JPH05106164A - Carbon fiber and carbon fiber-reinforced resin composition produced by using the same - Google Patents
Carbon fiber and carbon fiber-reinforced resin composition produced by using the sameInfo
- Publication number
- JPH05106164A JPH05106164A JP26645891A JP26645891A JPH05106164A JP H05106164 A JPH05106164 A JP H05106164A JP 26645891 A JP26645891 A JP 26645891A JP 26645891 A JP26645891 A JP 26645891A JP H05106164 A JPH05106164 A JP H05106164A
- Authority
- JP
- Japan
- Prior art keywords
- carbon fiber
- weight
- resin
- resin composition
- coated
- 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.)
- Granted
Links
Landscapes
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Inorganic Fibers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は帯電防止材料等に使用す
る炭素繊維及びその炭素繊維を熱可塑性樹脂に配合して
なる炭素繊維強化樹脂組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbon fiber used for an antistatic material and the like and a carbon fiber reinforced resin composition obtained by mixing the carbon fiber with a thermoplastic resin.
【０００２】[0002]
【従来の技術】一般に、プラスチックスは絶縁材料であ
るが、その量産性、デザインの自由度・軽量性等の観点
からプラスチックス、熱可塑性樹脂がハウジング材料の
主流となっている。しかし、絶縁材料であるためにその
ままでは著しく帯電するためにほこりやゴミが付着し
て、製品の汚染、装置の静電気による誤動作や火花放電
が生じやすい。そのためこの帯電を防止するためにプラ
スチックスの導電化が行われている。このプラスチック
スの導電化のためには、種々の方法が提案されている
が、通常は成形と同時に導電性が付与でき、従って工程
上低コストにできる導電性プラスチックが主流とされて
いる。そして、かかる導電性プラスチックとしては、一
般にポリエステル、ポリアミド、ポリオレフィン、アク
リル樹脂、エポキシ樹脂、フェノール樹脂等の各種マト
リックスにフィラーを混合、分散させて繊維強化樹脂材
料を得、次いで導電性を付与するに、導電性カーボンブ
ラック、金属フィラー、や金属繊維等の導電性フィラー
あるいは帯電防止剤を添加する。しかし導電性フィラー
の場合は、プラスチックスに導電性は付与するものの機
械的物性を低下させこそすれ改善することが出来ないと
いう問題があった。一方、帯電防止剤の場合は、成形品
の表面に塗布する方法と、成形体製造時に一緒に練り込
む方法が知られている。前者の場合は、高い効果が得ら
れるが、持久性に乏しく、また塗布面がベトツクとかブ
ロッキング等の課題があり、後者の場合は持久力が優れ
ているが、帯電防止効果が不十分のために多量の帯電防
止剤を添加せねば成らず、成形体表面にベトツキ感が現
れかつ耐熱性が低下し着色の問題も起こってくる。2. Description of the Related Art Generally, plastics are insulating materials, but plastics and thermoplastic resins are the mainstream of housing materials from the viewpoints of mass productivity, design flexibility and lightness. However, since it is an insulating material, it is significantly charged as it is, and dust and dirt are attached to it, which easily causes product malfunction, malfunction due to static electricity of the device, and spark discharge. Therefore, in order to prevent this charging, plastics are made conductive. Various methods have been proposed for making the plastics conductive, but conductive plastics are usually the mainstream because they can be made conductive at the same time as molding, and can therefore be manufactured at low cost. And, as such a conductive plastic, generally, a filler is mixed and dispersed in various matrices such as polyester, polyamide, polyolefin, acrylic resin, epoxy resin, and phenol resin to obtain a fiber-reinforced resin material, and then to impart conductivity. , Conductive carbon black, a metal filler, a conductive filler such as a metal fiber, or an antistatic agent is added. However, in the case of the conductive filler, there is a problem in that the conductivity can be imparted to the plastics, but the mechanical properties cannot be reduced to improve the mechanical properties. On the other hand, in the case of an antistatic agent, a method of applying it to the surface of a molded article and a method of kneading it together at the time of manufacturing a molded article are known. In the case of the former, a high effect is obtained, but the durability is poor, and there are problems such as sticky or blocking of the coated surface.In the case of the latter, the endurance is excellent, but the antistatic effect is insufficient. Since a large amount of antistatic agent must be added to the above, a sticky feeling appears on the surface of the molded product, heat resistance is lowered, and a coloring problem occurs.
