JP5257200B2 - Conductive resin composition and conductive resin molded product - Google Patents
Conductive resin composition and conductive resin molded product Download PDFInfo
- Publication number
- JP5257200B2 JP5257200B2 JP2009082559A JP2009082559A JP5257200B2 JP 5257200 B2 JP5257200 B2 JP 5257200B2 JP 2009082559 A JP2009082559 A JP 2009082559A JP 2009082559 A JP2009082559 A JP 2009082559A JP 5257200 B2 JP5257200 B2 JP 5257200B2
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- Prior art keywords
- resin
- thermoplastic resin
- conductive resin
- resin composition
- conductive
- Prior art date
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- 239000011347 resin Substances 0.000 title claims description 97
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- 239000011164 primary particle Substances 0.000 claims description 9
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
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- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
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Images
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Description
本発明は、導電性及び電磁波シールド性に優れた導電性樹脂組成物と、この導電性樹脂組成物を射出成形してなる導電性樹脂成形品に関する。 The present invention relates to a conductive resin composition excellent in conductivity and electromagnetic wave shielding properties, and a conductive resin molded article formed by injection molding the conductive resin composition.
近年、ＯＡ機器、電子機器の小型軽量化や高精度化といったハードの進歩や、インターネットの普及、ＩＴ革命の進行が急速であり、これに伴い、携帯用のＯＡ機器、電子機器、いわゆるモバイル機器の普及がめざましい。携帯端末の代表例としては、ノート型パソコン、電子手帳、携帯電話、ＰＤＡ等が挙げられるが、今後ますますの多様化、多機能化が予想される。 In recent years, OA devices and electronic devices have become smaller and lighter and have higher precision, and the spread of the Internet and the IT revolution have been rapidly progressing. Accordingly, portable OA devices and electronic devices, so-called mobile devices. The spread of is remarkable. Representative examples of portable terminals include notebook personal computers, electronic notebooks, mobile phones, PDAs, and the like, but further diversification and multifunctionality are expected in the future.
これらの携帯機器をはじめ、各種のＯＡ機器や電子機器の筐体に対する要求性能として、近年、特に注目されているのが、電磁波シールド性である。即ち、電子機器は、内部の電子部品から電磁波が発生するため、発生した電磁波を機器の外部に漏らさないために、電子機器の筐体には電磁波シールド性が要求される。 In recent years, electromagnetic shielding properties have attracted particular attention as the required performance for the housings of these portable devices, various OA devices, and electronic devices. That is, since an electronic device generates an electromagnetic wave from an internal electronic component, the casing of the electronic device is required to have an electromagnetic wave shielding property in order not to leak the generated electromagnetic wave to the outside of the device.
この電磁波シールド性の要求に対しては、通常、筐体にメッキを施したり、金属の蒸着を行ったりして対応しているが、筐体の構成材料である樹脂材料自体に電磁波シールド性を持たせることが、製造工程の削減及びコストの低減の点からも望ましい。 This requirement for electromagnetic wave shielding is usually dealt with by plating the case or vapor-depositing metal, but the resin material itself, which is a component of the case, has an electromagnetic wave shielding property. It is desirable from the viewpoint of reducing the manufacturing process and cost.
しかし、一般に樹脂材料は絶縁性であり、電磁波シールド性はないため、電磁波シールド性を付与するには導電性物質を配合する必要がある。従来、樹脂材料に配合する導電性物質としては、カーボンブラック、炭素繊維、金属繊維、金属で被覆した無機繊維等の導電性物質が用いられている。 However, since resin materials are generally insulative and do not have electromagnetic shielding properties, it is necessary to add a conductive substance to impart electromagnetic shielding properties. Conventionally, conductive substances such as carbon black, carbon fibers, metal fibers, and metal-coated inorganic fibers have been used as conductive substances to be blended with resin materials.
しかしながら、金属系繊維などの金属系の物質は、導電性（電磁波シールド性）付与効果には優れるものの、これを配合した樹脂は、耐食性に劣るものとなり、また、機械的強度も不足するという欠点がある。 However, although metal-based substances such as metal-based fibers are excellent in conductivity (electromagnetic wave shielding) imparting effect, a resin blended with them is inferior in corrosion resistance and lacks mechanical strength. There is.
一方、カーボンブラックや炭素繊維であれば、上述のような金属系物質の問題は少ないものの、多量に配合すると樹脂材料の成形性やその他の物性が損なわれ、少量配合の場合には、十分な導電性（電磁波シールド性）が得られないという欠点がある。即ち、カーボンブラックや炭素繊維の少量配合で十分な導電性（電磁波シールド性）を得るためには、これらを高い分散性で均一に分散させて、樹脂中に導電性のネットワークを形成する必要があるが、カーボンブラックや炭素繊維を樹脂中に均一分散させることは容易ではない。 On the other hand, if carbon black or carbon fiber is used, there are few problems with the above-mentioned metallic substances, but if blended in a large amount, the moldability and other physical properties of the resin material are impaired. There is a drawback that conductivity (electromagnetic wave shielding property) cannot be obtained. That is, in order to obtain sufficient conductivity (electromagnetic wave shielding property) with a small amount of carbon black or carbon fiber, it is necessary to uniformly disperse them with high dispersibility to form a conductive network in the resin. However, it is not easy to uniformly disperse carbon black or carbon fiber in the resin.
これに対して、導電性物質としてカーボンナノチューブを配合することも提案されている（例えば特許文献１〜５）。カーボンナノチューブは、カーボンブラックや炭素繊維と比べて高純度であり、それ自体の導電性が高い上に、アスペクト比の大きい極細繊維であるため、導電性ネットワークを形成し易く、少量の配合で高い導電性付与効果を得ることができる。
On the other hand, blending carbon nanotubes as a conductive substance has also been proposed (for example,
しかし、カーボンナノチューブはアスペクト比の大きい非直線状の極細繊維であることから、互いに凝集し易く、やはり樹脂中で分散し難いという欠点がある。
特に、電磁波シールド性の付与を目的とする場合、配合したカーボンナノチューブが、導電性ネットワークを形成した上で、その繊維長方向が成形品表面に沿うように配向した状態で存在することが良好な電磁波シールド性を得る上で好ましいが、カーボンナノチューブの配合量を抑えた上で、このような配向性をもたせて樹脂中に均一分散させることは非常に難しく、従来法では十分に満足のゆく結果は得られていない。
However, since the carbon nanotubes are non-linear ultrafine fibers having a large aspect ratio, they tend to aggregate with each other and still have a drawback of being difficult to disperse in the resin.
In particular, for the purpose of imparting electromagnetic wave shielding properties, it is preferable that the blended carbon nanotubes exist in a state in which the fiber length direction is aligned with the surface of the molded product after forming a conductive network. Although it is preferable for obtaining electromagnetic shielding properties, it is very difficult to uniformly disperse in the resin with such an orientation while suppressing the blending amount of carbon nanotubes, and the conventional method is sufficiently satisfactory. Is not obtained.
本発明は、上記従来の実状に鑑みてなされたものであって、カーボンナノチューブの配合効果が有効に発揮された、導電性及び電磁波シールド性に優れた導電性樹脂組成物と、この導電性樹脂組成物を成形してなる導電性樹脂成形品を提供することを目的とする。 The present invention has been made in view of the above-described conventional situation, and has a conductive resin composition excellent in conductivity and electromagnetic wave shielding properties, in which the compounding effect of carbon nanotubes is effectively exhibited, and the conductive resin. It aims at providing the conductive resin molded product formed by shape | molding a composition.
本発明者らは上記課題を解決すべく鋭意検討した結果、特定の２種類の熱可塑性樹脂で形成された共連続構造の一方の樹脂相にカーボンナノチューブを分散させることにより、カーボンナノチューブの分散性、配向性を高め、少ない配合量で優れた導電性と電磁波シールド性を得ることができることを見出した。また、無機微粒子をカーボンナノチューブに併せて添加することにより、カーボンナノチューブの配向性がより一層向上し、より一層優れた導電性及び電磁波シールド性が得られることを見出した。 As a result of intensive studies to solve the above problems, the present inventors have dispersed carbon nanotubes by dispersing carbon nanotubes in one resin phase of a co-continuous structure formed of two specific types of thermoplastic resins. The inventors have found that the conductivity and electromagnetic shielding properties can be improved with a small blending amount by increasing the orientation. Further, it has been found that by adding inorganic fine particles together with the carbon nanotubes, the orientation of the carbon nanotubes is further improved, and more excellent conductivity and electromagnetic wave shielding properties can be obtained.
本発明はこのような知見に基いて達成されたものであり、以下を要旨とする。 The present invention has been achieved on the basis of such findings, and the gist thereof is as follows.
［１］ 下記（Ａ）〜（Ｄ）成分を含み、（Ａ）成分と（Ｂ）成分による少なくとも（Ａ）成分が連続相を構成しうる２相構造が形成された導電性樹脂組成物であって、（Ｃ）成分が該２相構造のうち（Ａ）成分で構成される相中に偏在し、熱可塑性樹脂Ａがポリカーボネート樹脂であり、熱可塑性樹脂Ｂがスチレン系樹脂であり、無機微粒子がシリカ微粒子であり、無機微粒子の平均一次粒子径が３００ｎｍ〜１０μｍであることを特徴とする導電性樹脂組成物。
（Ａ）：熱可塑性樹脂（以下「熱可塑性樹脂Ａ」と称す。）
（Ｂ）：熱可塑性樹脂Ａより粘度が小さい熱可塑性樹脂（以下「熱可塑性樹脂Ｂ」と称す。）
（Ｃ）：カーボンナノチューブ
（Ｄ）：無機微粒子
[1] A conductive resin composition comprising the following components (A) to (D), wherein a two-phase structure in which at least the (A) component by the (A) component and the (B) component can form a continuous phase is formed. there are, unevenly distributed in the phase composed of the component (a) of the component (C) the two-phase structure, a thermoplastic resin a polycarbonate resin, a thermoplastic resin B is a styrene resin, an inorganic A conductive resin composition , wherein the fine particles are silica fine particles, and the average primary particle diameter of the inorganic fine particles is 300 nm to 10 μm .
(A): Thermoplastic resin (hereinafter referred to as “thermoplastic resin A”)
(B): a thermoplastic resin having a viscosity lower than that of the thermoplastic resin A (hereinafter referred to as “thermoplastic resin B”).
(C): Carbon nanotube (D): Inorganic fine particles
［２］ ［１］において、熱可塑性樹脂Ａと熱可塑性樹脂Ｂとの合計における熱可塑性樹脂Ａの割合が６０〜７０体積％であることを特徴とする導電性樹脂組成物。 [2] The conductive resin composition according to [1], wherein the ratio of the thermoplastic resin A in the total of the thermoplastic resin A and the thermoplastic resin B is 60 to 70% by volume.
［３］ ［１］または［２］において、カーボンナノチューブの含有割合が、０．０１〜５０質量％であることを特徴とする導電性樹脂組成物。 [3] [1] or Oite in [2], the content of carbon nanotubes, a conductive resin composition, which is a 0.01 to 50 wt%.
［４］ ［１］ないし［３］のいずれか１項において、無機微粒子の含有割合が、０．０１〜３０質量％であることを特徴とする導電性樹脂組成物。 [ 4 ] The conductive resin composition according to any one of [1] to [ 3 ], wherein the content ratio of the inorganic fine particles is 0.01 to 30% by mass.
［５］ ［１］ないし［４］のいずれかにおいて、カーボンナノチューブの平均繊維径が１〜２００ｎｍで、アスペクト比が５〜１０００であることを特徴とする導電性樹脂組成物。 [ 5 ] The conductive resin composition according to any one of [1] to [ 4 ], wherein the carbon nanotubes have an average fiber diameter of 1 to 200 nm and an aspect ratio of 5 to 1000.
［６］ ［１］ないし［５］のいずれかに記載の導電性樹脂組成物を射出成形してなることを特徴とする導電性樹脂成形品。 [ 6 ] A conductive resin molded product obtained by injection molding the conductive resin composition according to any one of [1] to [ 5 ].
