JP5388665B2 - Thermoplastic resin composition and molded article thereof - Google Patents
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本発明は、放熱性に優れた熱可塑性樹脂組成物及びその成形体に関するものである。 The present invention relates to a thermoplastic resin composition excellent in heat dissipation and a molded body thereof.
発熱性電子部品の高密度化、高集積化により発熱量が増大し、電子部品の温度上昇を極力抑えるため、発生した熱を効率良く放熱する要求が益々高まっている。また、携帯用パソコンなどの電子機器は小型化、薄型化、軽量化が進み、これらに用いられる部材、筐体も良放熱性のものが要求されている。更にＬＥＤを利用した照明機器の部材、筐体も高放熱性が必要とされている。従来、それらに用いられる部材の放熱性を向上させる方法として、例えば、部材をアルミニウム等の金属製にする方法や、部材表面に高熱伝導率塗料を塗布する方法、高熱伝導性フィラーとして酸化アルミニウム粉末を樹脂やゴムに高濃度で配合する方法等が提案されている（特許文献１、２、３参照）。更に、高熱伝導性フィラーとして特定の酸化アルミニウム粉末を樹脂に配合し、射出成形可能な熱可塑性樹脂とする技術も提案されている（特許文献４参照）。 The amount of heat generation is increased by increasing the density and integration of the heat-generating electronic components, and in order to suppress the temperature rise of the electronic components as much as possible, there is an increasing demand for efficiently radiating the generated heat. In addition, electronic devices such as portable personal computers are becoming smaller, thinner, and lighter, and members and casings used for these devices are required to have good heat dissipation. Furthermore, high heat dissipation is also required for members and casings of lighting equipment using LEDs. Conventionally, as a method for improving the heat dissipation of members used in them, for example, a method of making a member made of metal such as aluminum, a method of applying a high thermal conductivity paint on the surface of a member, aluminum oxide powder as a high thermal conductivity filler The method etc. which mix | blend this with resin and rubber | gum by high concentration are proposed (refer patent document 1, 2, 3). Furthermore, a technique has been proposed in which a specific aluminum oxide powder is blended with a resin as a high thermal conductive filler to form a thermoplastic resin that can be injection-molded (see Patent Document 4).
本発明は、新規な熱可塑性樹脂組成物及びその成形体を提供することを課題とする。 An object of the present invention is to provide a novel thermoplastic resin composition and a molded body thereof.
すなわち、本発明は、（１）（Ｉ）熱可塑性樹脂３０体積％と（II）平均粒径３〜５０μｍ、充填量５０〜６５体積％の球状アルミナと（III）充填量５〜２０体積％の水酸化マグネシウムを、セラミックコートを施したスクリューの押出機で混練することにより得られる色相の明度（Ｌ＊）が９０以上で且つ、熱伝導率が１．５Ｗ／ｍＫ〜５Ｗ／ｍＫであることを特徴とする熱可塑性樹脂組成物、（２）更に、白色系着色剤を配合することを特徴とする（１）記載の熱可塑性樹脂組成物、（３）白色系着色剤が酸化チタン、酸化亜鉛、及び沈降性硫酸バリウムの少なくとも１種であることを特徴とする（２）に記載の熱可塑性樹脂組成物、（４）（１）〜（３）のいずれか１項に記載の熱可塑性樹脂組成物からなる放熱部材である。
That is, the present invention comprises (1) (I) 30% by volume of thermoplastic resin, (II) spherical alumina having an average particle size of 3 to 50 μm, and a filling amount of 50 to 65 % by volume, and (III) a filling amount of 5 to 20% by volume The lightness (L * ) of the hue obtained by kneading the magnesium hydroxide with a ceramic-coated screw extruder is 90 or more and the thermal conductivity is 1.5 W / mK to 5 W / mK. (2) The thermoplastic resin composition according to (1), further comprising a white colorant, (3) The white colorant is titanium oxide, The thermoplastic resin composition according to (2) , which is at least one of zinc oxide and precipitated barium sulfate, (4) The heat according to any one of (1) to (3) It is a heat radiating member which consists of a plastic resin composition.
本発明によれば容易に射出成形可能な耐熱性、放熱性、色相に優れた組成物及びその成形体を提供することができる。発熱性電子部品の放熱部材、例えばＬＥＤ照明筐体、電源アダプター、パソコン用部品、携帯電話用部品、自動車部品、光学式ディスプレー装置、半導体及び熱を発する部分に接触している部品などの筐体用途に好適に用いることができる。 ADVANTAGE OF THE INVENTION According to this invention, the composition excellent in the heat resistance which can be easily injection-molded, heat dissipation, and a hue, and its molded object can be provided. Heat dissipating members for heat-generating electronic parts, such as LED lighting housings, power adapters, personal computer parts, mobile phone parts, automobile parts, optical display devices, semiconductors, and parts that are in contact with heat-generating parts It can use suitably for a use.
