JPH05263370A - Surface modifier for carbon fiber - Google Patents
Surface modifier for carbon fiberInfo
- Publication number
- JPH05263370A JPH05263370A JP4052297A JP5229792A JPH05263370A JP H05263370 A JPH05263370 A JP H05263370A JP 4052297 A JP4052297 A JP 4052297A JP 5229792 A JP5229792 A JP 5229792A JP H05263370 A JPH05263370 A JP H05263370A
- Authority
- JP
- Japan
- Prior art keywords
- carbon fiber
- aromatic groups
- group
- formula
- dianhydride
- 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]
【産業上の利用分野】本発明は新規な炭素繊維用表面改
質剤に関する。TECHNICAL FIELD The present invention relates to a novel surface modifier for carbon fiber.
【０００２】[0002]
【従来技術及びその問題点】炭素繊維はガラス繊維と比
べて高弾性、軽量性に優れており、特にポリイミド樹
脂、ポリエーテルエーテルケトン、ポリエーテルスルフ
ォン、ポリエーテルイミド、ポリフェニレンサルファイ
ドのような超耐熱樹脂の強化材として用いた場合、機械
強度等の特性を向上させ、自動車部品、機械部品等の優
れた素材と成り得る。2. Description of the Related Art Carbon fibers have higher elasticity and lighter weight than glass fibers, and are especially superior in heat resistance such as polyimide resin, polyether ether ketone, polyether sulfone, polyether imide, and polyphenylene sulfide. When it is used as a reinforcing material for resin, it improves properties such as mechanical strength and can be an excellent material for automobile parts, machine parts and the like.
【０００３】従来、炭素繊維用表面改質剤としてはエポ
キシ樹脂が広く用いられている。従って、マトリックス
がエポキシ樹脂のような熱硬化性樹脂の場合には表面改
質剤として有効であるが、マトリックスが熱可塑性樹脂
の場合にはマトリックスとの接着性に乏しいことが多
く、機械強度等の特性を十分に向上させるには到ってい
ない。Epoxy resins have been widely used as surface modifiers for carbon fibers. Therefore, when the matrix is a thermosetting resin such as an epoxy resin, it is effective as a surface modifier, but when the matrix is a thermoplastic resin, the adhesiveness with the matrix is often poor and the mechanical strength, etc. Has not yet been fully improved.
【０００４】この為、特開昭５３−１０６７５２号公報
に見られるごとく、熱可塑性樹脂に対してはポリアミド
樹脂を表面改質剤として用いることが試みられている。
しかし乍ら、超耐熱性熱可塑性樹脂をマトリックスとす
る場合、成形温度が３００℃を越える高温である為、表
面改質剤であるポリアミド樹脂が成形中に熱分解し、ボ
イドの生成、ウエルド部強度の低下等の問題が生じ、未
だ満足ゆく表面改質剤を得るには到っていない。Therefore, as seen in JP-A-53-106752, it has been attempted to use a polyamide resin as a surface modifier for a thermoplastic resin.
However, when the superheat-resistant thermoplastic resin is used as the matrix, the molding temperature is higher than 300 ° C., so that the polyamide resin, which is the surface modifier, is thermally decomposed during the molding, resulting in the formation of voids and welds. Problems such as a decrease in strength occur, and a satisfactory surface modifier has not yet been obtained.
【０００５】一方、上記熱分解の問題を解決する為に、
耐熱性に優れたポリエーテルイミド樹脂（特開昭６２−
２９９５８０）、ポリイミド樹脂（特開昭６４−４０５
６９）を表面改質剤として用いることが提案されている
が、マトリックスである熱可塑性樹脂との接着性に問題
を残し、未だ十分な補強効果を発揮するには到っていな
い。On the other hand, in order to solve the above thermal decomposition problem,
Polyetherimide resin having excellent heat resistance (Japanese Patent Laid-Open No. 62-
299580), a polyimide resin (JP-A-64-405)
It has been proposed to use 69) as a surface modifier, but it leaves a problem in adhesiveness with a thermoplastic resin as a matrix and has not yet exerted a sufficient reinforcing effect.
