JP7497871B2 - AlN particle dispersed resin compact and method for producing same - Google Patents
AlN particle dispersed resin compact and method for producing same Download PDFInfo
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- JP7497871B2 JP7497871B2 JP2020168666A JP2020168666A JP7497871B2 JP 7497871 B2 JP7497871 B2 JP 7497871B2 JP 2020168666 A JP2020168666 A JP 2020168666A JP 2020168666 A JP2020168666 A JP 2020168666A JP 7497871 B2 JP7497871 B2 JP 7497871B2
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- 229920005989 resin Polymers 0.000 title claims description 84
- 239000011347 resin Substances 0.000 title claims description 84
- 239000002245 particle Substances 0.000 title claims description 69
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000013078 crystal Substances 0.000 claims description 19
- 229920001187 thermosetting polymer Polymers 0.000 claims description 15
- 238000000465 moulding Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 44
- 239000000805 composite resin Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920002050 silicone resin Polymers 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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Description
本発明は、窒化アルミニウム（ＡｌＮ）粒子を分散させた樹脂成形体及びその製造方法に関する。 The present invention relates to a resin molded body containing dispersed aluminum nitride (AlN) particles and a method for manufacturing the same.
窒化アルミニウム（ＡｌＮ）は高い熱伝導性を有する絶縁体であることから、電子デバイスなどの絶縁性の放熱部材としての利用がされている。例えば、これを焼結させたＡｌＮ焼結体は、シリコン（Ｓｉ）に近い熱膨張係数を有するため、シリコンを用いた半導体装置の放熱板や基板として好適である。一方、ＡｌＮ粒子を分散させた樹脂成形体のような粒子分散複合材料の利用も提案されている。 Aluminum nitride (AlN) is an insulator with high thermal conductivity, and is therefore used as an insulating heat dissipation material for electronic devices. For example, an AlN sintered body made by sintering it has a thermal expansion coefficient close to that of silicon (Si), making it suitable as a heat sink or substrate for semiconductor devices that use silicon. On the other hand, the use of particle-dispersed composite materials such as resin molded bodies with AlN particles dispersed therein has also been proposed.
例えば、特許文献１では、熱伝導性と成形加工性とを兼ね備えた樹脂成形体として、ＡｌＮ単結晶粒子が融着して繊維状になった異方性形状のＡｌＮフィラーを等方性形状の粒子とともに含有する樹脂成形体を開示している。エポキシ樹脂やシリコン樹脂のような熱硬化性樹脂からなる樹脂成形体において、ＡｌＮフィラー１００重量部に対して、等方性形状の粒子１００重量部以上、及び、熱硬化性樹脂４０重量部以上として、１Ｗ／ｍ・Ｋ以上の高い熱伝導率を得られるとしている。このような高い熱伝導率を得られる理由として、成形体中の異方性形状のＡｌＮフィラーが等方性形状の粒子の存在により、成形加工中に折れ曲がりの少ない状態で存在できるため、熱伝導経路が確保されやすくなると説明している。 For example, Patent Document 1 discloses a resin molded body that combines thermal conductivity and moldability, and contains anisotropically shaped AlN filler in the form of fibrous AlN single crystal particles fused together with isotropically shaped particles. In a resin molded body made of a thermosetting resin such as epoxy resin or silicone resin, a high thermal conductivity of 1 W/m·K or more can be obtained by using 100 parts by weight of AlN filler, 100 parts by weight or more of isotropically shaped particles, and 40 parts by weight or more of thermosetting resin. The reason for obtaining such a high thermal conductivity is explained to be that the presence of the isotropically shaped particles allows the anisotropically shaped AlN filler in the molded body to exist in a state with less bending during molding, making it easier to ensure a heat conduction path.