＜用語の説明＞
本願明細書において、「〜」という記号は「以上」及び「以下」を意味する。例えば、「Ａ〜Ｂ」なる記載は、Ａ以上でありＢ以下であることを意味する。
<Explanation of terms>
In the present specification, the symbol “to” means “above” and “below”. For example, the description “A to B” means A or more and B or less.
以下、更に詳しく本発明について説明する。 Hereinafter, the present invention will be described in more detail.
本発明のセラミックコートは、特開平８−３５０７５号公報に開示されるように、第１ステップでは、金属部材を３００〜６５０℃の温度に保持し、アンモニアガスと水素ガスを用い、金属部材の表面に０．００１〜２．０ｍＡ／ｃｍ2 の電流密度のグロー放電を行いイオン窒化して窒化層を形成し、この窒化層の上に第２ステップにてＰＶＤ法によりＴｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ及びＣｒの少なくとも１種の窒化物、炭化物及び／又は炭窒化物からなる硬質被膜、あるいは前記硬質被膜の積層膜あるいは積層傾斜膜を形成するものである。 As disclosed in Japanese Patent Laid-Open No. 8-35075, the ceramic coat of the present invention, in the first step, holds the metal member at a temperature of 300 to 650 ° C., uses ammonia gas and hydrogen gas, A glow discharge with a current density of 0.001 to 2.0 mA / cm 2 is performed on the surface and ion nitrided to form a nitride layer. On the nitride layer, Ti, Zr, Hf, A hard film made of at least one nitride, carbide and / or carbonitride of V, Nb, Ta and Cr, or a laminated film or a laminated gradient film of the hard film is formed.
硬質被膜はセラミックス膜であり、従来の金属材料に比べてビッカース硬度で１５００〜３０００と高硬度で、かつ低摩擦係数を示すため優れた耐摩耗性を発揮する。しかし、膜厚が５μｍを超える厚膜になると、セラミックスの割れや欠け等を生じるため、硬質被膜の厚さは５μｍ以下が好ましい。２μｍ未満では硬質被膜としての特性が十分に発揮されない。硬質被膜の厚さは、２〜５μｍが好ましい。 The hard film is a ceramic film, and has a high Vickers hardness of 1500 to 3000 and a low friction coefficient as compared with conventional metal materials, and exhibits excellent wear resistance. However, when the film thickness exceeds 5 μm, cracks and chipping of ceramics occur, so the thickness of the hard coating is preferably 5 μm or less. When the thickness is less than 2 μm, the characteristics as a hard coating are not sufficiently exhibited. The thickness of the hard coating is preferably 2 to 5 μm.
また、基材表面に窒化層の第１層を設け、その上に第２層として硬質被膜を形成する複合処理により、基材表面での弾性変形又は塑性変形がほとんど起らない。このため、硬質被膜が破壊しない。 Further, the elastic treatment or plastic deformation on the surface of the base material hardly occurs by the composite treatment in which the first layer of the nitride layer is provided on the surface of the base material and the hard film is formed thereon as the second layer. For this reason, a hard film is not destroyed.
熱可塑性樹脂組成物の熱伝導率は、１．５Ｗ／ｍＫ〜５Ｗ／ｍＫであることが必要であるが、好ましくは２Ｗ／ｍｋ〜５Ｗ／ｍＫである。熱伝導率が小さいと放熱性が不十分となりやすく、熱伝導率を高めるためだけに高熱伝導率が高い無機フィラーを大量に配合すると、得られる熱可塑性樹脂組成物の射出成形性が劣る傾向となる。 The thermal conductivity of the thermoplastic resin composition is required to be 1.5 W / mK to 5 W / mK, and preferably 2 W / mk to 5 W / mK. When the thermal conductivity is small, the heat dissipation tends to be insufficient, and when a large amount of an inorganic filler having a high thermal conductivity is added only in order to increase the thermal conductivity, the injection moldability of the resulting thermoplastic resin composition tends to be inferior. Become.
熱可塑性樹脂組成物の流動性の指標であるメルトマスフローレイト（ＭＦＲ）３０ｇ／１０分以上であることが成形加工性の点から好ましい。 A melt mass flow rate (MFR) of 30 g / 10 min or more, which is an index of fluidity of the thermoplastic resin composition, is preferable from the viewpoint of moldability.
