JPH03126296A - Lightweight conductive composite molding - Google Patents
Lightweight conductive composite moldingInfo
- Publication number
- JPH03126296A JPH03126296A JP1263809A JP26380989A JPH03126296A JP H03126296 A JPH03126296 A JP H03126296A JP 1263809 A JP1263809 A JP 1263809A JP 26380989 A JP26380989 A JP 26380989A JP H03126296 A JPH03126296 A JP H03126296A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- carbon
- graphite intercalation
- graphite
- conductive
- 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
- 239000002131 composite material Substances 0.000 title claims description 24
- 238000000465 moulding Methods 0.000 title abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 112
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 80
- 239000010439 graphite Substances 0.000 claims abstract description 80
- 150000001875 compounds Chemical class 0.000 claims abstract description 64
- 239000011347 resin Substances 0.000 claims abstract description 49
- 229920005989 resin Polymers 0.000 claims abstract description 49
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000009830 intercalation Methods 0.000 claims description 51
- 230000002687 intercalation Effects 0.000 claims description 51
- 229920001187 thermosetting polymer Polymers 0.000 claims description 14
- 239000000835 fiber Substances 0.000 abstract description 19
- 239000000203 mixture Substances 0.000 abstract description 12
- 239000011229 interlayer Substances 0.000 abstract description 7
- 229940125904 compound 1 Drugs 0.000 abstract description 2
- 239000004634 thermosetting polymer Substances 0.000 abstract 4
- 239000006229 carbon black Substances 0.000 description 22
- 235000019241 carbon black Nutrition 0.000 description 22
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 22
- 239000005011 phenolic resin Substances 0.000 description 20
- 229920000049 Carbon (fiber) Polymers 0.000 description 19
- 239000004917 carbon fiber Substances 0.000 description 19
- 229960003280 cupric chloride Drugs 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 7
- 239000004020 conductor Substances 0.000 description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 229920001568 phenolic resin Polymers 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 241000282320 Panthera leo Species 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241001456553 Chanodichthys dabryi Species 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 240000000731 Fagus sylvatica Species 0.000 description 1
- 235000010099 Fagus sylvatica Nutrition 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、マトリクスとなる熱硬化性樹脂と繊維状の黒
鉛層間化合物を組合せた導電性複合成形体に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a conductive composite molded article that combines a thermosetting resin as a matrix and a fibrous graphite intercalation compound.
本発明の軽量導電性複合成形体は、金属に比べて軽量で
、かつ従来の導電性樹脂に比べて高強度かつ導電性が高
いことから、モーターブラシ、電磁波シールド材料、導
電性フンバウンド等、これまでに導電性樹脂組成物が用
いられている、あるいは将来用いられることが期待され
ている分野にて利用されるものである。The lightweight conductive composite molded article of the present invention is lighter than metal, and has higher strength and conductivity than conventional conductive resins, so it can be used in motor brushes, electromagnetic shielding materials, conductive humpbacks, etc. It is used in fields where conductive resin compositions have been used or are expected to be used in the future.
従来の技術
従来、樹脂にカーボンブラックまたは粉末黒鉛を配合す
ることにより、樹脂に導電性を付与することが知られて
いる。これらの導電性樹脂または導電性ゴムは、高圧ケ
ーブルの導電性材料、発熱体等の導電性材料、ＩＣ等の
電磁遮蔽材、ビデオディスク用導電材料、包装材や建築
材等の帯電防止材、導電性印刷インク、導電性塗料、導
電性接着剤、入力用鍵盤、スイッチ、圧力センサーなど
として広く使用されている。BACKGROUND ART Conventionally, it has been known to impart electrical conductivity to a resin by adding carbon black or powdered graphite to the resin. These conductive resins or conductive rubbers can be used as conductive materials for high-voltage cables, conductive materials for heating elements, electromagnetic shielding materials for ICs, conductive materials for video discs, antistatic materials for packaging materials, construction materials, etc. It is widely used as conductive printing ink, conductive paint, conductive adhesive, input keyboards, switches, pressure sensors, etc.
導電性樹脂または導電性ゴムに配合する導電性付与物質
としてのカーボンブラックは１通常、アセチレンブラッ
ク、副生カーボンブラック、あるいは導電性ファーネス
ブラックが用いられている。ところが、これらのカーボ
ンブラックを樹脂やゴムに配合して、充分なる導電性を
付与するためには、相当量のカーボンブラックを配合し
なければならない０例えばポリエチレンの体積固有抵抗
を１０４Ω・ｃｍ以下にするには、ポリエチレン１００
重量部に対してケッチエンブラックＥＣ（ライオンアク
ゾ社製、副生カーボンブラック）を１５重量部以上、配
合することが必要とされている（特公昭８３−５１４６
７号公報）。Carbon black as a conductivity imparting substance to be blended into a conductive resin or conductive rubber is usually acetylene black, by-product carbon black, or conductive furnace black. However, in order to blend these carbon blacks into resins and rubbers to impart sufficient electrical conductivity, a considerable amount of carbon black must be blended. To do this, use polyethylene 100
It is required to blend 15 parts by weight or more of Ketchen Black EC (manufactured by Lion Akzo, by-product carbon black) to parts by weight (Japanese Patent Publication No. 83-5146).