また、特許文献２では、不純物の混入を抑えて熱伝導性の低下を抑えたＡｌＮウィスカーを含むエポキシ樹脂やシリコン樹脂からなる樹脂組成物を開示している。外形のアスペクト比を５以上としたＡｌＮウィスカーを切断せず樹脂組成物中に均一に分散して存在するように剪断応力を小さくしつつミキサー等の混練機で混合して含むことで、ウィスカー同士を接触し易くして熱伝導パス（熱伝導経路）を確保し、熱伝導性の向上が図られることを述べている。かかるＡｌＮウィスカーは、長軸に垂直方向の断面における面積の平均が０．１μｍ２～５０μｍ２、当該ウィスカーの高さの平均が１０μｍ～５０ｍｍであって、樹脂組成物１００においてウィスカー及び樹脂部の重量比（配合比）は５～６０％程度であるとしている。 Patent Document 2 discloses a resin composition made of an epoxy resin or a silicone resin containing AlN whiskers that suppresses the inclusion of impurities and suppresses the decrease in thermal conductivity. It states that by mixing and including AlN whiskers with an aspect ratio of 5 or more in the resin composition while reducing the shear stress so that the AlN whiskers are uniformly dispersed in the resin composition without being cut, the whiskers are made to easily come into contact with each other, ensuring a thermal conduction path (thermal conduction route), and improving thermal conductivity. It states that the average area of such AlN whiskers in a cross section perpendicular to the long axis is 0.1 μm 2 to 50 μm 2 , the average height of the whiskers is 10 μm to 50 mm, and the weight ratio (mixing ratio) of the whiskers and the resin portion in the resin composition 100 is about 5 to 60%.
上記したように、アスペクト比の高いＡｌＮ粒子をその長さ方向にランダムな方向を向くように樹脂成形体中に分散させることで、分散量が少量であっても、樹脂成形体に高い熱伝導性を付与することができる。また、分散量を一定に抑えることで、樹脂成形体の機械的性質を維持できる。 As described above, by dispersing AlN particles with a high aspect ratio in a resin molded body so that they are randomly oriented along their length, it is possible to impart high thermal conductivity to the resin molded body even with a small amount of dispersion. In addition, by keeping the amount of dispersion constant, it is possible to maintain the mechanical properties of the resin molded body.
本発明は以上のような状況に鑑みてなされたものであって、その目的は、少ない分散量でありながら高い熱伝導率を与えるＡｌＮ粒子を分散させた樹脂成形体及びその製造方法を提供することにある。 The present invention was made in consideration of the above circumstances, and its purpose is to provide a resin molded body containing dispersed AlN particles that provide high thermal conductivity even with a small amount of dispersion, and a method for manufacturing the same.
本発明による樹脂成形体は、ＡｌＮからなる粒子を分散させた樹脂成形体であって、前記粒子の体積率を２０％以下としつつ、Ｄ５０での前記粒子の長径を３μｍ以上とした単結晶ウィスカーを熱硬化性樹脂に分散混合させて１～１０Ｗ／ｍ・Ｋの熱伝導率を有することを特徴とする。 The resin molded body according to the present invention is a resin molded body in which particles made of AlN are dispersed, and is characterized in that the volume fraction of the particles is 20% or less, and single crystal whiskers with a major axis of the particles of 3 μm or more at D50 are dispersed and mixed in a thermosetting resin, resulting in a thermal conductivity of 1 to 10 W/m·K.
かかる特徴によれば、ＡｌＮからなる粒子を少ない分散量で樹脂に与えつつ高い熱伝導率を得られ、熱硬化性樹脂の機械的性質を維持できるのである。 This feature makes it possible to obtain high thermal conductivity while providing the resin with a small amount of dispersed AlN particles, and to maintain the mechanical properties of the thermosetting resin.
上記した発明において、前記粒子のＤ５０でのアスペクト比を５以上とすることを特徴としてもよい。かかる特徴によれば、ＡｌＮからなる粒子を少ない分散量で樹脂に与えつつより高い熱伝導率を得られ、熱硬化性樹脂の機械的性質を維持できるのである。 In the above-mentioned invention, the aspect ratio of the particles at D50 may be 5 or more. With this feature, it is possible to obtain a higher thermal conductivity while providing the resin with a small amount of AlN particles dispersed therein, and to maintain the mechanical properties of the thermosetting resin.
