JPH1135835A - Electroconductive resin composition - Google Patents
Electroconductive resin compositionInfo
- Publication number
- JPH1135835A JPH1135835A JP19529097A JP19529097A JPH1135835A JP H1135835 A JPH1135835 A JP H1135835A JP 19529097 A JP19529097 A JP 19529097A JP 19529097 A JP19529097 A JP 19529097A JP H1135835 A JPH1135835 A JP H1135835A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- conductive
- resin
- conductive resin
- thermoplastic resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、プラスチック発熱
体、ＩＣトレイ、マガジンレール等の帯電防止資材、電
磁波シールド材などに用いられる導電性樹脂組成物に関
する。The present invention relates to a conductive resin composition used for an antistatic material such as a plastic heating element, an IC tray, and a magazine rail, and an electromagnetic wave shielding material.
【０００２】[0002]
【従来の技術】従来、導電性を有する成形物は、カーボ
ンブラックやグラファイト、金属粉、金属繊維等の導電
性フィラーと熱可塑性樹脂とをバンバリーミキサー、ニ
ーダー、押出機等を用いて溶融混練した後、所望のペレ
ット形状に加工した導電性樹脂組成物を得、係る導電性
樹脂組成物を成形加工することによって得ていた。2. Description of the Related Art Conventionally, a molded article having conductivity has been prepared by melt-kneading a conductive filler such as carbon black, graphite, metal powder or metal fiber and a thermoplastic resin using a Banbury mixer, a kneader, an extruder or the like. Thereafter, a conductive resin composition processed into a desired pellet shape was obtained, and the conductive resin composition was obtained by molding.
【０００３】導電性樹脂組成物及びその成形加工物の導
電性の程度、即ち体積固有抵抗値（以下ＶＲと略す）の
大きさは、導電性樹脂組成物及びその成形加工物中の導
電性フィラーの種類とその量に依存する。つまり、導電
性フィラーをより多く含有すれば低抵抗となり、少なく
すれば高抵抗となり、また到達し得る導電度は用いる導
電性フィラーの種類によってほぼ確定する。[0003] The degree of conductivity of the conductive resin composition and the molded product thereof, that is, the magnitude of the volume resistivity (hereinafter abbreviated as VR) is determined by the conductive filler in the conductive resin composition and the molded product thereof. Depends on the type and amount. In other words, the higher the conductive filler content, the lower the resistance, and the lower the resistance, the higher the resistance. The achievable conductivity is almost determined by the type of the conductive filler used.
【０００４】従って、より低抵抗の導電性フィラーをよ
り多く含有すれば、より低抵抗の導電性樹脂組成物やそ
の成形加工物を得ることは可能であったが、ある程度高
抵抗、例えば１０2 〜１０6 Ω・ｃｍの導電性樹脂組成
物やその成形加工物を得ることは従来極めて難しかっ
た。導電性フィラーの含有量を低減せしめればＶＲを大
きくすることは容易ではあることは前記した次第である
が、導電性フィラーの含有量を低減せしめると導電性樹
脂組成物やその成形加工物中の導電性フィラー同士の接
触が不安定となり、ＶＲの製品間ばらつきが大きくなり
一定の抵抗値の製品を再現性良く、安定して供給するこ
とが極めて困難であった。例えば、ポリプロピレンにカ
ーボンブラックを分散せしめた場合についてそのカーボ
ンブラック含有量とＶＲのばらつきを検討したところ、
カーボン種によらず、ＶＲ＝１０2 を発現させ得る含有
量（約２０Ｖｏｌ％）を下回ると、図３に示すように急
激にＶＲのばらつきが大きくなる。[0004] Therefore, if more containing a lower resistance of the conductive filler, but there was possible to obtain a lower resistance of the conductive resin composition or its molded product, somewhat high resistivity, for example 10 2 Conventionally, it has been extremely difficult to obtain a conductive resin composition of 10 to 10 6 Ω · cm and a molded product thereof. It has been described above that it is easy to increase the VR if the content of the conductive filler is reduced, but if the content of the conductive filler is reduced, the content of the conductive resin composition or the molded product thereof is reduced. The contact between the conductive fillers becomes unstable, the variation between VRs increases, and it is extremely difficult to stably supply a product having a constant resistance value with good reproducibility. For example, when carbon black was dispersed in polypropylene and the carbon black content and the variation in VR were examined,
Regardless of the carbon type, if the content is lower than the content capable of expressing VR = 10 2 (about 20 Vol%), the variation in VR sharply increases as shown in FIG.