【０００６】[0006]
【問題点を解決するための手段】本発明者らは前記問題
点を解決する為に種々検討した結果、遂に本発明をする
に到った。 即ち、本発明は炭素繊維表面を改質するも
のが、式（１）で表される繰り返し単位を有するポリイ
ミド樹脂であることを特徴とする炭素繊維用表面改質剤
である。[Means for Solving the Problems] The present inventors finally conducted the present invention as a result of various studies for solving the above problems. That is, the present invention is a surface modifying agent for carbon fibers, characterized in that what modifies the surface of the carbon fiber is a polyimide resin having a repeating unit represented by the formula (1).
【０００７】[0007]
【化２】 Ｒは炭素数２以上の脂肪族基、環式脂肪族基、単環式芳
香族基、縮合多環式芳香族基、芳香族基が直接又は架橋
員により相互に連結された非縮合多環式芳香族基から成
る群より選ばれた４価の基を表す。）このような本発明
の炭素繊維表面用改質剤である重合体はジアミン成分と
して１，３−ビス（３−アミノフェノキシ）ベンゼン
（以下、ＡＰＢと略記する。）を使用するものであり、
これと１種以上のテトラカルボン酸二無水物とを反応さ
せて得られるポリアミド酸を更に脱水環化して得られる
ポリイミドである。本発明で使用されるテトラカルボン
酸二無水物は、式（２）[Chemical 2] R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic groups are connected to each other directly or by a crosslinking member. Represents a tetravalent group selected from the group consisting of formula aromatic groups. ) Such a polymer which is a modifier for a carbon fiber surface of the present invention uses 1,3-bis (3-aminophenoxy) benzene (hereinafter abbreviated as APB) as a diamine component,
This is a polyimide obtained by further cyclodehydrating a polyamic acid obtained by reacting this with one or more tetracarboxylic dianhydrides. The tetracarboxylic dianhydride used in the present invention has the formula (2)
【０００８】[0008]
【化３】 （式中、Ｒは炭素数２以上の脂肪族基、環式脂肪族基、
単環式芳香族基、縮合多環式芳香族基、芳香族基が直接
又は架橋員により相互に連結された非縮合多環式芳香族
基から成る群より選ばれた４価の基を表す。）で表され
るテトラカルボン酸二無水物である。即ち、使用される
テトラカルボン酸としては、例えばエチレンテトラカル
ボン酸二無水物、シクロペンタンカルボン酸二無水物、
ピロメリット酸二無水物、３，３’，４，４’−ベンゾ
フェノンテトラカルボン酸二無水物、２，２’，３，
３’−ベンゾフェノンテトラカルボン酸二無水物、３，
３’，４，４’−ビフェニルテトラカルボン酸二無水
物、２，２’，３，３’−ビフェニルテトラカルボン酸
二無水物、２，２−ビス（３，４−ジカルボキシフェニ
ル）プロパン二無水物、２，２−ビス（２，３−ジカル
ボキシフェニル）プロパン二無水物、ビス（３，４−ジ
カルボキシフェニル）エ−テル二無水物、ビス（３，４
−ジカルボキシフェニル）スルホン二無水物、１，１−
ビス（２，３−ジカルボキシフェニル）エタン二無水
物、ビス（２，３−ジカルボキシフェニル）メタン二無
水物、ビス（３，４−ジカルボキシフェニル）メタン二
無水物、２，３，６，７−ナフタレンテトラカルボン酸
二無水物、１，４，５，８−ナフタレンテトラカルボン
酸二無水物、１，２，５，６−ナフタレンテトラカルボ
ン酸二無水物、１，２，３，４−ベンゼンテトラカルボ
ン酸二無水物、３，４，９，１０−ペリレンテトラカル
ボン酸二無水物、２，３，６，７−アントラセンテトラ
カルボン酸二無水物、１，２，７，８−フェナントレン
テトラカルボン酸二無水物等が挙げられる。これらテト
ラカルボン酸二無水物は、単独あるいは２種以上混合し
て用いられる。[Chemical 3] (In the formula, R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group,
Represents a tetravalent group selected from the group consisting of a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a bridging member. .. ) Is a tetracarboxylic dianhydride. That is, as the tetracarboxylic acid used, for example, ethylene tetracarboxylic dianhydride, cyclopentanecarboxylic dianhydride,
Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2', 3
3'-benzophenone tetracarboxylic acid dianhydride, 3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride Anhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4
-Dicarboxyphenyl) sulfone dianhydride, 1,1-
Bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,3,6 , 7-Naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4 -Benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrene Examples thereof include tetracarboxylic dianhydride. These tetracarboxylic dianhydrides may be used alone or in admixture of two or more.
