JPS6128074A - Sizing agent for carbon fiber - Google Patents
Sizing agent for carbon fiberInfo
- Publication number
- JPS6128074A JPS6128074A JP14517984A JP14517984A JPS6128074A JP S6128074 A JPS6128074 A JP S6128074A JP 14517984 A JP14517984 A JP 14517984A JP 14517984 A JP14517984 A JP 14517984A JP S6128074 A JPS6128074 A JP S6128074A
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- general formula
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Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は炭素繊維用サイジング剤に関し、更に詳しくは
炭素繊維の取扱いを容易にし且つそのコンポジット物性
を向上させるサイジング剤に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a sizing agent for carbon fibers, and more particularly to a sizing agent that facilitates handling of carbon fibers and improves the physical properties of the composite.
炭素繊維は軽量で、高強力且つ高モジ−ラスという特性
を有するため、コンポジット用補強材として注目されて
いる。ところが、該炭素繊維はもともと、伸度が小さく
、脆い繊維であるため、機械的摩擦によって容易に毛羽
や糸切れが発生する。Carbon fiber is lightweight, has high strength and high modulus, and is therefore attracting attention as a reinforcing material for composites. However, since carbon fibers originally have low elongation and are brittle fibers, they easily become fuzzed or broken due to mechanical friction.
そして、これらの毛羽や糸切れが炭素繊維の取扱い性を
著るしく低下させ、そのコンポジット物性も低下させる
。そこで、炭素繊維にサイジング剤を付与して、このサ
イジング剤により、該炭素繊維を集束し、該炭素繊維に
フレキシビリティ−を与え、該炭素繊維の耐摩耗性を向
上させるとともに、炭素繊維とマトリックスレジンとの
間の本質的には不充分な接着性を改善して、得られるコ
ンポジットの層間剪断強度を向上させることが行なわれ
ている。These fluffs and yarn breakage significantly reduce the handling properties of the carbon fibers and also reduce the physical properties of the composite. Therefore, a sizing agent is added to the carbon fibers, and the sizing agent bundles the carbon fibers, gives flexibility to the carbon fibers, improves the abrasion resistance of the carbon fibers, and improves the bond between the carbon fibers and the matrix. Efforts have been made to improve the essentially insufficient adhesion between resins and to improve the interlaminar shear strength of the resulting composites.
本発明はかかるサイジング剤に関するものである０
〈従来の技術とその問題点〉
従来、炭素繊維用サイジング剤として、次のような芳香
族グリシジルエーテルや芳香族グリシジルアミンを使用
するものが提案されている。The present invention relates to such a sizing agent. <Prior art and its problems> The following sizing agents for carbon fibers have been proposed using aromatic glycidyl ethers and aromatic glycidyl amines. There is.
先ス、ビスフェノールＡジグリシジルエーテルを使用す
るサイジング剤がある（特公昭５７−１５２２９）。こ
れは、炭素繊維とマトリックスレジンとの接着性をよく
するために、マトリックスレジンと同様の化合物を使用
するものである。この種のサイジング剤によると確かに
、前記接着性はよくなる。しかし、メチレンクロライド
やジクロルエタン等の有機溶剤を使用するものであるた
め、その毒性や引火性の危険が大きく、炭素繊維の製織
時における毛羽や糸切れの発生抑制効果が低いという問
題点がある。Previously, there is a sizing agent using bisphenol A diglycidyl ether (Japanese Patent Publication No. 57-15229). This uses a compound similar to that of the matrix resin in order to improve the adhesion between the carbon fiber and the matrix resin. Sizing agents of this type certainly improve the adhesion. However, since it uses organic solvents such as methylene chloride and dichloroethane, there is a high risk of toxicity and flammability, and there are problems in that it is less effective in suppressing the occurrence of fuzz and thread breakage during weaving of carbon fibers.
また、ビスフェノールＡ型エポキシ樹脂（エピコート８
２８とエビコー）１００１を特定割合で混合したもの、
いずれもシェル社製）を、ポリオキシエチレン系非イオ
ン界面活性剤を乳化剤とし、水性エマルジョンとして使
用するサイジング剤がある（特開昭５７−１７１７６７
）’。この場合、有機溶剤を使用しないため、それに
よる毒性や引火性の危険はない。しかし、乳化剤の種類
や使用量を特定しても、炭素繊維の製織時における毛羽
や糸切れの発生抑制と得られるコンポジットの層間剪断
強度との双方を充足することが困難という問題点がある
。In addition, bisphenol A type epoxy resin (Epicote 8
28 and Ebiko) 1001 in a specific ratio,
There is a sizing agent that is used as an aqueous emulsion using a polyoxyethylene nonionic surfactant as an emulsifier (both manufactured by Shell Co., Ltd.) (Japanese Patent Laid-Open No. 57-171767
)'. In this case, since no organic solvent is used, there is no danger of toxicity or flammability. However, even if the type and amount of emulsifier used is specified, there is a problem that it is difficult to satisfy both the suppression of fuzz and yarn breakage during weaving of carbon fibers and the interlayer shear strength of the resulting composite.