【０００５】ジュール熱を利用するプラスチック発熱体
のうち、並列電極型プラスチック発熱体の場合は、従来
の直列型の場合（１０0 〜１０1 Ω・ｃｍ）に比して、
１０ 4 Ω・ｃｍ前後の抵抗値が要求されるものである
が、製品の抵抗値が不均一になると、発熱ムラを生じる
ばかりでなく、部分的に極端に低抵抗の部分があるとこ
の部分が過熱し易く、安全上も好ましくない。また、押
出成形や射出成形により生産されるマガジンレール、Ｉ
Ｃトレイ等の帯電防止資材や電磁波シールド材には一般
的に１０2 〜１０6 Ω・ｃｍ程度の抵抗値が要求される
が、所望の抵抗値を達成すべく導電性フィラーの含有量
を低減せしめると、成形条件によって導電性フィラーの
分散状態が影響を受けやすくなり、製品間において抵抗
値がばらつくばかりでなく、１つの成形品中においても
部分的に低抵抗になったり高抵抗になったりするという
問題があった。さらに、射出成形の場合には、導電性フ
ィラーが流れ方向に配向し、その結果得られる成形品の
流れ方向とそれとは垂直の方向とでは大きく抵抗値が異
なるという問題もあった。[0005] Plastic heating element utilizing Joule heat
Of the parallel electrode type plastic heating elements,
Series type (100-101Ωcm)
10 FourΩ · cm resistance is required
However, if the resistance value of the product becomes uneven, heat generation unevenness will occur
Not only that, there are some parts with extremely low resistance
Is easily overheated, which is not preferable in terms of safety. Also, press
Magazine rails produced by injection molding or injection molding, I
Commonly used for antistatic materials such as C trays and electromagnetic wave shielding materials
10Two-106Ω · cm resistance is required
But the content of conductive filler to achieve the desired resistance value
Is reduced, the amount of conductive filler depends on molding conditions.
Dispersion is more sensitive and resistance between products
Not only does the value fluctuate, but also in one molded product
Partially low resistance or high resistance
There was a problem. In addition, in the case of injection molding, conductive
The filler is oriented in the flow direction and the resulting molded article
The resistance value differs greatly between the flow direction and the direction perpendicular to the flow direction.
There was also the problem of becoming.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、製品間及び
製品内の抵抗値のばらつきの少ない、ある程度高抵抗の
導電性樹脂組成物を安定して得ることを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to stably obtain a conductive resin composition having a relatively high resistance with little variation in resistance between products and within a product.
【０００７】[0007]
【課題を解決するための手段】即ち、第１の発明は、カ
ーボンブラック、グラファイト、金属粉、金属フレーク
及び金属酸化物よりなる群より選ばれる少なくとも１種
以上の導電性フィラーを熱可塑性樹脂（Ａ）中に分散せ
しめてなる導電性樹脂組成物（１）を、前記熱可塑性樹
脂（Ａ）とは異なる熱可塑性樹脂（Ｂ）中に分散せしめ
たことを特徴とする導電性樹脂組成物（２）である。That is, a first aspect of the present invention is to provide at least one kind of conductive filler selected from the group consisting of carbon black, graphite, metal powder, metal flake, and metal oxide with a thermoplastic resin ( The conductive resin composition (1) dispersed in the thermoplastic resin (A) is dispersed in a thermoplastic resin (B) different from the thermoplastic resin (A). 2).
【０００８】第２の発明は、導電性樹脂組成物（１）の
体積固有抵抗値が１０0 〜１０2 Ω・ｃｍであることを
特徴とする第１の発明記載の導電性樹脂組成物（２）で
ある。[0008] The second invention is a conductive resin composition (1) volume resistivity 10 0 ~10 2 Ω · cm conductive resin composition of the first invention, wherein it is the ( 2).
【０００９】第３の発明は、体積固有抵抗値が１０2 〜
１０6 Ω・ｃｍであることを特徴とする第１又は第２の
発明記載の導電性樹脂組成物（２）である。According to a third aspect of the present invention, the volume resistivity value is 10 2 to 10 2 .
The conductive resin composition (2) according to the first or second invention, which has a resistivity of 10 6 Ω · cm.
【００１０】第４の発明は、導電性樹脂組成物（１）中
に導電性フィラーを２０〜６０Ｖｏｌ％含有することを
特徴とする第１ないし第３の発明いずれか記載の導電性
樹脂組成物（２）である。A fourth aspect of the present invention is the conductive resin composition according to any one of the first to third aspects, wherein the conductive resin composition (1) contains 20 to 60% by volume of a conductive filler. (2).
【００１１】第５の発明は、導電性樹脂組成物（１）を
２０〜８０Ｖｏｌ％含有することを特徴とする第１ない
し第４の発明いずれか記載の導電性樹脂組成物（２）で
ある。A fifth invention is the conductive resin composition (2) according to any one of the first to fourth inventions, wherein the conductive resin composition (1) contains 20 to 80% by volume. .
【００１２】第６の発明は、熱可塑性樹脂（Ａ）がポリ
オレフィン系樹脂であり、熱可塑性樹脂（Ｂ）がポリス
チレン系樹脂、ポリアミド系樹脂、ポリエステル系樹脂
及びアクリル系樹脂からなる群より選ばれる少なくとも
１種以上であることを特徴とする第１ないし第５の発明
いずれか記載の導電性樹脂組成物（２）である。In a sixth aspect, the thermoplastic resin (A) is a polyolefin resin, and the thermoplastic resin (B) is selected from the group consisting of a polystyrene resin, a polyamide resin, a polyester resin, and an acrylic resin. The conductive resin composition (2) according to any one of the first to fifth inventions, which is at least one kind.