【０００９】重合体の生成反応は通常、有機溶剤中で実
施する。この反応に用いる有機溶媒としては、例えばＮ
−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトア
ミド、Ｎ，Ｎ−ジメチルホルムアミド、１，３−ジメチ
ル−２−イミダゾリジノン、Ｎ，Ｎ−ジエチルアセトア
ミド、Ｎ，Ｎ−ジメチルエトキシアセトアミド、ジメチ
ルスルホキシド、ピリジン、ジメチルスルホン、ヘキサ
メチルホスホルアミド、テトラメチル尿素、Ｎ−メチル
カプロラクタム、ブチロラクタム、テトラヒドロフラ
ン、ｍ−ジオキサン、ｐ−ジオキサン、１，２−ジメト
キシエタン、ビス（２−メトキシエチル）エーテル、
１，２−ビス（２−メトキシエトキシ）エタン、ビス
〔２−（２−メトキシエトキシ）エチル〕エーテル等が
挙げられる。The polymer formation reaction is usually carried out in an organic solvent. Examples of the organic solvent used in this reaction include N 2
-Methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, N, N-diethylacetamide, N, N-dimethylethoxyacetamide, dimethylsulfoxide , Pyridine, dimethyl sulfone, hexamethylphosphoramide, tetramethylurea, N-methylcaprolactam, butyrolactam, tetrahydrofuran, m-dioxane, p-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether,
1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether and the like can be mentioned.
【００１０】反応温度は通常６０℃以下、好ましくは５
０℃以下である。反応時間は使用テトラカルボン酸二無
水物、溶剤の種類および反応温度により異なり、通常下
記式（３）で表されるポリアミド酸の生成が完了するに
十分な時間反応させる。通常４〜２４時間で充分であ
る。このような反応により、下記式（３）の繰り返し単
位を有するポリアミド酸が得られる。The reaction temperature is usually 60 ° C. or lower, preferably 5
It is 0 ° C or lower. The reaction time varies depending on the tetracarboxylic dianhydride used, the type of solvent and the reaction temperature, and usually the reaction is performed for a time sufficient to complete the production of the polyamic acid represented by the following formula (3). Usually 4 to 24 hours is sufficient. By such a reaction, a polyamic acid having a repeating unit of the following formula (3) is obtained.
【００１１】[0011]
【化４】 Ｒは炭素数２以上の脂肪族基、環式脂肪族基、単環式芳
香族基、縮合多環式芳香族基、芳香族基が直接又は架橋
員により相互に連結された非縮合多環式芳香族基から成
る群より選ばれた４価の基を表す。）さらに得られたポ
リアミド酸を１００〜３００℃に加熱脱水することによ
り、下記式（１）の繰り返し単位を有する対応するポリ
イミドが得られる。[Chemical 4] R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic groups are connected to each other directly or by a crosslinking member. Represents a tetravalent group selected from the group consisting of formula aromatic groups. ) Further, by heating and dehydrating the obtained polyamic acid at 100 to 300 ° C, a corresponding polyimide having a repeating unit of the following formula (1) is obtained.