球形アルミナの平均球形度は、０．８０〜１．０が好ましい。平均球形度が０．８０未満では、熱可塑性樹脂組成物への充填するための溶融混練が困難となりやすく、得られる熱可塑性樹脂組成物の強度が低下する傾向がある。また、球状アルミナの分散性が悪くなり、得られた成形体の放熱効果が小さくなる傾向がある。 The average sphericity of the spherical alumina is preferably 0.80 to 1.0. If the average sphericity is less than 0.80, melt kneading for filling into the thermoplastic resin composition tends to be difficult, and the strength of the resulting thermoplastic resin composition tends to decrease. Further, the dispersibility of the spherical alumina is deteriorated, and the heat dissipation effect of the obtained molded product tends to be reduced.
なお、平均球形度は、実体顕微鏡（例えば、ニコン社製モデル「ＳＭＺ−１０型」）、走査型電子顕微鏡等にて撮影した粒子像を画像解析装置（日本アビオニクス社製）に取り込み、以下に示す方法にて測定することができる。この方法以外にも、粒子像分析装置（例えば、シスメックス社製商品名「ＦＰＩＡ−１０００」）にて定量的に自動計測された個々の粒子の新円度から、球形度＝（新円度）２により換算して求めることもできる。
すなわち、粒子像から粒子の投影面積（Ａ）と周辺長（ＰＭ）を測定する。周辺長（ＰＭ）に対応する真円の面積を（Ｂ）とすると、その粒子の真円度はＡ／Ｂとして表示できる。そこで、試料粒子の周囲長（ＰＭ）と同一の周囲長を持つ真円を想定すると、ＰＭ＝２πｒ、Ｂ＝πｒ２ であるから、Ｂ＝π×（ＰＭ／２π）２ となり、個々の粒子の球形度は、球形度＝Ａ／Ｂ＝Ａ×４π／（ＰＭ）２ として算出することができる。このようにして得られた任意の粒子の２００個の球形度を求め、その平均値を平均球形度とした。
The average sphericity is obtained by taking a particle image photographed with a stereomicroscope (for example, model “SMZ-10 type” manufactured by Nikon Corporation), a scanning electron microscope or the like into an image analyzer (manufactured by Nippon Avionics Co., Ltd.). It can be measured by the method shown. In addition to this method, sphericity = (new circularity) from the new circularity of individual particles quantitatively automatically measured by a particle image analyzer (for example, trade name “FPIA-1000” manufactured by Sysmex Corporation). It can also be obtained by conversion according to 2 .
That is, the projected area (A) and peripheral length (PM) of the particle are measured from the particle image. When the area of a perfect circle corresponding to the peripheral length (PM) is (B), the roundness of the particle can be displayed as A / B. Therefore, assuming a perfect circle having the same circumference as the sample particle (PM), PM = 2πr and B = πr 2 , so that B = π × (PM / 2π) 2 , and each particle Can be calculated as sphericity = A / B = A × 4π / (PM) 2 . The 200 sphericities of the arbitrary particles thus obtained were determined, and the average value was defined as the average sphericity.
球状アルミナの含有量は、５０〜７０体積％であり、好ましくは６０〜７０体積％である。含有量が５０体積％より少ないと放熱性の向上効果小さくなりやすく、含有量が７０体積％より多い射出成形が困難となる場合がある。 The content of spherical alumina is 50 to 70% by volume, preferably 60 to 70% by volume. If the content is less than 50% by volume, the effect of improving heat dissipation tends to be small, and injection molding having a content of more than 70% by volume may be difficult.
球状アルミナの平均粒径は、３〜５０μｍであり、平均粒径が３μｍより小さくなると放熱性の向上効果が小さくなりやすく、平均粒径が５０μｍより大きくなると、セラミックコートをしていても得られる熱可塑性樹脂組成物の色相Ｌ値が著しく低下する傾向がある。平均粒径が５０μｍより大きいと、セラミックコートを混練時に摩耗していると推察される。 The average particle diameter of the spherical alumina is 3 to 50 μm, and if the average particle diameter is smaller than 3 μm, the effect of improving the heat dissipation tends to be small, and if the average particle diameter is larger than 50 μm, it can be obtained even with ceramic coating. There exists a tendency for the hue L value of a thermoplastic resin composition to fall remarkably. If the average particle size is larger than 50 μm, it is assumed that the ceramic coat is worn during kneading.