上記した発明において、シート形状を有し、厚さ方向に対する面方向の熱伝導率を大とするように、前記粒子を配向させて分散していることを特徴としてもよい。また、前記厚さ方向の熱伝導率を２Ｗ／ｍ・Ｋ以下とするように前記粒子を配向させていることを特徴としてもよい。かかる発明によれば、ＡｌＮからなる粒子を少ない分散量で樹脂に与えつつ高い熱伝導率を得られ、シート成形体としての破断強度などの機械的性質を高め得る。 The above-mentioned invention may be characterized in that the particles are oriented and dispersed so as to have a sheet shape and to increase the thermal conductivity in the planar direction relative to the thickness direction. The particles may also be oriented so as to make the thermal conductivity in the thickness direction 2 W/m·K or less. According to this invention, it is possible to obtain high thermal conductivity while providing a resin with a small amount of dispersed particles made of AlN, and to improve mechanical properties such as the breaking strength of the sheet molded body.
本発明による製造方法は、ＡｌＮからなる粒子を分散させた樹脂成形体の製造方法であって、ＡｌＮからなる単結晶ウィスカーを体積率で２０％以下となるように溶融させた熱硬化性樹脂に混合し分散させた後に真空引きしつつ所定形状に成形加工し、Ｄ５０での前記粒子の長径を３μｍ以上とした前記粒子を分散混合させた１～１０Ｗ／ｍ・Ｋの熱伝導率を有する前記樹脂成形体とすることを特徴とする。 The manufacturing method according to the present invention is a method for manufacturing a resin molded body with dispersed particles made of AlN, which is characterized in that single crystal whiskers made of AlN are mixed and dispersed in a molten thermosetting resin so that the volume fraction is 20% or less, and then molded into a predetermined shape while drawing a vacuum, to produce a resin molded body having a thermal conductivity of 1 to 10 W/m·K in which the particles with a major axis of 3 μm or more at D50 are dispersed and mixed.
かかる特徴によれば、アスペクト比の高い粒子の混合時の破損を抑制できるとともに、単結晶ウィスカーと樹脂の接触を高めて、結果として、ＡｌＮからなる粒子を少ない分散量で樹脂に与えつつ高い熱伝導率を得られ、熱硬化性樹脂の機械的性質を維持する樹脂成形体を得られるのである。 This feature makes it possible to suppress breakage of particles with high aspect ratios when mixed, and to increase contact between the single crystal whiskers and the resin. As a result, it is possible to obtain a resin molded body that maintains the mechanical properties of thermosetting resin while providing the resin with a small amount of dispersed AlN particles and achieving high thermal conductivity.
上記した発明において、前記粒子のＤ５０でのアスペクト比を５以上とすることを特徴としてもよい。かかる特徴によれば、ＡｌＮからなる粒子を少ない分散量で樹脂に与えつつより高い熱伝導率を得られ、熱硬化性樹脂の機械的性質を維持できるのである。 In the above-mentioned invention, the aspect ratio of the particles at D50 may be 5 or more. With this feature, it is possible to obtain a higher thermal conductivity while providing the resin with a small amount of AlN particles dispersed therein, and to maintain the mechanical properties of the thermosetting resin.
上記した発明において、厚さ方向に対する面方向の熱伝導率を大とするように、前記ウィスカーを配向させて分散させるようにシート形状にコーターで成形加工し、真空引きしつつ乾燥させることを特徴としてもよい。かかる特徴によれば、シート形状に成形加工しつつ配向させようとしたときのアスペクト比の高い粒子の破損を抑制できるとともに、樹脂中に閉じ込められる空気を減じ得るから、結果として、ＡｌＮからなる粒子を少ない分散量で樹脂に与えつつ高い熱伝導率を得られ、熱硬化性樹脂の機械的性質を維持するシート形状の樹脂成形体を得られるのである。 In the above-mentioned invention, the whiskers may be oriented and dispersed in a sheet shape using a coater to increase the thermal conductivity in the surface direction relative to the thickness direction, and then dried under vacuum. This feature can suppress damage to particles with a high aspect ratio when attempting to orient the whiskers while shaping them into a sheet shape, and can reduce the amount of air trapped in the resin. As a result, a small amount of AlN particles can be dispersed in the resin while obtaining a high thermal conductivity, and a sheet-shaped resin molded body that maintains the mechanical properties of the thermosetting resin can be obtained.