【００１２】[0012]
【化５】 Ｒは炭素数２以上の脂肪族基、環式脂肪族基、単環式芳
香族基、縮合多環式芳香族基、芳香族基が直接又は架橋
員により相互に連結された非縮合多環式芳香族基から成
る群より選ばれた４価の基を表す。）本発明で使用され
る炭素繊維はアクリル系、レーヨン系、リグニン系、ピ
ッチ系等が挙げられる。当該炭素繊維の形態に関しては
特に制約はなく、チョップドストランド、トウ（ロービ
ング）、織物等何れでもよい。このようにして得られた
重合体を炭素繊維表面用改質剤として用いるに際して
は、（１）主として上記式（３）で表されるポリアミド
酸の溶液で炭素繊維表面を濡らした後、脱溶媒し、つい
でイミド化することにより炭素繊維表面を改質する場合
と、（２）主として上記式（４）で表されるポリイミド
を溶融状態で炭素繊維表面を被覆することにより炭素繊
維表面を改質する場合とに大別される。（１）の場合、
主として上記式（３）で表されるポリアミド酸の溶液と
は、ポリアミド酸を有機溶媒に溶解した溶液であり、有
機溶媒中でＡＰＢとテトラカルボン酸二無水物とを反応
させて得たポリアミド酸を含有する反応生成液であって
もよい。[Chemical 5] R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic groups are connected to each other directly or by a crosslinking member. Represents a tetravalent group selected from the group consisting of formula aromatic groups. The carbon fiber used in the present invention may be acrylic, rayon, lignin, pitch or the like. The form of the carbon fiber is not particularly limited, and may be any of chopped strand, tow (roving), woven fabric, and the like. When the polymer thus obtained is used as a carbon fiber surface modifier, (1) the carbon fiber surface is wetted mainly with a solution of the polyamic acid represented by the above formula (3), and then the solvent is removed. And then modifying the surface of the carbon fiber by imidizing, and (2) modifying the surface of the carbon fiber by coating the surface of the carbon fiber mainly with the polyimide represented by the formula (4) in a molten state. It is roughly divided into two cases. In case of (1),
The solution of the polyamic acid mainly represented by the above formula (3) is a solution in which the polyamic acid is dissolved in an organic solvent, and the polyamic acid obtained by reacting APB and tetracarboxylic dianhydride in the organic solvent. It may be a reaction product liquid containing.
【００１３】又、当該表面改質剤を適用し得る樹脂とし
ては熱可塑性樹脂であれば特に制約はなく、現在知られ
ている全ての熱可塑性樹脂に適用できる。具体的にはポ
リカーボネート樹脂、ポリアミド樹脂、ポリエチレンテ
レフタレート、ポリブチレンテレフタレート、ポリフェ
ニレンサルファイド、ポリエーテルイミド、熱可塑性イ
ミド樹脂、ポリエーテルサルフォン、ポリエーテルエー
テルケトン、ポリエーテルケトン等が挙げられる。The resin to which the surface modifier can be applied is not particularly limited as long as it is a thermoplastic resin, and it can be applied to all currently known thermoplastic resins. Specific examples include polycarbonate resin, polyamide resin, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyether imide, thermoplastic imide resin, polyether sulfone, polyether ether ketone, polyether ketone and the like.
【００１４】通常、炭素繊維に対する本発明の表面改質
剤の被覆量は炭素繊維１００重量部に対して０．１〜２
０重量部がよく、０．１重量部以下では本発明の効果は
得られず、又２０重量部以上では物性の向上は期待でき
ない。尚、上記炭素繊維用改質剤で処理するに当って、
予め炭素繊維を表面処理することは当該改質剤と炭素繊
維との接着性を高める上で好ましい。該表面処理の方法
としては特に制約はなく、通常の方法はすべて利用する
ことができる。例えば薬液酸化（硝酸、過マンガン酸／
硫酸、等）、電解酸化等の液相酸化、気相（空気、酸
素、オゾン、等）中での加熱、プラズマ処理、コロナ放
電等の気相酸化法等が挙げられる。Usually, the coating amount of the surface modifier of the present invention on carbon fiber is 0.1 to 2 per 100 parts by weight of carbon fiber.
