JP2003160673A - Resin composition for electromagnetic wave shielding and utilization thereof - Google Patents
Resin composition for electromagnetic wave shielding and utilization thereofInfo
- Publication number
- JP2003160673A JP2003160673A JP2002025198A JP2002025198A JP2003160673A JP 2003160673 A JP2003160673 A JP 2003160673A JP 2002025198 A JP2002025198 A JP 2002025198A JP 2002025198 A JP2002025198 A JP 2002025198A JP 2003160673 A JP2003160673 A JP 2003160673A
- Authority
- JP
- Japan
- Prior art keywords
- electromagnetic wave
- wave shielding
- fiber
- metal
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、金属コート有機繊
維を含む電磁波シールド用樹脂組成物、及びその利用に
関する。TECHNICAL FIELD The present invention relates to an electromagnetic wave shielding resin composition containing a metal-coated organic fiber, and its use.
【０００２】[0002]
【従来の技術】電磁波シールド性能を付与したプラスチ
ック成形品を製造する場合、熱可塑性樹脂と導電性繊維
とを含有したペレット状等の樹脂組成物が用いられる。
この導電性繊維は、長繊維を一方向に揃えた状態で熱可
塑性樹脂が含浸されたものであり、電磁波シールド性能
を有する射出成形品の材料として評価されている。導電
性繊維としてステンレス繊維、炭素繊維、金属コートガ
ラス繊維、金属コート炭素繊維、はんだを銅繊維にコー
トしたもの等の繊維が用いられているが、これらの中で
最も一般的に使用されているのは、ステンレス繊維と炭
素繊維、金属コート炭素繊維である。2. Description of the Related Art In the case of producing a plastic molded article having electromagnetic wave shielding performance, a pellet-like resin composition containing a thermoplastic resin and a conductive fiber is used.
This conductive fiber is one in which long fibers are aligned in one direction and is impregnated with a thermoplastic resin, and is evaluated as a material for an injection molded product having electromagnetic wave shielding performance. As the conductive fibers, stainless fibers, carbon fibers, metal-coated glass fibers, metal-coated carbon fibers, copper fibers coated with solder, etc. are used, but most commonly used among these. Are stainless steel fibers, carbon fibers, and metal-coated carbon fibers.
【０００３】これらの導電性繊維を用いた電磁波シール
ド用樹脂組成物から成る成形品は優れた特徴を有してい
る。例えばステンレス繊維を用いた成形品においては、
熱可塑性樹脂を含浸したステンレス繊維ペレット８〜１
５重量％程度の含有量で電磁波シールド性能を発現させ
ることができる。また、ステンレスの比重は８程度と大
きく、成形品におけるステンレスの体積分率は１〜２％
強程度になるため、機械特性を大きく損なう事が無く成
形品が得られる。Molded articles made of the resin composition for electromagnetic wave shielding using these conductive fibers have excellent characteristics. For example, in a molded product using stainless fiber,
Stainless fiber pellets 8 to 1 impregnated with thermoplastic resin
The electromagnetic wave shielding performance can be exhibited with a content of about 5% by weight. Further, the specific gravity of stainless steel is as high as about 8, and the volume fraction of stainless steel in the molded product is 1 to 2%.
Since the strength is high, a molded product can be obtained without significantly impairing the mechanical properties.
【０００４】[0004]
【発明が解決しようとする課題】しかし、このステンレ
ス繊維ペレットは、ステンレス繊維を７０〜８０重量％
含有しているため、ペレットの比重が２．５〜３．５程
度になる。そして、このペレットと成形用の熱可塑性樹
脂ペレットとの比重差が大きいため、攪拌混合の際に比
重差分離が生じ、均一化されることが難しかった。ま
た、射出成形機のホッパーに投入する際に配合状態がよ
り不均一になるので、一般に使用されている空送機が使
用できなかった。そして、各ペレットが均一に混合され
ないまま偏在した状態で成形されるため、成形ショット
の最初と最後では電磁波シールド性能や機械強度等の品
質が不均一になる原因となっていた。However, this stainless fiber pellet contains 70 to 80% by weight of stainless fiber.
Since it is contained, the specific gravity of the pellet becomes about 2.5 to 3.5. Since the difference in specific gravity between the pellets and the thermoplastic resin pellets for molding is large, specific gravity difference separation occurs during stirring and mixing, and it is difficult to make them uniform. In addition, since the blending state becomes more uneven when it is put into the hopper of an injection molding machine, a commonly used air-feeding machine cannot be used. Since each pellet is molded in a non-uniformly distributed state without being uniformly mixed, the quality of electromagnetic wave shielding performance, mechanical strength and the like becomes uneven at the beginning and end of the molding shot.
【０００５】電磁波シールド性能が規定以上でなけれ
ば、成形品内部に組み込まれる電子部品を誤動作させて
しまったり、安定した電磁波シールド性能が発揮されな
かったりして電子機器のハウジング用材料としての適正
を欠くおそれがあった。また、成形品における電磁波シ
ールド性能のバラツキを避けるための小規模生産では生
産効率の低下が生じコスト高の原因となっていた。If the electromagnetic wave shielding performance is not more than the specified value, the electronic parts incorporated in the molded product may malfunction, or the stable electromagnetic wave shielding performance may not be exhibited, so that the material is not suitable as a housing material for electronic equipment. There was a risk of missing. Further, in small-scale production for avoiding variations in electromagnetic wave shielding performance of molded products, production efficiency is reduced, resulting in high costs.
【０００６】また、炭素繊維の場合は３０〜４０重量％
程度の含有量で成形品に電磁波シールド性能を付与でき
る為、機械的特性において剛性は大きくなり、成形後の
収縮率が低いので寸法精度は高くなるが、柔軟性は乏し
く面衝撃強度が低下する点で、成形材料として適性が充
分あるとはいえなかった。そして、炭素繊維を配合によ
って熱可塑性樹脂の流動性が低くなることでショートシ
ョット（成型用金型の奥まで樹脂が流れないために生じ
る成形不良現象）になる場合もあった。その上、炭素繊
維は硬度が高く、そのために金型や射出成形機のスクリ
ュウ、バレルの磨耗を早めること等の加工上の問題も生
じていた。In the case of carbon fiber, 30-40% by weight
Since electromagnetic shielding performance can be imparted to molded products with a small amount of content, rigidity is high in mechanical properties and dimensional accuracy is high because the shrinkage rate after molding is low, but flexibility is poor and surface impact strength decreases. In this respect, it could not be said that it was sufficiently suitable as a molding material. In addition, the fluidity of the thermoplastic resin becomes low due to the addition of carbon fiber, which may result in a short shot (a defective molding phenomenon caused by the resin not flowing deep into the molding die). In addition, carbon fiber has a high hardness, which causes processing problems such as accelerated wear of the mold, the screw of the injection molding machine, and the barrel.