【０００３】これに対し、炭素繊維は強化繊維としては
導電性を有し上記用途に適している。炭素繊維は、高強
度、高剛性を保持しつつ、高電気伝導性であることから
繊維強化複合材の機械的物性を保持しつつ電気的に導電
性を付与する強化繊維として注目され使用されるように
なっている。On the other hand, carbon fiber has conductivity as a reinforcing fiber and is suitable for the above applications. Since carbon fiber has high electrical conductivity while maintaining high strength and high rigidity, it has attracted attention and is used as a reinforcing fiber that imparts electrical conductivity while maintaining the mechanical properties of the fiber-reinforced composite material. It is like this.
【０００４】[0004]
【発明が解決しようとする課題】しかし、通常の従来の
炭素繊維を使用しても帯電防止性を付与するためにはか
なりの量の炭素繊維を添加せねば成らずコストの面で課
題があった。また、通常の帯電防止剤では、上記課題の
他、表面の有機溶剤による洗浄によって一旦低下した導
電性の復元が起こりにくい点が課題となっていた。However, even if ordinary conventional carbon fibers are used, a considerable amount of carbon fibers must be added in order to impart antistatic properties, and there is a problem in terms of cost. It was In addition to the above-mentioned problems, the conventional antistatic agent has another problem that it is difficult to restore the conductivity once lowered by washing with the organic solvent on the surface.
【０００５】[0005]
【課題を解決するための手段】そこで本発明者等は、か
かる課題を解決すべく鋭意検討した結果、特定の組成か
らなる重合物と少量の界面活性剤で被覆した炭素繊維を
使用すると従来よりも少量の配合量で同等の帯電防止性
を発現し、かつ表面を有機溶剤により洗浄することによ
って一旦低下した導電性の復元が可能であり、しかも優
れた機械的物性を示す炭素繊維強化樹脂が得られること
を見いだし、本発明に到達した。The inventors of the present invention have made extensive studies in order to solve the above problems, and as a result, when a carbon fiber coated with a polymer having a specific composition and a small amount of a surfactant was used, A carbon fiber reinforced resin that exhibits the same antistatic property even with a small amount of compound and that can restore the conductivity once lowered by washing the surface with an organic solvent and that has excellent mechanical properties. The inventors have found what is obtained and have reached the present invention.
【０００６】即ち、本発明の目的は優れた帯電防止性、
機械的物性を発現する樹脂組成物を与える樹脂強化用炭
素繊維及びそれを用いた炭素繊維強化樹脂組成物を提供
することにある。そしてその目的は、炭素繊維として
は、モノマー組成として、ジアミン化合物、ジカルボン
酸化合物及び下記一般式（Ｉ）で示される１０〜３０重
量％のグリシジル化ポリアルキレンオキシド誘導体を含
んでなる共重合体並びに界面活性剤を含む帯電防止剤を
含有するサイジング剤で表面が被覆されていることを特
徴とする炭素繊維、That is, the object of the present invention is to provide excellent antistatic property,
It is an object of the present invention to provide a carbon fiber for resin reinforcement which gives a resin composition exhibiting mechanical properties and a carbon fiber reinforced resin composition using the same. The purpose of the carbon fiber is, as a monomer composition, a diamine compound, a dicarboxylic acid compound, and a copolymer containing 10 to 30% by weight of a glycidylated polyalkylene oxide derivative represented by the following general formula (I), and A carbon fiber whose surface is coated with a sizing agent containing an antistatic agent containing a surfactant,
【０００７】[0007]
【化３】 [Chemical 3]
【０００８】（式中Ｒ1 はＨまたは炭素数２０以下のア
ルキル基、Ｒ2 はＨまたはＣＨ3 、ｎは１〜４０の整数
を表わす。） さらに樹脂組成物としては、モノマー組成として、ジア
ミン化合物、ジカルボン酸化合物及び下記一般式（Ｉ）
で示される１０〜３０重量％のグリシジル化ポリアルキ
レンオキシド誘導体を含んでなる共重合体並びに界面活
性剤を含む帯電防止剤を含有するサイジング剤で表面が
被覆されている炭素繊維１〜４０重量部を熱可塑性樹脂
１００重量部に対して配合したことを特徴とする炭素繊
維強化樹脂組成物、(In the formula, R 1 is H or an alkyl group having 20 or less carbon atoms, R 2 is H or CH 3 , and n is an integer of 1 to 40.) Further, as the resin composition, the monomer composition is diamine. Compounds, dicarboxylic acid compounds and the following general formula (I)
1 to 40 parts by weight of carbon fiber whose surface is coated with a sizing agent containing a copolymer containing 10 to 30% by weight of a glycidylated polyalkylene oxide derivative and an antistatic agent containing a surfactant. Is added to 100 parts by weight of a thermoplastic resin, a carbon fiber reinforced resin composition,
【０００９】[0009]
【化４】 [Chemical 4]
【００１０】（式中Ｒ1 はＨまたは炭素数２０以下のア
ルキル基、Ｒ2 はＨまたはＣＨ3 、ｎは１〜４０の整数
を表わす。） によって達成される。以下本発明を詳細に説明する。(Wherein R 1 is H or an alkyl group having 20 or less carbon atoms, R 2 is H or CH 3 , and n is an integer of 1 to 40). The present invention will be described in detail below.