Publication No. 7).
また、従来より、炭素Ｊａ維をプラスチックに配合した
炭素繊維強化プラスチック（Ｃａｒｂｏｎ Ｆｉｂｅｒ
Ｒｅｉｎｆｏｒｃｅｄ Ｐｌａｓｔｉｃ、 ＣＦＲＰ）
が知られており、軽量かつ高強度の機械部品、構造材料
等に用いられている。しかしながら、この炭素繊維強化
プラスチックにおいては１強度、耐衝撃性等の機械的物
性こそ優れているものの、電気伝導性は前述の導電性プ
ラスチックに比べてはるかに劣り、はとんどが絶縁体で
ある。これは、従来用いられている炭素繊維強化プラス
チックの樹脂が、導電性を有しないこと、および用いら
れる炭素繊維の導電性が低いことに起因する。In addition, carbon fiber reinforced plastics (Carbon Fiber Reinforced Plastics), which are made by blending carbon Ja fibers into plastics
Reinforced Plastic, CFRP)
is known and is used in lightweight and high-strength mechanical parts, structural materials, etc. However, although this carbon fiber reinforced plastic has excellent mechanical properties such as strength and impact resistance, its electrical conductivity is far inferior to that of the conductive plastics mentioned above, and it is mostly an insulator. be. This is due to the fact that conventionally used carbon fiber reinforced plastic resins do not have electrical conductivity, and the carbon fibers used have low electrical conductivity.
即ち、ａ！ｌ状のフィラーを樹脂に配合させた場合、樹
脂が絶縁性であるために、繊維同志の電気的接触が不良
となり、これを導電体として用いることは困難であった
。また、フィラーの電気抵抗も１炭素ｍ維で２００〜数
１０００ｐΩＣ１ｍと金属に比べて大きく、導電性付与
体としては不適である。That is, a! When an L-shaped filler is blended into a resin, since the resin is insulating, electrical contact between the fibers becomes poor, making it difficult to use this as a conductor. Further, the electrical resistance of the filler is 200 to several thousand pΩC1m per carbon m fiber, which is larger than that of metal, and is therefore unsuitable as a conductive material.
従って、これまで炭素慮維強化プラスチックに導電性付
与体、あるいはそれ以上の導電性を付与することは出来
ず、これにより炭素＃ａ維強化プラスチックの用途はも
っばらその機械的特性を利用したものに限定されていた
。Therefore, until now, it has not been possible to impart conductivity or even higher conductivity to carbon fiber-reinforced plastics, and as a result, carbon fiber-reinforced plastics are mainly used to utilize their mechanical properties. was limited to.
また、黒鉛層間化合物を複合導電材料として用いた例が
いくつか報告されている（例えば米国特許４４１４１４
２、特開昭８４−８５１４４号公報、特開平１−１０１
３７２号公報、米国特許４７９９９５７等）、シかし。In addition, some examples of using graphite intercalation compounds as composite conductive materials have been reported (for example, U.S. Patent No. 441,414
2. JP-A-84-85144, JP-A-1-101
No. 372, U.S. Pat. No. 4,799,957, etc.), Shikashi.
これらにおいては、黒鉛層間化合物を複合材のフィラー
として用いているものの、樹脂中での配向を制御したり
、導電性粉末を分散させて、マトリクスの導電性、摩擦
特性を制御するなどの試みは行われておらず、また、フ
ィラー形状が粉末であるために多量の配合が必要である
など、実用に供するには問題があった。In these studies, graphite intercalation compounds are used as fillers in composite materials, but there have been no attempts to control the conductivity and frictional properties of the matrix by controlling the orientation in the resin or dispersing conductive powder. However, since the filler is in the form of a powder, a large amount of the filler must be added, which poses problems for practical use.
発明が解決しようとする課題
本発明の目的は、ｍ綾状の黒鉛層間化合物を用いて、従
来の材料に優り、軽量かつ高い導電性、優れた摩擦特性
を付与した軽量導電性樹脂成形体を提供することにある
。Problems to be Solved by the Invention The purpose of the present invention is to provide a lightweight conductive resin molded body using a m-shaped graphite intercalation compound, which is lighter, has higher conductivity, and has superior frictional properties than conventional materials. It is about providing.
課題を解決するための手段
本発明は、熱硬化性樹脂中に炭素粒子及び繊維状の黒鉛
層間化合物を配合し、且つ熱硬化性樹脂中に繊維状の黒
鉛層間化合物を一定方向に配向してなる軽量導電性複合
成形体である。Means for Solving the Problems The present invention comprises blending carbon particles and a fibrous graphite intercalation compound in a thermosetting resin, and orienting the fibrous graphite intercalation compound in a certain direction in the thermosetting resin. It is a lightweight conductive composite molded body.
すなわち本発明では、炭素繊維をホストとし、これまで
に黒鉛層間化合物を生成することが知られている各種の
化合物をゲストとして反応することにより得られる繊維
状の黒鉛層間化合物を、たとえばカーボンブラック、黒
鉛などの炭素粒子を配合した熱硬化性樹脂中に導電性付
与体として配合することを特徴とするものである。That is, in the present invention, a fibrous graphite intercalation compound obtained by using carbon fiber as a host and reacting various compounds known to produce a graphite intercalation compound as a guest, for example, carbon black, It is characterized by being blended as a conductivity imparter into a thermosetting resin blended with carbon particles such as graphite.