本発明の導電性樹脂組成物は、熱可塑性樹脂Ａと熱可塑性樹脂Ｂとで形成された２相構造のうちの粘度が高い熱可塑性樹脂Ａの相にカーボンナノチューブが分散されているため、次のような作用機構で、優れた導電性及び電磁波シールド性が得られる。
(1) ２相構造の一方の相にカーボンナノチューブが分散することにより、組成物中でのカーボンナノチューブの凝集が防止され、良好な導電性ネットワークを形成することができる。
(2) 粘度の高い熱可塑性樹脂Ａの相にカーボンナノチューブが分散していることにより、成形時に付与される剪断力等により、カーボンナノチューブの凝集物が分散し、また成形時の樹脂の流動方向に配向するため優れた配向性が得られる。
In the conductive resin composition of the present invention, carbon nanotubes are dispersed in the phase of the thermoplastic resin A having a high viscosity in the two-phase structure formed of the thermoplastic resin A and the thermoplastic resin B. With such an action mechanism, excellent conductivity and electromagnetic shielding properties can be obtained.
(1) By dispersing the carbon nanotubes in one phase of the two-phase structure, aggregation of the carbon nanotubes in the composition can be prevented and a good conductive network can be formed.
(2) Since the carbon nanotubes are dispersed in the phase of the thermoplastic resin A having a high viscosity, aggregates of the carbon nanotubes are dispersed due to a shearing force applied during molding, and the flow direction of the resin during molding Excellent orientation can be obtained.
しかも、このような熱可塑性樹脂Ａと熱可塑性樹脂Ｂとで形成された２相構造に、更に、無機微粒子が配合されていることにより、この２相構造、好ましくは後述の共連続構造が無機微粒子により微細化され、カーボンナノチューブの配向性をさらに向上させることができ、この結果、より一層優れた導電性及び電磁波シールド性が得られる。 In addition, since the two-phase structure formed of the thermoplastic resin A and the thermoplastic resin B is further mixed with inorganic fine particles, this two-phase structure, preferably a co-continuous structure described later, is inorganic. It can be refined by the fine particles to further improve the orientation of the carbon nanotubes, and as a result, more excellent conductivity and electromagnetic wave shielding properties can be obtained.
また、本発明に係る２相構造は、共連続構造であることが好ましく、このために、熱可塑性樹脂Ａと熱可塑性樹脂Ｂとの合計における熱可塑性樹脂Ａの割合は６０〜７０体積％であることが好ましい（請求項２）。 The two-phase structure according to the present invention, rather preferably be a co-continuous structure, for this, the proportion of the thermoplastic resin A in the total amount of the thermoplastic resin A and the thermoplastic resin B is 60 to 70 volume % Is preferable (Claim 2).
本発明において、導電性樹脂組成物中のカーボンナノチューブの含有割合は、０．０１〜５０重量％であることが好ましく（請求項３）、カーボンナノチューブの平均繊維径は１〜２００ｎｍで、アスペクト比（カーボンナノチューブの長さ／カーボンナノチューブの径）は５〜１０００程度であることが好ましい（請求項５）。 In the present invention, the content of carbon nanotubes in the conductive resin composition is preferably 0.01 to 50% by weight (Claim 3 ), the average fiber diameter of the carbon nanotubes is 1 to 200 nm, and the aspect ratio (Length of carbon nanotube / diameter of carbon nanotube) is preferably about 5 to 1,000.
また、本発明の導電性樹脂組成物中の無機微粒子の含有割合は、０．０１〜３０質量％であることが好ましく（請求項４）、相構造の相のサイズ（相の厚さ等）との関係から、この無機微粒子の平均一次粒子径は１０μｍ以下である。 Further, the content of the inorganic fine particles in the conductive resin composition of the present invention is preferably 0.01 to 30% by mass (Claim 4 ), and the phase size (phase thickness, etc.) of the phase structure. from the relationship between the average primary particle diameter of the inorganic fine particles Ru der below 10 [mu] m.
本発明の導電性樹脂成形品は、このような本発明の導電性樹脂組成物を射出成形してなり、射出成形工程で樹脂組成物に付与される剪断力でカーボンナノチューブが射出成形方向（樹脂の流動方向と略平行方向）に配向し、また、カーボンナノチューブが熱可塑性樹脂Ａ側に偏在して存在するため、カーボンナノチューブの存在密度（隣接する同士の接触可能性）が高くなり、この結果、良好な電磁波シールド性が得られる。 The conductive resin molded article of the present invention is obtained by injection molding of the conductive resin composition of the present invention, and the carbon nanotubes are in the injection molding direction (resin by the shearing force applied to the resin composition in the injection molding process. The carbon nanotubes are unevenly distributed on the thermoplastic resin A side, and the density of carbon nanotubes (the possibility of contact between adjacent ones) is increased. Good electromagnetic shielding properties can be obtained.
以下に本発明の導電性樹脂組成物及び導電性樹脂成形品の実施の形態を詳細に説明する。 Hereinafter, embodiments of the conductive resin composition and the conductive resin molded article of the present invention will be described in detail.
［物性等の説明］
＜粘度＞
本発明における粘度とは、２８０℃における樹脂の粘度（単位：Ｐａ・ｓ）であり、例えば次のようにして測定される。
１ｍｍφ×３０ｍｍＬのキャピラリーを備える東洋精機製作所製キャピログラフ（機械名：キャピログラフ１Ｃ、型式：ＰＭＤ-Ｃ）にて、剪断速度１２１６ｓ−１における樹脂粘度をＩＳＯ１１４４３規格に準じて測定する（測定グラフからデーターの値を読み取る）ことにより求められる。
[Explanation of physical properties]
<Viscosity>
The viscosity in the present invention is the viscosity of the resin at 280 ° C. (unit: Pa · s), and is measured, for example, as follows.
The resin viscosity at a shear rate of 1216 s −1 is measured according to the ISO 11443 standard with a capillograph (machine name: Capillograph 1C, model: PMD-C) manufactured by Toyo Seiki Seisakusho equipped with a 1 mmφ × 30 mmL capillary (from the measurement graph, the data Read the value).
＜共連続構造＞
本発明の導電性樹脂組成物は、好ましくは後述の熱可塑性樹脂Ａと熱可塑性樹脂Ｂとの共連続構造を形成したものである。
<Co-continuous structure>
The conductive resin composition of the present invention is preferably one in which a co-continuous structure of a thermoplastic resin A and a thermoplastic resin B described later is formed.
ここで、共連続構造とは、熱可塑性樹脂Ａと熱可塑性樹脂Ｂの２つの樹脂を混合したポリマーアロイで形成される２相分離構造のうち、両樹脂がそれぞれ連続相を形成したものである。 Here, the co-continuous structure is a two-phase separation structure formed of a polymer alloy obtained by mixing two resins of the thermoplastic resin A and the thermoplastic resin B, and both resins each form a continuous phase. .
即ち、樹脂Ａと樹脂Ｂとを混合してなるポリマーアロイは、樹脂Ａの割合が多く、樹脂Ｂの割合が少ないと、樹脂Ａよりなる海相中に、樹脂Ｂの島相が分散した海島構造となる。この場合、樹脂Ａは連続相であるが、樹脂Ｂは島状に分断された非連続相である。この状態から、樹脂Ａの配合量を減らし、樹脂Ｂの配合量を増やしてゆくと、海相と島相とが逆転し、樹脂Ｂよりなる海相中に、樹脂Ａの島相が分散した海島構造となり、この場合、樹脂Ｂは連続相であるが、樹脂Ａは島状に分断された非連続相となる。この樹脂Ａ／樹脂Ｂの海島構造となる配合割合と樹脂Ｂ／樹脂Ａの海島構造となる配合割合との間の配合領域において、このポリマーアロイは、樹脂Ａも樹脂Ｂも連続相様であり（両相共に連続相の様に観察され）、両樹脂が連続相を形成しつつ微細に分散したスポンジ様の２相分離構造となる。典型的にはこのような相構造を共連続相と呼んでいる。 That is, the polymer alloy formed by mixing the resin A and the resin B has a large proportion of the resin A, and when the proportion of the resin B is small, the sea island in which the island phase of the resin B is dispersed in the sea phase composed of the resin A. It becomes a structure. In this case, resin A is a continuous phase, while resin B is a discontinuous phase divided into islands. From this state, when the blending amount of the resin A is decreased and the blending amount of the resin B is increased, the sea phase and the island phase are reversed, and the island phase of the resin A is dispersed in the sea phase composed of the resin B. In this case, the resin B is a continuous phase, but the resin A is a discontinuous phase divided into islands. In the blending region between the blending ratio of the resin A / resin B with the sea-island structure and the blending ratio of the resin B / resin A with the sea-island structure, the polymer alloy is such that both the resin A and the resin B are continuous. (Both phases are observed as a continuous phase), resulting in a sponge-like two-phase separation structure in which both resins form a continuous phase and are finely dispersed. Typically, such a phase structure is called a co-continuous phase.
本発明における共連続構造についてより詳しく説明するために、図面を用いて説明する。
図１は、熱可塑性樹脂Ａと熱可塑性樹脂Ｂから形成された２相構造の共連続構造を示す模式図であり、図２は海島構造を示す模式図である。また、図３は共連続構造の一例の顕微鏡写真であり、図４は海島構造の一例の顕微鏡写真である。
In order to explain the co-continuous structure in the present invention in more detail, it will be described with reference to the drawings.
FIG. 1 is a schematic diagram showing a two-phase co-continuous structure formed from a thermoplastic resin A and a thermoplastic resin B, and FIG. 2 is a schematic diagram showing a sea-island structure. 3 is a photomicrograph of an example of a co-continuous structure, and FIG. 4 is a photomicrograph of an example of a sea-island structure.
本発明においては、共連続構造を以下の様に定義する。
図１、図２において、Ａ相（熱可塑性樹脂Ａで形成される相）と接するＢ相（熱可塑性樹脂Ｂで形成される相）の周囲（外周縁部）を任意の数（ｎ）に分割、すなわちｎ分割（ｎ≧３）する。分割したＢ相の外周縁部上の点をそれぞれ、Ｘ１、Ｘ２・・・・Ｘｎとする。任意の点Ｘｉ（i＝１〜ｎ）を始点として、Ｘｉ＋１へ引いた線分をベクトルＸｉＸｉ＋１、同様にＸｉ＋１を始点として、Ｘｉ＋２へ引いた線分をベクトルＸｉ＋１Ｘｉ＋２とする。ベクトルＸｉＸｉ＋１とベクトルＸｉ＋１Ｘｉ＋２が成す角度をθｉ（０≦θｉ≦π）とする。同様にベクトルＸｉ＋１Ｘｉ＋２とベクトルＸｉ＋２Ｘｉ＋３がなす角度をθｉ＋１（０≦θｉ≦π）とする。順次得られた角度をθ１、θ２・・・・θｎとし、θ１、θ２・・・・θｎの和Σθｉ（i＝１〜ｎ）を求める。ただし、精度よくΣθｉ（i＝１〜ｎ）を求めるためには、ｎを十分に大きくする（外周縁部を沢山に分割する）必要がある。そこで、分割数を２倍にした場合の角度（θ１、θ２・・・）の和Σθｉ（i＝１〜２ｎ）を求め、Σθｉ（i＝１〜２ｎ）−Σθｉ（i＝１〜ｎ）が０．１π以下となるまでｎを大きくしていくものとする。
In the present invention, the co-continuous structure is defined as follows.