【００１１】本発明では炭素繊維として従来公知の種々
の炭素繊維が使用でき、具体的にはポリアクリロニトリ
ル系、ピッチ系、レーヨン系等の炭素繊維が挙げられ
る。被覆に使用する重合物としてはジアミン、ジカルボ
ン酸とグリシジル化ポリアルキレンオキシドの共重合体
である。ジアミン化合物としては特に限定されないが一
般式（II）で示される化合物でＲ3 が炭素数１５以下の
アルキル基、およびその誘導体からなるものが好まし
い。具体的にはエチレンジアミン、テトラメチレンジア
ミン、ヘキサメチレンジアミン、オクタメチレンジアミ
ン、デカメチレンジアミンやそのメチル化、エチル化、
ハロゲン化物等の誘導体が挙げられる。In the present invention, various conventionally known carbon fibers can be used as the carbon fibers, and specific examples thereof include polyacrylonitrile-based, pitch-based and rayon-based carbon fibers. The polymer used for coating is a copolymer of diamine, dicarboxylic acid and glycidylated polyalkylene oxide. The diamine compound is not particularly limited, but a compound represented by the general formula (II) in which R 3 is an alkyl group having 15 or less carbon atoms and a derivative thereof is preferable. Specifically, ethylenediamine, tetramethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine and its methylation, ethylation,
Examples thereof include derivatives such as halides.
【００１２】Ｈ2 Ｎ−Ｒ3 −ＮＨ2 （II) ジカルボン酸化合物としては一般式(III) で示される化
合物であり、好ましくはＲ4 が炭素数１５以下のアルキ
ル基、単核または２核芳香族環及びこれらの誘導体から
なるものである。具体的にはコハク酸、グルタル酸、ア
ジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セ
バシン酸およびそのメチル化、エチル化、ハロゲン化物
等の誘導体や、テレフタル酸、イソフタル酸、２，６−
ナフタレンジカルボン酸等の芳香族ジカルボン酸等が挙
げられる。The H 2 N—R 3 —NH 2 (II) dicarboxylic acid compound is a compound represented by the general formula (III), preferably R 4 is an alkyl group having 15 or less carbon atoms, mononuclear or dinuclear. It is composed of an aromatic ring and derivatives thereof. Specifically, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and its derivatives such as methylation, ethylation and halides, terephthalic acid, isophthalic acid, 2,6-
Examples thereof include aromatic dicarboxylic acids such as naphthalenedicarboxylic acid.
【００１３】ＨＯＯＣ−Ｒ4 −ＣＯＯＨ （III) 一般式（Ｉ）で示されるグリシジル化ポリアルキレンオ
キシド誘導体は、片末端にグリシジル基を有するエチレ
ンオキシド、プロピレンオキシドの付加反応生成物のア
ルキルエーテルであり、ｎは１〜４０、好ましくは５〜
２０、Ｒ1は炭素数２０以下のアルキル基が挙げられ
る。具体的には、ポリオキシエチレンラウリルグリシジ
ルエーテル、ポリオキシエチレンオクチルグリシジルエ
ーテル等が挙げられる。HOOC-R 4 -COOH (III) The glycidylated polyalkylene oxide derivative represented by the general formula (I) is an alkyl ether of an addition reaction product of ethylene oxide and propylene oxide having a glycidyl group at one end, n is 1 to 40, preferably 5
Examples of 20 and R 1 include alkyl groups having 20 or less carbon atoms. Specific examples include polyoxyethylene lauryl glycidyl ether and polyoxyethylene octyl glycidyl ether.