本発明の成形体における黒鉛層間化合物の配合量は１〜
７０重量部、好ましくは３０〜５０重量部、炭素粒子の
配合量は１〜３０重量部、好ましくは３〜２０重量部で
、残部が熱硬化性樹脂であり、全体を１００重量部とす
る。The blending amount of the graphite intercalation compound in the molded article of the present invention is 1 to 1.
The amount of carbon particles is 1 to 30 parts by weight, preferably 3 to 20 parts by weight, and the remainder is a thermosetting resin, making the total 100 parts by weight.
以下、本発明をさらに詳細に説明する。The present invention will be explained in more detail below.
本発明においては、炭素ｍ維を原料とした繊維状の黒鉛
層Ｆｌｆｆ化合物を、導電性付与体として用いている。In the present invention, a fibrous graphite layer Flff compound made from carbon fibers is used as the conductivity imparting body.
この場合のｍ綾状とは、繊維径に対する繊維長の比が１
００以上であることをさすものとするが、樹脂中に一定
方向に配向させるためには、その長さが１ｃｍ以上であ
ることが望ましい。In this case, m-twilled means that the ratio of fiber length to fiber diameter is 1.
00 or more, but in order to orient it in a certain direction in the resin, it is desirable that the length is 1 cm or more.
繊維状の黒鉛層間化合物とは、炭素繊維の黒鉛層間に各
種の化合物を挿入することにより得られる。挿入する化
合物としては、これまでに黒鉛層間化合物を生成するこ
とが知られているものであれば金属、金属ハロゲン化物
、ハロゲン、有機物等を問わず何でも良い、これは、い
かなる化合物が黒鉛に挿入された場合でも、黒鉛へ正電
荷あるいは負電荷が移動して、これが黒鉛層面の伝導電
荷（黒鉛へ正電荷が移動した場合には正孔、負電荷が移
動した場合には電子）の増大をもたらすためである。た
だし、大部分の黒鉛層間化合物は大気中での安定性に問
題があり、分解が進行するため、挿入する化合物として
は、これまでに大気中で高い安定性を示すことが知られ
ている金属塩化物、金属フッ化物が望ましい。A fibrous graphite intercalation compound is obtained by inserting various compounds between graphite layers of carbon fiber. The compound to be inserted may be any compound known to produce graphite intercalation compounds, including metals, metal halides, halogens, organic substances, etc. This means that any compound can be inserted into graphite. Even in the case where a positive charge or a negative charge moves to the graphite, this causes an increase in the conduction charge on the graphite layer surface (holes when a positive charge moves to graphite, electrons when a negative charge moves). It is to bring about. However, most graphite intercalation compounds have stability problems in the atmosphere and decomposition progresses, so as compounds to be inserted, metals that are known to have high stability in the atmosphere are recommended. Chlorides and metal fluorides are preferred.
また、用いる炭素繊維としては、ピッチ系炭素繊維、気
相成長炭素繊維など、これまでに黒鉛層間化合物を生成
することが知られているものであれば良く、ＰＡＮ系炭
素ｕＩｉ維などの黒鉛層間化合物を生成しない炭素繊維
は原料として用いることは多くの場合困難であるが、黒
鉛構造が高度に発達したものは、使用可能である。In addition, the carbon fibers to be used may be those that are known to produce graphite interlayer compounds, such as pitch-based carbon fibers and vapor-grown carbon fibers, and graphite interlayer compounds such as PAN-based carbon uIi fibers. Carbon fibers that do not generate compounds are difficult to use as raw materials in many cases, but carbon fibers with highly developed graphite structures can be used.
用いる樹脂としてはフェノール樹脂、エポキシ樹脂など
従来知られている熱硬化性樹脂で良いが、炭素粒子や繊
維状黒鉛層間化合物を配合する際、取扱性の点から流動
状、たとえば液状、分散状等であることが望ましい、樹
脂が液状でないとき、溶剤や分散媒を用いて流動状態に
することができる。The resin to be used may be conventionally known thermosetting resins such as phenol resins and epoxy resins, but when blending carbon particles and fibrous graphite intercalation compounds, it is necessary to use fluidized resins such as liquid, dispersed, etc. for ease of handling. When the resin is not in a liquid state, it can be made into a fluid state using a solvent or a dispersion medium.
本発明で用いる炭素粒子とは、カーボンブラック、粉末
黒鉛、膨張黒鉛などの炭素質の粒子より選ばれた一種類
または二種類以上の粉末粒子である。この炭素粒子を樹
脂に配合する際の配合条件、配合量は、用いる樹脂およ
び炭素粒子の種類により決定されるが、樹脂中のｒａｍ
状黒鉛層間化合物同志の接触抵抗を小さくするために、
マトリクスを構成する炭素粒子を配合した熱硬化性樹脂
の電気抵抗を低くしておくことが望ましい。The carbon particles used in the present invention are one or more types of powder particles selected from carbonaceous particles such as carbon black, powdered graphite, and expanded graphite. The blending conditions and blending amount when blending these carbon particles into a resin are determined by the type of resin and carbon particles used, but the ram in the resin
In order to reduce the contact resistance between graphite intercalation compounds,
It is desirable to keep the electrical resistance of the thermosetting resin blended with carbon particles constituting the matrix low.