熱可塑性樹脂は、例えば、ＨＩＰＳ樹脂、ＡＢＳ樹脂、ＡＡＳ樹脂、ＳＡＳ樹脂、ＳＥＢＳ樹脂、ＭＢＳ樹脂、ＭＥＳ樹脂（メタクリル酸アルキル−エチレン・αオレフィン系ゴム−スチレン共重合体）及びＡＣＳ樹脂等のゴム強化スチレン系熱可塑性樹脂、メタクリル−スチレン共重合体、メタクリル樹脂、芳香族ビニル単量体単位、不飽和ジカルボン酸イミド誘導体単位、及びこれらと共重合可能なビニル単量体単位からなるマレイミド系共重合体、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート、ポリシクロヘキサンジメチレンテレフタレート、
ビスフェノールＡや４，４’−ジヒドロキシ−ジフェニルエーテル等のビスフェノールとイソフタル酸、テレフタル酸等の２塩基酸又はその誘導体から合成される芳香族ポリエステルやｐ−ヒドロキシ安息香酸／ビスフェノール／テレフタル酸、ｐ−ヒドロキシ安息香酸／６−ヒドロキシ−２−ナフタレンカルボン酸／テレフタル酸、ｐ−ヒドロキシ安息香酸／ポリブチレンテレフタレート等の液晶性ポリエステル等の芳香族ポリエステル、ポリアミド（ＰＡ）、ポリアミド／酸変性エチレン−プロピレンゴム、ポリアミド／酸変性エチレン−プロピレンゴム／マレイミド系共重合体アロイ、ポリカーボネート、ＡＢＳ／Ｐ
Ｃアロイ、ポリフェニレンスルフィド（ＰＰＳ）、ポリエチレン、ポリプロピレン等が挙げられる。これらの中で、相溶性又は混和性がよい樹脂同士であれば、混合して用いることもできる。
Examples of the thermoplastic resin include rubbers such as HIPS resin, ABS resin, AAS resin, SAS resin, SEBS resin, MBS resin, MES resin (alkyl methacrylate-ethylene / α-olefin rubber-styrene copolymer), and ACS resin. Maleimide copolymer comprising reinforced styrene thermoplastic resin, methacryl-styrene copolymer, methacrylic resin, aromatic vinyl monomer unit, unsaturated dicarboxylic imide derivative unit, and vinyl monomer unit copolymerizable therewith. Polymer, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycyclohexanedimethylene terephthalate,
Aromatic polyesters synthesized from bisphenols such as bisphenol A and 4,4′-dihydroxy-diphenyl ether and dibasic acids such as isophthalic acid and terephthalic acid or derivatives thereof, p-hydroxybenzoic acid / bisphenol / terephthalic acid, p-hydroxy Aromatic polyester such as benzoic acid / 6-hydroxy-2-naphthalenecarboxylic acid / terephthalic acid, liquid crystalline polyester such as p-hydroxybenzoic acid / polybutylene terephthalate, polyamide (PA), polyamide / acid-modified ethylene-propylene rubber, Polyamide / acid-modified ethylene-propylene rubber / maleimide copolymer alloy, polycarbonate, ABS / P
C alloy, polyphenylene sulfide (PPS), polyethylene, polypropylene and the like can be mentioned. Among these, resins having good compatibility or miscibility can be mixed and used.
熱可塑性樹脂組成物は、ハロゲン系難燃剤、酸化アンチモン、リン酸エステル系、水酸化マグネシウムの難燃剤等を含有させることにより難燃性を付与することができる。特に水酸化マグネシウムが好ましい。 The thermoplastic resin composition can impart flame retardancy by containing a halogen flame retardant, an antimony oxide, a phosphate ester, a magnesium hydroxide flame retardant, or the like. Magnesium hydroxide is particularly preferable.
水酸化マグネシウムの量としては、２〜２０体積％が好ましい。含有量が２体積％未満では難燃性が十分でなく、含有量が２０体積％超では、熱伝導率が低下する。 The amount of magnesium hydroxide is preferably 2 to 20% by volume. If the content is less than 2% by volume, the flame retardancy is not sufficient, and if the content exceeds 20% by volume, the thermal conductivity is lowered.
熱可塑性樹脂組成物は、白色系の着色剤を配合して更に色相値Ｌを上げることもできる。白色系の着色剤としては、酸化チタン、酸化亜鉛、沈降性バリウムが好適である。 The thermoplastic resin composition can further increase the hue value L by blending a white colorant. As the white colorant, titanium oxide, zinc oxide, and precipitated barium are preferable.
白色系の着色剤の含有量としては、０．５体積％〜５体積％が好ましい。
含有量０．５体積％未満では、配合による色相Ｌ値の改良効果が少なく、含有量５体積％超では、熱伝導率が低下する場合がある。
The content of the white colorant is preferably 0.5% by volume to 5% by volume.
If the content is less than 0.5% by volume, the effect of improving the hue L value by blending is small, and if the content exceeds 5% by volume, the thermal conductivity may decrease.
熱可塑性樹脂組成物は、放熱性、強度、成形性に影響のない範囲であれば、外部滑剤、内部滑剤、酸化防止剤、光安定剤、紫外線吸収剤、ガラス繊維、カーボン繊維等の補強材、各色着色剤等を配合することができる。無機フィラーは、シラン系及び／又はチタネート系カップリング剤などの粉体表面改質剤で表面改質して使用することも可能である。 The thermoplastic resin composition is a reinforcing material such as an external lubricant, an internal lubricant, an antioxidant, a light stabilizer, an ultraviolet absorber, glass fiber, and carbon fiber as long as it does not affect heat dissipation, strength, and moldability. Each color coloring agent can be blended. The inorganic filler can be used after being surface-modified with a powder surface modifier such as a silane-based and / or titanate-based coupling agent.