【００１４】[0014]
【化５】 [Chemical 5]
【００１５】モノマー組成比は混合物がほぼ完全に重合
し適当な分子量のポリマーが得られる範囲において決定
されるが、帯電防止性向上の効果を得るにはグリシジル
化ポリアルキレンオキシド誘導体の含有率としては、１
０〜３０重量％、好ましくは２５〜３０重量％の範囲と
するのがよい。含有率が高すぎても、また低すぎても良
好な帯電防止性が得られない。The monomer composition ratio is determined within a range in which the mixture is almost completely polymerized to obtain a polymer having an appropriate molecular weight. To obtain the effect of improving the antistatic property, the content ratio of the glycidylated polyalkylene oxide derivative is 1
The range is 0 to 30% by weight, preferably 25 to 30% by weight. If the content is too high or too low, good antistatic properties cannot be obtained.
【００１６】ついでアニオン系、ノニオン系もしくは両
性の界面活性剤としては、オレフィンの硫酸化エステル
油、硫酸化アミド油、脂肪族アルコールの硫酸エステル
塩、アルキル硫酸エステル塩、脂肪族エチルスルホン酸
塩、アルキルスルホン酸塩、アルキルナフタレンスルホ
ン酸塩、アルキルベンゼンスルホン酸塩等のアニオン界
面活性剤；多価アルコールの脂肪酸エステル、脂肪族ア
ルコールのエチレンオキサイド付加物、脂肪族酸のエチ
レンオキサイド付加物、脂肪族アミンもしくは脂肪族ア
ミドのエチレンオキサイド付加物、アルキルフェノール
のエチレンオキサイド付加物、ポリエチレングリコール
等のノニオン界面活性剤；カルボン酸型、スルホン酸型
等の両性界面活性剤が挙げられる。Next, as anionic, nonionic or amphoteric surfactants, sulfated ester oils of olefins, sulfated amide oils, sulfated ester salts of aliphatic alcohols, alkyl sulfated ester salts, aliphatic ethyl sulfonates, Anionic surfactants such as alkyl sulfonates, alkyl naphthalene sulfonates, alkyl benzene sulfonates; fatty acid esters of polyhydric alcohols, ethylene oxide adducts of aliphatic alcohols, ethylene oxide adducts of aliphatic acids, aliphatic amines Alternatively, ethylene oxide adducts of aliphatic amides, ethylene oxide adducts of alkylphenols, nonionic surfactants such as polyethylene glycol; and amphoteric surfactants such as carboxylic acid type and sulfonic acid type.
【００１７】通常炭素繊維は数千本から数万本の単糸を
束ねたストランドを樹脂により被覆集束することにより
取り扱い性を向上させたり、樹脂に配合し複合材とした
ときの特性向上を図っている。得られた重合物と上記界
面活性剤との混合液の炭素繊維表面への付着法に制約は
ないが水溶液とし炭素繊維束を含浸する方法が実用的で
ある。水溶液の濃度は炭素繊維に付着する量が所望する
レベルとなるよう設定すれば良い。重合物と界面活性剤
の混合割合としては、重合物に対して２０〜６０重量
％、好ましくは４０〜６０重量％である。界面活性剤の
量が多いと帯電防止性は発現するが、炭素繊維の集束性
が劣化する。また、少なすぎると表面の有機溶剤による
洗浄によって一旦低下した導電性は復元が困難になる。
炭素繊維に付着する量としては、０．５〜１０重量％、
好ましくは２〜１０重量％である。被覆量が少ないと、
集束剤による複合材特性向上の効果がみられなかった
り、炭素繊維の集束性が不十分だったりする。また、被
覆量が多すぎると、かえって複合材物性が低下したり、
集束後の炭素繊維ストランドの取扱い性が低下したりす
る。該混合物水溶液に含浸した炭素繊維ストランドは赤
外線、熱風等によって乾燥されるが、乾燥温度は集束剤
の分解が起こらないよう３００℃以下とする事が好まし
い。乾燥し集束された炭素繊維束は、樹脂との配合を容
易にするため１〜２０mm好ましくは３〜１０mmにカット
し使用する（カットされた炭素繊維ストランドをチョッ
プトストランドと呼ぶ。）。Normally, carbon fibers are used to improve the handleability by coating and concentrating strands obtained by bundling thousands to tens of thousands of single yarns with a resin, or to improve the characteristics when compounded with a resin to form a composite material. ing. Although there is no restriction on the method of adhering the mixed liquid of the obtained polymer and the above-mentioned surfactant to the carbon fiber surface, a method of impregnating the carbon fiber bundle as an aqueous solution is practical. The concentration of the aqueous solution may be set so that the amount attached to the carbon fibers is at a desired level. The mixing ratio of the polymer and the surfactant is 20 to 60% by weight, preferably 40 to 60% by weight, based on the polymer. When the amount of the surfactant is large, the antistatic property is exhibited, but the sizing property of the carbon fiber is deteriorated. On the other hand, if the amount is too small, it becomes difficult to restore the conductivity once lowered by washing with the organic solvent on the surface.