【０００７】金属コート炭素繊維においては、上記炭素
繊維より少ない１５〜３０重量％程度の含有量で成形品
に電磁波シールド性能を付与できるが、炭素繊維と同様
に機械的特性において剛性は大きくなり、成形後の収縮
率が低いので寸法精度は高くなるが柔軟性は乏しい。ま
た、炭素繊維より含有量が少ないので面衝撃強度や射出
成形機のスクリュウ、バレルの磨耗は改善されたが、成
形材料として充分とはいえなかった。In the metal-coated carbon fiber, the electromagnetic wave shielding performance can be imparted to the molded product with a content of about 15 to 30% by weight, which is smaller than that of the above-mentioned carbon fiber, but the rigidity becomes large in the mechanical property like carbon fiber. Since the shrinkage rate after molding is low, the dimensional accuracy is high, but the flexibility is poor. Further, since its content is smaller than that of carbon fiber, surface impact strength and abrasion of the screw and barrel of the injection molding machine were improved, but it was not sufficient as a molding material.
【０００８】[0008]
【課題を解決するための手段】すなわち、本発明の第１
の発明は、熱可塑性樹脂（ａ）を含浸した金属コート有
機繊維を含むことを特徴とする電磁波シールド用樹脂組
成物である。That is, the first aspect of the present invention
The invention of No. 1 is a resin composition for electromagnetic wave shielding, which comprises a metal-coated organic fiber impregnated with a thermoplastic resin (a).
【０００９】本発明の第２の発明は、第1の発明に記載
の電磁波シールド用樹脂組成物と熱可塑性樹脂（ｂ）と
から成る成形品である。A second invention of the present invention is a molded article comprising the electromagnetic wave shielding resin composition according to the first invention and a thermoplastic resin (b).
【００１０】本発明の第３の発明は、電磁波シールド用
樹脂組成物の比重が、熱可塑性樹脂（ｂ）の２倍未満で
あることを特徴とする第２の発明に記載の成形品であ
る。The third invention of the present invention is the molded article according to the second invention, wherein the specific gravity of the resin composition for electromagnetic wave shielding is less than twice that of the thermoplastic resin (b). .
【００１１】本発明の第４の発明は、比重差が２倍未満
の電磁波シールド用樹脂組成物と熱可塑性樹脂（ｂ）の
混合物を射出成形することを特徴とする成形品の製造方
法である。A fourth invention of the present invention is a method for producing a molded article, which comprises injection-molding a mixture of an electromagnetic wave shielding resin composition having a specific gravity difference of less than 2 times and a thermoplastic resin (b). .
【００１２】[0012]
【発明の実施の形態】本発明の電磁波シールド用樹脂組
成物における金属コート有機繊維に用いられる有機繊維
は、含浸工程の際の温度においても形状が保持されてい
ること、また、成形品製造の際に、過剰な混錬等の物理
的な力により有機繊維が折損して電磁波シールド性能の
低下を防ぐ観点から、成形工程の際の温度においても形
状が保持されていることが必要であるが、それ以外の制
限は特にない。BEST MODE FOR CARRYING OUT THE INVENTION The organic fiber used as the metal-coated organic fiber in the resin composition for electromagnetic wave shielding of the present invention has a shape that is maintained even at the temperature during the impregnation step, and is used for the production of molded articles. At this time, from the viewpoint of preventing deterioration of the electromagnetic wave shielding performance due to breakage of the organic fibers due to physical force such as excessive kneading, it is necessary that the shape is maintained even at the temperature during the molding step. , There are no other restrictions.
【００１３】代表的なものを例示すれば高強度ポリエス
テル繊維、ポリブチレンテレフタレート（ＰＢＴ）繊
維、ポリフェニレンサルファイド（ＰＰＳ）繊維、アラ
ミド繊維、ポリイミド繊維、綿、麻等の天然繊維等が挙
げられる。繊維表面が化学処理や電子線照射等の物理的
処理をされたものでもよい。これらの１種、または２種
以上の組み合わせも可能であり、目的とする成形品の要
求特性に応じて適宜選択して使用すれば良い。Typical examples include high strength polyester fibers, polybutylene terephthalate (PBT) fibers, polyphenylene sulfide (PPS) fibers, aramid fibers, polyimide fibers, and natural fibers such as cotton and hemp. The fiber surface may be chemically treated or subjected to physical treatment such as electron beam irradiation. It is possible to use one kind or a combination of two or more kinds of these, and it is appropriate to select and use them according to the desired characteristics of the intended molded product.
【００１４】引張強度と耐熱性の観点からはＰＰＳ繊
維、耐熱性の観点からアラミド繊維が好ましい。アラミ
ド繊維で代表的なものを例示すれば、分子骨格が全体と
して直線状のパラ型タイプと、分子骨格がジグザグ状の
メタ型タイプが挙げられる。PPS fibers are preferred from the viewpoint of tensile strength and heat resistance, and aramid fibers are preferred from the viewpoint of heat resistance. Typical examples of the aramid fiber include a para type in which the molecular skeleton is linear as a whole and a meta type in which the molecular skeleton is zigzag.
【００１５】有機繊維のコートに用いられる金属として
は、導電性が良好で酸化し難い金属が好ましい。具体例
としては金、銀、銅、ニッケル、アルミ、亜鉛、錫等が
挙げられる。これらの１種、または２種以上の組み合わ
せが可能である。特に導電性の観点からは金、銀、コス
トの観点からはニッケル、銅が好ましく用いられる。有
機繊維への金属コート方法は特に限定されないが、無電
解メッキによるのが一般的である。この他、真空蒸着、
スパッタリング等の方法でも可能である。ニッケルの場
合はニッケル精錬時に発生するニッケルカーボニルガス
中でのニッケルコート方法も挙げられる。The metal used for coating the organic fibers is preferably a metal having good conductivity and being difficult to oxidize. Specific examples include gold, silver, copper, nickel, aluminum, zinc and tin. One of these or a combination of two or more thereof is possible. Particularly, gold and silver are preferably used from the viewpoint of conductivity, and nickel and copper are preferably used from the viewpoint of cost. The method for coating the metal on the organic fiber is not particularly limited, but electroless plating is generally used. Besides this, vacuum deposition,
A method such as sputtering is also possible. In the case of nickel, a nickel coating method in nickel carbonyl gas generated during nickel refining may be used.