In FIG. 1 and FIG. 2, the circumference (outer peripheral edge) of the B phase (phase formed with the thermoplastic resin B) in contact with the A phase (phase formed with the thermoplastic resin A) is an arbitrary number (n). Divide, i.e., n-divide (n ≧ 3). The points on the outer peripheral edge of the divided B phase are denoted as X 1 , X 2 ... X n , respectively. An arbitrary point X i (i = 1 to n) is used as a starting point, a line segment drawn to X i + 1 is a vector X i X i + 1 , and similarly, a line segment drawn from X i + 1 is used as a starting point to X i + 2 to be a vector X i + 1 X Let i + 2 . The angle formed by the vector X i X i + 1 and the vector X i + 1 X i + 2 is defined as θ i (0 ≦ θ i ≦ π). Similarly, an angle formed by the vector X i + 1 X i + 2 and the vector X i + 2 X i + 3 is θ i + 1 (0 ≦ θ i ≦ π). The obtained angles are θ 1 , θ 2 ... Θn, and the sum Σθ i (i = 1 to n) of θ 1 , θ 2 . However, in order to obtain Σθ i (i = 1 to n) with high accuracy, it is necessary to sufficiently increase n (divide the outer peripheral edge into many parts). Therefore, a sum Σθ i (i = 1 to 2n) of angles (θ 1 , θ 2 ...) When the number of divisions is doubled is obtained, and Σθ i (i = 1 to 2n) −Σθ i (i = 1 to n) n is increased until it becomes 0.1π or less.
図２の海島構造の場合、ｎを十分に大きくしても２πに近い値となる。 In the case of the sea-island structure of FIG. 2, even if n is sufficiently large, the value is close to 2π.
図１の共連続２相構造において、海島構造の模式図（図２）の場合と同様にΣθｉ（i＝１〜ｎ）を求めると、Σθｉ（i＝１〜ｎ）は７πよりも大きくなる。成形品中心層の電子顕微鏡写真で上述した共連続相構造が２５μｍ×２５μｍの領域において少なくとも１個以上存在する場合を共連続構造が形成されている、とする。 In the bicontinuous two-phase structure of FIG. 1, when Σθ i (i = 1 to n) is obtained as in the case of the schematic diagram of the sea-island structure (FIG. 2), Σθ i (i = 1 to n) is more than 7π. growing. The case where at least one co-continuous phase structure described above in the electron micrograph of the center layer of the molded article is present in a region of 25 μm × 25 μm is defined as a co-continuous structure.
本発明に云う共連続構造とは上述のような場合を定義する。熱可塑性樹脂Ａと熱可塑性樹脂Ｂとの配合比によっては海島構造様を呈する場合もあるが、この場合にも上記定義が適用される。すなわち、熱可塑性樹脂Ｂが円形、楕円形ではない、相当複雑なランダム形状を呈して、熱可塑性樹脂Ａと絡み合ったような状態も、本発明の共連続構造である。 The co-continuous structure referred to in the present invention defines the case as described above. Depending on the blending ratio of the thermoplastic resin A and the thermoplastic resin B, a sea-island structure may be exhibited. In this case as well, the above definition is applied. That is, the state in which the thermoplastic resin B has a considerably complicated random shape that is not circular or elliptical and is intertwined with the thermoplastic resin A is also a co-continuous structure of the present invention.
［（Ａ）成分，（Ｂ）成分（熱可塑性樹脂）］
本発明は、（Ａ）成分及び（Ｂ）成分として、以下の関係を満たす少なくとも２種類の熱可塑性樹脂Ａ，Ｂを用いることを特徴とする。これにより２層構造、共連続構造となりやすい組成物となる。
ＶＡ＞ＶＢ
ＶＡ：熱可塑性樹脂Ａの粘度
ＶＢ：熱可塑性樹脂Ｂの粘度
[(A) component, (B) component (thermoplastic resin)]
The present invention is characterized in that at least two types of thermoplastic resins A and B satisfying the following relationship are used as the component (A) and the component (B). As a result, a composition that tends to have a two-layer structure or a co-continuous structure is obtained.
V A > V B
V A : Viscosity of thermoplastic resin A V B : Viscosity of thermoplastic resin B
また、熱可塑性樹脂Ａの粘度に特に制限はないが、熱可塑性樹脂Ｂの粘度よりも大きいことを特徴とする。 Further, the viscosity of the thermoplastic resin A is not particularly limited, but is characterized by being larger than the viscosity of the thermoplastic resin B.
本発明で用いられる熱可塑性樹脂としては、ポリアミド−６、ポリアミド−６，６などのポリアミド樹脂；ポリカーボネート樹脂；熱可塑性ポリエステル樹脂；ポリスチレン樹脂、高衝撃ポリスチレン樹脂（ＨＩＰＳ）、アクリロニトリル−スチレン共重合体（ＡＳ樹脂）、アクリロニトリル−ブタジエン−スチレン共重合体（ＡＢＳ樹脂）、アクリロニトリル−スチレン−アクリルゴム共重合体（ＡＳＡ樹脂）、アクリロニトリル−エチレンプロピレン系ゴム−スチレン共重合体（ＡＥＳ樹脂）などのスチレン系樹脂；等が挙げられ、本発明では、これらの熱可塑性樹脂の中から、粘度が上記条件を満たし、共連続構造を形成するものを選択して、それぞれ熱可塑性樹脂Ａ、熱可塑性樹脂Ｂとして用いれば良い。 Examples of the thermoplastic resin used in the present invention include polyamide resins such as polyamide-6 and polyamide-6,6; polycarbonate resins; thermoplastic polyester resins; polystyrene resins, high impact polystyrene resins (HIPS), acrylonitrile-styrene copolymers. Styrene such as (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin) In the present invention, those having a viscosity satisfying the above conditions and forming a co-continuous structure are selected from these thermoplastic resins, and thermoplastic resin A and thermoplastic resin B, respectively. It may be used as.
本発明においてはこのような２相分離構造（特に共連続構造）を発現するような熱可塑性樹脂Ａと熱可塑性樹脂Ｂの組み合わせを選択することが重要である。この選択は種々の組み合わせがあるが、特に、ポリカーボネート樹脂（樹脂Ａ）とスチレン系樹脂（樹脂Ｂ）との組み合わせが良好な２相分離構造を発現することが確認されている。 In the present invention, it is important to select a combination of the thermoplastic resin A and the thermoplastic resin B that expresses such a two-phase separation structure (particularly a co-continuous structure). Although there are various combinations for this selection, it has been confirmed that the combination of the polycarbonate resin (resin A) and the styrene resin (resin B) exhibits a good two-phase separation structure.
本発明において、特に熱可塑性樹脂Ａとしては、ポリカーボネート樹脂が好ましく用いられ、特に、粘度が３７０〜１０００Ｐａ・ｓ（２８０℃、剪断速度１２１６ｓ−１）程度のポリカーボネート樹脂を用いることが好ましい。 In the present invention, a polycarbonate resin is preferably used as the thermoplastic resin A, and it is particularly preferable to use a polycarbonate resin having a viscosity of about 370 to 1000 Pa · s (280 ° C., shear rate 1216 s −1 ).
ポリカーボネート樹脂としては、芳香族ポリカーボネート樹脂、脂肪族ポリカーボネート樹脂、芳香族−脂肪族ポリカーボネート樹脂を用いることができるが、中でも芳香族ポリカーボネート樹脂が好ましい。これらのポリカーボネート樹脂は１種を単独で用いても良く、２種以上を併用しても良い。 As the polycarbonate resin, an aromatic polycarbonate resin, an aliphatic polycarbonate resin, and an aromatic-aliphatic polycarbonate resin can be used, and among them, an aromatic polycarbonate resin is preferable. These polycarbonate resins may be used alone or in combination of two or more.
芳香族ポリカーボネート樹脂としては、芳香族ジヒドロキシ化合物をホスゲン又は炭酸のジエステルと反応させることによって得られる熱可塑性芳香族ポリカーボネート重合体又は共重合体が挙げられる。反応に用いる芳香族ジヒドロキシ化合物としては、２，２−ビス（４−ヒドロキシフェニル）プロパン（＝ビスフェノールＡ）、テトラメチルビスフェノールＡ、ビス（４−ヒドロキシフェニル）−ｐ−ジイソプロピルベンゼン、ハイドロキノン、レゾルシノール、４，４−ジヒドロキシビフェニルなどが挙げられ、好ましくはビスフェノールＡが挙げられる。さらに、難燃性をさらに高める目的で上記の芳香族ジヒドロキシ化合物にスルホン酸テトラアルキルホスホニウムが１個以上結合した化合物や、シロキサン構造を有する両末端フェノール性ＯＨ基含有のポリマーあるいはオリゴマーを使用することもできる。 Examples of the aromatic polycarbonate resin include thermoplastic aromatic polycarbonate polymers or copolymers obtained by reacting an aromatic dihydroxy compound with phosgene or a carbonic acid diester. As aromatic dihydroxy compounds used in the reaction, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, Examples include 4,4-dihydroxybiphenyl, and bisphenol A is preferable. Further, for the purpose of further enhancing the flame retardancy, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the above aromatic dihydroxy compound, or a polymer or oligomer having a siloxane structure and containing both terminal phenolic OH groups is used. You can also.
本発明で用いる芳香族ポリカーボネート樹脂としては、好ましくは、２，２−ビス（４−ヒドロキシフェニル）プロパンから誘導されるポリカーボネート樹脂、又は２，２−ビス（４−ヒドロキシフェニル）プロパンと他の芳香族ジヒドロキシ化合物とから誘導されるポリカーボネート共重合体が挙げられる。 The aromatic polycarbonate resin used in the present invention is preferably a polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, or 2,2-bis (4-hydroxyphenyl) propane and other fragrances. And a polycarbonate copolymer derived from an aromatic dihydroxy compound.
ポリカーボネート樹脂の分子量は、溶媒としてメチレンクロライドを用い、温度２５℃で測定された溶液粘度より換算した粘度平均分子量で、通常１４，０００〜３０，０００の範囲であり、好ましくは１５，０００〜２８，０００、より好ましくは１６，０００〜２６，０００である。粘度平均分子量が１４，０００未満では機械的強度が不足し、３０，０００を超えると成形性に難を生じやすく好ましくない。 The molecular weight of the polycarbonate resin is a viscosity average molecular weight converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent, and is usually in the range of 14,000 to 30,000, preferably 15,000 to 28. 16,000, more preferably 16,000-26,000. If the viscosity average molecular weight is less than 14,000, the mechanical strength is insufficient, and if it exceeds 30,000, the moldability is likely to be difficult.
このような芳香族ポリカーボネート樹脂の製造方法については、限定されるものでは無く、ホスゲン法（界面重合法）あるいは、溶融法（エステル交換法）等で製造することができる。さらに、溶融法で製造された、末端基のＯＨ基量を調整した芳香族ポリカーボネート樹脂を使用することができる。 The method for producing such an aromatic polycarbonate resin is not limited, and the aromatic polycarbonate resin can be produced by a phosgene method (interfacial polymerization method), a melting method (transesterification method), or the like. Furthermore, the aromatic polycarbonate resin which adjusted the amount of OH groups of the terminal group manufactured by the melting method can be used.
さらに、芳香族ポリカーボネート樹脂としては、バージン原料だけでなく、使用済みの製品から再生された芳香族ポリカーボネート樹脂、いわゆるマテリアルリサイクルされた芳香族ポリカーボネート樹脂の使用も可能である。使用済みの製品としては、光学ディスクなどの光記録媒体、導光板、自動車窓ガラスや自動車ヘッドランプレンズ、風防などの車両透明部材、水ボトルなどの容器、メガネレンズ、防音壁やガラス窓、波板などの建築部材などが好ましく挙げられる。また、再生芳香族ポリカーボネート樹脂としては、製品の不適合品、スプルー、又はランナーなどから得られた粉砕品又はそれらを溶融して得たペレットなども使用可能である。 Furthermore, as the aromatic polycarbonate resin, not only virgin raw materials but also aromatic polycarbonate resins regenerated from used products, so-called material recycled aromatic polycarbonate resins can be used. Used products include optical recording media such as optical disks, light guide plates, automobile window glass and automobile headlamp lenses, vehicle transparent members such as windshields, containers such as water bottles, glasses lenses, soundproof walls and glass windows, waves A building member such as a plate is preferred. In addition, as the recycled aromatic polycarbonate resin, non-conforming product, pulverized product obtained from sprue or runner or pellets obtained by melting them can be used.