そして、Ｎ、Ｎ、ＹＮ’−テトラグリシジルフェニレン
ジアミンを使用するサイジング剤がある（特公昭５９
９６６４）ｏこれは、炭素繊維とマトリックスレジンと
の接着性をよくするものである。Then, there is a sizing agent that uses N,N,YN'-tetraglycidylphenylenediamine (Japanese Patent Publication No. 59
9664) o This improves the adhesion between the carbon fiber and the matrix resin.
この種のサイジング剤によると、前記したビスフェノー
ルＡジグリシジルエーテルを使用する従来のサイジング
剤よシも、炭素繊維とマトリックスレジンとの接着性は
よくなシ、得られるコンポジットの層間剪断強度は向上
する。しかし、三級アミノ基を含有するものであるため
にエポキシ基が経時変化し、その結果該サイジング剤で
処理された炭素繊維は経時的にそのフレキシビリティ−
を失なって固くなシ、該炭素繊維の製織時における毛羽
や糸切れが増加するという問題点がある。With this type of sizing agent, the adhesion between carbon fibers and matrix resin is better than with the conventional sizing agent that uses bisphenol A diglycidyl ether, and the interlaminar shear strength of the resulting composite is improved. . However, since the sizing agent contains a tertiary amino group, the epoxy group changes over time, and as a result, the flexibility of carbon fiber treated with the sizing agent decreases over time.
There are problems in that the carbon fiber loses its strength and hardness, and the occurrence of fluff and thread breakage during weaving of the carbon fiber increases.
以上型するに、従来提案されている炭素繊維用サイジン
グ剤には、毒性や引火性の危険がないもの、或いは炭素
繊維とマトリックスレジンとの接着性をよくして得られ
るコンポジットの層間剪断強度を向上するものがあるが
、これらの効果を併せて充分に発揮し、同時に炭素繊維
の製織時における毛羽や糸切れの発生を抑制する効果も
充分に発揮するというものはないのである。In summary, conventionally proposed sizing agents for carbon fibers are those that are free of toxicity or flammability, or those that improve the interlaminar shear strength of the composite obtained by improving the adhesion between carbon fibers and matrix resin. Although there are some methods that can improve the effect, there is no one that fully exhibits both of these effects and at the same time sufficiently exhibits the effect of suppressing the occurrence of fuzz and thread breakage during weaving of carbon fibers.
〈発明が解決しようとする問題点〉
本発明は、成上の如き従来の問題点を解決するもので、
有機溶剤を使用する必須性をなくしてその毒性や引火性
の危険を排除し、また炭素繊維に充分な抱合力並びに耐
摩耗性を与え、毛羽や糸切れの発生を抑制して該炭素繊
維の取扱い性を大いに向上し、更に炭素繊維とマトリッ
クスレジンとの接着性をよくして得られるコンポジット
に優れた層間剪断強度を付与する、炭素繊維用サイジン
グ剤を提供するものである。<Problems to be solved by the invention> The present invention solves the conventional problems as described above.
It eliminates the necessity of using organic solvents and eliminates the danger of toxicity and flammability, and also provides carbon fibers with sufficient binding power and abrasion resistance, suppressing the occurrence of fluff and thread breakage, and improving the carbon fibers. The object of the present invention is to provide a sizing agent for carbon fibers that greatly improves handleability and further improves the adhesion between carbon fibers and matrix resin, thereby imparting excellent interlaminar shear strength to the resulting composite.
〈問題点を解決するだめの手段〉
しかして本発明者らは、以上の観点で鋭意研究シタ結果
、特定のビスフェノール型ポリアルキレンエーテルエポ
キシ化合物が正しく好適であることを見出し、本発明を
完成するに到った。<Means to Solve the Problem> However, as a result of intensive research from the above viewpoint, the present inventors discovered that a specific bisphenol type polyalkylene ether epoxy compound is correct and suitable, and completed the present invention. reached.