【００１３】第７の発明は、熱可塑性樹脂（Ａ）がポリ
スチレン系樹脂、ポリアミド系樹脂、ポリエステル系樹
脂及びアクリル系樹脂からなる群より選ばれる少なくと
も１種以上であり、熱可塑性樹脂（Ｂ）がポリオレフィ
ン系樹脂であることを特徴とする第１ないし第５の発明
いずれか記載の導電性樹脂組成物（２）である。According to a seventh aspect, the thermoplastic resin (A) is at least one selected from the group consisting of a polystyrene resin, a polyamide resin, a polyester resin and an acrylic resin, and the thermoplastic resin (B) Is a polyolefin-based resin, the conductive resin composition (2) according to any one of the first to fifth inventions.
【００１４】[0014]
【発明の実施の形態】本発明は、まず熱可塑性樹脂
（Ａ）中に導電性フィラーを比較的多く含有し、安定し
た低ＶＲを呈する導電性樹脂組成物（１）を得、次いで
係る導電性樹脂組成物（１）を前記熱可塑性樹脂（Ａ）
とは相溶し難い熱可塑性樹脂（Ｂ）中に分散させること
により、導電性樹脂組成物（１）と熱可塑性樹脂（Ｂ）
とがいわゆる「海島構造」を呈し、その結果導電性樹脂
組成物（１）中の導電性フィラー同士の安定した接触状
態を保ちながら、「島」である導電性樹脂組成物（１）
同士の接触が「海」である熱可塑性樹脂（Ｂ）によって
適度に寸断されるためにばらつきの少ない高抵抗の導電
性樹脂組成物（２）を得ることができるようになったも
のである。熱可塑性樹脂（Ａ）と熱可塑性樹脂（Ｂ）と
が相溶性が良く溶融混練によって容易に均一になってし
まうと、結局少量の導電性フィラーを熱可塑性樹脂中に
分散せしめた状態と同様となり、ＶＲが不安定になり、
製品間及び製品内ばらつきが大きくなる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention first obtains a conductive resin composition (1) which contains a relatively large amount of conductive filler in a thermoplastic resin (A) and exhibits a stable low VR. The thermoplastic resin (A) with the thermoplastic resin (A)
The conductive resin composition (1) and the thermoplastic resin (B) are dispersed in a thermoplastic resin (B) that is hardly compatible with
Exhibit a so-called "sea-island structure". As a result, the conductive resin composition (1) which is an "island" while maintaining a stable contact state between the conductive fillers in the conductive resin composition (1).
Since the mutual contact is appropriately cut by the thermoplastic resin (B) which is "sea", the conductive resin composition (2) having a small variation and a high resistance can be obtained. When the thermoplastic resin (A) and the thermoplastic resin (B) have good compatibility and are easily homogenized by melt-kneading, it becomes similar to a state in which a small amount of conductive filler is dispersed in the thermoplastic resin. , VR becomes unstable,
Variations between products and within products increase.
【００１５】本発明において用いられる導電性フィラー
としては、カーボンブラック、グラファイト、金属粉、
金属フレーク及び金属酸化物が挙げられ、成形品の軽量
化の点からはカーボンブラック、グラファイトが好まし
く、また成形品を黒色にはしたくない場合には、金属粉
や金属フレークが好適に用いられる。また、これらの導
電性フィラーは２種以上を併用しても良い。The conductive filler used in the present invention includes carbon black, graphite, metal powder,
Metal flakes and metal oxides are mentioned, and carbon black and graphite are preferred from the viewpoint of reducing the weight of the molded product.If the molded product is not desired to be black, metal powder and metal flakes are suitably used. . Further, two or more of these conductive fillers may be used in combination.
【００１６】本発明における熱可塑性樹脂（Ａ）、
（Ｂ）とは、熱可塑性樹脂及び熱可塑性エラストマーを
包含するものであり、本発明において導電性樹脂組成物
（１）を得るために用いられる熱可塑性樹脂（Ａ）とし
ては、ポリオレフィン系樹脂、ポリスチレン系樹脂、ポ
リアミド系樹脂、ポリエステル系樹脂、アクリル系樹脂
が挙げられる。ポリオレフィン系樹脂としては、ポリエ
チレン、ポリプロピレンの他にポリプロピレン骨格にＥ
ＰＭ（エチレン−プロピレン−メチレンゴム）やＥＰＤ
Ｍ（エチレン−プロピレン−ジエン−メチレンゴム）等
を部分架橋させたエラストマーが挙げられ、ポリエステ
ル系樹脂としては、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等のホモポリマーの他に、ポリ
ブチレンテレフタレート骨格にエーテルゴムを物理的に
架橋させたエラストマー等が挙げられる。The thermoplastic resin (A) according to the present invention,
(B) includes a thermoplastic resin and a thermoplastic elastomer, and the thermoplastic resin (A) used to obtain the conductive resin composition (1) in the present invention includes a polyolefin resin, Polystyrene-based resin, polyamide-based resin, polyester-based resin, and acrylic-based resin are exemplified. As polyolefin resin, besides polyethylene and polypropylene, E
PM (ethylene-propylene-methylene rubber) and EPD
M (ethylene-propylene-diene-methylene rubber) and the like are partially crosslinked. As the polyester resin, in addition to homopolymers such as polyethylene terephthalate and polybutylene terephthalate, ether rubber is used as a polybutylene terephthalate skeleton. Examples include physically crosslinked elastomers.