一方、熱可塑性樹脂Ａとしてのポリカーボネート樹脂に対して併用する熱可塑性樹脂Ｂとしては、ポリエステル樹脂、スチレン系樹脂、ポリアミド樹脂等が挙げられるが、特にスチレン系樹脂が好ましい。このポリカーボネート樹脂とスチレン系樹脂の組み合わせが良好な２相構造を形成する。 On the other hand, examples of the thermoplastic resin B used in combination with the polycarbonate resin as the thermoplastic resin A include polyester resins, styrene resins, polyamide resins, and the like, and styrene resins are particularly preferable. The combination of the polycarbonate resin and the styrene resin forms a good two-phase structure.
スチレン系樹脂としては、アクリロニトリルースチレン共重合体、アクリロニトリル−スチレン−ブタジエン共重合体、アクリロニトリル−エチレンプロピレンゴム−スチレン共重合体、アクリロニトリル−スチレン−アクリルゴム共重合体等が挙げられ、より好ましくは、アクリロニトリル−スチレン共重合体である。これらのスチレン系樹脂は、１種を単独で用いても良く、２種以上を併用しても良い。 Examples of the styrene resin include acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, acrylonitrile-ethylenepropylene rubber-styrene copolymer, acrylonitrile-styrene-acrylic rubber copolymer, and more preferably. , An acrylonitrile-styrene copolymer. These styrenic resins may be used alone or in combination of two or more.
これらスチレン系樹脂の重合方法として塊状重合法や乳化重合法が例示できるが、塊状重合法により重合された樹脂が望ましい。 A bulk polymerization method or an emulsion polymerization method can be exemplified as a polymerization method of these styrene resins, and a resin polymerized by the bulk polymerization method is desirable.
なお、スチレン系樹脂としては、バージン原料だけでなく、使用済みの製品から再生されたスチレン系樹脂、いわゆるマテリアルリサイクルされたスチレン系樹脂の使用も可能である。使用済みの製品としては、ハウジング等が主として挙げられる。また再生スチレン系樹脂としては、製品の不適合品、スプルー、ランナー等から得られた粉砕品又はそれらを溶融して得たペレット等も使用可能である。 As the styrene resin, not only a virgin raw material but also a styrene resin regenerated from a used product, that is, a so-called material-recycled styrene resin can be used. As a used product, a housing etc. are mainly mentioned. In addition, as the regenerated styrene resin, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.
なお、熱可塑性樹脂Ｂとして用いるポリエステル樹脂のうち、ポリエチレンテレフタレート樹脂（ＰＥＴ）としては、ジメチルテレフタレートとエチレングリコールのエステル交換反応、又はテレフタル酸とエチレングリコールの直接エステル化反応のいずれで製造されたものでも良い。ポリブチレンテレフタレート樹脂（ＰＢＴ）としては、ジメチルテレフタレートと１，４−ブタンジオールのエステル交換反応によるＤＭＴ法、テレフタル酸と１，４−ブタンジオールの直接重合法のいずれで製造されたものでも良い。 Of the polyester resins used as the thermoplastic resin B, the polyethylene terephthalate resin (PET) is produced by either a transesterification reaction between dimethyl terephthalate and ethylene glycol or a direct esterification reaction between terephthalic acid and ethylene glycol. But it ’s okay. The polybutylene terephthalate resin (PBT) may be produced by either a DMT method by transesterification of dimethyl terephthalate and 1,4-butanediol, or a direct polymerization method of terephthalic acid and 1,4-butanediol.
また、該ＰＥＴ、ＰＢＴのいずれの場合においても、重縮合反応時に、テレフタル酸又はそのジアルキルエステルと共に、フタル酸、イソフタル酸、ナフタレンジカルボン酸、ジフェニルジカルボン酸、アジピン酸、セバシン酸、トリメリット酸やそれらのジアルキルエステル等の二塩基酸、三塩基酸等や、またそれらのジアルキルエステルを使用することができる。これらの使用量は、テレフタル酸又はそのジアルキルエステル１００重量部に対して４０重量部以下の範囲であることが好ましい。 In either case of the PET or PBT, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, together with terephthalic acid or a dialkyl ester thereof during the polycondensation reaction Dibasic acids such as dialkyl esters, tribasic acids and the like, and dialkyl esters thereof can be used. The amount of these used is preferably in the range of 40 parts by weight or less with respect to 100 parts by weight of terephthalic acid or a dialkyl ester thereof.
また、同じく重縮合反応時に、該エチレングリコール、又は１，４−ブタンジオールと共に、他の脂肪族グリコールとして、例えば、エチレングリコール、プロピレングリコール、１，４−ブタンジオール、ヘキサメチレングリコール等や、脂肪族グリコール以外に例えばシクロヘキサンジオール、シクロヘキサンジメタノール、キシレングリコール、２、２−ビス（４−ヒドロキシフェニル）プロパン、グリセリン、ペンタエリスリトール等の他のジオール類や多価アルコール類を併用することができる。これらジオール類又は多価アルコール類の使用量は、脂肪族グリコール１００質量部に対して４０質量部以下の範
囲であることが好ましい。また、これらの使用量は、テレフタル酸又はそのジアルキルエステル１００質量部に対して４０質量部以下の範囲であることが好ましい。
Similarly, during the polycondensation reaction, together with the ethylene glycol or 1,4-butanediol, other aliphatic glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, hexamethylene glycol, In addition to the group glycol, for example, other diols such as cyclohexanediol, cyclohexanedimethanol, xylene glycol, 2,2-bis (4-hydroxyphenyl) propane, glycerin, pentaerythritol, and polyhydric alcohols can be used in combination. The amount of these diols or polyhydric alcohols used is preferably in the range of 40 parts by mass or less with respect to 100 parts by mass of the aliphatic glycol. Moreover, it is preferable that these usage-amounts are the range of 40 mass parts or less with respect to 100 mass parts of terephthalic acid or its dialkyl ester.
ポリエステル樹脂の分子量としては、フェノールとテトラクロロエタンの混合溶媒（質量比＝５０／５０）中、３０℃で測定される極限粘度で、好ましくは０．５〜１．８であり、さらに好ましくは０．７〜１．５である。さらに、ＰＥＴ又はＰＢＴとしては、バージン原料だけでなく、使用済みの製品から再生されたＰＥＴ又はＰＢＴ、いわゆるマテリアルリサイクルされたＰＥＴとＰＢＴの使用も可能である。使用済みの製品としては、容器、フィルム、シート、繊維等が主として挙げられるが、より好適なものはＰＥＴボトル等の容器である。また、再生ＰＥＴ、ＰＢＴとしては、製品の不適合品、スプルー、ランナー等から得られた粉砕品又はそれらを溶融して得たペレット等も使用可能である。 The molecular weight of the polyester resin is an intrinsic viscosity measured at 30 ° C. in a mixed solvent of phenol and tetrachloroethane (mass ratio = 50/50), preferably 0.5 to 1.8, and more preferably 0. .7 to 1.5. Furthermore, as PET or PBT, it is possible to use not only virgin raw materials but also PET or PBT regenerated from used products, so-called material recycled PET and PBT. Spent products include mainly containers, films, sheets, fibers, etc., but more suitable are containers such as PET bottles. In addition, as recycled PET and PBT, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.
本発明においては、熱可塑性樹脂Ａとして上述の熱可塑性樹脂の２種以上を併用しても良く、また、熱可塑性樹脂Ｂとしても上述の熱可塑性樹脂の２種以上を併用しても良い。また、ポリマーアロイの２相構造を形成する熱可塑性樹脂Ａと熱可塑性樹脂Ｂを基本組成とし、これに、熱可塑性樹脂Ａと熱可塑性樹脂Ｂのいずれにも該当しない熱可塑性樹脂を配合しても良い。 In the present invention, two or more of the above-mentioned thermoplastic resins may be used in combination as the thermoplastic resin A, and two or more of the above-mentioned thermoplastic resins may be used in combination as the thermoplastic resin B. In addition, a thermoplastic resin A and a thermoplastic resin B that form a two-phase structure of a polymer alloy are used as a basic composition, and a thermoplastic resin that does not correspond to either the thermoplastic resin A or the thermoplastic resin B is blended with this. Also good.
ただし、熱可塑性樹脂Ａと熱可塑性樹脂Ｂとを用いることによるポリマーアロイの２相構造として好ましい共連続構造を形成するために、熱可塑性樹脂Ａ及び熱可塑性樹脂Ｂとして、それぞれ１種類の樹脂を用いることが好ましい。 However, in order to form a preferable co-continuous structure as a two-phase structure of a polymer alloy by using the thermoplastic resin A and the thermoplastic resin B, one type of resin is used as each of the thermoplastic resin A and the thermoplastic resin B. It is preferable to use it.
［（Ａ）成分と（Ｂ）成分の配合比］
本発明の導電性樹脂組成物に含まれる（Ａ）成分としての熱可塑性樹脂Ａと、（Ｂ）成分としての熱可塑性樹脂Ｂとの割合は、本発明に好適な２相分離構造（共連続構造）を形成するために、適宜調整されることが好ましく、用いる熱可塑性樹脂の種類によっても異なるが、通常、熱可塑性樹脂Ａと熱可塑性樹脂Ｂとの合計における熱可塑性樹脂Ａ（２種以上の熱可塑性樹脂Ａを用いる場合はその合計）の体積割合が６０〜７０体積％で、熱可塑性樹脂Ｂ（２種以上の熱可塑性樹脂Ｂを用いる場合はその合計）の体積割合が３０〜４０体積％であることが好ましい。このような配合比とすることにより、本組成物を溶融混練した場合に、良好な２相構造が形成される。
[Blending ratio of component (A) and component (B)]
The ratio of the thermoplastic resin A as the component (A) and the thermoplastic resin B as the component (B) contained in the conductive resin composition of the present invention is a two-phase separation structure (co-continuous) suitable for the present invention. In order to form (structure), it is preferable to adjust appropriately, and although it changes also with the kind of thermoplastic resin to be used, usually the thermoplastic resin A (two or more types) in the sum total of the thermoplastic resin A and the thermoplastic resin B The total volume of the thermoplastic resin A is 60 to 70% by volume, and the volume ratio of the thermoplastic resin B (the total when two or more thermoplastic resins B are used) is 30 to 40%. It is preferable that it is volume%. By setting it as such a compounding ratio, when this composition is melt-kneaded, a favorable two-phase structure is formed.
この範囲よりも熱可塑性樹脂Ａが多くても少なくても、ポリマーアロイの２相構造が本発明に好適な共連続構造を形成し得ない場合がある。 Even if there is more or less thermoplastic resin A than this range, the two-phase structure of the polymer alloy may not be able to form a co-continuous structure suitable for the present invention.
なお、上記体積割合は、用いる樹脂の種類によっても異なるが、質量割合として、熱可塑性樹脂Ａと熱可塑性樹脂Ｂとの合計における熱可塑性樹脂Ａの質量割合が６２〜７２質量％程度で、熱可塑性樹脂Ｂの重量割合が２８〜３８質量％程度の範囲となる。 In addition, although the said volume ratio changes also with the kind of resin to be used, as a mass ratio, the mass ratio of the thermoplastic resin A in the sum total of the thermoplastic resin A and the thermoplastic resin B is about 62-72 mass%, The weight ratio of the plastic resin B is in the range of about 28 to 38% by mass.
［（Ｃ）成分］
カーボンナノチューブは、通常は、単繊維が絡み合った毛玉状、直線状等の形状を有する中空繊維であると云われており、その製造方法としては、化学的気相成長法、レーザーアブレーション、アーク放電等の種々の方法が提案されている。
チューブの形状も単層、多層が見られ、典型的な単管（パイプ）状、パイプが何層にも重なった多層管状、魚の中骨のように円錐台形状が積み重なったような形状等があるとされている。単管状の場合は直径が１〜５ｎｍ程度のものが多く、多層管状や中骨状の場合は１０〜５０ｎｍ程度の径を有するものや、場合によっては径が１００ｎｍを超えるものもある。
長さは長尺（径に対して長さが長い）なものであるが、アスペクト比（長さ／直径）は１００〜１０，０００程度とされている。
本発明の導電性樹脂組成物は、（Ｃ）成分としてカーボンナノチューブを、熱可塑性樹脂Ａと熱可塑性樹脂Ｂとで形成される２相構造のうち、熱可塑性樹脂Ａの相中に多く含む。
[Component (C)]
Carbon nanotubes are usually said to be hollow fibers having a pill-like shape or a linear shape in which single fibers are intertwined, and the production method thereof includes chemical vapor deposition, laser ablation, arc discharge, etc. Various methods have been proposed.