熱可塑性樹脂組成物は、通常の溶融混練装置を用いて得ることができるが、好適に使用できる溶融混練装置としては、単軸押出機、噛合形同方向回転又は噛合形異方向回転二軸押出機、非又は不完全噛合形二軸押出機等のスクリュー押出機等がある。 The thermoplastic resin composition can be obtained by using an ordinary melt-kneading apparatus. Examples of the melt-kneading apparatus that can be suitably used include a single-screw extruder, a meshing-type co-rotating or a meshing-type counter-rotating twin-screw extrusion. And screw extruders such as non- or incomplete meshing twin screw extruders.
熱可塑性樹脂組成物は、成形して筐体に用いることができるが、その成形法は、熱可塑性樹脂を成形する方法が利用できる。例えば、プレス法、押出し法、射出成形法、二色成形等挙げられるが、量産性、デザイン性を勘案すると射出成形法が好適である The thermoplastic resin composition can be molded and used for a casing. As the molding method, a method of molding a thermoplastic resin can be used. For example, a press method, an extrusion method, an injection molding method, a two-color molding method, etc. can be mentioned, but an injection molding method is preferable in consideration of mass productivity and design.
射出成形機のスクリュウをセラミックコートすることも、色相Ｌ値を向上させる観点から、好ましい。 It is also preferable to ceramic coat the screw of the injection molding machine from the viewpoint of improving the hue L value.
特に、成形時に、成形体表面を低光沢あるいはシボ面になるような金型を用いることにより、より放熱性に優れた成形体を得ることができる。 In particular, at the time of molding, it is possible to obtain a molded body having more excellent heat dissipation by using a mold having a surface with a low gloss or texture.
以下、本発明を実施例により更に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these.
球状アルミナは、下記のものを用いた（密度３．９７）。
Ｂ−１：球状アルミナ 平均粒径１μｍ、平均球形度０．８８
Ｂ−２：球状アルミナ 平均粒径３μｍ、平均球形度０．８８
Ｂ−３：球状アルミナ 平均粒径２０μｍ、平均球形度０．８７
Ｂ−４：球状アルミナ 平均粒径５０μｍ、平均球形度０．８９
Ｂ−５：球状アルミナ 平均粒径６０μｍ、平均球形度０．８７
尚、球状アルミナの熱伝導率（Ｗ／ｍＫ）は３０であった。
The following spherical alumina was used (density 3.97).
B-1: Spherical alumina Average particle diameter 1 μm, average sphericity 0.88
B-2: Spherical alumina Average particle size 3 μm, average sphericity 0.88
B-3: Spherical alumina Average particle size 20 μm, average sphericity 0.87
B-4: Spherical alumina Average particle size 50 μm, Average sphericity 0.89
B-5: Spherical alumina Average particle size 60 μm, average sphericity 0.87
The spherical alumina had a thermal conductivity (W / mK) of 30.
熱可塑性樹脂は、下記のものを用いた。
Ａ−１：ＡＢＳ樹脂 電気化学工業社製、ＧＲ−２０００（密度：１．０５）
Ａ−２：ＰＡ（ポリアミド６） 東レ社製 アミラン ＣＭ１０１７（密度１．１４）
Ａ−３：ＰＣ（ポリカーボネート） 三菱エンジニアリングプラスチック社製
Ｅ−２０００（密度 １．２０）
The following were used for the thermoplastic resin.
A-1: ABS resin, manufactured by Denki Kagaku Kogyo Co., Ltd., GR-2000 (density: 1.05)
A-2: PA (polyamide 6) Amilan CM1017 (density 1.14) manufactured by Toray Industries, Inc.
A-3: PC (polycarbonate) Mitsubishi Engineering Plastics E-2000 (density 1.20)
水酸化マグネシウムは、下記のものを用いた。
Ｃ−１：神島化学工業社製 マグシーズ Ｎ−４
The following magnesium hydroxide was used.
C-1: Magsees N-4 manufactured by Kamishima Chemical Industry Co., Ltd.
白色系着色剤は、酸化チタン、酸化亜鉛（亜鉛華）、沈降性硫酸バリウムを用いた。 As the white colorant, titanium oxide, zinc oxide (zinc white), and precipitated barium sulfate were used.