次に、本発明の導電性複合成形体を製造するには、上記
、炭素ｍ＃Ｉを原料とする繊維状の黒鉛層間化合物と、
炭素粒子を含む硬化前の熱硬化性樹脂より、いわゆるプ
リプレグと呼ばれる前駆体をまず製造する方法が好適で
ある。このプリプレグの製造例を以下に詳細に説明する
。Next, in order to produce the conductive composite molded body of the present invention, the above-mentioned fibrous graphite intercalation compound made from carbon m#I as a raw material,
A preferred method is to first produce a precursor called a prepreg from a thermosetting resin containing carbon particles before curing. An example of manufacturing this prepreg will be described in detail below.
まず、硬化前の液状の熱硬化性樹脂を容器中で攪拌しな
がら、炭素粒子を少量づつ添加する。添加が終わった後
も、炭素粒子が樹脂中に均一に分散するよう、３０分か
ら１時間程度攪拌を継続する１次に、この導電性樹脂を
分散させた液状の熱硬化性樹脂に、ｍ雄状黒鉛層間化合
物を浸す。First, while stirring the liquid thermosetting resin before hardening in a container, carbon particles are added little by little. After the addition is finished, stirring is continued for about 30 minutes to 1 hour so that the carbon particles are uniformly dispersed in the resin. Soak graphite intercalation compound.
この際の方法としては、連続繊維の場合であれば、例え
ば、一方で解いた繊維を容器中の液状樹脂に含浸させた
後、もう一方で巻取りを行う連続含浸装置を用いてプリ
プレグ繊維を得ることができる。また、ａｍ状の黒鉛層
間化合物が比較的短かい繊維である場合は、これを液状
樹脂に浸した後引き上げ、離型紙で、過剰の樹脂を押し
絞った後に一定方向にそろえることにより、プリプレグ
繊維を得る。In the case of continuous fibers, for example, prepreg fibers can be made using a continuous impregnation device that impregnates the unraveled fibers in liquid resin in a container on one side, and then winds them up on the other side. Obtainable. In addition, if the am-like graphite intercalation compound is a relatively short fiber, it can be soaked in liquid resin and then pulled up, and after squeezing out the excess resin with release paper, the prepreg fibers can be aligned in a certain direction. get.
このプリプレグ繊維を、プレス成型により、繊維状の黒
鉛層間化合物が成形体の一方向に配向した導電性樹脂成
形体とする。このプレス成型の方法、条件は、使用する
熱硬化性樹脂、炭素粒子粉末の種類および配合割合等に
より決定されるが、多くの場合に、プレスの前段階で、
プレス成型用金型のプレス面と同じ離型紙の型紙状に、
前述のプリプレグ繊維を一方向に配向させて敷つめたも
のを加熱して部分的に硬化させた後、金型に積層させて
、プレス成型する方法が有効である。こうして製造され
た導電性複合成形体は、導電性樹脂中に繊維状の黒鉛層
間化合物が一方向に配向した構造を有している。This prepreg fiber is press-molded into a conductive resin molded body in which the fibrous graphite intercalation compound is oriented in one direction of the molded body. The method and conditions for this press molding are determined by the thermosetting resin used, the type and blending ratio of carbon particle powder, etc., but in many cases, in the pre-pressing stage,
On the same pattern of release paper as the press surface of the press mold,
An effective method is to heat the aforementioned prepreg fibers oriented in one direction and partially cure them, then laminate them in a mold and press mold them. The conductive composite molded article manufactured in this manner has a structure in which fibrous graphite intercalation compounds are oriented in one direction in a conductive resin.
作用
本発明により得られた複合成形体は、その長さ方向に高
い導電性を示す、その概念図を第１図に示す８図の成形
体中には！ａ線維状黒鉛層間化合物ｌが、炭素粒子２を
均一に分散配合した熱硬化性樹脂３の中に、長さ方向に
沿って一定方向に配合されている。この方向の導電性は
、黒鉛層間化合物の繊維方向と同一であるため大きくな
っている。Function: The composite molded body obtained by the present invention exhibits high electrical conductivity in the longitudinal direction, and the conceptual diagram of the molded body shown in FIG. (a) A fibrous graphite intercalation compound 1 is blended in a constant direction along the length direction in a thermosetting resin 3 in which carbon particles 2 are uniformly dispersed and blended. The conductivity in this direction is high because it is the same as the fiber direction of the graphite intercalation compound.
また、従来、繊維状のフィラーを樹脂に配合させた場合
、樹脂が絶縁性であるために、繊維同志の電気的接触が
不良となり、これを導電性として用いることは困難であ
った。これに対して本発明では、樹脂に炭素粒子を分散
させていることから、配向した繊維同志の接触が起こら
ない場合でも、成形体の導電性は損われない。Furthermore, conventionally, when a fibrous filler is blended into a resin, since the resin is insulating, electrical contact between the fibers becomes poor, making it difficult to use the filler as a conductive material. In contrast, in the present invention, since carbon particles are dispersed in the resin, the conductivity of the molded body is not impaired even when oriented fibers do not come into contact with each other.