【００１７】一方、本発明において用いられる熱可塑性
樹脂（Ｂ）としては、成形品の用途に応じて適宜選択
し、前記熱可塑性樹脂（Ａ）とは異なる種類のものであ
ればよく、例えば、熱可塑性樹脂（Ａ）としてポリオレ
フィン系の樹脂を用いるのならば熱可塑性樹脂（Ｂ）と
しては、ポリスチレン系樹脂、ポリアミド系樹脂、ポリ
エステル系樹脂、アクリル系樹脂を用いればよいし、逆
に熱可塑性樹脂（Ｂ）としてポリオレフィン系の樹脂を
用いるのならば熱可塑性樹脂（Ａ）としては、ポリスチ
レン系樹脂、ポリアミド系樹脂、ポリエステル系樹脂、
アクリル系樹脂を用いればよい。尚、ポリスチレン系樹
脂、ポリアミド系樹脂、ポリエステル系樹脂、アクリル
系樹脂は互いに異種の熱可塑性樹脂であるので、これら
のうちの１種を熱可塑性樹脂（Ａ）として、その１種以
外の樹脂を熱可塑性樹脂（Ｂ）として用いることもでき
る。On the other hand, the thermoplastic resin (B) used in the present invention may be appropriately selected depending on the use of the molded article, and may be of a different type from the thermoplastic resin (A). If a polyolefin resin is used as the thermoplastic resin (A), a polystyrene resin, a polyamide resin, a polyester resin, or an acrylic resin may be used as the thermoplastic resin (B). If a polyolefin resin is used as the resin (B), as the thermoplastic resin (A), a polystyrene resin, a polyamide resin, a polyester resin,
An acrylic resin may be used. Since the polystyrene resin, the polyamide resin, the polyester resin, and the acrylic resin are different types of thermoplastic resins, one of them is referred to as a thermoplastic resin (A), and the other resin is used. It can also be used as a thermoplastic resin (B).
【００１８】導電性樹脂組成物（１）は、導電フィラー
と熱可塑性樹脂（Ａ）とをニーダー、バンバリーミキサ
ー、単軸および２軸押出機、コニーダー、ＦＣＭ等の混
練機を用いて溶融混練することによって得ることができ
る。溶融混練後、ペレット化することが望ましい。The conductive resin composition (1) is melt-kneaded with a conductive filler and a thermoplastic resin (A) using a kneader such as a kneader, a Banbury mixer, a single-screw or twin-screw extruder, a co-kneader, or an FCM. Can be obtained by: After melt-kneading, it is desirable to form pellets.
【００１９】導電性樹脂組成物（１）のＶＲは、１０0
〜１０2 Ω・ｃｍであることが好ましく、かかるＶＲを
安定的に発現せしめるためには用いる導電フィラーの種
類にもよるが、導電性樹脂組成物（１）中に導電フィラ
ーを２０〜６０Ｖｏｌ％含有せしめることが好ましい。
２０Ｖｏｌ％未満だと、十分安定したＶＲを有すること
が困難となり、一方、６０Ｖｏｌ％を越えると混練が困
難となる。混練の作業性を考えると２０〜４０Ｖｏｌ％
の範囲がさらに望ましい。尚、「Ｖｏｌ％」は、使用す
る導電性フィラー及び熱可塑性樹脂の重量をそれぞれ比
重で除して、それぞれの占める体積を求め、その割合を
求めたものである。[0019] VR of the conductive resin composition (1) 10 0
Is preferably ~10 2 Ω · cm, depending on the kind of the conductive filler used is such VR to allowed to stably express, a conductive resin composition (1) 20~60Vol% conductive filler in It is preferable to include them.
If it is less than 20 vol%, it is difficult to have a sufficiently stable VR, while if it exceeds 60 vol%, kneading becomes difficult. 20-40% by volume considering the workability of kneading
Is more desirable. In addition, "Vol%" is obtained by dividing the weight of the conductive filler and the thermoplastic resin to be used by the specific gravity to obtain the volume occupied by each, and obtaining the ratio.
【００２０】本発明の導電性樹脂組成物（２）は、上記
導電性樹脂組成物（１）と熱可塑性樹脂（Ｂ）とを汎用
的に用いられる混練機、例えばニーダー、バンバリーミ
キサー、単軸および２軸押出機、コニーダー、ＦＣＭ等
を用いて混練すれば良いが、導電フィラーと熱可塑性樹
脂（Ａ）とを混練する際ほどは、強く混練する必要はな
い。The conductive resin composition (2) of the present invention can be obtained by kneading the conductive resin composition (1) and the thermoplastic resin (B) for general use, for example, a kneader, a Banbury mixer, a single shaft. Kneading may be performed using a twin-screw extruder, a kneader, an FCM, or the like, but it is not necessary to knead as strongly as when kneading the conductive filler and the thermoplastic resin (A).