The shape of the tube can also be seen as a single layer or multiple layers, such as a typical single tube (pipe) shape, a multi-layered tube with multiple layers of pipes, or a shape in which truncated cones are stacked like a fish bone. It is said that there is. In the case of a single tube, many have a diameter of about 1 to 5 nm, and in the case of a multi-layer tube or a medium bone, there are those having a diameter of about 10 to 50 nm, and in some cases, the diameter exceeds 100 nm.
The length is long (the length is long with respect to the diameter), but the aspect ratio (length / diameter) is about 100 to 10,000.
The conductive resin composition of the present invention contains a large amount of carbon nanotubes as the component (C) in the phase of the thermoplastic resin A in the two-phase structure formed of the thermoplastic resin A and the thermoplastic resin B.
この「熱可塑性樹脂Ａの相中に多く含む」とはカーボンナノチューブが熱可塑性樹脂Ａの相中に多く存在（偏在）していることをいう。すなわち、樹脂Ａと樹脂Ｂを選択する際に、樹脂に対するカーボンナノチューブの分散性（親和性）を考慮（経験的考慮）し、カーボンナノチューブが樹脂Ａに偏在するように選択することが重要である。 The phrase “contains a large amount in the phase of the thermoplastic resin A” means that a large amount of carbon nanotubes are present (unevenly distributed) in the phase of the thermoplastic resin A. That is, when selecting the resin A and the resin B, it is important to consider the dispersibility (affinity) of the carbon nanotubes with respect to the resin (empirical consideration) and select the carbon nanotubes so as to be unevenly distributed in the resin A. .
カーボンナノチューブとしては、平均繊維径が１〜２００ｎｍ、特に１０〜１００ｎｍで、アスペクト比（繊維長／繊維径の比率を云い、顕微鏡等で観察して得る）が５〜１０００、特に１００〜１０００のものが好ましく、このような高アスペクト比の極細繊維を用い、かつ、カーボンナノチューブを樹脂Ａに偏在させることにより、著しく良好な導電性、電磁波シールド性の向上効果を得ることができる。 The carbon nanotube has an average fiber diameter of 1 to 200 nm, particularly 10 to 100 nm, and an aspect ratio (referring to the ratio of fiber length / fiber diameter, obtained by observation with a microscope) of 5 to 1000, particularly 100 to 1000. Those having such a high aspect ratio and using carbon nanotubes unevenly distributed in the resin A can provide extremely good conductivity and electromagnetic wave shielding improvement effects.
本発明の導電性樹脂組成物中の（Ｃ）成分としてのカーボンナノチューブの含有量は、０．０１〜５０質量％、特に１〜３０質量％、とりわけ３〜２０質量％で、熱可塑性樹脂の合計１００質量部に対して１〜３１質量部、特に３〜２０質量部であることが好ましい。カーボンナノチューブの含有量が少な過ぎると、カーボンナノチューブを配合したことによる導電性、電磁波シールド性の向上効果を十分に得ることができず、多過ぎると、成形性、機械的特性等が損なわれるおそれがある。 The content of the carbon nanotube as the component (C) in the conductive resin composition of the present invention is 0.01 to 50% by mass, particularly 1 to 30% by mass, especially 3 to 20% by mass. It is preferable that it is 1-31 mass parts with respect to a total of 100 mass parts, especially 3-20 mass parts. If the content of carbon nanotubes is too small, the effect of improving the conductivity and electromagnetic wave shielding properties due to the incorporation of carbon nanotubes cannot be sufficiently obtained, and if too much, moldability, mechanical properties, etc. may be impaired. There is.
なお、カーボンナノチューブは平均繊維径やアスペクト比など、規格の異なるものの２種以上を併用しても良い。 In addition, two or more types of carbon nanotubes having different standards such as an average fiber diameter and an aspect ratio may be used in combination.
［（Ｄ）成分］
本発明において用いる無機微粒子としては、アルミナ、シリカ、酸化亜鉛、酸化チタン、酸化マグネシウム、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、チッ化アルミニウム、ハイドロタルサイト、硫酸バリウムなど特に限定されないが、その中でもシリカ微粒子が好ましい。
[(D) component]
The inorganic fine particles used in the present invention are not particularly limited, such as alumina, silica, zinc oxide, titanium oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, calcium carbonate, aluminum nitride, hydrotalcite, and barium sulfate. Among these, silica fine particles are preferable.
無機微粒子は、本発明の導電性樹脂組成物において、熱可塑性樹脂Ａと熱可塑性樹脂Ｂ中に存在し、顕微鏡で観察すると２相構造の界面部分に多く存在しているように観察される。無機微粒子は、樹脂の混練、成形時の剪断力により熱可塑性樹脂Ａ，Ｂをより細かく切断し、これにより、より微細な２相構造を形成する機能を発揮し、カーボンナノチューブの配向性を高める作用を奏する。 In the conductive resin composition of the present invention, the inorganic fine particles are present in the thermoplastic resin A and the thermoplastic resin B, and when observed with a microscope, they are observed to exist in a large amount at the interface portion of the two-phase structure. The inorganic fine particles cut the thermoplastic resins A and B more finely by the shearing force at the time of resin kneading and molding, thereby exhibiting the function of forming a finer two-phase structure and enhancing the orientation of the carbon nanotubes Has an effect.
この無機微粒子としては、表面処理を行っていない通常の無機微粒子であっても、表面処理を行った無機微粒子であっても良い。前記無機微粒子の中でも、シリカ微粒子は、熱可塑性樹脂Ａ及び熱可塑性樹脂Ｂとの混練時に分解しにくく、また、後述のカーボンブラック等の炭素系充填剤に比べて成形品から粉落ちしにくい点においても配合成分として好ましい。 The inorganic fine particles may be ordinary inorganic fine particles not subjected to surface treatment or inorganic fine particles subjected to surface treatment. Among the inorganic fine particles, the silica fine particles are less likely to be decomposed when kneaded with the thermoplastic resin A and the thermoplastic resin B, and more difficult to fall off from the molded product as compared with a carbon-based filler such as carbon black described later. Is preferable as a blending component.
また、無機微粒子は平均一次粒子径が１０μｍ以下、特に３００〜２０００ｎｍのものが好ましい。無機微粒子の粒子径が大き過ぎると樹脂の成形性や機械的特性に悪影響を及ぼすおそれがあり、小さ過ぎると、無機微粒子を配合したことによる上記効果を十分に得ることができない。 The inorganic fine particles preferably have an average primary particle size of 10 μm or less, particularly 300 to 2000 nm. If the particle size of the inorganic fine particles is too large, the moldability and mechanical properties of the resin may be adversely affected. If the particle size is too small, the above-described effects due to the incorporation of the inorganic fine particles cannot be sufficiently obtained.
ここで、無機微粒子の平均一次粒子径は、ＳＥＭ又はＴＥＭにより２０００〜３０００個の粒子径を観察し、その累積分布により求めたメジアン径（ｄ−５０）に準拠した平均粒径である。ここで述べるメジアン径とは、粉体をある粒子径から２つに分けたとき、大きい側と小さい側が等量となる径のことである。 Here, the average primary particle diameter of the inorganic fine particles is an average particle diameter based on the median diameter (d-50) obtained by observing 2000 to 3000 particle diameters by SEM or TEM and determining the cumulative distribution. The median diameter described here is a diameter in which when the powder is divided into two from a certain particle diameter, the larger side and the smaller side are equivalent.
本発明の導電性樹脂組成物中の無機微粒子の含有量は、０．０１〜３０質量％、特に１〜２５質量％、とりわけ３〜２０質量％で、熱可塑性樹脂の合計１００質量部に対して０．０１〜３０質量部、特に１〜２５質量部、とりわけ３〜２０質量部であることが好ましい。無機微粒子の含有量が少な過ぎると、無機微粒子を配合したことによる上記効果を十分に得ることができず、多過ぎると、成形性、機械的特性等が損なわれるおそれがある。 The content of the inorganic fine particles in the conductive resin composition of the present invention is 0.01 to 30% by mass, particularly 1 to 25% by mass, especially 3 to 20% by mass, with respect to a total of 100 parts by mass of the thermoplastic resin. 0.01 to 30 parts by mass, particularly 1 to 25 parts by mass, particularly 3 to 20 parts by mass is preferable. If the content of the inorganic fine particles is too small, the above-mentioned effect due to the blending of the inorganic fine particles cannot be obtained sufficiently, and if it is too large, the moldability, mechanical properties, etc. may be impaired.
なお、無機微粒子は１種を単独で用いても良く、２種以上を混合して用いても良い。また、表面処理の異なるものや、異なる粒径のものを２種以上併用しても良い。 The inorganic fine particles may be used alone or in combination of two or more. Two or more types having different surface treatments or different particle sizes may be used in combination.
［その他の成分］
本発明の導電性樹脂組成物は、上記（Ａ）〜（Ｄ）成分の他、本発明の目的を損なわない範囲で、以下のようなその他の成分を含有していても良い。
[Other ingredients]
In addition to the above components (A) to (D), the conductive resin composition of the present invention may contain the following other components as long as the object of the present invention is not impaired.
（１）導電性物質
本発明の導電性樹脂組成物には、導電性の更なる改善のために、導電性物質として、カーボンブラック、黒鉛などの炭素系充填剤、好ましくはカーボンブラックを配合しても良い。
(1) Conductive substance The conductive resin composition of the present invention is blended with a carbon-based filler such as carbon black or graphite, preferably carbon black, as a conductive substance for further improvement in conductivity. May be.
カーボンブラック等の炭素系充填剤としては、平均粒子径１０〜５０ｎｍ、特に１０〜３０ｎｍのものが好ましく、かつＤＢＰ吸油量１００以上のものが好ましい。導電性樹脂組成物中のカーボンブラック等の炭素系充填剤の含有量は、２５質量％以下、特に５〜２０質量％、とりわけ１０〜２０質量％で、熱可塑性樹脂の合計１００質量部に対して４５質量部以下、特に５〜３５質量部、とりわけ１５〜３５質量部であることが好ましい。 The carbon-based filler such as carbon black preferably has an average particle diameter of 10 to 50 nm, particularly 10 to 30 nm, and preferably has a DBP oil absorption of 100 or more. The content of the carbon-based filler such as carbon black in the conductive resin composition is 25% by mass or less, particularly 5 to 20% by mass, especially 10 to 20% by mass, and the total amount of the thermoplastic resin is 100 parts by mass. It is preferably 45 parts by mass or less, particularly preferably 5 to 35 parts by mass, particularly preferably 15 to 35 parts by mass.
カーボンブラック等の炭素系充填剤の粒子径が大き過ぎると樹脂の成形性や機械的特性が損なわれるおそれがある。カーボンブラック等の炭素系充填剤の粒子径が小さ過ぎると溶融混練時の吐出率が悪化するため、生産性が低くなるおそれがある。また、カーボンブラック等の炭素系充填剤の含有量が少な過ぎると、カーボンブラック等の炭素系充填剤を配合したことによる導電性の向上効果を十分に得ることができず、多過ぎると、成形性、機械的特性等が損なわれる。 If the particle size of a carbon-based filler such as carbon black is too large, the resin moldability and mechanical properties may be impaired. If the particle size of the carbon-based filler such as carbon black is too small, the discharge rate at the time of melt-kneading deteriorates, so that productivity may be lowered. In addition, if the content of the carbon-based filler such as carbon black is too small, the effect of improving the conductivity due to the blending of the carbon-based filler such as carbon black cannot be sufficiently obtained. Properties and mechanical properties are impaired.