実施例
実施例１
ピッチ系炭素繊維に無水塩化第二銅を挿入することによ
り合成した繊維状の黒鉛層間化合物を長さ５０■に切り
そろえ、カーボンブラックを分散させたフェノール樹脂
中に配向配合させて導電性複合成形体を得た。Examples Example 1 A fibrous graphite intercalation compound synthesized by inserting anhydrous cupric chloride into a pitch-based carbon fiber was cut to a length of 50 cm, and oriented and blended into a phenol resin in which carbon black was dispersed. A conductive composite molded body was obtained.
ピッチ系炭素ｍ維はＡｍｏｃｏ社製Ｐ １２０を、無水
塩化第二銅は和光純薬製の特級試薬を、カーボンブラッ
クはライオンアクゾ社製ケッチエンブラックＥＣを、フ
ェノール樹脂は旭有機材製ＲＭ３０００を用いた。成形
体中の組成は、ｍｔａ状の黒鉛層間化合物が４０重量部
、フェノール樹脂が５４重量部、カーボンブラックが６
重量部であった。以下に製造法を詳細に記す。The pitch-based carbon fiber was P 120 manufactured by Amoco, the anhydrous cupric chloride was a special grade reagent manufactured by Wako Pure Chemical Industries, the carbon black was Ketchen Black EC manufactured by Lion Akzo, and the phenol resin was RM3000 manufactured by Asahi Yokuzai. Using. The composition of the molded body is 40 parts by weight of mta-like graphite intercalation compound, 54 parts by weight of phenol resin, and 6 parts by weight of carbon black.
Parts by weight. The manufacturing method will be described in detail below.
■ カーボンブラックを分散させた液状フェノール樹脂
の準備
フェノール樹脂ＲＭ３０００を２００ｇ量り取り、金属
ビーカー中で攪拌されている２００ｇの１ｗｔ％水醜化
ナトリウム水溶液中に注ぎ、全量注ぎ込んだ後も、その
まま３０分間攪拌を継続した０次に、攪拌を続けながら
、この溶液中にカーボンブラックを１５ｇを加えた後、
そのまま３０分間攪拌を継続する。■ Preparation of liquid phenolic resin in which carbon black is dispersed Weigh 200g of phenolic resin RM3000 and pour it into 200g of 1wt% water oxidizing sodium aqueous solution being stirred in a metal beaker.After pouring the entire amount, continue to stir for 30 minutes. Next, while continuing to stir, 15g of carbon black was added to this solution,
Continue stirring for 30 minutes.
■ 繊維状黒鉛層間化合物の合成
塩化第二銅とピッチ系炭素ｍ維により黒鉛層間化合物を
合成する。ｍｔａは長さ５ｃｍに切りそろえたものを用
いた１合成は、従来の方法（炭素、Ｎｏ。■ Synthesis of fibrous graphite intercalation compound A graphite intercalation compound is synthesized using cupric chloride and pitch-based carbon fibers. 1 Synthesis using mta cut to a length of 5 cm was performed using a conventional method (carbon, No.
１３５ 、２６７［１９８８］）に従い、反応後はエタ
ノールで洗？％Ｌ１２０℃、１２時間乾燥させた。生成
物の組成がＣ１２ＣＬＩＣ１２の繊維状黒鉛層間化合物
を得た。135, 267 [1988]), wash with ethanol after the reaction. %L 120°C for 12 hours. A fibrous graphite intercalation compound having a product composition of C12CLIC12 was obtained.
■ ｂステージプリプレグの作成
■のカーボンブラックを分散させた液状フェノール樹脂
に、■の黒鉛層間化合物を浸した後に離型紙上に置き、
この上から離型紙を一定方向にそろえて置き上から手で
押さえて、離型紙で、過剰の樹脂を押し絞ることにより
プリプレグ繊維を得た。このプリプレグｍ雄を、離型紙
に多数描かれたプレス面と同型の枠へｍ！ｌを一定方向
に薄く敷き詰める。このｍ型紙ごと１２０℃の恒温槽に
４分間入れて取り出す、こうして室温で固体状態のｂス
テージプリプレグが得られた。■ Creation of b-stage prepreg After soaking the graphite intercalation compound (■) in the liquid phenol resin in which carbon black is dispersed (■), place it on release paper.
A prepreg fiber was obtained by placing release paper aligned in a certain direction on top of this, pressing it down with your hands, and squeezing out excess resin with the release paper. Place this male prepreg m into a frame of the same type as the press surface drawn on the release paper. Spread l thinly in a certain direction. This M-pattern paper was placed in a constant temperature bath at 120° C. for 4 minutes and then taken out, thereby obtaining a b-stage prepreg that was in a solid state at room temperature.