【００２１】本発明の導電性樹脂組成物（２）のＶＲ
は、１０2 〜１０6 Ω・ｃｍであることが好ましく、か
かるＶＲを安定的に発現せしめるためには用いる導電フ
ィラーの種類にもよるが、導電性樹脂組成物（１）を導
電性樹脂組成物（２）中に２０〜８０Ｖｏｌ％含有せし
めることが好ましい。２０Ｖｏｌ％未満だと、導電性樹
脂組成物（１）の「島」が少なくなり「島」同士の接触
が極めて疎になる結果、導電性樹脂組成物のＶＲが所望
のＶＲよりも大きくなるとともに不安定になり易い。一
方、８０Ｖｏｌ％を越えると、導電性樹脂組成物（１）
の「島」が多くなり「島」同士の接触も増える結果、導
電性樹脂組成物（２）のＶＲが低下する傾向にある。所
望の抵抗値とその安定性とを考慮すると２０〜５０Ｖｏ
ｌ％の範囲がさらに望ましい。VR of the conductive resin composition (2) of the present invention
Is preferably 10 2 to 10 6 Ω · cm, and depending on the type of conductive filler used to stably exhibit such VR, the conductive resin composition (1) may be It is preferred that 20 to 80 Vol% be contained in the product (2). When the content is less than 20% by volume, the "islands" of the conductive resin composition (1) are reduced and the contact between the "islands" becomes extremely sparse, so that the VR of the conductive resin composition becomes larger than a desired VR. Easy to become unstable. On the other hand, if it exceeds 80% by volume, the conductive resin composition (1)
As a result, the number of “islands” increases and the contact between “islands” increases, and as a result, the VR of the conductive resin composition (2) tends to decrease. Considering a desired resistance value and its stability, 20 to 50 Vo
A range of 1% is more desirable.
【００２２】尚、本発明者らの検討によれば、導電性フ
ィラーとしてカーボンブラックを、熱可塑性樹脂（Ａ）
としてポリエステルエラストマーを用い、導電性樹脂組
成物（１）を得、この導電性樹脂組成物（１）の粉砕粒
度を６０メッシュ以上と以下の２種類を作成し、熱可塑
性樹脂（Ｂ）である低密度ポリエチレン中に２種類の粒
度の導電性樹脂組成物（１）をそれぞれ加熱しながら２
本ロールにて剪断力を僅かに加えて導電性樹脂組成物
（２）を得、ＶＲのばらつき度（標準偏差／平均値）を
評価したところ、６０メッシュ以上品は以下品にくら
べ、ばらつき度が４倍大きくなる。従って、より短時
間、より小さなエネルギーで導電性樹脂組成物のＶＲを
安定化すべく、より均一な「海島構造」を達成し得るた
めには、導電性樹脂組成物（１）を熱可塑性樹脂（Ｂ）
中に分散せしめるに際し、導電性樹脂組成物（１）の大
きさをより小さくすることが好ましい。According to the study of the present inventors, carbon black was used as a conductive filler and thermoplastic resin (A)
A conductive resin composition (1) is obtained using a polyester elastomer as a thermoplastic resin (B). The conductive resin composition (1) has a pulverized particle size of 60 mesh or more and the following two types, and is a thermoplastic resin (B). While heating the conductive resin composition (1) having two particle sizes in low-density polyethylene,
The conductive resin composition (2) was obtained by slightly applying a shearing force with this roll, and the degree of variation (standard deviation / average value) of VR was evaluated. Is four times larger. Therefore, in order to stabilize the VR of the conductive resin composition in a shorter time and with smaller energy, and to achieve a more uniform “sea-island structure”, the conductive resin composition (1) is made of a thermoplastic resin ( B)
In dispersing the conductive resin composition in the conductive resin composition, it is preferable to reduce the size of the conductive resin composition (1).
【００２３】さらに、本発明は、熱可塑性樹脂（Ａ）、
（Ｂ）が互いに相溶し難いことが重要であるが、全く相
溶性がないと導電性樹脂組成物（２）中において導電性
樹脂組成物（１）の「島」が極端に大きくなり、安定し
たＶＲが得にくくなるので、導電性樹脂組成物（１）を
熱可塑性樹脂（Ｂ）中に分散せしめるに際し、必要に応
じて若干量の相溶化剤、例えばマレイン酸変性ポリエチ
レン等を用いてもよい。The present invention further provides a thermoplastic resin (A),
It is important that (B) is hardly compatible with each other, but if there is no compatibility at all, the “islands” of the conductive resin composition (1) in the conductive resin composition (2) become extremely large, Since it becomes difficult to obtain a stable VR, when dispersing the conductive resin composition (1) in the thermoplastic resin (B), a small amount of a compatibilizer, for example, maleic acid-modified polyethylene or the like may be used as necessary. Is also good.
