーニング社製、製品名：Ｚ６０４０）１．６体積部と、湿潤分散剤（ビックケミージャパン社製、製品名：ＤＩＳ－１１１）０．３体積部と、表面調整剤（ビックケミージャパン社製、製品名：ＢＹＫ－３００）０．４体積部と、これらの各成分の合計１００質量部に対して、揮発成分である溶媒（東京化成工業社製、製品名：ジアセトンアルコール）６．５質量部とを、遊星式撹拌機（シンキー社「あわとり練太郎ＡＲ－２５０」を用いて、公転速度２０００ｒｐｍ、自転速度８００ｒｐｍで×２分間）の条件で混練して組成物を得た。 50 parts by volume of aggregated particles of boron nitride primary particles (average particle size: 87 μm, porosity: 49%), 41.5 parts by volume of epoxy resin (manufactured by DIC Corporation, product name: HP4032), and a curing agent (manufactured by DIC Corporation). , product name: VH4150) 5.1 parts by volume, 0.3 parts by volume of two types of curing accelerator (curing catalyst) (manufactured by Hokuko Chemical Co., Ltd., product name: TPP) and (manufactured by Shikoku Kasei Kogyo Co., Ltd., product name: 2PHZ-PW) 0.5 parts by volume, 1.6 parts by volume of a coupling agent (manufactured by Toray Dow Corning, product name: Z6040), and a wetting and dispersing agent (manufactured by Bic Chemie Japan, product name: DIS-111). ), 0.4 parts by volume of a surface conditioner (manufactured by BYK-Chemie Japan, product name: BYK-300), and a solvent, which is a volatile component, for a total of 100 parts by mass of each of these components. (manufactured by Tokyo Kasei Kogyo Co., Ltd., product name: diacetone alcohol) using a planetary stirrer (Shinky Co., Ltd. "Awatori Rentaro AR-250") at a revolution speed of 2000 rpm and an autorotation speed of 800 rpm. x 2 minutes) to obtain a composition.
続いて、フィルムアプリケーターを用いて、得られた組成物を厚さ１００μｍのシート状に成形した後、熱風乾燥機を用いて、６０℃で３０分間及び１００℃で７０分間の条件で、エポキシ樹脂を半硬化させた。 Subsequently, the obtained composition was formed into a sheet with a thickness of 100 μm using a film applicator, and then the epoxy resin was formed using a hot air dryer at 60°C for 30 minutes and at 100°C for 70 minutes. was semi-hardened.
続いて、凍結粉砕機（安井器機株式会社社製、ＰＶ１００１（Ｓ））を用いて、半硬化させた後のシート状組成物３ｇに対して、２８００ｒｐｍで１５秒間の条件で凍結粉砕を行った。これにより、複合粒子からなる粉体を得た。 Subsequently, 3 g of the semi-cured sheet composition was freeze-pulverized at 2800 rpm for 15 seconds using a freeze-pulverizer (manufactured by Yasui Kiki Co., Ltd., PV1001 (S)). . As a result, powder consisting of composite particles was obtained.
得られた複合粒子（粉体）の外観を観察したＳＥＭ画像を図１に示す。また、得られた複合粒子（粉体）４個の断面をそれぞれ観察したＳＥＭ画像のうちの一つを図２に示す。比較のため、窒化ホウ素一次粒子の凝集粒子（樹脂を含まない状態）の外観を観察したＳＥＭ画像を図３に示す。なお、図１（ａ）及び図３（ａ）は５００倍、図１（ｂ）及び図３（ｂ）は２０００倍、図２は１０００倍でのＳＥＭ画像である。 FIG. 1 shows a SEM image showing the appearance of the obtained composite particles (powder). Further, one of the SEM images obtained by observing the cross sections of four composite particles (powder) obtained is shown in FIG. 2. For comparison, FIG. 3 shows an SEM image of the appearance of aggregated particles of boron nitride primary particles (without resin). Note that FIGS. 1(a) and 3(a) are SEM images at 500x, FIGS. 1(b) and 3(b) are SEM images at 2000x, and FIG. 2 is SEM images at 1000x.
図１及び図２（更には図３との比較）から分かるとおり、得られた複合粒子では、エポキシ樹脂が、凝集粒子内の複数の窒化ホウ素一次粒子同士の隙間に配置されていると共に、凝集粒子の外表面にも配置されている。また、図２から分かるとおり、凝集粒子の外表面上に、エポキシ樹脂の塊は存在していない。観察した４個の複合粒子のうち残りの３個の複合粒子についても同様であった。 As can be seen from Figures 1 and 2 (and a comparison with Figure 3), in the obtained composite particles, the epoxy resin is arranged in the gaps between the plurality of boron nitride primary particles within the aggregated particles, and the epoxy resin is It is also located on the outer surface of the particle. Moreover, as can be seen from FIG. 2, no lumps of epoxy resin were present on the outer surface of the aggregated particles. The same was true for the remaining three composite particles among the four composite particles observed.
また、複合粒子の密度を水中置換法（アルキメデス法）により測定したところ、理論密度１．７３５ｇ／ｃｍ３と略同じであった。このことからも、エポキシ樹脂が、凝集粒子内の複数の窒化ホウ素一次粒子同士の隙間に配置されているといえる。 Further, when the density of the composite particles was measured by an underwater displacement method (Archimedes method), it was found to be approximately the same as the theoretical density of 1.735 g/cm 3 . From this, it can be said that the epoxy resin is arranged in the gaps between the plurality of boron nitride primary particles within the aggregated particles.
Claims (3)
前記複数の複合粒子のそれぞれは、複数の窒化ホウ素一次粒子が凝集してなる凝集粒子と、樹脂Ａとを含み、
前記凝集粒子の平均径が４０μｍ以上であり、
前記樹脂Ａが、前記凝集粒子内の前記複数の窒化ホウ素一次粒子同士の隙間に配置されており、
前記凝集粒子の外表面上に前記樹脂Ａの塊が存在しない、粉体。 A powder containing a plurality of composite particles,
Each of the plurality of composite particles includes agglomerated particles formed by aggregation of a plurality of boron nitride primary particles and resin A,
The average diameter of the aggregated particles is 40 μm or more,
The resin A is disposed in the gaps between the plurality of boron nitride primary particles within the aggregated particles,
A powder in which no lumps of the resin A are present on the outer surface of the aggregated particles.
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| JP2015195292A (en) | 2014-03-31 | 2015-11-05 | 三菱化学株式会社 | Heat dissipation sheet, manufacturing method of heat dissipation sheet, slurry for heat dissipation sheet and power device |
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| JP2015195292A (en) | 2014-03-31 | 2015-11-05 | 三菱化学株式会社 | Heat dissipation sheet, manufacturing method of heat dissipation sheet, slurry for heat dissipation sheet and power device |
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