■ ホットプレス成型
■で得られたｂステージプリプレグをプレス金型の型枠
に積層させ、プレス成型する。この場合の条件として金
型を１２０℃に加熱後、プレス圧力２０〜５０ｋｇ／ｃ
ｍ２に保って１６０℃まで昇温、そのまま３０分間保っ
た。こうして製造された導電性複合成形体は、導電性樹
脂中に繊維状の黒鉛層間化合物が一方向に配向した構造
を持っていた。■ Hot press molding The b-stage prepreg obtained in ■ is laminated on the formwork of a press mold and press molded. The conditions in this case are that after heating the mold to 120°C, press pressure is 20 to 50 kg/c.
The temperature was raised to 160° C. and kept at that temperature for 30 minutes. The conductive composite molded article thus produced had a structure in which fibrous graphite intercalation compounds were oriented in one direction in the conductive resin.
得られた、導電性複合成形体を、切断、研磨し、測定し
たところ、密度が１．７０ｇ／ｃ塵２、長さ方向の電気
抵抗が４００ｇ量ｃｍであった。The obtained conductive composite molded body was cut, polished, and measured, and the density was 1.70 g/c dust 2 and the electric resistance in the longitudinal direction was 400 g/cm.
実施例２
ピッチ系炭素繊維に無水塩化第二銅を挿入することによ
り合成した繊維状の黒鉛層間化合物を長さ５ｃ篇に切り
そろえ、カーボンブラックおよび粉末黒鉛を分散させた
フェノール樹脂中に配向配合させて導電性複合成形体を
得た。Example 2 A fibrous graphite intercalation compound synthesized by inserting anhydrous cupric chloride into pitch-based carbon fibers was cut into lengths of 5 cm, and oriented and blended into a phenol resin in which carbon black and powdered graphite were dispersed. A conductive composite molded body was obtained.
ピッチ系炭素ｍ維はＡｙａｏｃｏ社製Ｐ １２０を、無
水塩化第二銅は和光純薬製の特級試薬を、カーボンブラ
ックはライオンアクゾ社製ケッチエンブラックＥＣを、
粉末黒鉛はＬｏｎｚａ社製ＫＳ１５を、フェノール樹脂
は旭有機材製ＲＭ３０００を用いた。製造法は、実施例
１に準じた。ただし、用いたカーボンブラックの門をｌ
Ｏｇとじ、黒鉛粉末の量を３０ｇとした。成形体中の組
成は、繊維状の黒鉛層間化合物が４０重量部、フェノー
ル樹脂が４７重量部、カーボンブラックが３重量部、粉
末黒鉛が１０重量部であった。The pitch-based carbon fiber was P 120 manufactured by Ayaoco, the anhydrous cupric chloride was a special grade reagent manufactured by Wako Pure Chemical Industries, and the carbon black was Ketchen Black EC manufactured by Lion Akzo.
KS15 manufactured by Lonza was used as the powdered graphite, and RM3000 manufactured by Asahi Yukizai was used as the phenolic resin. The manufacturing method was the same as in Example 1. However, the carbon black gate used
The amount of graphite powder was 30 g. The composition of the molded body was 40 parts by weight of fibrous graphite intercalation compound, 47 parts by weight of phenol resin, 3 parts by weight of carbon black, and 10 parts by weight of powdered graphite.
得られた。導電性複合成形体を、切断、研磨し、測定し
たところ、密度が１．７４ｇ／Ｃｍ２．長さ方向の電気
抵抗が２８０１ＬΩｃｍであった。Obtained. When the conductive composite molded body was cut, polished, and measured, the density was found to be 1.74 g/Cm2. The electrical resistance in the length direction was 2801 LΩcm.
実施例３
ピッチ系炭素繊維に無水塩化第二銅を挿入することによ
り合成した繊維状の黒鉛層間化合物を長さ５Ｃ厘に切り
そろえ、粉末黒鉛を分散させたフェノール樹脂中に配向
配合させて導電性複合成形体を得た。Example 3 A fibrous graphite intercalation compound synthesized by inserting anhydrous cupric chloride into pitch-based carbon fibers was cut to a length of 5C, and oriented and blended into a phenol resin in which powdered graphite was dispersed to make it conductive. A composite molded body was obtained.
ピッチ系炭素繊維はＡｍｏｃｏ社製Ｐ １２０を、無水
塩化第二銅は和光純薬製の特級試薬を、粉末黒鉛はＬａ
ｎｚａ社製ＫＳ社製全Ｓ１５ノール樹脂は旭有機材製Ｒ
Ｍ ３０００を用いた。製造法は、実施例１に準じた。The pitch-based carbon fiber was P 120 manufactured by Amoco, the anhydrous cupric chloride was a special grade reagent manufactured by Wako Pure Chemical Industries, and the powdered graphite was La.
All S15 kol resins manufactured by NZA and KS are R manufactured by Asahi Yukizai.
M3000 was used. The manufacturing method was the same as in Example 1.
ただし、黒鉛粉末の量を４０ｇとした。成形体中の組成
は、ａｍ状の黒鉛層間化合物が４０重量部、フェノール
樹脂が４７重量部、粉末黒鉛が１３重置部であった・
得られた、導電性複合成形体を、切断、研磨し、測定し
たところ、密度が１．７０ ｇ ／ ａｍ２．長さ方向
の電気抵抗が３８０ルΩＣｍｌであった。However, the amount of graphite powder was 40 g. The composition of the molded body was 40 parts by weight of am-shaped graphite intercalation compound, 47 parts by weight of phenolic resin, and 13 parts by weight of powdered graphite.The obtained conductive composite molded body was cut and polished. However, when measured, the density was 1.70 g/am2. The electrical resistance in the longitudinal direction was 380 ΩCml.