【００１６】金属のコート量は使用する繊維や金属の種
類、必要な体積抵抗率によって適宜決められるが、繊維
表面上に厚さ０．１〜１．０μｍでコートされることが
好ましい。銀、ニッケル、ニッケル銅の場合は０．１〜
０．７μｍが好ましい。本発明で用いられる金属コート
有機繊維の繊維径や本数等は特に限定されないが、含浸
工程やその後の取り扱いの観点から１本あたりの繊維径
が６〜２０μｍ、１束あたりの本数が２５００〜１６０
００の範囲が好ましい。The coating amount of metal is appropriately determined depending on the type of fiber or metal used and the required volume resistivity, but it is preferable to coat the fiber surface with a thickness of 0.1 to 1.0 μm. 0.1 for silver, nickel and nickel copper
0.7 μm is preferable. The fiber diameter and the number of the metal-coated organic fibers used in the present invention are not particularly limited, but from the viewpoint of the impregnation step and subsequent handling, the fiber diameter per fiber is 6 to 20 μm, and the number per bundle is 2500 to 160.
A range of 00 is preferred.
【００１７】本発明の電磁波シールド用樹脂組成物にお
ける金属コート有機繊維の含有量はペレット成形性や充
分な導電率効果の観点から２０〜６０重量％が好まし
く、特に４０〜６０重量％が好ましい。The content of the metal-coated organic fiber in the electromagnetic wave shielding resin composition of the present invention is preferably 20 to 60% by weight, and particularly preferably 40 to 60% by weight from the viewpoint of pellet moldability and sufficient conductivity effect.
【００１８】本発明における金属コート有機繊維は、従
来の金属繊維に比べて比重が小さいことに特徴がある。
そして、この金属コート有機繊維を含有した本発明の電
磁波シールド用樹脂組成物も同様に比重が小さく、成形
品製造の際に用いられる熱可塑性樹脂（ｂ）である一般
の樹脂ペレットの比重の２．０倍未満の値にある。これ
により、成形品製造の際に金属コート有機繊維ペレット
と成形用の樹脂ペレットとの比重が違いすぎるための比
重差分離が生じにくく、電磁波シールド性能や機械強度
等の均一な成形品の製造が可能となる。The metal-coated organic fiber of the present invention is characterized by having a smaller specific gravity than conventional metal fibers.
The electromagnetic wave shielding resin composition of the present invention containing the metal-coated organic fiber also has a small specific gravity, which is 2 of the specific gravity of a general resin pellet which is the thermoplastic resin (b) used in the production of molded articles. The value is less than 0.0 times. This makes it difficult to cause specific gravity difference separation because the specific gravity of the metal-coated organic fiber pellets and the resin pellets for molding are too different during the manufacturing of molded products, and it is possible to manufacture uniform molded products such as electromagnetic wave shielding performance and mechanical strength. It will be possible.
【００１９】本発明で用いられる含浸用の熱可塑性樹脂
（ａ）の種類に格別の制限はないが、不飽和ポリエステ
ル、ポリアミド、重合脂肪酸ポリアミド、ポリエチレ
ン、ポリプロピレン、ポリエチレンテレフタレート、Ｐ
ＢＴ等の熱可塑性樹脂が好ましい。そして、金属繊維に
良好に含浸されるための条件として、含浸時の温度条件
下においてＪＩＳ Ｋ ６８６２に規定された方法にて
測定された溶融粘度の値が、４０００ｍＰａ・ｓ以下で
あることが好ましい。また、熱可塑性樹脂を高温状態に
保つと上記溶融粘度が低下する傾向にあるが、４時間程
度では上記溶融粘度は低下せず一定であることが作業効
率及び品質管理の観点から好ましい。The type of the impregnating thermoplastic resin (a) used in the present invention is not particularly limited, but unsaturated polyester, polyamide, polymerized fatty acid polyamide, polyethylene, polypropylene, polyethylene terephthalate, P
Thermoplastic resins such as BT are preferred. Then, as a condition for satisfactorily impregnating the metal fiber, it is preferable that a value of melt viscosity measured by a method defined in JIS K 6862 under a temperature condition at the time of impregnation is 4000 mPa · s or less. . Further, when the thermoplastic resin is kept at a high temperature, the melt viscosity tends to decrease, but the melt viscosity does not decrease in about 4 hours and is preferably constant from the viewpoint of work efficiency and quality control.
【００２０】金属コート有機繊維１００重量部に対する
熱可塑性樹脂（ａ）の含浸量は５０〜３００重量部が好
ましく、特に１００〜２００重量部が好ましい。The impregnation amount of the thermoplastic resin (a) with respect to 100 parts by weight of the metal-coated organic fiber is preferably 50 to 300 parts by weight, and particularly preferably 100 to 200 parts by weight.
【００２１】熱可塑性樹脂の含浸方法には特に制限無く
公知の方法を用いることができるが、含浸樹脂の含浸の
際の温度は、含浸樹脂の融点または軟化温度より高いこ
とが必要である。次いで、使用目的に合わせて任意の長
さ（通常、数ｍｍ〜１０数ｍｍ）に切断されてペレット
化され、本発明の電磁波シールド用樹脂組成物が得られ
る。Any known method can be used for impregnating the thermoplastic resin, but the temperature for impregnating the impregnating resin must be higher than the melting point or softening temperature of the impregnating resin. Then, the resin composition for electromagnetic wave shielding of the present invention is obtained by cutting into an arbitrary length (usually several mm to several tens of mm) and pelletizing according to the purpose of use.