上記した発明において、基板の上に前記コーターで成形後、前記基板のまま乾燥させることを特徴としてもよい。かかる特徴によれば、高い熱伝導率を有しつつ、熱硬化性樹脂の機械的性質を維持するシート形状の樹脂成形体を簡便に得られるのである。 In the above-mentioned invention, a feature may be that after molding on a substrate with the coater, the substrate is dried as is. With this feature, a sheet-shaped resin molded body that has high thermal conductivity and maintains the mechanical properties of a thermosetting resin can be easily obtained.
上記した発明において、前記厚さ方向の熱伝導率を２Ｗ／ｍ・Ｋ以下とするように前記粒子を配向させることを特徴としてもよい。かかる発明によれば、ＡｌＮからなる粒子を少ない分散量で樹脂に与えつつ高い熱伝導率を得られ、シート成形体としての破断強度などの機械的性質を高め得る。 The above-mentioned invention may be characterized in that the particles are oriented so that the thermal conductivity in the thickness direction is 2 W/m·K or less. According to this invention, it is possible to obtain high thermal conductivity while providing a resin with a small amount of dispersed particles made of AlN, and to improve mechanical properties such as the breaking strength of the sheet molded body.
以下、本発明の代表的な一例としての樹脂成形体について、図１を用いて説明する。 Below, a resin molded body as a representative example of the present invention will be described with reference to Figure 1.
図１に示すように、本実施例における樹脂成形体１０は樹脂２の内部にＡｌＮからなる粒子１を分散させた樹脂成形体である。特に、粒子１の体積率を２０％以下とした上で、熱伝導率を１～１０Ｗ／ｍ・Ｋとする。このような熱伝導率を得るために、粒子１はＡｌＮの単結晶ウィスカーからなり、かかる粒子の長径をＤ５０で３μｍ以上としている。 As shown in FIG. 1, the resin molded body 10 in this embodiment is a resin molded body in which particles 1 made of AlN are dispersed inside the resin 2. In particular, the volume ratio of the particles 1 is set to 20% or less, and the thermal conductivity is set to 1 to 10 W/m·K. To obtain such a thermal conductivity, the particles 1 are made of single crystal whiskers of AlN, and the major axis of the particles is set to 3 μm or more in D50.
粒子１は、単結晶ウィスカーからなるので多結晶体に比べて熱伝導率が高い。また、粒子１は、その長径をＤ５０で３μｍ以上と比較的大きくすることで粒子１同士での接触箇所を多くすることができる。そのため、上記したように体積率２０％以下と少ない量で粒子１が分散されていても、粒子１同士の接触による熱伝導経路を多く確保でき、樹脂成形体１０として高い熱伝導率を維持することができる。なお、粒子１としては、純度の高い単結晶ウィスカーを用いることで、不純物の多い単結晶体に比べても熱伝導率を高くでき、体積率を低下させ得て好ましい。また、粒子１として用いる単結晶ウィスカーは、その結晶構造を六方晶のウルツ鉱型構造としており、ｃ軸方向と垂直に（０００２）面が位置することが好ましい。このような単結晶ウィスカーは、熱伝導率として１２０～３２０Ｗ／ｍ・Ｋを得ることができる。 The particles 1 are made of single crystal whiskers, and therefore have a higher thermal conductivity than polycrystals. In addition, the particles 1 can have a relatively large major axis of 3 μm or more in D50, which allows for a large number of contact points between the particles 1. Therefore, even if the particles 1 are dispersed in a small amount of 20% or less by volume as described above, many thermal conduction paths can be secured through contact between the particles 1, and the resin molded body 10 can maintain a high thermal conductivity. It is preferable to use single crystal whiskers with high purity as the particles 1, since it is possible to increase the thermal conductivity and reduce the volume fraction compared to single crystals with a large amount of impurities. In addition, it is preferable that the single crystal whiskers used as the particles 1 have a hexagonal wurtzite structure as their crystal structure, and the (0002) plane is located perpendicular to the c-axis direction. Such single crystal whiskers can achieve a thermal conductivity of 120 to 320 W/m·K.