スクリュウのセラミックコートは以下のように実施した。特開平８−３５０７５号公報の実施例１に準じて、ダルメージスクリュー（鋼材ＳＣＭ４３５）にセラミックコートを行った。このセラミックＴｉＮ膜厚は、３〜４μｍであった。 The ceramic coating of the screw was performed as follows. According to Example 1 of JP-A-8-35075, a ceramic coating was applied to a dalmage screw (steel material SCM435). The ceramic TiN film thickness was 3-4 μm.
［実施例８，１０，１１，１５、比較例１〜１４及び参考例１〜１１］
表１〜表４に示した配合になるように、ヘンシェルミキサーに各無機フィラーと各熱可塑性樹脂を仕込み、低速回転で３分間混合した。この混合物を真空ベント付きの４０ｍｍ単軸押出し機・ダルメージスクリュー（ＩＫＧ製、ＭＳ４０−３２Ｖ）で下記設定温度及び、スクリュー回転数８０〜１００ｒｐｍで、溶融混練し、ペレットを得た。
熱可塑性樹脂 溶融混練時の温度設定
Ａ−１ ２５０〜２８０℃
Ａ−２ ２５０〜２８０℃
Ａ−３ ３００〜３３０℃
このペレットを使用して、射出成形機により評価用試験片を作成し、各種物性を評価した。結果を表１〜４に示す。
[ Examples 8, 10, 11, 15, Comparative Examples 1-14 and Reference Examples 1-11 ]
Each inorganic filler and each thermoplastic resin were charged into a Henschel mixer so as to have the composition shown in Tables 1 to 4, and mixed at a low speed for 3 minutes. This mixture was melt-kneaded with a 40 mm single-screw extruder / dull image screw (manufactured by IKG, MS40-32V) with a vacuum vent at the following set temperature and a screw rotation speed of 80 to 100 rpm to obtain pellets.
Thermoplastic resin Temperature setting during melt-kneading A-1 250-280 ° C
A-2 250-280 ° C
A-3 300-330 ° C
Using these pellets, test specimens for evaluation were prepared by an injection molding machine, and various physical properties were evaluated. The results are shown in Tables 1-4.
表１、表２の実施例１〜実施例１６に示すように、熱可塑性樹脂と平均粒径３〜５０μｍ、充填量５０〜７０体積％の球状アルミナを、セラミックコートを施したスクリューの押出機で混練することにより得られる色相の明度（Ｌ＊）が９０以上で且つ、熱伝導率が１．５Ｗ／ｍＫ〜５Ｗ／ｍＫである物性バランスと色相のバランスが優れた樹脂組成物が得られる。表３、表４の比較例１〜９ではセラミックコートの無いスクリューの押出機で混練することで、色相の明度（Ｌ＊）が６５〜７２と低くなり、灰色になってしまう。特に、比較例８、９では白色顔料である酸化チタンを配合しているが、特に大きな効果は無く、色相の明度（Ｌ＊）は７０までしか向上せず、灰色であった。
比較例１１では、球状アルミナの充填量が７０体積％を超えているので、放熱性は良好であるが、色相の明度（Ｌ＊）が５６に低下し、灰色になってしまい、射出成形性も著しく低下する。比較例１２では水酸化マグネシウムの配合量が５体積％未満なので、水酸化マグネシムを配合した難燃性付与効果が発現しない。比較例１３では水酸化マグネシウムの配合量が２０体積％を超えているため、難燃性付与効果はあるが射出成形性が著しく低下する。比較例１４では、球状アルミナの平均粒径が５０μｍを超えているため、セラミックコートしたスクリューの押出機で混練しているにも関わらず色相の明度（Ｌ＊）が５８に低下し、灰色になってしまう。
As shown in Examples 1 to 16 of Tables 1 and 2, a screw extruder in which a thermoplastic resin and spherical alumina having an average particle diameter of 3 to 50 μm and a filling amount of 50 to 70% by volume are coated with ceramics. A resin composition having an excellent balance of physical properties and hue, in which the lightness (L * ) of the hue obtained by kneading at 90 is 90 or more and the thermal conductivity is 1.5 W / mK to 5 W / mK is obtained. . In Comparative Examples 1 to 9 in Tables 3 and 4, the lightness (L * ) of the hue is lowered to 65 to 72 and becomes gray by kneading with a screw extruder without a ceramic coat. In particular, in Comparative Examples 8 and 9, titanium oxide, which is a white pigment, was blended, but there was no particularly great effect, and the lightness (L * ) of the hue was improved only to 70 and was gray.