【００２２】本発明において金属コート有機繊維は、熱
可塑性樹脂の含浸工程により、繊維の束をコンパクトに
して取り扱い容易にし、更に成形品における繊維の分散
を良好にする効果が得られる。すなわち、繊維がばらば
らの状態であると嵩高くなり、均一な電磁波シールド用
樹脂組成物が得られないおそれがある。また、樹脂未含
浸の場合、繊維が樹脂に濡れていないため繊維中に空気
が入っている状態にある。この状態の繊維を用いて成形
品を製造すると、気泡が成形品中に入り、機械物性や外
観を不良にするおそれがある。また、含浸工程により繊
維と繊維の間に樹脂が入り込むため、繊維束のまわりだ
けをコーティングする場合よりも繊維と繊維の間の滑り
が良くなり成形時に、成形品中において繊維の円滑な分
散が行われる。In the present invention, the metal-coated organic fiber has the effect of making the fiber bundle compact and easy to handle by the step of impregnating the thermoplastic resin, and further improving the dispersion of the fiber in the molded product. That is, if the fibers are in a loose state, the fibers become bulky, and there is a possibility that a uniform resin composition for electromagnetic wave shielding cannot be obtained. Further, when the resin is not impregnated, the fibers are not wet with the resin, so that the fibers are in a state of containing air. When a molded product is manufactured using fibers in this state, air bubbles may enter the molded product, resulting in poor mechanical properties and appearance. In addition, since the resin enters between the fibers during the impregnation process, the slip between the fibers becomes better than when coating only around the fiber bundle, and the smooth dispersion of the fibers in the molded product during molding is possible. Done.
【００２３】本発明の成形品は、電磁波シールド用樹脂
組成物（ペレット）と熱可塑性樹脂（ｂ）ペレットとを
均一に攪拌混合したものを射出成形機に投入し、成形さ
れて得られる。The molded article of the present invention is obtained by molding a mixture of the electromagnetic wave shielding resin composition (pellets) and the thermoplastic resin (b) pellets, which are uniformly stirred and mixed, into an injection molding machine.
【００２４】成形の際に用いられる熱可塑性樹脂（ｂ）
としては、ポリプロピレン、ポリエチレン、ポリカーボ
ネート、ＡＢＳ等が挙げられるが、用いられる有機繊維
の耐熱性や成形品への要求性能により適宜選択される。
例えば、有機繊維がポリエステル、ＰＢＴ、綿、麻の場
合はポリプロピレン、ポリエチレン、ＰＰＳの場合はＡ
ＢＳ、ＡＢＳとポリカーボネートのアロイ、アラミド及
びポリイミドの場合はポリカーボネート、ポリプロピレ
ン等の組み合わせが挙げられる。Thermoplastic resin (b) used in molding
Examples thereof include polypropylene, polyethylene, polycarbonate, ABS, etc., which are appropriately selected depending on the heat resistance of the organic fiber used and the performance required for the molded product.
For example, if the organic fiber is polyester, PBT, cotton, hemp, polypropylene, polyethylene, PPS: A
In the case of BS, ABS and an alloy of polycarbonate and aramid and polyimide, a combination of polycarbonate, polypropylene and the like can be mentioned.
【００２５】成形品製造の際、電磁波シールド用樹脂組
成物中の樹脂部分が溶融し、金属コート有機繊維の束が
ばらばらになって、金属コート有機繊維が成形用の熱可
塑性樹脂中に均一分散される。そして成形された成形品
中において、金属コート有機繊維が互いに接して分散状
態になることにより、繊維表面上の金属を介して電磁波
シールド性能を有した状態になる。During the production of a molded product, the resin portion in the electromagnetic wave shielding resin composition is melted and the bundles of metal-coated organic fibers are separated, so that the metal-coated organic fibers are uniformly dispersed in the molding thermoplastic resin. To be done. Then, in the formed molded product, the metal-coated organic fibers are in contact with each other to be in a dispersed state, so that the metal coated organic fiber has a state of having electromagnetic wave shielding performance through the metal on the fiber surface.
【００２６】本発明における成形品の好ましい体積抵抗
率は１０-1〜１０1Ω・ｃｍである。尚、本発明におけ
る体積抵抗率とは、３ｍｍ×５０ｍｍ×７５ｍｍの試験
片の３ｍｍ×７５ｍｍの両側面に電極として銀ペースト
を塗布し乾燥させた後、電極間の電気抵抗をデジタルマ
ルチメーターにて測定し、δ＝Ｒ・Ｓ／Ｌの式により算
出した値である。（但し、δ：体積抵抗率、Ｒ：電気抵
抗測定値、Ｓ：試験片の断面積、Ｌ：電極間の長さ を
表す。）The volume resistivity of the molded article of the present invention is preferably 10 −1 to 10 1 Ω · cm. The volume resistivity in the present invention means that silver paste is applied as electrodes to both sides of 3 mm × 75 mm of a test piece of 3 mm × 50 mm × 75 mm and dried, and then the electrical resistance between the electrodes is measured by a digital multimeter. It is a value measured and calculated by the formula of δ = R · S / L. (However, δ: volume resistivity, R: electric resistance measurement value, S: cross-sectional area of test piece, L: length between electrodes.)
【００２７】上記のような電磁波シールド性能を得る為
には、成形品における金属コート有機繊維の含有量は６
〜２０重量％が好ましい。また、成形品における電磁波
シールド用樹脂組成物の割合は、充分な電磁波シールド
効果、混練・成形の容易性及び成形品における機械強度
等の観点から１０〜５０重量％が好ましい。In order to obtain the above electromagnetic wave shielding performance, the content of the metal-coated organic fiber in the molded product is 6
-20% by weight is preferred. The ratio of the electromagnetic wave shielding resin composition in the molded product is preferably 10 to 50% by weight from the viewpoint of sufficient electromagnetic wave shielding effect, ease of kneading and molding, mechanical strength of the molded product, and the like.
【００２８】本発明において、組み合わせて使用される
有機繊維、コート用の金属、含浸用熱可塑性樹脂（ａ）
と、成形用熱可塑性樹脂（ｂ）の溶融粘度、融点を適宜
選択することにより、電磁波シールド性能を有する成形
品を安定して得ることができる。In the present invention, the organic fibers used in combination, the metal for coating, the thermoplastic resin for impregnation (a)
By appropriately selecting the melt viscosity and melting point of the molding thermoplastic resin (b), it is possible to stably obtain a molded product having electromagnetic wave shielding performance.