【００２４】[0024]
【実施例１】 ポリエステルエラストマー（ハイトレル
４７６７ 東レデュポン社製）７５Ｖｏｌ％とカーボ
ンブラック（バルカン９Ａ３２ キャボット社製）２５
Ｖｏｌ％をバンバリーミキサーにて５分間混練し、ペレ
ット状の導電性樹脂組成物（１）を得た。得られた導電
性樹脂組成物（１−１）のＶＲは３．２Ω・ｃｍであっ
た。次いで、得られた導電性樹脂組成物（１−１）３５
Ｖｏｌ％とＰＰエラストマー（ミラストマーＭ４４０
０、三井石油化学工業製）６５Ｖｏｌ％をＬ／Ｄ＝３
０、ダルメージスクリュー入り単軸押出機で２３０℃で
溶融混練しペレット状の導電性樹脂組成物（２−１）を
得た。得られたペレットを用いて、４８mm×３０mm×２
mmの射出成形試験片を得、得られた試験片について流れ
方向と流れに垂直方向のＶＲを測定した。また、前記の
ペレット状の導電性樹脂組成物を用いて、成形温度を変
えて直径２mmの押出成形試験片（ストランド）を得、得
られた試験片についてＶＲを測定した。結果を表１に示
す。Example 1 75% by volume of polyester elastomer (Hytrel 4767 manufactured by Toray DuPont) and carbon black (Vulcan 9A32 manufactured by Cabot) 25
Vol% was kneaded with a Banbury mixer for 5 minutes to obtain a pellet-shaped conductive resin composition (1). VR of the obtained conductive resin composition (1-1) was 3.2 Ω · cm. Next, the obtained conductive resin composition (1-1) 35
Vol% and PP elastomer (Millastomer M440)
0, manufactured by Mitsui Petrochemical Industries) 65 Vol% L / D = 3
0, and melt-kneaded at 230 ° C. with a single screw extruder containing a dalmage screw to obtain a pellet-shaped conductive resin composition (2-1). Using the obtained pellets, 48mm x 30mm x 2
Injection-molded test specimens of mm were obtained, and the obtained test specimens were measured for VR in the flow direction and the direction perpendicular to the flow. Further, an extruded test piece (strand) having a diameter of 2 mm was obtained using the above-mentioned pellet-shaped conductive resin composition while changing the molding temperature, and the VR of the obtained test piece was measured. Table 1 shows the results.
【００２５】[0025]
【実施例２】 ナイロン１２（ダイアミドＬ１９０１
ダイセル・ヒュルス社製）７０Ｖｏｌ％と、人造グラフ
ァイト（ＰＯＧ４０ エスイーシー社製）３０Ｖｏｌ％
をＬ／Ｄ＝２８の２軸押出機にて２２０℃で溶融混練
後、ペレット状の導電性樹脂組成物（１−２）とした。
得られた導電性樹脂組成物（１−２）のＶＲは７．５Ω
・ｃｍであった。次いで、得られた導電性樹脂組成物
（１−２）４０Ｖｏｌ％とブロックＰＰ（ハイポールＪ
３４０ 三井石油化学社製）６０Ｖｏｌ％を実施例１と
同様に混練し、ペレット状の導電性樹脂組成物（２−
２）を得、実施例１と同様にして射出成形試験片及び押
出成形試験片を得、同様にＶＲを測定した。結果を表２
に示す。Example 2 Nylon 12 (Diamid L1901)
70% by volume of Daicel Huls and 30% by volume of artificial graphite (POG40 manufactured by SSC)
Was melt-kneaded at 220 ° C. in a twin-screw extruder with L / D = 28 to obtain a pellet-shaped conductive resin composition (1-2).
VR of the obtained conductive resin composition (1-2) is 7.5Ω.
Cm. Subsequently, 40 Vol% of the obtained conductive resin composition (1-2) and block PP (Hypol J
340 Mitsui Petrochemical Co., Ltd.) 60 Vol% was kneaded in the same manner as in Example 1, and the conductive resin composition (2-
2) was obtained, and an injection molded test piece and an extruded test piece were obtained in the same manner as in Example 1, and the VR was measured in the same manner. Table 2 shows the results
Shown in
【００２６】[0026]
【実施例３】 実施例１で作成した導電性樹脂組成物
（１−３）３５Ｖｏｌ％とＰＰエラストマー（ミラスト
マーＭ４４００Ｎ）６３．５Ｖｏｌ％、さらに相溶化剤
としてマレイン酸変性ＰＰ（ユーメックス１０１０ 三
洋化成工業製）１．５Ｖｏｌ％を用い、実施例１と同様
にして、ペレット状の導電性樹脂組成物（２−３）を
得、実施例１と同様にして射出成形試験片及び押出成形
試験片を得、同様にＶＲを測定した。結果を表３に示
す。Example 3 35% by volume of the conductive resin composition (1-3) prepared in Example 1 and 63.5% by volume of PP elastomer (Milastomer M4400N), and maleic acid-modified PP (UMEX 1010 SANYO CHEMICAL INDUSTRIES, LTD.) As a compatibilizer Using 1.5 Vol%, a pellet-shaped conductive resin composition (2-3) was obtained in the same manner as in Example 1, and an injection-molded test piece and an extrusion-molded test piece were formed in the same manner as in Example 1. Obtained and measured VR similarly. Table 3 shows the results.