すなわち本発明は、次の一般式（Ｉ）又は（Ｉｆ）で示
すれるビスフェノール型ポリアルキレンエーテルエポキ
シ化合物を含有することを特徴とする炭素繊維用サイジ
ング剤に係る。That is, the present invention relates to a sizing agent for carbon fibers characterized by containing a bisphenol type polyalkylene ether epoxy compound represented by the following general formula (I) or (If).
一般式（Ｉ）ニ
一般式（■）：
〔但し、Ｒは炭素数２〜４のアルキレン基（単独又は混
合のいずれでもよく、混合の場合にブロック結合又はラ
ンダム結合のいずれでもよい）Ｏｌ−ｌ３０
０の整数。Ｘは次の１）又はｌＩ）よシ選ばれる残基（
これらの残基中、−〇−は一般式（Ｉ）の末端グリシジ
ル基へ結合する）Ｏ
１）−ｏ−ｐ＝又は−〇−Ｐ−（Ｚ３はＲ’Ｏ−又は３
Ｚ３
数１〜１８の、アルキル基、アルケ
＝／Ｌ＝基又１ｄ置換フェニル基）〕
前記一般式（Ｉ）又は（Ｉ）において、ｎは５〜２０の
整数が好ましい。毛羽や糸切れの発生を抑制する効果及
び得られるコンポジットの層間剪断強度を向上する効果
で優れているからである。また前記一般式（Ｉ）又は（
ＩＩ）において、ｎが５〜２０の整数であシ、且つＲが
エチレン基／プロピレン基＋ブチレン基≧８／２ （モ
ル比）であると、一層好ましい。この場合、該一般式（
Ｉ）又は（Ｉｔ）で示されるビスフェノール型ポリアル
キレンエーテルエポキシ化合物は水に対して自己乳化性
を発揮するようになシ、得られるコンポジットの層間剪
断強度が一層向上する等、本発明の効果の発現が更に著
るしくなるからである。General formula (I) General formula (■): [However, R is an alkylene group having 2 to 4 carbon atoms (which may be used alone or as a mixture, and in the case of a mixture, a block bond or a random bond may be used) Ol- l30 An integer of 0. X is a residue selected from the following 1) or lI) (
Among these residues, - - is bonded to the terminal glycidyl group of general formula (I)) O 1) -o-p= or -〇-P- (Z3 is R'O- or 3
Z3 an alkyl group, an alke=/L= group, or a 1d-substituted phenyl group of numbers 1 to 18)] In the general formula (I) or (I), n is preferably an integer of 5 to 20. This is because it has an excellent effect of suppressing the occurrence of fuzz and yarn breakage, and an effect of improving the interlayer shear strength of the resulting composite. Also, the general formula (I) or (
In II), it is more preferable that n is an integer of 5 to 20, and R is ethylene group/propylene group+butylene group≧8/2 (molar ratio). In this case, the general formula (
The bisphenol-type polyalkylene ether epoxy compound represented by I) or (It) exhibits self-emulsifying properties in water, further improving the interlayer shear strength of the resulting composite, and other effects of the present invention. This is because the expression becomes even more remarkable.
本発明に係るサイジング剤は、前記一般式（Ｉ）又は（
ｎ）で示されるビスフェノール型ポリアルキレンエーテ
ルエポキシ化合物の他に、必要に応じて、従来のサイジ
ング剤、平滑剤、界面活性剤等を適宜、本発明の効果を
損なわ々い範囲で含有することができる。これらを例示
すると、サイジング剤としては、ビスフェノールＡジグ
リシジルエーテル系、ノボラック型グリシジルエーテル
系又はＮ、 Ｎ、 Ｎ： Ｎ’−テトラグリシジルジア
ミノジフェニルメタン等のエポキシ化合物があシ、マた
平滑剤としでは、ステアリルラウレート、ラウリルステ
アレート又はオレイルオレート等の脂肪酸エステルがあ
シ、更に界面活性剤としては、ポリオキ７ ・エチレ
ン（６モル）ノニルフェニルエーテル又ハポリオキシエ
チレン（３０モル）トリスチレン化フェニルエーテル等
の非イオン型界面活性剤がある。いずれの場合も、本発
明に係るサイジング剤は、前記一般式（Ｉ）又は（ＩＩ
）で示されるビスフェノール型ポリアルキレンエーテル
エポキシ化合物を、通常は１０重量係以上、好ましくは
５０重量係以上含有するものである。The sizing agent according to the present invention has the general formula (I) or (
In addition to the bisphenol-type polyalkylene ether epoxy compound represented by n), conventional sizing agents, smoothing agents, surfactants, etc. may be contained as appropriate within a range that does not impair the effects of the present invention. can. Examples of these include sizing agents such as bisphenol A diglycidyl ether, novolak glycidyl ether, and epoxy compounds such as N, N, N'-tetraglycidyldiaminodiphenylmethane; , fatty acid esters such as stearyl laurate, lauryl stearate or oleyl oleate, and surfactants such as polyoxyethylene (6 mol) nonylphenyl ether or hapolyoxyethylene (30 mol) tristyrenated phenyl There are nonionic surfactants such as ethers. In either case, the sizing agent according to the present invention has the general formula (I) or (II)
) The bisphenol type polyalkylene ether epoxy compound represented by the following formula is usually contained in an amount of 10 weight percent or more, preferably 50 weight percent or more.