The amount attached to the carbon fiber is 0.5 to 10% by weight,
It is preferably 2 to 10% by weight. When the coating amount is small,
The effect of improving the properties of the composite material by the sizing agent is not observed, or the sizing property of the carbon fiber is insufficient. Further, if the coating amount is too large, the physical properties of the composite material are rather deteriorated,
The handleability of the carbon fiber strand after bundling may be reduced. The carbon fiber strands impregnated with the aqueous solution of the mixture are dried by infrared rays, hot air or the like, but the drying temperature is preferably 300 ° C. or lower so that the sizing agent is not decomposed. The dried and bundled carbon fiber bundle is used after being cut into 1 to 20 mm, preferably 3 to 10 mm to facilitate blending with the resin (the cut carbon fiber strand is referred to as chopped strand).
【００１８】次に、本発明の樹脂強化用炭素繊維を熱可
塑性樹脂に配合した優れた帯電防止性を有する炭素繊維
強化樹脂組成物について説明する。マトリックス樹脂と
しては、ポリカーボネート、アクリロニトリル−ブタジ
エン−スチレン樹脂（ＡＢＳ樹脂）、ポリブチレンテレ
フタレート、ポリフェニレンオキシド、ポリスチレン、
ポリエステル、ポリオレフィン、アクリル樹脂、ポリオ
キシメチレン、ポリフェニレンエーテル、ポリフェニレ
ンオキシド、ポリブチレンテレフタレート、ポリエーテ
ルエーテルケトン、ポリフェニレンスルホン、フッ素樹
脂などのポリマー類またはこれらのコポリマー類などの
公知の熱可塑性樹脂が挙げられる。Next, a carbon fiber-reinforced resin composition having excellent antistatic properties, which is obtained by blending the resin-reinforced carbon fiber of the present invention with a thermoplastic resin, will be described. As the matrix resin, polycarbonate, acrylonitrile-butadiene-styrene resin (ABS resin), polybutylene terephthalate, polyphenylene oxide, polystyrene,
Known thermoplastic resins such as polyesters, polyolefins, acrylic resins, polyoxymethylene, polyphenylene ethers, polyphenylene oxides, polybutylene terephthalates, polyether ether ketones, polyphenylene sulfones, fluororesins and other polymers or copolymers thereof can be mentioned. ..
【００１９】上述した樹脂強化用炭素繊維とマトリック
ス樹脂の配合割合は、熱可塑性樹脂１００重量部に対し
て、炭素繊維を１〜５０重量部、好ましくは、５〜３０
重量部の範囲である。炭素繊維の配合量が１重量部未満
では炭素繊維の帯電防止効果が発揮されず、また５０重
量部を越えるとマトリックス樹脂への混合、分散の工程
に於て種々の問題が発生しやすい。The mixing ratio of the carbon fiber for resin reinforcement and the matrix resin is 1 to 50 parts by weight, preferably 5 to 30 parts by weight of carbon fiber to 100 parts by weight of the thermoplastic resin.
The range is parts by weight. If the blending amount of the carbon fibers is less than 1 part by weight, the antistatic effect of the carbon fibers is not exhibited, and if it exceeds 50 parts by weight, various problems are likely to occur in the steps of mixing and dispersing in the matrix resin.