【００２７】[0027]
【比較例１】 ＰＰエラストマー（ミラストマーＭ４４
００Ｎ）９１Ｖｏｌ％と、カーボンブラック（バルカン
９Ａ３２）９Ｖｏｌ％をバンバリーミキサーにてて５分
間混練し、ペレット状のた導電性樹脂組成物を得た。得
られた導電性樹脂組成物について実施例１と同様にし
て、射出成形試験片及び押出成形試験片を得、同様にＶ
Ｒを測定した。結果を表１に示す。Comparative Example 1 PP Elastomer (Millastomer M44)
(00N) 91% by volume and 9% by volume of carbon black (Vulcan 9A32) were kneaded with a Banbury mixer for 5 minutes to obtain a pellet-shaped conductive resin composition. An injection molded test piece and an extruded test piece were obtained in the same manner as in Example 1 for the obtained conductive resin composition.
R was measured. Table 1 shows the results.
【００２８】[0028]
【比較例２】 ブロックＰＰ（ハイポールＪ３４０）８
８Ｖｏｌ％と、人造グラファイト（ＰＯＧ４０ エスイ
ーシー社製）７０重量％をＬ／Ｄ＝２８の２軸押出機に
て２２０℃で溶融混練後、ペレット状のた導電性樹脂組
成物を得た。得られた導電性樹脂組成物について実施例
１と同様にして、射出成形試験片及び押出成形試験片を
得、同様にＶＲを測定した。結果を表２に示す。Comparative Example 2 Block PP (Hypole J340) 8
8 Vol% and 70% by weight of artificial graphite (manufactured by POG40 S.C.) were melt-kneaded at 220 ° C. in a twin screw extruder with L / D = 28 to obtain a pellet-shaped conductive resin composition. For the obtained conductive resin composition, an injection molded test piece and an extrusion molded test piece were obtained in the same manner as in Example 1, and the VR was measured in the same manner. Table 2 shows the results.
【００２９】[0029]
【表１】 [Table 1]
【００３０】[0030]
【表２】 [Table 2]
【００３１】[0031]
【表３】 [Table 3]
【００３２】[0032]
【発明の効果】少量の導電フィラーを熱可塑性樹脂中に
直接混練する従来の方法に比べ、導電フィラーを高濃度
に分散させた導電性樹脂組成物（１）を相溶性の悪い熱
可塑性樹脂（Ｂ）中に分散せしめることによって、比較
的高いＶＲでありながらＶＲのばらつきの小さな導電性
樹脂組成物（２）を安定的に得ることができるようにな
った。According to the present invention, the conductive resin composition (1) in which the conductive filler is dispersed at a high concentration is compared with the conventional method in which a small amount of the conductive filler is directly kneaded in the thermoplastic resin. By dispersing in B), a conductive resin composition (2) having a relatively high VR and a small variation in VR can be stably obtained.
【図１】 本発明の導電性樹脂組成物（２）中における
導電性樹脂組成物（１）、及び導電性樹脂組成物（１）
中の導電性フィラーの分散状態の模式図。FIG. 1 shows a conductive resin composition (1) and a conductive resin composition (1) in a conductive resin composition (2) of the present invention.
FIG. 3 is a schematic view of a dispersed state of a conductive filler therein.
【図２】 従来の高抵抗の場合の導電性フィラーの分散
状態の模式図。FIG. 2 is a schematic view showing a state of dispersion of a conductive filler in the case of a conventional high resistance.
【図３】 カーボンブラックをポリプロピレン樹脂に添
加した場合の、カーボンブラックの含有量と体積固有抵
抗値のばらつき度の関係を示すグラフ。FIG. 3 is a graph showing the relationship between the carbon black content and the degree of variation in volume resistivity when carbon black is added to a polypropylene resin.
【符号の説明】 ：導電性樹脂組成物（１） ：導電フィラー ：熱可塑性樹脂（Ｂ） ：熱可塑性樹脂[Description of Signs]: Conductive resin composition (1): Conductive filler: Thermoplastic resin (B): Thermoplastic resin
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０８Ｌ 25/04 Ｃ０８Ｌ 25/04 33/08 33/08 67/00 67/00 77/00 77/00 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C08L 25/04 C08L 25/04 33/08 33/08 67/00 67/00 77/00 77/00
Claims (7)
粉、金属フレーク及び金属酸化物よりなる群より選ばれ
る少なくとも１種以上の導電性フィラーを熱可塑性樹脂
（Ａ）中に分散せしめてなる導電性樹脂組成物（１）
を、前記熱可塑性樹脂（Ａ）とは異なる熱可塑性樹脂
（Ｂ）中に分散せしめたことを特徴とする導電性樹脂組
成物（２）。1. A conductive resin composition obtained by dispersing at least one or more conductive fillers selected from the group consisting of carbon black, graphite, metal powder, metal flakes and metal oxides in a thermoplastic resin (A). Things (1)
Is dispersed in a thermoplastic resin (B) different from the thermoplastic resin (A). (2) A conductive resin composition (2).
値が１０0 〜１０2 Ω・ｃｍであることを特徴とする請
求項１記載の導電性樹脂組成物（２）。2. A conductive resin composition (1) volume resistivity 10 0 ~10 2 Ω · cm conductive resin composition according to claim 1, characterized in that the (2).