In Comparative Example 11, since the filling amount of spherical alumina exceeds 70% by volume, the heat dissipation is good, but the lightness (L * ) of the hue is lowered to 56 and becomes gray, and the injection moldability. Is also significantly reduced. In Comparative Example 12, since the blending amount of magnesium hydroxide is less than 5% by volume, the flame retardancy imparting effect by blending magnesium hydroxide is not exhibited. In Comparative Example 13, since the blending amount of magnesium hydroxide exceeds 20% by volume, there is an effect of imparting flame retardancy, but the injection moldability is significantly lowered. In Comparative Example 14, since the average particle diameter of the spherical alumina exceeds 50 μm, the lightness (L * ) of the hue decreases to 58 despite being kneaded by the extruder of the ceramic-coated screw, and becomes gray. turn into.
尚、実施例で得られた熱可塑性樹脂組成物を射出成形して得られた成形体を用いた電源アダプター、パソコン用部品、携帯電話用部品、自動車部品、光学式ディスプレー装置、半導体材料、ＬＥＤ照明筐体を作成したところ従来製品に比較して良好な放熱性の優れた製品が得られた。 In addition, the power adapter using the molded object obtained by injection-molding the thermoplastic resin composition obtained in the Example, parts for personal computers, parts for mobile phones, automobile parts, optical display devices, semiconductor materials, LEDs When an illumination case was created, a product with better heat dissipation than the conventional product was obtained.
各種物性の評価測定法は下記の通りである。
（１）流動性：ＪＩＳ Ｋ−７２１０に従い、メルトマスフローレイト（ＭＦＲ）を測定した。
（２）衝撃強度：ＪＩＳ Ｋ−７１１１に従い、ノッチ有りシャルピー衝撃強度を測定した。
（３）耐熱性：ＪＩＳ Ｋ−７１０６に従い、５０Ｎ荷重、ビカット軟化点を測定した。
（４）難燃性：射出成形機・東芝ＩＳ８０Ｇ−２Ａにより、長さ５インチ×幅１／２インチ×厚さ１／１６インチの試験片を作成し、米国におけるアンダーライターズ・ラボラトリーズ（ＵＬ）で規格化されたサブジェクト９４号（略称ＵＬ−９４）に基づき難燃性の判定を行った。
（５）明度（Ｌ＊）：ペレットを２６０℃で熱プレス成形を行い、３０ｍｍ×３０ｍｍ×２ｍｍの試験片を作成した。この試験片を日本電色社製測色色差計ＺＥ６０００にてＪＩＳＺ８７２９に準じて明度（Ｌ＊）を測定した。
（６）放熱性評価：次の方法に従って評価した。
射出成形機：東芝機械社製ＩＳ５０ＥＰＮにより、外寸１００ｍｍ×５０ｍｍ×高さ１５ｍｍ（２ｍｍ厚）の箱型成形品を射出成形し、得られた成形品を２個貼り合わせ、外寸１００ｍｍ×５０ｍｍ×高さ３０ｍｍ（２ｍｍ厚）の半密閉六面体筐体（温度測定用熱電対及び発熱部電子部品への通電用リード線用に５０ｍｍ×３０ｍｍ面側面中央部に約８ｍｍφの穴を開けてある）を作成した。横置き（１００×５０面下側）した半密閉筐体内部に発熱体としてＮＥＣ製ＩＣ素子（Ｃ２３３５、Ｋ３４Ｓ）をハンダで取り付けたアルミニウム板（４０ｍｍ×３０ｍｍ×２ｍｍ）を筐体内側底部中央部壁面に密着させた。半密閉筐体温度２３℃（室温２３℃）から測定を開始し、ＩＣ素子に１．５Ｗ負荷で通電を行い、通電開始後から上記発熱体直近アルミニウム（以下発熱部）の温度を測定した。発熱部温度がほぼ一定化する３０分後の温度を比較し、放熱性の評価とした。発熱部温度が低いほど（温度上昇が低いほど）外部への熱放出が多く、熱可塑性樹脂組成物の放熱性が優れることとなる。
（７）熱伝導率：熱伝導率測定装置（アグネ社製「ＡＲＴ−ＴＣ−１型」）を用い、射出成形したプレートを直径２８ｍｍ、厚さ３ｍｍの円盤状サイズに加工後、室温において温度傾斜法で測定した。
（８）射出成形性：射出成形機・東芝機械ＩＳ５０ＥＰＮにより、一点ピンゲート（１ｍｍφ）外寸１００ｍｍ×５０ｍｍ×１５ｍｍ（２ｍｍ厚）の箱型成形品を下記設定温度で射出成形し成形性をＡ〜Ｄランク評価した。
熱可塑性樹脂 射出成形時の温度設定
Ａ−１ ２５０〜２８０℃
Ａ−２ ２５０〜２８０℃
Ａ−３ ３００〜３３０℃
＜射出成形性の評価＞
Ａ：特に問題なく容易に箱型成形品が成形可能。
Ｂ：箱型成形品に多少フラッシュ等の外観不良が見られるが成形可能。
Ｃ：箱型成形品にフラッシュ、焼け、フローマーク等の外観不良が目立つが成形可能。
Ｄ：樹脂組成物が金型に完全に充填できず射出成形により箱型成形品得られない。
（９）平均粒径
本発明の平均粒径はレーザー散乱光法による粒度測定法に基づく値であり。コールター粒度測定器（モデルＬＳ−２３０；コールター社製）により測定した平均径である。
Evaluation and measurement methods for various physical properties are as follows.