また、粒子１は、Ｄ５０でのアスペクト比を５以上とすることが好ましい。上記したように粒子１同士の接触箇所を多くすることができ、これによっても樹脂成形体１０としての熱伝導率を維持しつつ、体積率を低下させ得る。 In addition, it is preferable that the particle 1 has an aspect ratio of 5 or more at D50. As described above, the number of contact points between the particles 1 can be increased, which also makes it possible to reduce the volume fraction while maintaining the thermal conductivity of the resin molded body 10.
なお、樹脂成形体１０として得られる熱伝導率について上限値を１０Ｗ／ｍ・Ｋと定めたが、これによって粒子１のアスペクト比を極端に大きくすることを防止している。アスペクト比が極端に大きいと製造途中に粒子１を折損させるなど破損させやすくして微粉末を増加させてしまい、Ｄ５０での長径を維持できず、却って熱伝導率を低下させてしまうためである。 The upper limit of the thermal conductivity of the resin molded body 10 is set to 10 W/m·K, which prevents the aspect ratio of the particles 1 from becoming too large. If the aspect ratio is too large, the particles 1 will be easily broken or damaged during production, resulting in an increase in fine powder, and the major axis at D50 cannot be maintained, which would actually decrease the thermal conductivity.
次に、樹脂成形体１０の製造方法について図２を用いて説明する。 Next, the manufacturing method of the resin molded body 10 will be explained with reference to FIG.
図２に示すように、まず、粒子１として所定形状のＡｌＮからなる単結晶ウィスカーを用意し、溶融した熱硬化性樹脂と混合して分散させ、複合樹脂材料を得る（混合：Ｓ１）。このとき、単結晶ウィスカーからなるアスペクト比の大きな粒子１の破損を抑制するように混合する。例えば、ボールミルなどの高い剪断力を付与するような装置は使用せず、付与される剪断力の比較的小さい攪拌装置を用いたり、手作業による攪拌を行ったりして混合させる。なお、上記したように体積分率を２０％以下とするように粒子１を含ませているため、粒子同士が絡むことを減じて、破損を抑制できる。 As shown in FIG. 2, first, single crystal whiskers made of AlN with a predetermined shape are prepared as particles 1, and mixed and dispersed with molten thermosetting resin to obtain a composite resin material (mixing: S1). At this time, mixing is performed to suppress damage to particles 1 made of single crystal whiskers with a large aspect ratio. For example, mixing is performed using a stirring device that applies a relatively small shear force or by manual stirring, rather than using a device that applies a high shear force such as a ball mill. Note that, as described above, particles 1 are included so that the volume fraction is 20% or less, which reduces entanglement between particles and suppresses damage.
次いで、複合樹脂材料を真空引きしつつ所定形状に成形加工する（成形：Ｓ２）。真空引きするのは粒子１と樹脂２とを密着させて空気等のガス成分を排除し、得られる樹脂成形体１０の熱伝導率の低下を抑制するためである。例えば、真空引きしながら焼成して熱硬化性樹脂を硬化させて成形することができる。 Next, the composite resin material is molded into a predetermined shape while being evacuated (molding: S2). The purpose of evacuating is to bring the particles 1 and the resin 2 into close contact with each other, to eliminate gas components such as air, and to prevent a decrease in the thermal conductivity of the resulting resin molded body 10. For example, the thermosetting resin can be cured and molded by baking while being evacuated.
以上によって、上記したような樹脂成形体１０を得ることができる。 By the above steps, the resin molded body 10 as described above can be obtained.
［製造試験］
次に、実際にシート状の樹脂成形体を作製した結果について、図３乃至図６を用いて説明する。
[Production testing]
Next, the results of actually producing a sheet-shaped resin molding will be described with reference to FIGS.