【００２０】また、この様なマトリックス樹脂と本発明
の炭素繊維との配合方法としては特に限定されるもので
はないが、通常一軸押し出し機、二軸押し出し機、プレ
ス機、高速ミキサー、射出成形機、引き抜き成形機等の
方法により行なわれる。更に、上記成分以外に本発明の
効果を損なわない程度に例えば、他種炭素繊維、ガラス
繊維、アラミド繊維、ボロン繊維、炭化ケイ素繊維など
の短繊維及び長繊維、ホイスカー類、これらにニッケ
ル、アルミニウム、銅などの金属をコーティングした繊
維あるいは金属繊維などの繊維状強化材類、あるいはカ
ーボンブラック、二硫化モリブデン、マイカ、タルク、
炭酸カルシウムなどのフィラー類からなる強化材、安定
剤、滑剤、その他添加剤などを加えることが出来る。The method of blending such a matrix resin with the carbon fiber of the present invention is not particularly limited, but is usually a single-screw extruder, a twin-screw extruder, a press machine, a high speed mixer, an injection molding machine. , A pultrusion molding machine or the like. Further, to the extent that the effects of the present invention other than the above components are not impaired, for example, other types of carbon fibers, glass fibers, aramid fibers, boron fibers, short fibers and long fibers such as silicon carbide fibers, whiskers, nickel, aluminum in these. , Fiber coated with metal such as copper or fibrous reinforcing material such as metal fiber, carbon black, molybdenum disulfide, mica, talc,
Reinforcing agents made of fillers such as calcium carbonate, stabilizers, lubricants, and other additives can be added.
【００２１】この様にして得られた炭素繊維強化熱可塑
性樹脂組成物は従来の炭素繊維で強化された場合に比べ
高い帯電防止性を示す。The carbon fiber reinforced thermoplastic resin composition thus obtained exhibits a higher antistatic property than the case of being reinforced with conventional carbon fibers.
【００２２】[0022]
【実施例】次に実施例により本発明を更に詳細に説明す
るが、本発明はその要旨を超えない限り、これら実施例
に制限されない。 ＜帯電防止性の評価＞帯電防止性の評価は、炭素繊維強
化熱可塑性樹脂の平板をスタティックオネストメーター
（シシド静電気株式会社製）にて帯電圧および減衰半減
値を測定することで行った。 EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. <Evaluation of Antistatic Property> The antistatic property was evaluated by measuring the electrification voltage and the attenuation half value of a flat plate of carbon fiber reinforced thermoplastic resin with a static Honest meter (manufactured by Shishido Electrostatic Co., Ltd.).
【００２３】実施例１ （Ａ）サイジング剤の調製 ヘキサメチレンジアミン３６重量部、アジピン酸３６重
量部、ポリオキシエチレンラウリルグリシジルエーテル
（分子量約７００）２８重量部を加え窒素置換後２２０
℃に加熱、脱水しながらこれらのモノマーを重合せしめ
重合物を得た。この重合物とアルキルフェノールのエチ
レンオキサイド付加物の６０／４０の割合に配合した水
溶液を調製し炭素繊維束の含浸用サイジング剤液として
使用した。Example 1 (A) Preparation of sizing agent 36 parts by weight of hexamethylene diamine, 36 parts by weight of adipic acid, and 28 parts by weight of polyoxyethylene lauryl glycidyl ether (molecular weight about 700) were added and after substitution with nitrogen 220
These monomers were polymerized while heating at 0 ° C. and dehydration to obtain a polymer. An aqueous solution was prepared by mixing this polymer with an ethylene oxide adduct of alkylphenol in a ratio of 60/40 and used as a sizing agent liquid for impregnating carbon fiber bundles.
【００２４】（Ｂ）チョップトストランドの製造 ピッチ系炭素繊維（“ダイアリード”Ｋ２２３、三菱化
成（株）製）連続糸６０００本フィラメントを、前記混
合物８％水溶液中に含浸させた後、約１２０℃で２０分
間加熱乾燥し、更に切断機で６mm長のチョップトストラ
ンドを製造した。得られたチョップトストランドの重合
物付着量を比較例１〜２の結果とともに表１に示す。(B) Production of chopped strands 6000 continuous filaments of pitch-based carbon fiber ("Dialeed" K223, manufactured by Mitsubishi Kasei Co., Ltd.) were impregnated in an aqueous solution of 8% of the above mixture, and then about 120 It was heated and dried at 0 ° C. for 20 minutes, and further, a chopped strand having a length of 6 mm was produced by a cutting machine. The amount of the polymer adhering to the obtained chopped strands is shown in Table 1 together with the results of Comparative Examples 1 and 2.