(1) Fluidity: Melt mass flow rate (MFR) was measured according to JIS K-7210.
(2) Impact strength: Notched Charpy impact strength was measured according to JIS K-7111.
(3) Heat resistance: 50N load and Vicat softening point were measured according to JIS K-7106.
(4) Flame retardancy: Test pieces of length 5 inches x width 1/2 inches x thickness 1/16 inch were made by an injection molding machine Toshiba IS80G-2A, and underwriters laboratories (UL in the United States) The flame retardancy was determined on the basis of Subject No. 94 (abbreviation UL-94) standardized.
(5) Lightness (L * ): The pellets were hot press molded at 260 ° C. to prepare test pieces of 30 mm × 30 mm × 2 mm. The lightness (L * ) of this test piece was measured according to JISZ8729 with a colorimetric color difference meter ZE6000 manufactured by Nippon Denshoku.
(6) Heat dissipation evaluation: Evaluation was performed according to the following method.
Injection molding machine: A box-shaped product with an outer dimension of 100 mm x 50 mm x height 15 mm (2 mm thickness) was injection-molded by IS50EPN manufactured by Toshiba Machine Co., Ltd., and two of the obtained molded articles were bonded together to obtain an outer dimension of 100 mm x 50 mm. × Semi-enclosed hexahedron case with a height of 30mm (2mm thickness) (A hole of about 8mmφ is drilled in the center of the side of 50mm × 30mm side surface for lead wire for energizing thermocouple for temperature measurement and heating part electronic parts) It was created. An aluminum plate (40 mm x 30 mm x 2 mm) with soldered NEC IC elements (C2335, K34S) as a heating element in a semi-sealed case placed horizontally (below the 100 x 50 surface) is the center of the bottom inside the case. Adhered to the wall. The measurement was started from a semi-sealed housing temperature of 23 ° C. (room temperature of 23 ° C.), the IC element was energized with a load of 1.5 W, and the temperature of the aluminum immediately adjacent to the heating element (hereinafter referred to as the heat generating portion) was measured after the energization started. The temperature after 30 minutes when the temperature of the heat generating part became almost constant was compared to evaluate heat dissipation. The lower the temperature of the heat generating part (the lower the temperature rise), the more heat is released to the outside, and the better the heat dissipation of the thermoplastic resin composition.
(7) Thermal conductivity: Using a thermal conductivity measuring device ("ART-TC-1 type" manufactured by Agne), the injection-molded plate was processed into a disk-like size having a diameter of 28 mm and a thickness of 3 mm, and then the temperature at room temperature. Measured by the gradient method.
(8) Injection moldability: A box-shaped molded product with a single-point pin gate (1 mmφ) outer dimensions of 100 mm x 50 mm x 15 mm (2 mm thickness) is injection molded at the following set temperature using an injection molding machine / Toshiba machine IS50EPN. D rank evaluation.
Thermoplastic resin Temperature setting during injection molding
A-1 250-280 ° C
A-2 250-280 ° C
A-3 300-330 ° C
<Evaluation of injection moldability>
A: A box-shaped product can be easily molded without any particular problem.
B: Although some appearance defects such as flash are seen in the box-shaped molded product, molding is possible.
C: Although the appearance defects such as flash, burn, and flow mark are conspicuous on the box-shaped molded product, it can be molded.
D: The resin composition cannot be completely filled in the mold, and a box-shaped product cannot be obtained by injection molding.
(9) Average particle diameter The average particle diameter of the present invention is a value based on a particle size measurement method by a laser scattering light method. It is an average diameter measured by a Coulter particle size measuring device (model LS-230; manufactured by Coulter).
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| JPH057435U (en) * | 1991-07-12 | 1993-02-02 | 積水化学工業株式会社 | Extruder for extrusion molding equipment |
| JP3652460B2 (en) * | 1996-12-02 | 2005-05-25 | 株式会社メイト | Resin composition |
| JPH1143610A (en) * | 1997-07-28 | 1999-02-16 | Fujikura Ltd | Highly thermal conductive insulating material for cryogenic temperatures and superconductive cable |
| JP2000190367A (en) * | 1998-12-28 | 2000-07-11 | S D R Kk | Structure of cylinder and screw having sliding surface subjected to superabrasion resistant surface treatment for resin injection molding machine, resin melt extruder or the like |
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