実施例４
ピッチ系炭素繊維に無水塩化ニッケルを挿入することに
より合成した繊維状の黒鉛層間化合物を長さ５ｃｍに切
りそろえ、カーボンブラックおよび粉末黒鉛を分散させ
たフェノール樹脂中に配向配合させて導電性複合成形体
を得た。Example 4 A fibrous graphite intercalation compound synthesized by inserting anhydrous nickel chloride into pitch-based carbon fibers was cut to a length of 5 cm, and oriented and blended into a phenol resin in which carbon black and powdered graphite were dispersed to make it conductive. A composite molded body was obtained.
ピッチ系炭素繊維はＡｍｏｃｏ社製Ｐ１２０を、無水塩
化ニッケルは和光紬薬製の特轟試薬を、カーボンブラッ
クはライオンアクゾ社製ケッチエンブラックＥＣを、粉
末黒鉛はＬｏｎｚａ社製ＫＳ社製全Ｓ１５ノール樹脂は
旭有機材製ＲＭ３０００を用いた。製造法は、実施例１
に準じた。ただし、用いたカーボンブラックの量を１０
ｇとし、黒鉛粉末の量を３０ｇとした。また、黒鉛層間
化合物の合成は従来法に準じ、生成した黒鉛層間化合物
の組成はＣ、ｕＮ ｉ ０１□であった１、成形体中の
組成は、繊維状の黒鉛居間化合物が４０重量部、フェノ
ール樹脂が４７重量部、カーボンブラックが３重量部、
粉末黒鉛が１０重量部であった。The pitch-based carbon fiber was P120 manufactured by Amoco, the anhydrous nickel chloride was Tokudo Reagent manufactured by Wako Tsumugi, the carbon black was Ketchen Black EC manufactured by Lion Akzo, and the powdered graphite was All S15 Nord manufactured by Lonza KS. As the resin, RM3000 manufactured by Asahi Yukizai was used. The manufacturing method is Example 1
According to. However, the amount of carbon black used was
g, and the amount of graphite powder was 30 g. In addition, the graphite intercalation compound was synthesized according to the conventional method, and the composition of the graphite intercalation compound produced was C, uN i 01 □1, and the composition in the molded body was 40 parts by weight of the fibrous graphite living compound, 47 parts by weight of phenolic resin, 3 parts by weight of carbon black,
Powdered graphite was 10 parts by weight.
得られた、導電性複合成形体を、切断、研磨し、測定し
たところ、密度が１．６５ｇ ／ ｃｍ２．長さ方向の
電気抵抗が４２０ ＬＬΩｃｍであった。The resulting conductive composite molded body was cut, polished, and measured, and the density was found to be 1.65 g/cm2. The electrical resistance in the longitudinal direction was 420 LLΩcm.
比較例１
ピッチ系炭素繊維に無水塩化第二銅を挿入することによ
り合成した繊維状の黒鉛層間化合物を長さ５０層に切り
そろえ、フェノール樹脂中に混練、配合させてプレス成
型を行うことにより複合成形体を得た。Comparative Example 1 A fibrous graphite intercalation compound synthesized by inserting anhydrous cupric chloride into pitch-based carbon fibers was cut into 50 layers, kneaded and blended into a phenol resin, and press-molded to create a composite. A molded body was obtained.
ビー７チ系炭素繊維はＡｍｏｃｏ社製Ｐ１２０を、無水
塩化第二銅は和光紬薬製の特級試薬を、フェノール樹脂
は旭有機材製ＲＭ３０００を用いた。混線はロールミル
にて行った。黒鉛層間化合物の合成は従来法に準じ、生
成した黒鉛層間化合物の組成はＣＩ２ ＣｕＣ２２であ
った。成形体中組成は、黒鉛層間化合物が４０重量部、
フェノール樹脂が６０重量部であった。The Beech carbon fiber used was P120 manufactured by Amoco, the anhydrous cupric chloride used a special grade reagent manufactured by Wako Tsumugi, and the phenol resin used RM3000 manufactured by Asahi Yokuzai. Crosstalk was done using a roll mill. The graphite intercalation compound was synthesized according to a conventional method, and the composition of the graphite intercalation compound produced was CI2 CuC22. The composition of the molded body is 40 parts by weight of graphite intercalation compound,
The phenolic resin was 60 parts by weight.
得られた、複合成形体を、切断、研磨し、長さ方向の電
気抵抗を測定したところ、１０７ΩＣ膳であった・
本比較例１から、導電性の固体粒子を配合することなく
、また、ｍ雄状の黒鉛層間化合物を一定方向に配向させ
ることを行わない場合には、成形体の導電性はきわめて
悪いことがわかる。これは、比較例１の場合に樹脂中に
導電性を改善する炭素粒子が存在しないため黒鉛層間化
合物同志の電気的接触が起こりにくくなっていることに
よると考えられる。The obtained composite molded body was cut and polished, and the electric resistance in the longitudinal direction was measured, and it was found to be 107 ΩC. From this comparative example 1, without blending conductive solid particles, and It can be seen that when the m-male graphite intercalation compound is not oriented in a certain direction, the conductivity of the molded body is extremely poor. This is considered to be because, in the case of Comparative Example 1, there are no carbon particles that improve conductivity in the resin, making it difficult for the graphite intercalation compounds to make electrical contact with each other.