【００２５】（Ｃ）炭素短繊維強化樹脂成形体の製造 予め乾燥した１０重量部の前記チョップトストランドと
ポリプロピレン樹脂（三菱化成（株）製“三菱ポリプロ
８８００Ｊ”）のペレット１００重量部をドライブレン
ドした後、スクリュー押し出し機に投入、溶融混合し、
押し出し物を水冷後ペレット状に切断した。この様にし
て得られた炭素繊維配合樹脂材料を１２０℃５時間乾燥
した後、射出成形機にて成形し試験片を得て帯電防止
性、剛性を測定した。比較例１〜３とともに測定結果を
表１に示す。(C) Production of Short Carbon Fiber Reinforced Resin Molded Body 10 parts by weight of previously dried chopped strands and 100 parts by weight of pellets of polypropylene resin (“Mitsubishi Polypro 8800J” manufactured by Mitsubishi Kasei Co., Ltd.) are dry blended. After that, put it into the screw extruder, melt mix,
The extrudate was cooled in water and cut into pellets. The carbon fiber-containing resin material thus obtained was dried at 120 ° C. for 5 hours and then molded with an injection molding machine to obtain a test piece, and the antistatic property and the rigidity were measured. The measurement results are shown in Table 1 together with Comparative Examples 1 to 3.
【００２６】比較例１ 実施例１のサイジング剤水溶液のアルキルフェノールの
エチレンオキサイド付加物を除いたサイジング剤を使用
した他は実施例１と同様の方法で試作を行ない試験片を
得た。Comparative Example 1 A test piece was obtained by carrying out trial production in the same manner as in Example 1 except that the sizing agent obtained by removing the ethylene oxide adduct of alkylphenol in the aqueous sizing agent solution of Example 1 was used.
【００２７】比較例２ 実施例１のサイジング剤水溶液として“エピコート８３
４”（シェル化学社製）３０重量部と“エピコート１０
０４”（シェル化学社製）７０重量部のエポキシ樹脂と
アルキルフェノールのエチレンオキサイド付加物の６０
／４０の割合に配合して調製したエマルジョン溶液（濃
度３重量％）を使用した他は実施例１と同様の方法で試
作を行ない試験片を得た。Comparative Example 2 As an aqueous solution of the sizing agent of Example 1, "Epicoat 83" was used.
4 "(manufactured by Shell Kagaku) and 30 parts by weight of" Epicoat 10 "
04 ″ (manufactured by Shell Chemical Co.) 60 parts by weight of epoxy resin and ethylene oxide adduct of alkylphenol
A test piece was obtained by carrying out trial production in the same manner as in Example 1 except that an emulsion solution (concentration: 3% by weight) prepared by mixing in a ratio of / 40 was used.
【００２８】比較例３ 実施例１のポリプロピレン樹脂（三菱化成（株）製“三
菱ポリプロ８８００Ｊ”）のペレット１００重量部にア
ルキルフェノールのエチレンオキサイド付加物を０．３
２重量％をドライブレンドした後、スクリュー押し出し
機に投入、溶融混合し、押し出し物を水冷後ペレット状
に切断した。この様にして得られた配合樹脂材料を１２
０℃５時間乾燥した後、射出成形機にて成形し試験片を
得た。Comparative Example 3 100 parts by weight of pellets of the polypropylene resin of Example 1 (“Mitsubishi Polypro 8800J” manufactured by Mitsubishi Kasei Co., Ltd.) were mixed with 0.3 parts of an ethylene oxide adduct of alkylphenol.
After dry blending 2% by weight, the mixture was put into a screw extruder, melt-mixed, and the extruded product was cooled with water and cut into pellets. The compounded resin material thus obtained is
After drying at 0 ° C. for 5 hours, it was molded by an injection molding machine to obtain a test piece.