0 parts by weight is preferable, and if it is 0.1 parts by weight or less, the effect of the present invention cannot be obtained, and if it is 20 parts by weight or more, improvement in physical properties cannot be expected. Incidentally, in treating with the above-mentioned carbon fiber modifier,
It is preferable to pre-treat the surface of the carbon fiber in order to enhance the adhesiveness between the modifier and the carbon fiber. The surface treatment method is not particularly limited, and all ordinary methods can be used. For example, chemical oxidation (nitric acid, permanganate /
Sulfuric acid, etc.), liquid phase oxidation such as electrolytic oxidation, heating in a gas phase (air, oxygen, ozone, etc.), plasma treatment, and gas phase oxidation such as corona discharge.
【００１５】又、当該炭素繊維表面改質剤で処理した
後、更に加熱処理することもできる。加熱温度としては
５００℃、好ましくは３００〜４５０℃である、３００
℃以下では加熱処理の効果が発揮できず、又５００以上
では当該表面改質剤が熱分解する為好ましくない。尚、
加熱時間は通常、０．１〜３０時間である。Further, after the treatment with the carbon fiber surface modifier, it is possible to further heat-treat. The heating temperature is 500 ° C., preferably 300 to 450 ° C., 300
If the temperature is lower than 0 ° C, the effect of heat treatment cannot be exhibited, and if it is higher than 500, the surface modifier is thermally decomposed, which is not preferable. still,
The heating time is usually 0.1 to 30 hours.
【００１６】以上のようにして当該ポリイミド樹脂で表
面改質した炭素繊維のロービングは１〜１５０mmの長さ
に切断してチョプドストランドとした後、所望の耐熱熱
可塑性樹脂、例えばポリイミド樹脂、ポリエーテルエー
テルケトン、ポリエーテルスルホン等とドライブレンド
し、ついで押出機内で溶融・混練しながら押し出した
後、所定の長さに切断することによりペレットとするこ
とができる。当該ペレットは通常公知の成形方法、すな
わち圧縮成形、射出成形、押出成形により所望する成形
体を得ることができる。The roving of the carbon fiber surface-modified with the polyimide resin as described above is cut to a length of 1 to 150 mm to form chopped strands, and then a desired heat resistant thermoplastic resin such as polyimide resin or poly Pellets can be obtained by dry-blending with ether ether ketone, polyether sulfone, etc., extruding while melting and kneading in an extruder, and then cutting into a predetermined length. The pellet can be obtained by a generally known molding method, that is, compression molding, injection molding, and extrusion molding to obtain a desired molded body.
【００１７】さらには、当該ポリイミド樹脂で表面改質
した炭素繊維を一方向に引き揃えた後、通常の方法で耐
熱性熱可塑性樹脂を含浸させることでプリプレグとする
こともできる。上記含浸方法としては、例えば特開平１
−１２１３６３で開示されている溶融含浸が挙げられ
る。このようにして得られたプリプレグはついで、一定
長さに切断後、所定の方向に繊維が配向するように積層
し、ついで熱プレス等の通常の方法により成形体を得る
こともできる。Further, it is also possible to prepare a prepreg by aligning the carbon fibers surface-modified with the polyimide resin in one direction and then impregnating the heat-resistant thermoplastic resin by a usual method. As the above-mentioned impregnation method, for example, JP-A-1
The melt impregnation disclosed in -1213163 may be mentioned. The prepreg thus obtained can then be cut into a certain length, laminated so that the fibers are oriented in a predetermined direction, and then a molded body can be obtained by a usual method such as hot pressing.