【００２９】例えば、銀コートのポリエステル繊維が、
ポリエステル繊維の融点より低い融点の重合脂肪酸ポリ
アミド樹脂を含浸した状態で含有された電磁波シールド
用樹脂ペレットを、成形用熱可塑性樹脂としてポリプロ
ピレン樹脂に配合し均一に混合したものを射出成形する
と、重量比率で同配合量のステンレス繊維含有ペレット
と同等の電磁波シールド性能が得られる。そして銀コー
トポリエステル繊維ペレットはステンレス繊維含有ペレ
ットの比重の約０．３倍であり、成形用のポリプロピレ
ン樹脂の比重の約１．５倍である。このため、導電性ペ
レットと成形用樹脂ペレットを混合した際に生じる比重
差による偏在がステンレス繊維含有ペレットより少なく
なり、射出成形のショット間の電磁波シールド性能バラ
ツキが少なくなる。For example, a silver-coated polyester fiber is
Resin pellets for electromagnetic wave shielding contained in a state of being impregnated with a polymerized fatty acid polyamide resin having a melting point lower than the melting point of polyester fibers are mixed with polypropylene resin as a thermoplastic resin for molding and uniformly mixed, and injection molding is carried out to obtain a weight ratio. The electromagnetic wave shielding performance equivalent to that of the pellets containing the same amount of stainless fiber can be obtained. The silver-coated polyester fiber pellets have a specific gravity about 0.3 times that of the stainless fiber-containing pellets and about 1.5 times the specific gravity of the polypropylene resin for molding. Therefore, uneven distribution due to a difference in specific gravity that occurs when the conductive pellets and the molding resin pellets are mixed is less than that of the stainless fiber-containing pellets, and variations in electromagnetic wave shielding performance between shots of injection molding are reduced.
【００３０】本発明の成形品の例として高周波用配線
材、電磁波シールド材が挙げられる。更に詳しくはＯＡ
機器、ＡＶ機器、測定機器、輸送機器、通信機器等のハ
ウジング用途やコネクタ、包装材等が挙げられる。Examples of the molded article of the present invention include high frequency wiring materials and electromagnetic wave shielding materials. More details OA
Examples thereof include housing applications such as equipment, AV equipment, measuring equipment, transportation equipment, and communication equipment, connectors, and packaging materials.
【００３１】尚、本発明の電磁波シールド用樹脂組成物
及び成形品には、本発明の効果を阻害しない範囲内で耐
熱安定剤、耐侯剤、滑剤、スリップ剤、難燃剤、核剤、
顔料、染料等を配合することが出来る。The electromagnetic wave shielding resin composition and the molded article of the present invention include a heat-resistant stabilizer, a weather-resistant agent, a lubricant, a slip agent, a flame retardant, a nucleating agent, within a range that does not impair the effects of the present invention.
Pigments, dyes, etc. can be added.
【００３２】[0032]
【実施例】以下、実施例を挙げて本発明の構成及び作用
効果をより具体的に説明するが、本発明はもとより下記
実施例によって制限を受けるものではなく、本発明の趣
旨に適合し得る範囲で適当に変更して実施することも可
能であり、それらは全て本発明の技術的範囲に含まれ
る。尚、実施例における軟化温度は、ＪＩＳ Ｋ ７２
３４に規定された方法（環球法）にて測定された値であ
る。EXAMPLES Hereinafter, the constitution and effects of the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples and may be adapted to the gist of the present invention. It is also possible to appropriately change and implement the range, and they are all included in the technical scope of the present invention. The softening temperature in the examples is JIS K 72
It is a value measured by the method (ring and ball method) specified in No. 34.
【００３３】実施例１
（金属コート有機繊維樹脂組成物の作成条件−１）下記
の条件で、金属コート有機繊維４９重量％、含浸樹脂５
１重量％の金属コート有機繊維樹脂組成物（ペレット、
比重１．３）を作成した。
金属コート有機繊維：銀コートポリエステル繊維（金属
コート厚さ０．１μｍ、ポリエステル繊維の融点２５０
℃、繊維径２０μｍ、２９６０本／束）
含浸樹脂：重合脂肪酸ポリアミド樹脂（軟化温度９６
℃、溶融粘度３０００ｍＰａ・ｓ（ＪＩＳ Ｋ ６８６
２、測定温度１４０℃））
含浸条件：樹脂温度 １３０〜１４０℃
引取速度：６ｍ/min
ノズル径：２．１ｍｍφ Example 1 (Conditions for preparing metal-coated organic fiber resin composition-1) Under the following conditions, 49% by weight of metal-coated organic fiber and impregnated resin 5
1% by weight of metal-coated organic fiber resin composition (pellet,
A specific gravity of 1.3) was created. Metal coated organic fiber: silver coated polyester fiber (metal coated thickness 0.1 μm, melting point of polyester fiber 250)
C, fiber diameter 20 μm, 2960 fibers / bundle Impregnating resin: Polymerized fatty acid polyamide resin (softening temperature 96
° C, melt viscosity 3000 mPa · s (JIS K 686
2, measurement temperature 140 ° C)) Impregnation condition: resin temperature 130 to 140 ° C, take-up speed: 6 m / min, nozzle diameter: 2.1 mmφ
【００３４】（射出成形条件−１）次に、下記の条件で
金属コート有機繊維樹脂ペレット１２重量％（金属繊維
含有量６重量％）、成形用熱可塑性樹脂ペレット８８重
量％の割合で成形し、矩形の試験片（寸法；３ｍｍ×５
０ｍｍ×７５ｍｍ）を３４枚作成した。最初の４ショッ
トを廃棄し、５ショット目から番号付け（１〜３０）し
た。
熱可塑性樹脂ペレット：ポリプロピレン（比重０．９
１、融点１６０℃）
成形機：東芝機械製「IS100F-3A」
シリンダー温度：１７０〜１８０℃
金型温度：４０℃
スクリュウ回転数：８０ｒｐｍ
スクリュウ径：３６ｍｍφ
射出速度：４０ｍｍ/sec
冷却時間：３０sec(Injection molding condition-1) Next, metal-coated organic fiber resin pellets 12% by weight (metal fiber content 6% by weight) and molding thermoplastic resin pellets 88% by weight were molded under the following conditions. , Rectangular test piece (dimensions: 3 mm x 5
34 sheets of 0 mm × 75 mm) were prepared. The first four shots were discarded and numbered from the fifth shot (1-30). Thermoplastic resin pellets: polypropylene (specific gravity 0.9
1, melting point 160 ℃) Molding machine: Toshiba Machine "IS100F-3A" Cylinder temperature: 170-180 ℃ Mold temperature: 40 ℃ Screw rotation speed: 80rpm Screw diameter: 36mmφ Injection speed: 40mm / sec Cooling time: 30sec
【００３５】（体積抵抗率の測定）各試験片の体積抵抗
率を以下の様に得、ショット間の変動を図１に示した。
電極塗布
電極の材質：銀ペースト（シルコートＲＬ−１０：福田
金属箔粉工業製）
試験片の３ｍｍ×７５ｍｍの両側面に銀ペーストを塗布
し乾燥。
測定機：デジタルマルチメーター（ＣＤＭ−５０００：
ＣＵＳＴＯＭ社製）
体積抵抗率の算出方法
δ＝Ｒ・Ｓ／Ｌ（但し、δ：体積抵抗率、Ｒ：電気抵抗
測定値、Ｓ：試験片の断面積、Ｌ：電極間の長さ を表
す。）(Measurement of Volume Resistivity) The volume resistivity of each test piece was obtained as follows, and the variation between shots is shown in FIG. Electrode coating Electrode material: silver paste (Silcoat RL-10: manufactured by Fukuda Metal Foil & Powder Co., Ltd.) Silver paste was coated on both sides of a test piece of 3 mm × 75 mm and dried. Measuring machine: Digital multimeter (CDM-5000:
Calculation method of volume resistivity δ = R · S / L (where δ: volume resistivity, R: electric resistance measurement value, S: cross-sectional area of test piece, L: length between electrodes) .)