ただし、カーボンブラック等の炭素系充填剤は、成形品から脱落し易く、粉落ち（耐チョーク性の低下）の原因となる。
一方で、本発明では、無機微粒子を配合することによるカーボンナノチューブの配向性の向上効果で、導電性及び電磁波シールド性を十分に高めることができることから、本発明においては、カーボンブラック等の炭素系充填剤を配合することなく、無機微粒子の配合によるカーボンナノチューブの配向性の向上効果で、目的とする導電性及び電磁波シールド性を確保することが好ましい。
However, carbon-based fillers such as carbon black are easy to fall off from the molded product and cause powder falling (decrease in chalk resistance).
On the other hand, in the present invention, the conductivity and electromagnetic wave shielding properties can be sufficiently enhanced by the effect of improving the orientation of carbon nanotubes by blending inorganic fine particles. It is preferable to ensure the intended conductivity and electromagnetic wave shielding property by the effect of improving the orientation of the carbon nanotubes by blending inorganic fine particles without blending a filler.
（２） 難燃剤
本発明の導電性樹脂組成物には、難燃性を付与するために難燃剤を配合することができる。
(2) Flame retardant A flame retardant can be blended with the conductive resin composition of the present invention in order to impart flame retardancy.
難燃剤としては、組成物の難燃性を向上させるものであれば特に限定されないが、リン酸エステル化合物、有機スルホン酸金属塩、シリコーン化合物等が好適である。これらは、１種を単独で用いても良く、２種以上を併用しても良い。 The flame retardant is not particularly limited as long as it improves the flame retardancy of the composition, but a phosphoric acid ester compound, an organic sulfonic acid metal salt, a silicone compound, and the like are preferable. These may be used alone or in combination of two or more.
難燃剤の配合量としては、好ましくは導電性樹脂組成物中、リン酸エステル化合物は５〜２０質量％、有機スルホン酸金属塩は０．０２〜０．２質量％、シリコーン化合物は０．３〜３質量％である。 As a compounding quantity of a flame retardant, Preferably in a conductive resin composition, a phosphate ester compound is 5-20 mass%, an organic sulfonic acid metal salt is 0.02-0.2 mass%, and a silicone compound is 0.3. ˜3 mass%.
（３） 滴下防止剤
本発明の導電性樹脂組成物には、燃焼時の滴下防止を目的として、滴下防止剤を配合することができる。滴下防止剤としては好ましくはフッ素樹脂を用いることができる。
(3) Anti-dripping agent The conductive resin composition of the present invention may contain an anti-drip agent for the purpose of preventing dripping during combustion. As the anti-dripping agent, a fluororesin can be preferably used.
ここでフッ素樹脂とは、フルオロエチレン構造を含む重合体、共重合体であり、例えば、ジフルオロエチレン重合体、テトラフルオロエチレン重合体、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体、テトラフルオロエチレンとフッ素を含まないエチレン系モノマーとの共重合体が挙げられ、好ましくは、ポリテトラフルオロエチレン（ＰＴＦＥ）であり、その平均分子量は、５００，０００以上であることが好ましく、特に好ましくは５００，０００〜１０，０００，０００である。 Here, the fluororesin is a polymer or copolymer containing a fluoroethylene structure, such as a difluoroethylene polymer, a tetrafluoroethylene polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene and fluorine. And a copolymer with an ethylene-based monomer that does not contain polytetrafluoroethylene (PTFE), preferably having an average molecular weight of 500,000 or more, particularly preferably 500,000 to 10,000,000.
本発明で用いることができるポリテトラフルオロエチレンとしては、現在知られているすべての種類のものを用いることができるが、ポリテトラフルオロエチレンのうち、フィブリル形成能を有するものを用いると、さらに高い溶融滴下防止性を付与することができる。フィブリル形成能を有するポリテトラフルオロエチレン（ＰＴＦＥ）には特に制限はないが、例えば、ＡＳＴＭ規格において、タイプ３に分類されるものが挙げられる。その具体例としては、例えばテフロン（登録商標）６−Ｊ（三井・デュポンフロロケミカル（株）製）、ポリフロンＤ−１、ポリフロンＦ−１０３、ポリフロンＦ２０１（ダイキン工業（株）製）、ＣＤ０７６（旭アイシーアイフロロポリマーズ（株）製）等が挙げられる。また、上記タイプ３に分類されるもの以外では、例えばアルゴフロンＦ５（モンテフルオス（株）製）、ポリフロンＭＰＡ、ポリフロンＦＡ−１００（ダイキン工業（株）製）等が挙げられる。これらのポリテトラフルオロエチレン（ＰＴＦＥ）は、単独で用いてもよいし、２種以上を組み合わせてもよい。上記のようなフィブリル形成能を有するポリテトラフルオロエチレン（ＰＴＦＥ）は、例えばテトラフルオロエチレンを水性溶媒中で、ナトリウム、カリウム、アンモニウムパーオキシジスルフィドの存在下で、１〜１００ｐｓｉの圧力下、温度０〜２００℃、好ましくは２０〜１００℃で重合させることによって得られる。また、溶媒にて分散されたテフロン（登録商標）３０−Ｊ（三井・デュポンフロロケミカル（株）製）であっても構わない。 As the polytetrafluoroethylene that can be used in the present invention, all types of polytetrafluoroethylene that are currently known can be used. However, when polytetrafluoroethylene having a fibril-forming ability is used, it is even higher. Melting dripping prevention property can be provided. Although there is no restriction | limiting in particular in the polytetrafluoroethylene (PTFE) which has a fibril formation ability, For example, what is classified into the type 3 in ASTM standard is mentioned. Specific examples thereof include, for example, Teflon (registered trademark) 6-J (manufactured by Mitsui DuPont Fluorochemical Co., Ltd.), Polyflon D-1, Polyflon F-103, Polyflon F201 (Daikin Industries, Ltd.), CD076 ( Asahi IC Fluoropolymers Co., Ltd.). Other than those classified as type 3, for example, Argoflon F5 (manufactured by Montefluos Co., Ltd.), polyflon MPA, polyflon FA-100 (manufactured by Daikin Industries, Ltd.) and the like can be mentioned. These polytetrafluoroethylene (PTFE) may be used independently and may combine 2 or more types. Polytetrafluoroethylene (PTFE) having the fibril-forming ability as described above is prepared by, for example, using tetrafluoroethylene in an aqueous solvent in the presence of sodium, potassium, ammonium peroxydisulfide, at a pressure of 1 to 100 psi, at a temperature of 0. It is obtained by polymerizing at ˜200 ° C., preferably 20˜100 ° C. Alternatively, Teflon (registered trademark) 30-J (Mitsui / Dupont Fluorochemical Co., Ltd.) dispersed in a solvent may be used.
また、滴下防止剤は、ポリテトラフルオロエチレン粒子と有機系重合体粒子とからなるポリテトラフルオロエチレン含有混合粉体であってもよい。有機系重合体粒子を生成するための単量体の具体例としては、スチレン、ｐ−メチルスチレン、ｏ−メチルスチレン、ｐ−クロルスチレン、ｏ−クロルスチレン、ｐ−メトキシスチレン、ｏ−メトキシスチレン、２，４−ジメチルスチレン、α−メチルスチレン等のスチレン系単量体、アクリル酸メチル、メタクリル酸メチル、アクリル酸エチル、メタクリル酸エチル、アクリル酸ブチル、メタクリル酸ブチル、アクリル酸−２−エチルヘキシル、メタクリル酸−２−エチルヘキシル、アクリル酸ドデシル、メタクリル酸ドデシル、アクリル酸トリドデシル、メタクリル酸トリドデシル、アクリル酸オクタデシル、メタクリル酸オクタデシル、アクリル酸シクロヘキシル、メタクリル酸シクロヘキシル等の（メタ）アクリル酸エステル系単量体、アクリロニトリル、メタクリロニトリル等のシアン化ビニル系単量体、ビニルメチルエーテル、ビニルエチルエーテル等のビニルエーテル系単量体、酢酸ビニル、酪酸ビニル等のカルボン酸ビニル単量体、エチレン、プロピレン、イソブチレン等のオレフィン系単量体、ブタジエン、イソプレン、ジメチルブタジエン等のジエン系単量体等を挙げることができるが、これらに限定されるものではない。好ましくは、これらの単量体の重合体又は共重合体を２種以上用い、有機系重合体粒子を得ることができる。 The anti-dripping agent may be a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and organic polymer particles. Specific examples of monomers for producing organic polymer particles include styrene, p-methylstyrene, o-methylstyrene, p-chlorostyrene, o-chlorostyrene, p-methoxystyrene, o-methoxystyrene. Styrene monomers such as 2,4-dimethylstyrene, α-methylstyrene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate (Meth) acrylic acid ester-based single quantities such as 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridodecyl acrylate, tridodecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate , Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether, vinyl carboxylate monomers such as vinyl acetate and vinyl butyrate, ethylene, propylene, isobutylene Examples thereof include, but are not limited to, olefin monomers such as diene monomers such as butadiene, isoprene and dimethylbutadiene. Preferably, two or more kinds of polymers or copolymers of these monomers can be used to obtain organic polymer particles.
滴下防止剤の配合量としては、好ましくは導電性樹脂組成物中０．０５〜０．５質量％であり、より好ましくは０．２〜０．５質量％である。 As a compounding quantity of a dripping inhibitor, Preferably it is 0.05-0.5 mass% in a conductive resin composition, More preferably, it is 0.2-0.5 mass%.
（４） 耐衝撃性改良剤
本発明の導電性樹脂組成物には、衝撃強度向上のために、耐衝撃性改良剤としてエラストマーを配合することができる。
(4) Impact resistance improver The conductive resin composition of the present invention can be blended with an elastomer as an impact resistance improver in order to improve impact strength.
該エラストマーとしては、特に限定されるものではないが、多層構造重合体が好ましい。多層構造重合体としては、例えば、アルキル（メタ）アクリレート系重合体を含むものが挙げられる。これらの多層構造重合体としては、例えば、先の段階の重合体を後の段階の重合体が順次被覆するような連続した多段階シード重合によって製造される重合体であり、基本的な重合体構造としては、ガラス転移温度の低い架橋成分である内核層と組成物のマトリックスとの接着性を改善する高分子化合物から成る最外核層を有する重合体である。これら多層構造重合体の最内核層を形成する成分としては、ガラス転移温度が０℃以下のゴム成分が選択される。これらゴム成分としては、ブタジエン等のゴム成分、スチレン／ブタジエン等のゴム成分、アルキル（メタ）アクリレート系重合体のゴム成分、ポリオルガノシロキサン系重合体とアルキル（メタ）アクリレート系重合体が絡み合って成るゴム成分、あるいはこれらの併用されたゴム成分が挙げられる。さらに、最外核層を形成する成分としては、芳香族ビニル単量体又は非芳香族系単量体あるいはそれらの２種類以上の共重合体が挙げられる。芳香族ビニル単量体としては、スチレン、ビニルトルエン、α−メチルスチレン、モノクロルスチレン、ジクロルスチレン、ブロモスチレン等を挙げることができる。これらの中では、特にスチレンが好ましく用いられる。非芳香族系単量体としては、エチル（メタ）アクリレート、ブチル（メタ）アクリレート等のアルキル（メタ）アクリレート、アクリロニトリル、メタクリロニトリル等のシアン化ビニルやシアン化ビニリデン等を挙げることができる。これらは１種を単独で用いても良く、２種以上を併用しても良い。 The elastomer is not particularly limited, but a multilayer structure polymer is preferable. Examples of the multilayer structure polymer include those containing an alkyl (meth) acrylate polymer. These multi-layered polymers include, for example, polymers produced by continuous multi-stage seed polymerization in which a polymer in a previous stage is sequentially coated with a polymer in a subsequent stage, and a basic polymer. As a structure, it is a polymer having an outermost core layer made of a polymer compound that improves the adhesion between the inner core layer, which is a crosslinking component having a low glass transition temperature, and the matrix of the composition. A rubber component having a glass transition temperature of 0 ° C. or lower is selected as a component that forms the innermost core layer of these multilayer polymers. These rubber components include rubber components such as butadiene, rubber components such as styrene / butadiene, rubber components of alkyl (meth) acrylate polymers, polyorganosiloxane polymers and alkyl (meth) acrylate polymers. Or a rubber component using these in combination. Furthermore, examples of the component forming the outermost core layer include an aromatic vinyl monomer, a non-aromatic monomer, or a copolymer of two or more thereof. Examples of the aromatic vinyl monomer include styrene, vinyl toluene, α-methyl styrene, monochloro styrene, dichloro styrene, bromo styrene, and the like. Of these, styrene is particularly preferably used. Examples of non-aromatic monomers include alkyl (meth) acrylates such as ethyl (meth) acrylate and butyl (meth) acrylate, vinyl cyanide such as acrylonitrile and methacrylonitrile, and vinylidene cyanide. These may be used alone or in combination of two or more.