まず、アルミナ板にアルミニウムと他の金属との混合物を載せ、加熱炉に装入した。炉内をアルゴン雰囲気としてから加熱し、所定の加熱温度に到達後に窒素を炉内に導入し保持した。これによってアルミニウムを窒化させて析出させ、結晶成長させた。その後２日間かけて徐冷し、白い棉状のＡｌＮウィスカーを得た。加熱炉から取り出されたアルミナ板上のＡｌＮウィスカーは、ピンセットを用いて手作業で回収し、又は、有機溶媒中に分散して吸引ろ過によって回収し、必要に応じて分級された。このような製造方法により純度の高いＡｌＮ単結晶ウィスカーを得ることができた。 First, a mixture of aluminum and other metals was placed on an alumina plate and then loaded into a heating furnace. The furnace was heated after creating an argon atmosphere, and once the specified heating temperature was reached, nitrogen was introduced into the furnace and maintained there. This caused the aluminum to be nitrided and precipitated, resulting in crystal growth. It was then slowly cooled over two days, yielding white, cotton-like AlN whiskers. The AlN whiskers on the alumina plate removed from the heating furnace were either manually collected using tweezers, or dispersed in an organic solvent and collected by suction filtration, and classified as necessary. This manufacturing method made it possible to obtain high-purity AlN single crystal whiskers.
得られたＡｌＮウィスカーを溶融させた熱硬化性のシリコン樹脂とともに容器に計り入れて攪拌した。攪拌装置によって攪拌した他、さらに手作業でも攪拌した。つまり、ＡｌＮウィスカーは破損を防止するように攪拌され、シリコン樹脂に分散された。 The resulting AlN whiskers were weighed into a container along with molten thermosetting silicone resin and stirred. The mixture was stirred using a stirring device and also by hand. In other words, the AlN whiskers were stirred to prevent breakage and dispersed in the silicone resin.
撹拌されたＡｌＮウィスカーとシリコン樹脂との複合樹脂材料を、コーターを用いてポリテトラフルオロエチレン(polytetrafluoroethylene, ＰＴＦＥ)板上に一方向に塗布し、５００μｍ厚さのシート状体に成形した。 The mixed composite resin material of AlN whiskers and silicone resin was applied in one direction onto a polytetrafluoroethylene (PTFE) plate using a coater and formed into a sheet-like body with a thickness of 500 μm.
ついで、ＰＴＦＥ板ごと定温乾燥機内に装入し、真空引きして減圧下で焼成した。焼成においては、１６０℃で３時間の加熱条件とした。これにてシート状の樹脂成形体１０を得ることができた。 Then, the PTFE plate was placed in a constant temperature dryer, evacuated, and baked under reduced pressure. The baking was performed at 160°C for 3 hours. This resulted in a sheet-shaped resin molded body 10.
図３に示すように、このようにして製造された樹脂成形体１０について、断面を電子顕微鏡にて観察した。ＡｌＮウィスカーによる粒子がその長手方向を複合樹脂材料の塗布された方向（同図において紙面左右方向）に向けて配向されていることが判る。 As shown in Figure 3, the cross section of the resin molded body 10 produced in this manner was observed under an electron microscope. It can be seen that the AlN whisker particles are oriented with their longitudinal direction facing the direction in which the composite resin material was applied (the left-right direction on the paper in the figure).