【００３６】実施例２
（金属コート有機繊維樹脂組成物の作成条件−２）下記
の条件で金属コート有機繊維４９重量％、含浸樹脂５１
重量％の金属コート有機繊維樹脂組成物（ペレット、比
重１．４）を作成した。
金属コート有機繊維：ニッケル銅コートアクリル繊維
（金属コート厚さ０．２μｍ、アクリル繊維の軟化温度
１５０℃、繊維径１２μｍ、４８００本／束）
含浸樹脂：重合脂肪酸ポリアミド樹脂（軟化温度９６
℃、溶融粘度３７００ｍＰａ・ｓ（ＪＩＳ Ｋ ６８６
２、測定温度１１０℃））
含浸条件：樹脂温度 １００〜１１０℃
引取速度：６ｍ/min
ノズル径：１．９ｍｍφ Example 2 (Conditions for Preparing Metal-Coated Organic Fiber Resin Composition-2) Under the following conditions, 49% by weight of metal-coated organic fiber and impregnated resin 51 were used.
A wt% metal coated organic fiber resin composition (pellets, specific gravity 1.4) was prepared. Metal coated organic fiber: Nickel copper coated acrylic fiber (metal coated thickness 0.2 μm, acrylic fiber softening temperature 150 ° C., fiber diameter 12 μm, 4800 fibers / bundle) Impregnation resin: polymerized fatty acid polyamide resin (softening temperature 96
° C, melt viscosity 3700 mPa · s (JIS K 686
2. Measuring temperature 110 ° C)) Impregnation condition: Resin temperature 100-110 ° C Take-off speed: 6m / min Nozzle diameter: 1.9mmφ
【００３７】（射出成形条件−２）次に、下記の条件で
金属コート有機繊維樹脂ペレット１２重量％（金属繊維
含量６重量％）、成形用熱可塑性樹脂ペレット８８重量
％の割合で成形し、矩形の試験片（寸法；３ｍｍ×５０
ｍｍ×７５ｍｍ）を３４枚作成した。最初の４ショット
を廃棄し、５ショット目から番号付け（１〜３０）し
た。
熱可塑性樹脂ペレット：ポリプロピレン（比重０．９
１、融点１６０℃）
成形機：東芝機械製「IS100F-3A」
シリンダー温度：１７０〜１８０℃
金型温度：４０℃
スクリュウ回転数：８０ｒｐｍ
スクリュウ径：３６ｍｍφ
射出速度：４０ｍｍ/sec
冷却時間：３０sec
各試験片の体積抵抗率を実施例１と同様に測定し、ショ
ット間の変動を図１に示した。(Injection molding condition-2) Next, metal-coated organic fiber resin pellets 12% by weight (metal fiber content 6% by weight) and molding thermoplastic resin pellets 88% by weight were molded under the following conditions, Rectangular test piece (dimensions: 3 mm x 50
mm × 75 mm) was prepared. The first four shots were discarded and numbered from the fifth shot (1-30). Thermoplastic resin pellets: polypropylene (specific gravity 0.9
1, melting point 160 ℃) Molding machine: Toshiba Machine "IS100F-3A" Cylinder temperature: 170-180 ℃ Mold temperature: 40 ℃ Screw rotation speed: 80rpm Screw diameter: 36mmφ Injection speed: 40mm / sec Cooling time: 30sec each The volume resistivity of the test piece was measured in the same manner as in Example 1, and the variation between shots is shown in FIG.
【００３８】実施例３
（金属コート有機繊維樹脂組成物の作成条件−３）下記
の条件で金属コート有機繊維５４重量％、含浸樹脂４６
重量％の金属コート有機繊維樹脂組成物（ペレット、比
重１．４５）を作成した。
金属コート有機繊維：ニッケルコートアラミド繊維（金
属コート厚さ０．３μｍ、アラミド繊維の５０％強度低
下温度２７０℃、繊維径１６μｍ、１５０００本／束）
（５０％強度低下温度とは、ＪＩＳ Ｌ１０１３の化学
繊維フィラメント糸試験方法の、引張強さの標準試験に
準拠して、単繊維の環境温度を常温から３００℃まで変
化させた引張強さ曲線を作成し、得られた引張強さ最大
値の５０％値のときの温度をいう。この温度において繊
維形状は保持されている。）
含浸樹脂：重合脂肪酸ポリアミド樹脂（軟化温度１７０
℃、溶融粘度１６００ｍＰａ・ｓ（ＪＩＳ Ｋ ６８６
２、測定温度２５０℃））
含浸条件：樹脂温度 ２５０〜２７０℃
引取速度：１２ｍ/min
ノズル径：２．５ｍｍφ Example 3 (Preparation conditions for metal-coated organic fiber resin composition-3) 54% by weight of metal-coated organic fibers and impregnated resin 46 were prepared under the following conditions.