耐衝撃性改良剤の配合量としては、好ましくは導電性樹脂組成物中１〜１０質量％であり、より好ましくは２〜５質量％である。 As a compounding quantity of an impact resistance improving agent, Preferably it is 1-10 mass% in a conductive resin composition, More preferably, it is 2-5 mass%.
（５） 補強材
本発明の導電性樹脂組成物には、弾性率、強度、荷重たわみ温度の向上のために、補強材を添加することができる。
(5) Reinforcing Material A reinforcing material can be added to the conductive resin composition of the present invention in order to improve the elastic modulus, strength, and deflection temperature under load.
ここで、補強材としては、シリカ、珪藻土、軽石粉、軽石バルーン、水酸化アルミニウム、水酸化マグネシウム、塩基性炭酸マグネシウム、硫酸カルシウム、チタン酸カリウム、硫酸バリウム、亜硫酸カルシウム、タルク、クレー、マイカ、ガラス繊維、ガラスフレーク、ガラスビーズ、珪酸カルシウム、モンモリロナイト、ベントナイト、硫化モリブデン、ボロン繊維、炭化珪素繊維、ポリエステル繊維、ポリアミド繊維、ホウ酸アルミニウム等を例示できる。これらは１種を単独で用いても良く、２種以上を併用しても良い。特に限定されるものではないが、補強材としてはガラス繊維、ガラスフレーク、タルク、マイカが好ましい。 Here, as a reinforcing material, silica, diatomaceous earth, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, Examples thereof include glass fiber, glass flake, glass bead, calcium silicate, montmorillonite, bentonite, molybdenum sulfide, boron fiber, silicon carbide fiber, polyester fiber, polyamide fiber, and aluminum borate. These may be used alone or in combination of two or more. Although not particularly limited, the reinforcing material is preferably glass fiber, glass flake, talc, or mica.
補強材の配合量としては、好ましくは樹脂成分１００質量部に対し、１〜１００質量部であり、より好ましくは１０〜８０質量部である。 As a compounding quantity of a reinforcing material, Preferably it is 1-100 mass parts with respect to 100 mass parts of resin components, More preferably, it is 10-80 mass parts.
（６） その他
本発明の導電性樹脂組成物には、上記の成分以外に、必要に応じて、紫外線吸収剤、酸化防止剤等の安定剤、顔料、染料、滑剤、離型剤等の添加剤をそれぞれ必要量配合しても良い。
(6) Others The conductive resin composition of the present invention may contain, in addition to the above components, stabilizers such as ultraviolet absorbers and antioxidants, pigments, dyes, lubricants, mold release agents, and the like as necessary. Each agent may be blended in the required amount.
［製造方法］
本発明の導電性樹脂組成物を得るための方法としては、特に限定されず、各種混練機、例えば、一軸又は多軸混練機、バンバリーミキサー、ロール、ブラベンダープラストグラム等で、上記成分を所定の配合で混練した後、冷却固化する方法や、適当な溶媒、例えば、ヘキサン、ヘプタン、ベンゼン、トルエン、キシレン等の炭化水素及びその誘導体に上記成分を添加し、溶解する成分同志、あるいは溶解する成分と不溶解成分を懸濁状態で混ぜる溶液混合法等が用いられる。工業的コストからは溶融混練法が好ましいが、これに限定されるものではない。溶融混練においては、単軸や二軸の押出機を用いることが好ましい。より好ましくは、二軸の押出機を用いるのが良い。
[Production method]
The method for obtaining the conductive resin composition of the present invention is not particularly limited, and the above components are predetermined using various kneaders such as a uniaxial or multiaxial kneader, a Banbury mixer, a roll, and a Brabender plastogram. The above components are added to and dissolved in a method of cooling and solidifying after kneading by blending, or a suitable solvent such as hexane, heptane, benzene, toluene, xylene and other hydrocarbons and derivatives thereof. A solution mixing method or the like in which components and insoluble components are mixed in a suspended state is used. The melt-kneading method is preferable from the industrial cost, but is not limited thereto. In melt kneading, it is preferable to use a single-screw or twin-screw extruder. More preferably, a twin screw extruder is used.
本発明の導電性樹脂組成物を製造する際には、すべての成分を一度に混合しても良く、また、カーボンナノチューブや無機微粒子を、熱可塑性樹脂の一部、又は全部と予め混合したり、熱可塑性樹脂の一部でカーボンナノチューブ及び／又は無機微粒子を被覆したりして、マスターバッチを調製した後、残りの熱可塑性樹脂に配合する方法でも良い。また、カーボンナノチューブや無機微粒子が複数種から構成される場合は、それら全てを同時にマスターバッチにしてもよいし、その一部をマスターバッチにしたり、複数のマスターバッチにしたりしても良い。また、カーボンナノチューブや無機微粒子の分散性に差がある場合は、それらが良く分散する樹脂で、マスターバッチを調製するのが良い。
本発明では、カーボンナノチューブを熱可塑性樹脂Ａの相中に存在（偏在）させることから、少なくともカーボンナノチューブについては、これをマスターバッチ化する場合には、熱可塑性樹脂Ａ中に配合してマスターバッチ化することが好ましい。
When producing the conductive resin composition of the present invention, all components may be mixed at once, or carbon nanotubes and inorganic fine particles may be mixed in advance with a part or all of the thermoplastic resin. Alternatively, a method may be used in which a master batch is prepared by coating carbon nanotubes and / or inorganic fine particles with a part of the thermoplastic resin, and then blended with the remaining thermoplastic resin. Moreover, when carbon nanotubes and inorganic fine particles are composed of a plurality of types, all of them may be made into a master batch at the same time, or a part of them may be made into a master batch or a plurality of master batches. When there is a difference in dispersibility between carbon nanotubes and inorganic fine particles, a masterbatch is preferably prepared with a resin in which they are well dispersed.
In the present invention, since the carbon nanotubes are present (unevenly distributed) in the phase of the thermoplastic resin A, at least the carbon nanotubes are blended into the thermoplastic resin A when masterbatched. Is preferable.
［成形方法］
本発明の導電性樹脂組成物を用いて導電性樹脂成形品を得る方法は、特に限定されるものでなく、熱可塑性樹脂組成物について一般に用いられている成形法、例えば、射出成形、中空成形、押出成形、シート成形、熱成形、回転成形、積層成形等の成形方法を適用できるが、特に、本発明の導電性樹脂組成物は、射出成形法、押出成形法等のように、成形中に樹脂組成物に剪断力が付与され、この結果、組成物中のカーボンナノチューブが配向するような成形法を採用するのが好ましい。
なお、本発明における２相構造は成形された成形品の組成構造を云っていることは云うまでもないであろう。
[Molding method]
The method for obtaining a conductive resin molded product using the conductive resin composition of the present invention is not particularly limited, and a molding method generally used for thermoplastic resin compositions, for example, injection molding, hollow molding. The molding method such as extrusion molding, sheet molding, thermoforming, rotational molding, and lamination molding can be applied. In particular, the conductive resin composition of the present invention is being molded like the injection molding method, extrusion molding method, etc. It is preferable to adopt a molding method in which a shearing force is applied to the resin composition, and as a result, the carbon nanotubes in the composition are oriented.
In addition, it cannot be overemphasized that the two-phase structure in this invention says the composition structure of the shape | molded molded article.
［導電性樹脂（電磁波シールド）成形品］
本発明の導電性樹脂組成物を射出成形法等で成形してなる導電性樹脂（電磁波シールド）成形品は、特にＯＡ機器の筐体や電気電子機器の筐体に好適であり、適用される機器としては、例えば、ノート型パソコン、電子手帳、携帯電話、ＰＤＡ等が挙げられるが、本発明の特徴である電磁波シールド性を最も活かせる用途として、ノート型パソコンの筐体が挙げられる。
[Conductive resin (electromagnetic wave shield) molded product]
A conductive resin (electromagnetic wave shield) molded product obtained by molding the conductive resin composition of the present invention by an injection molding method or the like is particularly suitable for and applied to OA equipment casings and electrical / electronic equipment casings. Examples of the device include a notebook personal computer, an electronic notebook, a mobile phone, and a PDA. As an application that makes the most of the electromagnetic wave shielding property of the present invention, there is a case of a notebook personal computer.
以下に実施例、参考例及び比較例を挙げて本発明をより具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples , reference examples, and comparative examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
なお、以下の実施例、参考例及び比較例において、導電性樹脂組成物の配合成分として用いたものは次の通りである。 In the following examples , reference examples, and comparative examples, the components used as blending components of the conductive resin composition are as follows.