【００２９】表１に示したように本特許請求の範囲に記
載した組成の樹脂で被覆した炭素繊維を用いると他の樹
脂で被覆した炭素繊維より良好な帯電防止性を有する樹
脂組成物が得られる。As shown in Table 1, when the carbon fiber coated with the resin having the composition described in the claims is used, a resin composition having a better antistatic property than the carbon fiber coated with other resin is obtained. Be done.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【発明の効果】このように本実施例の複合材料は、帯電
圧も低くかつエタノール脱脂後しばらく置くと半減期が
復元するため、材料の帯電防止性を大幅に改善する事に
なり工業上極めて有用である。As described above, the composite material of this example has a low electrification voltage and the half-life is restored if left for a while after degreasing with ethanol, so that the antistatic property of the material is greatly improved, which is extremely industrially significant. It is useful.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｄ０６Ｍ 13/217 15/59 // Ｄ０６Ｍ 101:40 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location D06M 13/217 15/59 // D06M 101: 40
Claims (2)
ジカルボン酸化合物及び下記一般式（Ｉ）で示される１
０〜３０重量％のグリシジル化ポリアルキレンオキシド
誘導体を含んでなる共重合体並びに界面活性剤を含む帯
電防止剤を含有するサイジング剤で表面が被覆されてい
ることを特徴とする炭素繊維。 【化１】 （式中Ｒ1 はＨまたは炭素数２０以下のアルキル基、Ｒ
2 はＨまたはＣＨ3 、ｎは１〜４０の整数を表わす。）1. A diamine compound as a monomer composition,
Dicarboxylic acid compound and 1 represented by the following general formula (I)
A carbon fiber whose surface is coated with a sizing agent containing an antistatic agent containing a copolymer and a copolymer containing 0 to 30% by weight of a glycidylated polyalkylene oxide derivative. [Chemical 1] (In the formula, R 1 is H or an alkyl group having 20 or less carbon atoms, R 1
2 represents H or CH 3 , and n represents an integer of 1 to 40. )
ジカルボン酸化合物及び下記一般式（Ｉ）で示される１
０〜３０重量％のグルシジル化ポリアルキレンオキシド
誘導体を含んでなる共重合体並びに界面活性剤を含む帯
電防止剤を含有するサイジング剤で表面が被覆されてい
る炭素繊維１〜４０重量部を熱可塑性樹脂１００重量部
に対して配合したことを特徴とする炭素繊維強化樹脂組
成物。 【化２】 （式中Ｒ1 はＨまたは炭素数２０以下のアルキル基、Ｒ
2 はＨまたはＣＨ3 、ｎは１〜４０の整数を表わす。）2. A diamine compound as a monomer composition,
Dicarboxylic acid compound and 1 represented by the following general formula (I)
1-40 parts by weight of carbon fiber whose surface is coated with a sizing agent containing an antistatic agent containing a copolymer and a surfactant containing 0 to 30% by weight of a glycidylated polyalkylene oxide derivative. A carbon fiber reinforced resin composition, which is blended with 100 parts by weight of a resin. [Chemical 2] (In the formula, R 1 is H or an alkyl group having 20 or less carbon atoms, R 1
2 represents H or CH 3 , and n represents an integer of 1 to 40. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26645891A JP2946872B2 (en) | 1991-10-15 | 1991-10-15 | Carbon fiber and carbon fiber reinforced resin composition using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26645891A JP2946872B2 (en) | 1991-10-15 | 1991-10-15 | Carbon fiber and carbon fiber reinforced resin composition using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05106164A true JPH05106164A (en) | 1993-04-27 |
| JP2946872B2 JP2946872B2 (en) | 1999-09-06 |
Family
ID=17431210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26645891A Expired - Fee Related JP2946872B2 (en) | 1991-10-15 | 1991-10-15 | Carbon fiber and carbon fiber reinforced resin composition using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2946872B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003012188A1 (en) * | 2001-07-31 | 2003-02-13 | Mitsubishi Rayon Co., Ltd. | Sizing agent for carbon fiber, method for sizing carbon fiber by said sizing agent, sized carbon fiber and knitted or woven fabric using said carbon fiber |
| JP2009013390A (en) * | 2007-06-04 | 2009-01-22 | Teijin Ltd | Thermally conductive sheet |
-
1991
- 1991-10-15 JP JP26645891A patent/JP2946872B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003012188A1 (en) * | 2001-07-31 | 2003-02-13 | Mitsubishi Rayon Co., Ltd. | Sizing agent for carbon fiber, method for sizing carbon fiber by said sizing agent, sized carbon fiber and knitted or woven fabric using said carbon fiber |
| US7135516B2 (en) | 2001-07-31 | 2006-11-14 | Mitsubishi Rayon Co., Ltd. | Sizing agent for carbon fiber, method for sizing carbon fiber by said sizing agent, sized carbon fiber and knitted or woven fabric using said carbon fiber |
| JP2009013390A (en) * | 2007-06-04 | 2009-01-22 | Teijin Ltd | Thermally conductive sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2946872B2 (en) | 1999-09-06 |
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