【００１８】[0018]
【実施例】以下、本発明を実施例及び比較例により更に
詳細に説明する。 実施例１ 窒素雰囲気において、ビス（２−メトキシエチル）エー
テル溶媒中でＡＰＢと３，３’，４，４’−ベンゾフェ
ノンテトラカルボン酸二無水物を反応させて溶液濃度１
０重量％のポリアミド酸溶液を得た。ついで、アクリル
系炭素繊維束（東邦レ−ヨン社製、商標ＨＴＡ、フィラ
メント数１２０００本）を６０ｍ／分の速度で上記ポリ
アミド酸溶液に浸漬し、１００℃で風乾して脱溶剤した
後、窒素雰囲気下で３００℃、１時間加熱してポリイミ
ド化を行い、ポリイミド樹脂３重量％を表面に有する炭
素繊維を得た。ついで、得られた炭素繊維を長さ３mmに
切断してチョップドストランドとし、該ストランド３０
wt％と熱可塑性ポリイミド樹脂であるＡＵＲＵＭ４５０
（三井東圧化学社製；商標）７０wt％とをドライブレン
ドした後、４０mm径押出幾にて押出温度４００℃で溶融
混練しながら押し出す操作を行って均一配合ペレットを
得た。次に上記の均一配合ペレットを通常の射出成形機
を用いてシリンダー温度４００℃、金型温度２１０℃の
温度条件でダンベル試験片を作成し、引張速度５mm／mi
n で引張強度を測定したところ２８００Kg/c であっ
た。EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. Example 1 APB was reacted with 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride in a bis (2-methoxyethyl) ether solvent in a nitrogen atmosphere to give a solution concentration of 1
A 0% by weight polyamic acid solution was obtained. Then, an acrylic carbon fiber bundle (trade name HTA, manufactured by Toho Rayon Co., Ltd., 12,000 filaments) was immersed in the polyamic acid solution at a speed of 60 m / min, air-dried at 100 ° C. to remove the solvent, and then nitrogen. It was heated in an atmosphere at 300 ° C. for 1 hour for polyimidization to obtain a carbon fiber having 3% by weight of a polyimide resin on the surface. Next, the obtained carbon fiber is cut into a length of 3 mm to form chopped strands,
wt% and AURUM450, a thermoplastic polyimide resin
(Mitsui Toatsu Chemical Co., Ltd .; trademark) 70 wt% was dry-blended, and then extruded while being melt-kneaded at an extrusion temperature of 400 ° C. with a 40 mm diameter extrusion machine to obtain a uniformly mixed pellet. Next, a dumbbell test piece was prepared from the above homogeneously mixed pellets using a normal injection molding machine under the conditions of a cylinder temperature of 400 ° C and a mold temperature of 210 ° C.
The tensile strength measured with n was 2800 Kg / c.
【００１９】実施例２ 溶媒としてビス（２−メトキシエチル）エ−テルの代わ
りにＮ，Ｎ−ジメチルアセトアミドを、テトラカルボン
酸二無水物として３，３’，４，４’−ベンゾフェノン
テトラカルボン酸二無水物の代わりにピロメリット酸二
無水物を用いた以外は実施例１と同様に処理して引張強
度を測定したところ２８５０Kg/cm2であった。Example 2 N, N-dimethylacetamide was used as the solvent instead of bis (2-methoxyethyl) ether, and 3,3 ', 4,4'-benzophenonetetracarboxylic acid was used as the tetracarboxylic dianhydride. The tensile strength was measured as in Example 1 except that pyromellitic dianhydride was used instead of dianhydride, and the tensile strength was 2850 kg / cm 2 .
【００２０】実施例３ ポリアミド酸溶液に浸漬する前に炭素繊維表面を照射時
間５秒、マイクロ波発振出力１．０ＫＷ、処理ガスが酸
素である条件でプラズマ処理した炭素繊維を用いた以外
は実施例１と同様に処理して引張強度を測定したところ
３０００Kg/cm2であった。Example 3 The procedure was carried out except that the carbon fiber surface was irradiated with plasma for 5 seconds before being immersed in the polyamic acid solution, the microwave oscillation output was 1.0 kW, and the processing gas was oxygen. When treated in the same manner as in Example 1 and measured for tensile strength, it was 3000 kg / cm 2 .