＜熱可塑性樹脂Ａ＞
芳香族ポリカーボネート樹脂（ＰＣ）：三菱エンジニアリングプラスチックス（株）製、商品名：ユーピロン（登録商標）、粘度：８５９Ｐａ・ｓ（２８０℃、剪断速度：３６．５ｓ−１）、４６７Ｐａ・ｓ（２８０℃、剪断速度：１２１６ｓ−１）
<Thermoplastic resin A>
Aromatic polycarbonate resin (PC): manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name: Iupilon (registered trademark), viscosity: 859 Pa · s (280 ° C., shear rate: 36.5 s −1 ), 467 Pa · s (280) ° C, shear rate: 1216 s −1 )
＜熱可塑性樹脂Ｂ＞
アクリロニトリル−スチレン共重合体（ＡＳ）：テクノポリマー（株）製、商品名：ＳＡＮ−Ｃ、粘度＝３３９Ｐａ・ｓ（２８０℃、剪断速度：３６．５ｓ−１）、８９．５Ｐａ・ｓ（２８０℃、剪断速度：１２１６ｓ−１）
<Thermoplastic resin B>
Acrylonitrile-styrene copolymer (AS): manufactured by Technopolymer Co., Ltd., trade name: SAN-C, viscosity = 339 Pa · s (280 ° C., shear rate: 36.5 s −1 ), 89.5 Pa · s (280) ° C, shear rate: 1216 s −1 )
＜（Ｃ）成分＞
カーボンナノチューブ：多層カーボンナノチューブ、平均繊維径１５ｎｍ、アスペクト比１００〜１０００
<(C) component>
Carbon nanotubes: multi-walled carbon nanotubes, average fiber diameter 15 nm, aspect ratio 100-1000
＜(Ｄ）成分＞
無機微粒子ａ：扶桑化学（株）製シリカ微粒子、商品名：ＡＥＲＯＳＩＬ２００、平均一次粒子径約１２ｎｍ、比表面積（ＢＥＴ法）２００±２５ｍ２／ｇ、見かけ比重約５０ｇ／Ｌ
無機微粒子ｂ：扶桑化学（株）製シリカ微粒子、商品名：ＡＥＲＯＳＩＬＲＸ２００、平均一次粒子径約１２ｎｍ、比表面積（ＢＥＴ法）１４０±２５ｍ２／ｇ、見かけ比重約５０ｇ／Ｌ
無機微粒子ｃ：扶桑化学（株）製シリカ微粒子、商品名：クォートロンＳＰ−３Ｆ、平均一次粒子径２００〜３００ｎｍ、比表面積（ＢＥＴ法）１５ｍ２／ｇ、真比重２．２ｇ／Ｌ
無機微粒子ｄ：扶桑化学（株）製シリカ微粒子、商品名：クォートロンＳＰ−１Ｂ、平均一次粒子径約１μｍ、比表面積（ＢＥＴ法）３．４ｍ２／ｇ、真比重２．２ｇ／Ｌ
<(D) component>
Inorganic fine particles a: silica fine particles manufactured by Fuso Chemical Co., Ltd., trade name: AEROSIL 200, average primary particle diameter of about 12 nm, specific surface area (BET method) 200 ± 25 m 2 / g, apparent specific gravity of about 50 g / L
Inorganic fine particles b: silica fine particles manufactured by Fuso Chemical Co., Ltd., trade name: AEROSILRX200, average primary particle diameter of about 12 nm, specific surface area (BET method) 140 ± 25 m 2 / g, apparent specific gravity of about 50 g / L
Inorganic fine particles c: Silica fine particles manufactured by Fuso Chemical Co., Ltd., trade name: Quatron SP-3F, average primary particle size 200-300 nm, specific surface area (BET method) 15 m 2 / g, true specific gravity 2.2 g / L
Inorganic fine particles d: silica fine particles manufactured by Fuso Chemical Co., Ltd., trade name: Quatron SP-1B, average primary particle diameter of about 1 μm, specific surface area (BET method) 3.4 m 2 / g, true specific gravity 2.2 g / L
＜その他＞
カーボンブラック：三菱化学（株）製、商品名＃３２３０、粒子径約２３ｎｍ（粒子径は、電子顕微鏡により平均直径として算出したもの）、ＢＥＴ比表面積２２０ｍ２／ｇ、ＤＢＰ吸油量１４０ｃｍ３／１００ｇ
離型剤：クラリアントジャパン（株)製、商品名：ＬＩＣＯＷＡＸ ＰＥ５２０ＰＯＷＤＥＲ
<Others>
Carbon black: Mitsubishi Chemical Co., Ltd., trade name # 3230, particle size about 23 nm (the particle diameter, which was calculated as the mean diameter by electron microscopy), BET specific surface area of 220 m 2 / g, DBP oil absorption 140cm 3/100 g
Mold release agent: manufactured by Clariant Japan Co., Ltd., trade name: LICOWAX PE520POWDER
［参考例１〜６、実施例７、比較例１〜３］
表１に示す割合にて各成分を配合し、タンブラーミキサーにて均一に混合した後、二軸押出機（日本製鋼所製、ＴＥＸ３０ＸＣＴ、Ｌ／Ｄ＝４２、バレル数１２）を用いて、シリンダー温度２８０℃、スクリュー回転数２００ｒｐｍにて押出機上流部のバレルより押出機にフィードし、溶融混練させて樹脂組成物のペレットを得た。この樹脂組成物のペレットを用いて、以下の（１）〜（３）の評価を行い、結果を表１に示した。
[Reference Examples 1-6 , Example 7 , Comparative Examples 1-3]
After blending each component in the ratio shown in Table 1 and uniformly mixing with a tumbler mixer, using a twin screw extruder (Nippon Steel Works, TEX30XCT, L / D = 42, barrel number 12), cylinder The resin composition pellets were obtained by feeding to the extruder from the barrel upstream of the extruder at a temperature of 280 ° C. and a screw speed of 200 rpm, and melt-kneading. Using the pellets of this resin composition, the following (1) to (3) were evaluated, and the results are shown in Table 1.
なお、参考例１〜６、実施例７及び比較例２，３におけるＰＣ樹脂とＡＳ樹脂の配合割合はいずれもＰＣ樹脂６８体積％、ＡＳ樹脂３２体積％であり、ＰＣ樹脂：ＡＳ樹脂≒７：３（体積比）である。 The blend ratios of PC resin and AS resin in Reference Examples 1 to 6 , Example 7 and Comparative Examples 2 and 3 are 68% by volume of PC resin and 32% by volume of AS resin, and PC resin: AS resin≈7. : 3 (volume ratio).
［評価方法］
（１）導電性
体積抵抗率：射出成形機（住友重機械工業製、ＳＨ１００、型締め力１００Ｔ）により、樹脂温度（パージ樹脂の実測温度）：２９０℃、金型温度：８０℃、金型：縦１００ｍｍ、横１００ｍｍ、厚み２ｍｍの条件で射出成形した成形品を抵抗率計（（株）アドバンテスト製：Ｒ８３４０デジタル超高抵抗／微少電流計およびＲ１２７０４レジスティビティ・チェンバ）にて測定した。体積抵抗率はΩ・ｃｍの単位で表示する。この値は１０７Ω・ｃｍ以下であることが好ましい。
表面抵抗率：射出成形機（住友重機械工業製、ＳＨ１００、型締め力１００Ｔ）により、樹脂温度（パージ樹脂の実測温度）：２９０℃、金型温度：８０℃、金型：縦１００ｍｍ、横１００ｍｍ、厚み２ｍｍの条件で射出成形した成形品を抵抗率計（（株）アドバンテスト製：Ｒ８３４０デジタル超高抵抗／微少電流計およびＲ１２７０４レジスティビティ・チェンバ）にて測定した。表面抵抗率はΩ／□の単位で表示する。この値は１０６Ω／□以下であることが好ましい。
[Evaluation method]
(1) Conductivity Volume resistivity: Injection molding machine (manufactured by Sumitomo Heavy Industries, SH100, mold clamping force 100T), resin temperature (measured temperature of purge resin): 290 ° C, mold temperature: 80 ° C, mold : A molded product injection-molded under the conditions of 100 mm in length, 100 mm in width and 2 mm in thickness was measured with a resistivity meter (manufactured by Advantest Corporation: R8340 digital ultrahigh resistance / microammeter and R12704 resiliency chamber). Volume resistivity is expressed in units of Ω · cm. This value is preferably 10 7 Ω · cm or less.
Surface resistivity: injection molding machine (manufactured by Sumitomo Heavy Industries, SH100, mold clamping force 100T), resin temperature (measured temperature of purge resin): 290 ° C, mold temperature: 80 ° C, mold: vertical 100mm, horizontal A molded product injection-molded under the conditions of 100 mm and
（２）電磁波シールド性
射出成形機（住友重機械工業製、ＳＨ１００、型締め力１００Ｔ）を用いて、樹脂温度（パージ樹脂の実測温度）：２９０℃、金型温度：８０℃にて、金型：縦１００ｍｍ、横１００ｍｍ、厚み２ｍｍの成形品を射出成形し、得られた射出成形品を５枚用いて、（株）アドバンテスト製ＴＲ−１７３０１ＡとＲ３３６１Ａを用いて、周波数５００ＭＨｚにおける電界波と磁界波のシールド性を測定した。この値は、電気用品安全法による製品試験値によって必要値が決まっていて、また製品から発生する周波数やその強さにも依存するため一概に決められる値ではないが、１０ｄＢ以上であることが好ましい。
(2) Electromagnetic shielding properties Using an injection molding machine (manufactured by Sumitomo Heavy Industries, SH100, mold clamping force 100T), resin temperature (measured temperature of purge resin): 290 ° C, mold temperature: 80 ° C, Mold: 100 mm long, 100 mm wide, 2 mm thick molded products were injection molded, and 5 pieces of the obtained injection molded products were used to measure electric field waves at a frequency of 500 MHz using TR-17301A and R3361A manufactured by Advantest Corporation. The shielding property of the magnetic field wave was measured. This value is determined by the product test value according to the Electrical Appliance and Material Safety Law, and is not generally determined because it depends on the frequency generated from the product and its strength, but it must be 10 dB or more. preferable.
（３）耐チョーク性
上記（２）電磁波シールド性と同様にして射出成形して得られた射出成形品について、そのエッジ部を白紙に擦ったときの紙面の着色具合を目視により観察することにより、耐チョーク性を「○：良好」、「×：不良」に分けて判定した。
(3) Choke resistance For the injection molded product obtained by injection molding in the same manner as the above (2) electromagnetic wave shielding property, by visually observing the coloring of the paper surface when the edge portion is rubbed against white paper The choke resistance was judged by dividing into “◯: good” and “×: bad”.
参考例１〜６、実施例７と比較例１〜３を比較することにより、特定の熱可塑性樹脂及び組成を有するポリマーアロイに、カーボンナノチューブと無機微粒子を配合することにより、導電性及び電磁波シールド性が改善されることが分かる。
さらに、無機微粒子の粒子径および添加量を制御することにより、電磁波シールド性が改善されることが分かる。
また、参考例１〜６、実施例７と比較例３を比較することにより、カーボンブラックを含むと導電性及び電磁波シールド性が改善されるものの耐チョーク性が低下することが分かる。
By comparing Reference Examples 1 to 6 and Example 7 and Comparative Examples 1 to 3, a polymer alloy having a specific thermoplastic resin and composition is blended with carbon nanotubes and inorganic fine particles, thereby providing conductivity and electromagnetic wave shielding. It can be seen that the sex is improved.
Furthermore, it can be seen that the electromagnetic wave shielding property is improved by controlling the particle size and the amount of the inorganic fine particles.
Further, by comparing Reference Examples 1 to 6 and Example 7 with Comparative Example 3, it can be seen that the inclusion of carbon black improves the conductivity and electromagnetic wave shielding properties but reduces the choke resistance.
なお、参考例１〜６、実施例７の樹脂組成物のペレットについて、成形片を切削し、そのＴＥＭ観察を行うことによりＰＣ樹脂とＡＳ樹脂とで形成される樹脂相を観察したところ、微細な共連続構造が形成されていることが確認された。また。カーボンナノチューブは、その殆ど全量がＰＣ樹脂の相中において、射出成形の方向に配向して分散していた。また、無機微粒子はＰＣとＡＳの界面に存在することが確認された。 In addition, about the pellet of the resin composition of Reference Examples 1-6 and Example 7 , when the resin phase formed by PC resin and AS resin was observed by cutting a molded piece and performing the TEM observation, it was fine. It was confirmed that a co-continuous structure was formed. Also. Almost all of the carbon nanotubes were oriented and dispersed in the direction of injection molding in the PC resin phase. Moreover, it was confirmed that the inorganic fine particles exist at the interface between PC and AS.
本発明の導電性樹脂組成物は、導電性及び電磁波シールド性に優れるため、その工業的有用性は大きい。また、それを用いた成形品は、ＯＡ機器、電気・電子部品、精密機器の筐体を始めとする、多くの分野に有用なものである。 Since the conductive resin composition of the present invention is excellent in conductivity and electromagnetic wave shielding properties, its industrial utility is great. In addition, a molded product using the same is useful in many fields including OA equipment, electrical / electronic parts, and precision equipment casings.
Ｘ：分割したＢ相の外周縁部上の点
θ：隣り合うベクトルが成す角度
X: Points on the outer peripheral edge of the divided B phase θ: Angle formed by adjacent vectors
Claims (6)
（Ａ）：熱可塑性樹脂（以下「熱可塑性樹脂Ａ」と称す。）
（Ｂ）：熱可塑性樹脂Ａより粘度が小さい熱可塑性樹脂（以下「熱可塑性樹脂Ｂ」と称す。）
（Ｃ）：カーボンナノチューブ
（Ｄ）：無機微粒子 A conductive resin composition comprising the following components (A) to (D), wherein a two-phase structure in which at least the (A) component by the (A) component and the (B) component can form a continuous phase is formed, (C) component is unevenly distributed in the phase composed of the component (a) of the two-phase structure thermoplastic resin a is a polycarbonate resin, a thermoplastic resin B is a styrene resin, an inorganic fine particles are silica A conductive resin composition, wherein the conductive resin composition is a fine particle and has an average primary particle diameter of 300 nm to 10 μm .
(A): Thermoplastic resin (hereinafter referred to as “thermoplastic resin A”)
(B): a thermoplastic resin having a viscosity lower than that of the thermoplastic resin A (hereinafter referred to as “thermoplastic resin B”).
(C): Carbon nanotube (D): Inorganic fine particles
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