A weight-% metal-coated organic fiber resin composition (pellets, specific gravity 1.45) was prepared. Metal coated organic fiber: Nickel coated aramid fiber (metal coated thickness 0.3 μm, 50% strength reduction temperature of aramid fiber 270 ° C., fiber diameter 16 μm, 15000 fibers / bundle)
(The 50% strength reduction temperature is a tensile strength curve obtained by changing the environmental temperature of single fiber from room temperature to 300 ° C. in accordance with the standard test of tensile strength of the chemical fiber filament yarn test method of JIS L1013. The temperature at the time of 50% of the maximum value of the tensile strength that was prepared and obtained. The fiber shape is maintained at this temperature.) Impregnating resin: Polymerized fatty acid polyamide resin (softening temperature 170
° C, melt viscosity 1600 mPa · s (JIS K 686
2, measurement temperature 250 ℃)) Impregnation condition: Resin temperature 250-270 ℃ Take-up speed: 12 m / min Nozzle diameter: 2.5 mm
【００３９】（射出成形条件−３）次に、下記の条件で
金属コート有機繊維樹脂ペレット１５重量％（金属コー
ト有機繊維含量８重量％）、成形用熱可塑性樹脂ペレッ
ト８５重量％の割合で成形し、矩形の試験片（寸法；３
ｍｍ×５０ｍｍ×７５ｍｍ）を３４枚作成した。最初の
４ショットを廃棄し、５ショット目から番号付け（１〜
３０）した。
熱可塑性樹脂ペレット：ポリカーボネート（比重１．２
０、融点１５２℃）
成形機：東芝機械製「IS100F-3A」
シリンダー温度：３１０〜３２０℃
金型温度：９０℃
スクリュウ回転数：８０ｒｐｍ
スクリュウ径：３６ｍｍφ
射出速度：４０ｍｍ/sec
冷却時間：３０sec
各試験片の体積抵抗率を実施例１と同様に測定し、ショ
ット間の変動を図１に示した。(Injection molding condition-3) Next, molding was performed under the following conditions at a ratio of 15% by weight of metal-coated organic fiber resin pellets (metal-coated organic fiber content 8% by weight) and 85% by weight of molding thermoplastic resin pellets. A rectangular test piece (dimensions: 3
mm × 50 mm × 75 mm) was prepared. Discard the first 4 shots and number from the 5th shot (1-
30) I did. Thermoplastic resin pellets: Polycarbonate (specific gravity 1.2
Molding machine: Toshiba Machine "IS100F-3A" Cylinder temperature: 310-320 ° C Mold temperature: 90 ° C Screw rotation speed: 80rpm Screw diameter: 36mmφ Injection speed: 40mm / sec Cooling time: 30sec each The volume resistivity of the test piece was measured in the same manner as in Example 1, and the variation between shots is shown in FIG.
【００４０】比較例１
下記の条件で金属繊維７７重量％、含浸樹脂２３重量％
の金属繊維配合ペレット（比重３．１）を作成した。
（金属繊維配合ペレットの作成−１）
金属繊維：ステンレス繊維（ベカルト社製商品名Bu8/12
000、304special、繊維径８μｍ、一束１２０００本）
含浸樹脂：重合脂肪酸ポリアミド樹脂（軟化温度９６
℃、溶融粘度３０００ｍＰａ・ｓ（ＪＩＳ Ｋ ６８６
２、測定温度１４０℃））
含浸条件：樹脂温度 １３０〜１４０℃
引取速度：６ｍ/min
ノズル径：２．１ｍｍφ
実施例１と同様に射出成形して試験片を得、同様に体積
抵抗率を測定しショット間の変動を図１に示した。 Comparative Example 1 Metal fiber 77% by weight and impregnated resin 23% by weight under the following conditions
A metal fiber-containing pellet (specific gravity 3.1) was prepared. (Preparation of metal fiber-containing pellets-1) Metal fiber: Stainless steel fiber (Beckert Co., Ltd., trade name Bu8 / 12
000, 304 special, fiber diameter 8 μm, 12000 bundles) Impregnating resin: Polymerized fatty acid polyamide resin (softening temperature 96
° C, melt viscosity 3000 mPa · s (JIS K 686
2. Measurement temperature 140 ° C.)) Impregnation condition: Resin temperature 130 to 140 ° C. Take-off speed: 6 m / min Nozzle diameter: 2.1 mmφ Injection molding was carried out in the same manner as in Example 1 to obtain a test piece, and similarly the volume resistivity was determined. The variation between the measured shots is shown in FIG.
【００４１】[0041]
【発明の効果】本発明の電磁波シールド用樹脂組成物
は、熱可塑性樹脂（ａ）を含浸した金属コート有機繊維
を含んでいるので、これを用いて成る成形品は電磁波シ
ールド性能と機械的物性が良好である。The resin composition for electromagnetic wave shielding of the present invention contains the metal-coated organic fiber impregnated with the thermoplastic resin (a). Therefore, the molded product using the same has electromagnetic wave shielding performance and mechanical properties. Is good.
【００４２】また、本発明の成形品の製造において用い
られる電磁波シールド用樹脂組成物の比重は、成形加工
の際に混合される希釈樹脂である熱可塑性樹脂（ｂ）の
２倍未満であるので、成形品製造の際に発生する材料の
偏在が防止できる。そのため、射出成形のショット間バ
ラツキが少なく、安定した電磁波シールド性能、機械物
性等を有する成形品が効率よく生産出来る。Further, the specific gravity of the electromagnetic wave shielding resin composition used in the production of the molded article of the present invention is less than twice the specific gravity of the thermoplastic resin (b) which is a dilute resin mixed during the molding process. It is possible to prevent uneven distribution of materials that occur during the production of molded products. Therefore, there is little variation between shots in injection molding, and a molded product having stable electromagnetic wave shielding performance and mechanical properties can be efficiently produced.