【００２１】実施例４ 実施例３と同様な条件でプラズマ処理した炭素繊維を用
いた以外は実施例２と同様に処理して引張強度を測定し
たところ３０２０Kg/cm2であった。Example 4 The tensile strength was measured in the same manner as in Example 2 except that the carbon fiber treated by plasma under the same conditions as in Example 3 was used, and the tensile strength was 3020 kg / cm 2 .
【００２２】比較例１ 本発明の表面改質剤で改質された炭素繊維の代わりにエ
ポキシ樹脂で表面改質されたアクリル系炭素繊維（東邦
レーヨン社製、商品名ＨＴＡ）を用いた以外は実施例１
と同様に処理して引張強度を測定したところ２３００Kg
/cm2であった。 比較例２ 本発明の表面改質剤で改質された炭素繊維の代わりに、
特開昭６２−２９９５８０の実施例１に示される方法に
よりポリエーテルイミド（エンジニアリングプラスチッ
クス社製、ウルテム１０００）を塗布、表面改質された
アクリル系炭素繊維（東邦レーヨン社製、商品名ＨＴ
Ａ）を用いた以外は実施例１と同様に処理して引張強度
を測定したところ２２５０Kg/cm2であった。Comparative Example 1 Acrylic carbon fiber (trade name HTA, manufactured by Toho Rayon Co., Ltd.) surface-modified with epoxy resin was used in place of the carbon fiber modified with the surface modifier of the present invention. Example 1
When the same treatment as above was performed and the tensile strength was measured, it was 2300 Kg.
It was / cm 2 . Comparative Example 2 Instead of the carbon fiber modified with the surface modifier of the present invention,
Acrylic carbon fiber (trade name HT, manufactured by Toho Rayon Co., Ltd.) surface-modified by coating polyetherimide (Ultem 1000, manufactured by Engineering Plastics Co., Ltd.) by the method shown in Example 1 of JP-A-62-299580.
When the same treatment as in Example 1 was carried out except that A) was used and the tensile strength was measured, it was 2250 Kg / cm 2 .
【００２３】比較例３ 本発明の表面改質剤で改質された炭素繊維の代わりに、
特開昭６４−４０５６９の実施例１に示される方法によ
り４，４’−ビス（３−アミノフェノキシ）ジフェニル
とピロメリット酸とから得られるポリアミド酸を塗布、
イミド化して表面改質したアクリル系炭素繊維（東邦レ
ーヨン社製、商品名ＨＴＡ）を用いた以外は実施例１と
同様に処理して引張強度を測定したところ２３５０Kg/c
m2であった。Comparative Example 3 Instead of the carbon fiber modified with the surface modifier of the present invention,
A polyamic acid obtained from 4,4′-bis (3-aminophenoxy) diphenyl and pyromellitic acid was applied by the method described in Example 1 of JP-A-64-40569,
When the tensile strength was measured in the same manner as in Example 1 except that an imidized and surface-modified acrylic carbon fiber (trade name: HTA manufactured by Toho Rayon Co., Ltd.) was used, it was 2350 Kg / c.
It was m 2 .
【００２４】実施例４ 実施例１に於て樹脂として熱可塑性ポリイミド樹脂の代
わりにポリエーテルエーテルケトン樹脂（英国ＩＣＩ社
製、商標ビクトレックスＰＥＥＫ４５０Ｐ）を用い、押
出温度を４００から３８０℃に、又金型温度を２１００
℃から２００℃に変えた他は実施例１と同様に処理して
引張強度を測定したところ２４５０Kg/cm2 であった。Example 4 In Example 1, a polyetheretherketone resin (trade name Victorex PEEK450P, manufactured by ICI, England) was used as the resin instead of the thermoplastic polyimide resin, and the extrusion temperature was changed from 400 to 380 ° C. Mold temperature 2100
When the tensile strength was measured by treating in the same manner as in Example 1 except that the temperature was changed from 200 ° C. to 200 ° C., it was 2450 Kg / cm 2 .