図４に示すように、ＡｌＮウィスカーの体積分率を変化させたときの樹脂成形体１０の熱伝導率について測定した。「シート成形方向」（上記した複合樹脂の塗布された方向）の熱伝導率は、ＡｌＮウィスカーの体積分率を５％、１０％、２０％としたいずれにおいても１～１０Ｗ／ｍ・Ｋの範囲内であり、体積分率を高くすると熱伝導率も向上する傾向にあった。ところで、体積分率を２０％よりも大きくすると、体積分率の増加に対して熱伝導率の増加を鈍化させ得る。つまり、上記した熱伝導率には、体積分率の増加による効果以外に、粒子１の長径の大きさによる粒子１同士の接触箇所の増加の効果が含まれていることを推定できる。一方、配向の結果、シート状体の樹脂成形体１０の「厚さ方向」の熱伝導率はＡｌＮウィスカーの体積分率を変化させてもほとんど変化せず、いずれも２Ｗ／ｍ・Ｋ以下であった。好ましくは、１Ｗ／ｍ・Ｋ未満とする。 As shown in FIG. 4, the thermal conductivity of the resin molded body 10 was measured when the volume fraction of the AlN whiskers was changed. The thermal conductivity in the "sheet molding direction" (the direction in which the composite resin was applied) was in the range of 1 to 10 W/m·K for all AlN whisker volume fractions of 5%, 10%, and 20%, and there was a tendency for the thermal conductivity to improve as the volume fraction was increased. However, if the volume fraction is increased to more than 20%, the increase in thermal conductivity with respect to the increase in volume fraction can be slowed down. In other words, it can be estimated that the above-mentioned thermal conductivity includes the effect of increasing the contact points between particles 1 due to the size of the major axis of the particles 1 in addition to the effect of increasing the volume fraction. On the other hand, as a result of the orientation, the thermal conductivity in the "thickness direction" of the resin molded body 10 in the sheet-like body hardly changed even when the volume fraction of the AlN whiskers was changed, and was 2 W/m·K or less in all cases. It is preferably less than 1 W/m·K.
さらに、測定に用いた樹脂成形体１０に含まれるＡｌＮウィスカーの詳細について調査するため、大気中で樹脂成形体１０を加熱して樹脂成分を揮発させた。加熱温度は、例えば、６００～８００℃の範囲内とすることで、樹脂だけを揮発させてＡｌＮウィスカーを反応させないようにできる。残存したＡｌＮウィスカーについてその粒子のアスペクト比及び長径を調査し、粒子数基準での度数（頻度）分布を１００分率でまとめた。 Furthermore, in order to investigate the details of the AlN whiskers contained in the resin molded body 10 used in the measurement, the resin molded body 10 was heated in the atmosphere to volatilize the resin components. By setting the heating temperature within the range of, for example, 600 to 800°C, it is possible to volatilize only the resin and prevent the AlN whiskers from reacting. The particle aspect ratio and major axis of the remaining AlN whiskers were investigated, and the frequency distribution based on the particle number was summarized as a percentage.
図５に示すように、長径はＤ５０で１８μｍであった。このように、長径をＤ５０で３μｍ以上とすることで、樹脂成形体１０に１～１０Ｗ／ｍ・Ｋの熱伝導率を付与できた。なお、製造過程における粒子同士の絡みなどによるＡｌＮウィスカーの破損も想定され得たが、体積分率を２０％以下とすることでそのような破損をほとんど生じなかったものと考えられる。なお、ＡｌＮウィスカーの長径をＤ５０で３μｍ以上と定めたことについては、３μｍ以上の長い粒子の体積分率、すなわち数密度を一定以上にすることである。つまり、ＡｌＮウィスカー同士の接触箇所の数密度とＡｌＮウィスカー１本で熱伝導させる距離とを長径を大とする粒子によって向上させ、これによって熱伝導率を向上させることができたと考えられる。 As shown in FIG. 5, the long diameter was 18 μm at D50. In this way, by making the long diameter 3 μm or more at D50, it was possible to impart a thermal conductivity of 1 to 10 W/m·K to the resin molded body 10. It is possible to imagine that the AlN whiskers would be damaged due to entanglement between particles during the manufacturing process, but by setting the volume fraction to 20% or less, it is believed that such damage hardly occurred. The reason why the long diameter of the AlN whiskers is set to 3 μm or more at D50 is to set the volume fraction of long particles of 3 μm or more, i.e., the number density, to a certain level or higher. In other words, it is believed that the number density of contact points between AlN whiskers and the distance through which heat is conducted by a single AlN whisker are improved by particles with a large long diameter, which in turn improves the thermal conductivity.
図６に示すように、アスペクト比はＤ５０で５であった。このようにアスペクト比を５以上とすることで上記した熱伝導率の向上に寄与したものと考えられる。なお、アスペクト比の高いＡｌＮウィスカーを主面に平行な面方向に配向分散させたことで、樹脂成形体１０はシート体としての破断強度に優れるものになったものと考えられる。 As shown in FIG. 6, the aspect ratio was 5 at D50. It is believed that making the aspect ratio 5 or more contributed to the improvement in thermal conductivity mentioned above. In addition, it is believed that by orienting and dispersing the AlN whiskers with a high aspect ratio in a planar direction parallel to the main surface, the resin molding 10 has excellent breaking strength as a sheet body.