【図１】成形品製造過程における体積抵抗率の変化Fig. 1 Changes in volume resistivity during the manufacturing process of molded products
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｌ 101:00 Ｃ０８Ｌ 101:00 Ｆターム(参考） 4F071 AA02 AA20 AA43 AA50 AA54 AD01 AE15 AF37 AH04 AH12 BA01 BB05 4F072 AB05 AB06 AC16 AD04 AD37 AD38 AD44 AL11 4F206 AB24 AB28 AE03 AR15 JA07 JF01 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C08L 101: 00 C08L 101: 00 F term (reference) 4F071 AA02 AA20 AA43 AA50 AA54 AD01 AE15 AF37 AH04 AH12 BA01 BB05 4F072 AB05 AB06 AC16 AD04 AD37 AD38 AD44 AL11 4F206 AB24 AB28 AE03 AR15 JA07 JF01
Claims (4)
ト有機繊維を含むことを特徴とする電磁波シールド用樹
脂組成物。1. An electromagnetic wave shielding resin composition comprising a metal-coated organic fiber impregnated with a thermoplastic resin (a).
組成物と熱可塑性樹脂（ｂ）とから成る成形品。2. A molded article comprising the resin composition for electromagnetic wave shielding according to claim 1 and a thermoplastic resin (b).
熱可塑性樹脂（ｂ）の２倍未満であることを特徴とする
請求項２に記載の成形品。3. The specific gravity of the electromagnetic wave shielding resin composition is
The molded product according to claim 2, which is less than twice the thermoplastic resin (b).
脂組成物と熱可塑性樹脂（ｂ）の混合物を射出成形する
ことを特徴とする成形品の製造方法。4. A method for producing a molded article, which comprises injection-molding a mixture of an electromagnetic wave shielding resin composition having a specific gravity difference of less than 2 times and a thermoplastic resin (b).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002025198A JP2003160673A (en) | 2001-09-11 | 2002-02-01 | Resin composition for electromagnetic wave shielding and utilization thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001-274394 | 2001-09-11 | ||
| JP2001274394 | 2001-09-11 | ||
| JP2002025198A JP2003160673A (en) | 2001-09-11 | 2002-02-01 | Resin composition for electromagnetic wave shielding and utilization thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003160673A true JP2003160673A (en) | 2003-06-03 |
Family
ID=26621962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002025198A Pending JP2003160673A (en) | 2001-09-11 | 2002-02-01 | Resin composition for electromagnetic wave shielding and utilization thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003160673A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006283243A (en) * | 2005-04-01 | 2006-10-19 | Toyo Ink Mfg Co Ltd | Conductive resin composition and molded product thereof |
| JP2007262246A (en) * | 2006-03-28 | 2007-10-11 | Matsushita Electric Works Ltd | Resin composition for electromagnetic wave shielding and its molded product |
| JP2008001757A (en) * | 2006-06-20 | 2008-01-10 | Kyocera Chemical Corp | Resin composition for semiconductor sealing use and resin-sealed type semiconductor device |
| JP2009019148A (en) * | 2007-07-13 | 2009-01-29 | Daicel Polymer Ltd | Electroconductive resin composition |
-
2002
- 2002-02-01 JP JP2002025198A patent/JP2003160673A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006283243A (en) * | 2005-04-01 | 2006-10-19 | Toyo Ink Mfg Co Ltd | Conductive resin composition and molded product thereof |
| JP2007262246A (en) * | 2006-03-28 | 2007-10-11 | Matsushita Electric Works Ltd | Resin composition for electromagnetic wave shielding and its molded product |
| JP2008001757A (en) * | 2006-06-20 | 2008-01-10 | Kyocera Chemical Corp | Resin composition for semiconductor sealing use and resin-sealed type semiconductor device |
| JP2009019148A (en) * | 2007-07-13 | 2009-01-29 | Daicel Polymer Ltd | Electroconductive resin composition |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20040029085A (en) | Method for forming electrically conductive impregnated fibers and fiber pellets | |
| US7078098B1 (en) | Composites comprising fibers dispersed in a polymer matrix having improved shielding with lower amounts of conducive fiber | |
| KR20160006677A (en) | Moldable capsule and method of manufacture | |
| CN103975023A (en) | Composite and molded product thereof | |
| US7708920B2 (en) | Conductively doped resin moldable capsule and method of manufacture | |
| US20120321836A1 (en) | Variable-thickness elecriplast moldable capsule and method of manufacture | |
| US20140322532A1 (en) | Variable-thickness elecriplast moldable capsule and method of manufacture | |
| JP5173143B2 (en) | Electromagnetic wave shielding resin composition and molded product thereof | |
| JP2003160673A (en) | Resin composition for electromagnetic wave shielding and utilization thereof | |
| JP5224686B2 (en) | Mixture for molding conductive thermoplastic resin composition and molded article formed by molding the mixture | |
| EP0304435B1 (en) | Electrically conductive material for molding | |
| JP2006283243A (en) | Conductive resin composition and molded product thereof | |
| JPH01284000A (en) | Composite element containing metallized fiber and manufacture of electromagnetic shielding molded product by employing the element | |
| JP2002155471A (en) | Carbon fiber and resin composition using the same, molding material and molded article | |
| JPS63272536A (en) | Manufacture of conductive resin molded product | |
| JP2005225126A (en) | Method for producing molding of conductive thermoplastic resin | |
| JP2991891B2 (en) | Metal-coated carbon fiber chopped strand, method for producing the same, and fiber-reinforced resin composition | |
| WO1988004986A1 (en) | Process for molding resin composition containing metallic fibers | |
| JP3937560B2 (en) | Discontinuous fiber reinforced resin molding material and molded product using the same | |
| JPH0757489B2 (en) | Method for producing conductive fiber composite resin | |
| JPS61287962A (en) | Electrically conductive composite resin composition | |
| JP2523098B2 (en) | Conductive resin composition and molded article thereof | |
| JPS6026043A (en) | Electrically conductive thermoplastic resin composition | |
| JPH039956A (en) | Highly conductive resin composition | |
| JPH02155724A (en) | Manufacture of molded electromagnetic shield product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040903 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20060707 |
|
| A131 | Notification of reasons for refusal |
Effective date: 20060718 Free format text: JAPANESE INTERMEDIATE CODE: A131 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060919 |
|
| A02 | Decision of refusal |
Effective date: 20061017 Free format text: JAPANESE INTERMEDIATE CODE: A02 |