【００２５】比較例４ 比較例１で用いた炭素繊維を用いた以外は実施例４と同
様に処理して引張強度を測定したところ２１００Kg/cm2
であった。Comparative Example 4 The same treatment as in Example 4 was carried out except that the carbon fiber used in Comparative Example 1 was used, and the tensile strength was measured to be 2100 Kg / cm 2.
Met.
【００２６】[0026]
【発明の効果】本発明による表面が改質された炭素繊維
は、高耐熱性エンジニアリング樹脂に充填することによ
り機械強度等を大幅に向上させることができ、工業的意
義は大きい。Effects of the Invention The surface-modified carbon fiber according to the present invention can be greatly improved in mechanical strength and the like by being filled with a highly heat-resistant engineering resin, and has great industrial significance.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 富本 裕昭 神奈川県横浜市栄区笠間町1190番地 三井 東圧化学株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroaki Tomimoto 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.
Claims (1)
（１）で表される繰り返し単位を有するポリイミド樹脂
であることを特徴とする炭素繊維用表面改質剤。 【化１】 Ｒは炭素数２以上の脂肪族基、環式脂肪族基、単環式芳
香族基、縮合多環式芳香族基、芳香族基が直接又は架橋
員により相互に連結された非縮合多環式芳香族基からな
る群より選ばれた４価の基を表わす。）1. A surface-modifying agent for carbon fiber, characterized in that a material for modifying the surface of the carbon fiber is a polyimide resin having a repeating unit represented by the formula (1). [Chemical 1] R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic groups are connected to each other directly or by a crosslinking member. It represents a tetravalent group selected from the group consisting of formula aromatic groups. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4052297A JPH05263370A (en) | 1992-03-11 | 1992-03-11 | Surface modifier for carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4052297A JPH05263370A (en) | 1992-03-11 | 1992-03-11 | Surface modifier for carbon fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05263370A true JPH05263370A (en) | 1993-10-12 |
Family
ID=12910866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4052297A Pending JPH05263370A (en) | 1992-03-11 | 1992-03-11 | Surface modifier for carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05263370A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913781A (en) * | 2010-08-06 | 2010-12-15 | 东华大学 | Quartz fiber surface treating agent and preparation method thereof |
| CN111250059A (en) * | 2019-12-17 | 2020-06-09 | 鲁东大学 | Hyperbranched polyethyleneimine modified carbon fiber adsorption material for adsorbing indium (III) and preparation method thereof |
| WO2020262314A1 (en) | 2019-06-28 | 2020-12-30 | 東洋紡株式会社 | Polyamide resin composition for foam molding and foam molded body |
| CN115873249A (en) * | 2022-12-26 | 2023-03-31 | 黄山金石木塑料科技有限公司 | Plasma-treated fiber-reinforced polyimide material and preparation method thereof |
-
1992
- 1992-03-11 JP JP4052297A patent/JPH05263370A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913781A (en) * | 2010-08-06 | 2010-12-15 | 东华大学 | Quartz fiber surface treating agent and preparation method thereof |
| WO2020262314A1 (en) | 2019-06-28 | 2020-12-30 | 東洋紡株式会社 | Polyamide resin composition for foam molding and foam molded body |
| KR20220029552A (en) | 2019-06-28 | 2022-03-08 | 도요보 가부시키가이샤 | Polyamide resin composition for foam molding and expanded molded article |
| CN111250059A (en) * | 2019-12-17 | 2020-06-09 | 鲁东大学 | Hyperbranched polyethyleneimine modified carbon fiber adsorption material for adsorbing indium (III) and preparation method thereof |
| CN115873249A (en) * | 2022-12-26 | 2023-03-31 | 黄山金石木塑料科技有限公司 | Plasma-treated fiber-reinforced polyimide material and preparation method thereof |
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