ｍであることを特徴とする請求項１又は２記載の導電性
樹脂組成物（２）。3. A volume resistivity value of 10 2 to 10 6 Ω · c.
The conductive resin composition (2) according to claim 1 or 2, wherein m is m.
ラーを２０〜６０Ｖｏｌ％含有することを特徴とする請
求項１ないし３いずれか記載の導電性樹脂組成物
（２）。4. The conductive resin composition (2) according to claim 1, wherein the conductive resin composition (1) contains 20 to 60% by volume of a conductive filler.
ｏｌ％含有することを特徴とする請求項１ないし４いず
れか記載の導電性樹脂組成物（２）。5. A conductive resin composition (1) having a voltage of 20 to 80 V
The conductive resin composition (2) according to any one of Claims 1 to 4, wherein the conductive resin composition (2) contains ol%.
樹脂であり、熱可塑性樹脂（Ｂ）がスチレン系樹脂、ポ
リアミド系樹脂、ポリエステル系樹脂及びアクリル系樹
脂からなる群より選ばれる少なくとも１種以上であるこ
とを特徴とする請求項１ないし５いずれか記載の導電性
樹脂組成物（２）。6. The thermoplastic resin (A) is a polyolefin resin, and the thermoplastic resin (B) is at least one selected from the group consisting of a styrene resin, a polyamide resin, a polyester resin, and an acrylic resin. The conductive resin composition (2) according to any one of claims 1 to 5, wherein
脂、ポリアミド系樹脂、ポリエステル系樹脂及びアクリ
ル系樹脂からなる群より選ばれる少なくとも１種以上で
あり、熱可塑性樹脂（Ｂ）がポリオレフィン系樹脂であ
ることを特徴とする請求項１ないし５いずれか記載の導
電性樹脂組成物（２）。7. The thermoplastic resin (A) is at least one selected from the group consisting of a polystyrene resin, a polyamide resin, a polyester resin and an acrylic resin, and the thermoplastic resin (B) is a polyolefin resin. The conductive resin composition (2) according to any one of claims 1 to 5, wherein
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19529097A JP3463520B2 (en) | 1997-07-22 | 1997-07-22 | Conductive resin composition and molded product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19529097A JP3463520B2 (en) | 1997-07-22 | 1997-07-22 | Conductive resin composition and molded product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1135835A true JPH1135835A (en) | 1999-02-09 |
| JP3463520B2 JP3463520B2 (en) | 2003-11-05 |
Family
ID=16338701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19529097A Expired - Fee Related JP3463520B2 (en) | 1997-07-22 | 1997-07-22 | Conductive resin composition and molded product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3463520B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001021713A1 (en) * | 1999-09-24 | 2001-03-29 | The Yokohama Rubber Co., Ltd. | Thermoplastic resin composition and method for producing the same |
| JP2001254022A (en) * | 2000-01-07 | 2001-09-18 | Fuji Xerox Co Ltd | Semiconductive member, semiconductive belt, semiconductive roll, and image formation apparatus |
| WO2006049139A1 (en) * | 2004-11-04 | 2006-05-11 | Lion Corporation | Electroconductive masterbatch and resin composition including the same |
| JP2012122057A (en) * | 2010-11-15 | 2012-06-28 | Nagoya Institute Of Technology | Inorganic organic composite composition |
| KR101349029B1 (en) * | 2012-04-04 | 2014-01-10 | 현대자동차주식회사 | Composite for shielding broadband electromagnetic wave |
| US9050774B2 (en) | 2010-04-30 | 2015-06-09 | Fujifilm Corporation | Antistatic laminate, optical film, polarizing plate, and image display device |
-
1997
- 1997-07-22 JP JP19529097A patent/JP3463520B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001021713A1 (en) * | 1999-09-24 | 2001-03-29 | The Yokohama Rubber Co., Ltd. | Thermoplastic resin composition and method for producing the same |
| JP2001254022A (en) * | 2000-01-07 | 2001-09-18 | Fuji Xerox Co Ltd | Semiconductive member, semiconductive belt, semiconductive roll, and image formation apparatus |
| WO2006049139A1 (en) * | 2004-11-04 | 2006-05-11 | Lion Corporation | Electroconductive masterbatch and resin composition including the same |
| US7914708B2 (en) | 2004-11-04 | 2011-03-29 | Lion Corporation | Conductive masterbatch and resin composition including the same |
| JP5221876B2 (en) * | 2004-11-04 | 2013-06-26 | ライオン株式会社 | Conductive masterbatch and resin composition containing the same |
| US9050774B2 (en) | 2010-04-30 | 2015-06-09 | Fujifilm Corporation | Antistatic laminate, optical film, polarizing plate, and image display device |
| JP2012122057A (en) * | 2010-11-15 | 2012-06-28 | Nagoya Institute Of Technology | Inorganic organic composite composition |
| KR101349029B1 (en) * | 2012-04-04 | 2014-01-10 | 현대자동차주식회사 | Composite for shielding broadband electromagnetic wave |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3463520B2 (en) | 2003-11-05 |
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