比較例２
粉末黒鉛に無水塩化第二銅を挿入することにより合成し
た粉末状の黒鉛層間化合物を、フェノール樹脂中に混練
、配合させてプレス成型を行うことにより複合成形体を
得た。Comparative Example 2 A powdered graphite intercalation compound synthesized by inserting anhydrous cupric chloride into powdered graphite was kneaded and blended into a phenol resin and press-molded to obtain a composite molded body.
粉末黒鉛はＬ）ｎｚａ社製を、無水塩化第二銅は和光紬
薬製の特級試薬を、フェノール樹脂は旭有機材製ＲＭ３
（１００を用いた。混練はロールミルにて行った。黒鉛
層間化合物の合成は従来法に準じ、生成した黒鉛層間化
合物の組成はＣ１１ＣｕＣ之２であった。ｒ＆形体中の
組成は、粉末の黒鉛層間化合物が４０重量部、フェノー
ル樹脂が８０重量部であった。Powdered graphite was made by L) NZA, anhydrous cupric chloride was a special grade reagent made by Wako Tsumugi, and phenol resin was made by Asahi Yokuzai RM3.
(100 was used. Kneading was performed in a roll mill. The graphite intercalation compound was synthesized according to the conventional method, and the composition of the graphite intercalation compound produced was C11CuC2. The composition in the r& shape was powdered graphite. The intercalation compound was 40 parts by weight, and the phenol resin was 80 parts by weight.
得られた。複合成形体を、切断、研磨し、長さ方向の電
気抵抗を測定したところ、１０７ΩＣ１１であった・
本比較例２から、繊維状の黒鉛層間化合物を用いること
なく粉末の黒鉛層間化合物を用いる場合には、成形体の
導電性はきわめて悪いことがわかる。これは、比較例２
の場合に樹脂中で粉末の黒鉛層間化合物同志の電気的接
触がきわめて起こりにくくなっていることによると考え
られる。Obtained. When the composite molded body was cut and polished and the electrical resistance in the longitudinal direction was measured, it was 107ΩC11. From this comparative example 2, when using a powdered graphite intercalation compound without using a fibrous graphite intercalation compound It can be seen that the conductivity of the molded body is extremely poor. This is Comparative Example 2
This is thought to be due to the fact that electrical contact between the powdered graphite intercalation compounds in the resin becomes extremely difficult to occur in this case.
発明の効果
本発明の成形体は、金属に比べて軽量で、かつ従来の導
電性樹脂に比べて導電性が高いことから、モーターブラ
シ、電磁波シールド材料４導電性フンパウンド等への応
用が期待される。Effects of the Invention The molded product of the present invention is lighter than metal and has higher conductivity than conventional conductive resins, so it is expected to be applied to motor brushes, electromagnetic shielding material 4 conductive powder, etc. be done.
第１図は導電性複合成形体を透視した場合の概念図であ
る。
１
・繊維状の黒鉛層間化合物、
２・ ・ φ炭
素粒子、
３・−・熱硬化性樹脂。FIG. 1 is a conceptual diagram when the conductive composite molded body is seen through. 1. Fibrous graphite intercalation compound, 2. φ carbon particles, 3. --Thermosetting resin.
Claims (1)
物を配合し、且つ熱硬化性樹脂中に繊維状の黒鉛層間化
合物を一定方向に配向してなる軽量導電性複合成形体。A lightweight conductive composite molded article, which is formed by blending carbon particles and a fibrous graphite intercalation compound in a thermosetting resin, and orienting the fibrous graphite intercalation compound in a certain direction in the thermosetting resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1263809A JPH03126296A (en) | 1989-10-12 | 1989-10-12 | Lightweight conductive composite molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1263809A JPH03126296A (en) | 1989-10-12 | 1989-10-12 | Lightweight conductive composite molding |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03126296A true JPH03126296A (en) | 1991-05-29 |
Family
ID=17394543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1263809A Pending JPH03126296A (en) | 1989-10-12 | 1989-10-12 | Lightweight conductive composite molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03126296A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0546182A1 (en) * | 1991-05-28 | 1993-06-16 | Osaka Gas Co., Ltd. | Method for absorbing electromagnetic wave |
| JPH05155610A (en) * | 1991-11-29 | 1993-06-22 | Mitsubishi Pencil Co Ltd | Carbon material for electrode and its production |
-
1989
- 1989-10-12 JP JP1263809A patent/JPH03126296A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0546182A1 (en) * | 1991-05-28 | 1993-06-16 | Osaka Gas Co., Ltd. | Method for absorbing electromagnetic wave |
| EP0546182A4 (en) * | 1991-05-28 | 1995-01-11 | Osaka Gas Co Ltd | |
| JPH05155610A (en) * | 1991-11-29 | 1993-06-22 | Mitsubishi Pencil Co Ltd | Carbon material for electrode and its production |
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