以上のように、体積分率で２０％以下の少ない量でＡｌＮウィスカーを分散させても、１～１０Ｗ／ｍ・Ｋの高い熱伝導率を得ることができた。 As described above, even when AlN whiskers are dispersed in a small amount (volume fraction of 20% or less), a high thermal conductivity of 1 to 10 W/m·K can be obtained.
ここまで本発明による実施例及びこれに基づく変形例を説明したが、本発明は必ずしもこれらの例に限定されるものではない。また、当業者であれば、本発明の主旨又は添付した特許請求の範囲を逸脱することなく、様々な代替実施例及び改変例を見出すことができるであろう。 Although the present invention has been described above with reference to examples and variations thereof, the present invention is not necessarily limited to these examples. Furthermore, a person skilled in the art will be able to find various alternative embodiments and modifications without departing from the spirit of the present invention or the scope of the appended claims.
１ 粒子
２ 樹脂
１０ 樹脂成形体
1 Particle 2 Resin 10 Resin molded body
Claims (9)
１～１０Ｗ／ｍ・Ｋの熱伝導率を有し、
ＡｌＮ単結晶ウィスカーからなる前記粒子をＤ５０での長径を３μｍ以上とし２０％以下の体積率で含むことを特徴とするＡｌＮ粒子分散樹脂成形体。 A resin molded body in which particles made of AlN are dispersed in a thermosetting resin ,
It has a thermal conductivity of 1 to 10 W/m K,
An AlN particle-dispersed resin molding comprising AlN single crystal whiskers having a major axis of 3 μm or more at D50 and a volume ratio of 20% or less.
ＡｌＮ単結晶ウィスカーを溶融させた熱硬化性樹脂に混合し分散させた後に所定形状に成形加工し、前記粒子をＤ５０での長径を３μｍ以上として２０％以下の体積率で分散させ、１～１０Ｗ／ｍ・Ｋの熱伝導率を有する前記樹脂成形体とすることを特徴とするＡｌＮ粒子分散樹脂成形体の製造方法。 A method for producing a resin molded body having AlN particles dispersed therein, comprising the steps of:
A method for producing an AlN particle-dispersed resin molded body, comprising mixing and dispersing AlN single crystal whiskers in a molten thermosetting resin, forming the mixture into a predetermined shape, dispersing the particles at a volume ratio of 20% or less with a major axis of 3 μm or more at D50, and producing the resin molded body having a thermal conductivity of 1 to 10 W/m·K.
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| JP2010235842A (en) | 2009-03-31 | 2010-10-21 | Mitsubishi Chemicals Corp | Thermosetting resin composition containing anisotropic aluminum nitride filler |
| JP2016145120A (en) | 2015-02-06 | 2016-08-12 | 株式会社フジクラ | Aluminum nitride whisker, resin composition, method for manufacturing aluminum nitride whisker |
| JP2020105242A (en) | 2018-12-26 | 2020-07-09 | 東レ株式会社 | Resin film and method for producing resin film |
| WO2020145083A1 (en) | 2019-01-07 | 2020-07-16 | 日東シンコー株式会社 | Resin composition, method for producing said resin composition, and thermally conductive sheet |
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| JP2010235842A (en) | 2009-03-31 | 2010-10-21 | Mitsubishi Chemicals Corp | Thermosetting resin composition containing anisotropic aluminum nitride filler |
| JP2016145120A (en) | 2015-02-06 | 2016-08-12 | 株式会社フジクラ | Aluminum nitride whisker, resin composition, method for manufacturing aluminum nitride whisker |
| JP2020105242A (en) | 2018-12-26 | 2020-07-09 | 東レ株式会社 | Resin film and method for producing resin film |
| WO2020145083A1 (en) | 2019-01-07 | 2020-07-16 | 日東シンコー株式会社 | Resin composition, method for producing said resin composition, and thermally conductive sheet |
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