〈作用等〉
本発明に係るサイジング剤は、ＰＡＮ系、ピッチ系又は
レーヨン系等の各種炭素繊維（黒鉛繊維を含む）に適用
され、所期効果を発揮する。適用の具体的手段は、ディ
ップ法、スプレー法又はローラー法等、従来手段のいず
れでもよく、サイジング剤を炭素繊維に含浸後、熱風や
赤外線ランプ等で乾燥する。適用に際してサイジング剤
を、そのまま又は少量の乳化剤で水性エマルジョンとし
、有効成分換算で、通常は２５重重量板下、好ましくは
０５〜５５〜５重量％する。該サイジング剤の炭素繊維
への付着量は、有効成分換算で、通常は０．２〜６重量
％、好ましくは０．３〜２重量％である。<Effects, etc.> The sizing agent according to the present invention is applied to various types of carbon fibers (including graphite fibers) such as PAN-based, pitch-based, or rayon-based fibers, and exhibits the desired effects. The specific application method may be any conventional method such as a dipping method, a spray method, or a roller method, and after impregnating the carbon fiber with the sizing agent, it is dried with hot air, an infrared lamp, or the like. When applied, the sizing agent is used as is or in the form of an aqueous emulsion with a small amount of emulsifier, and the amount is usually 25% by weight or less, preferably 0.5 to 55 to 5% by weight, calculated as the active ingredient. The amount of the sizing agent attached to the carbon fiber is usually 0.2 to 6% by weight, preferably 0.3 to 2% by weight in terms of the active ingredient.
〈発明の効果〉
以上説明した通シであるから、本発明には、要約すると
次のような効果がある。<Effects of the Invention> As explained above, the present invention has the following effects in summary.
（Ｉ）その′！、まで又は少量の乳化剤で均一安定な水
性エマルジョンとすることができ、この状態で炭素繊維
に適用することができるため、毒性や引火性の危険がな
い。(I) That'! , or a small amount of emulsifier can be used to form a homogeneous and stable aqueous emulsion, and in this state it can be applied to carbon fibers, so there is no danger of toxicity or flammability.
（２）炭素繊維に優れた抱合力及び耐摩耗性を付与する
ことができるため、該炭素繊維の製織時における毛羽や
糸切れの発生を抑制し、その取扱い性を大幅に向上する
。(2) Since carbon fibers can be endowed with excellent binding strength and abrasion resistance, the occurrence of fuzz and thread breakage during weaving of the carbon fibers is suppressed, and the handling properties thereof are greatly improved.
（３）前記（Ｉ）及び（２）の効果と相まって、炭素繊
維とマトリックスレジンとの接着性もよいため、得られ
るコンポジットの層間剪断強度も向上する０
〈実施例〉
先ず、前記一般式（Ｉ）又は（ＩＩ）で示されるビスフ
ェノール型ポリアルキレンエーテルエボキシ化合物につ
き、次のＡ−１〜Ａ−７を合成した○・Ａ−１ニ一般式
（■）において、Ｒがエチレン？Ｈ３
基、Ｙが−Ｃ−１ｎが１０゜
■
Ｈ３
・Ａ−２ニ一般式（ＩＩ）において、Ｒがエチレン？Ｈ
３
基、Ｙが−Ｃ−１ｎが１５、Ｘが
■
Ｈｓ
？Ｈａ
−Ｏ−８ｔ−。(3) Coupled with the effects of (I) and (2) above, the adhesion between the carbon fiber and the matrix resin is also good, which improves the interlaminar shear strength of the resulting composite. Regarding the bisphenol type polyalkylene ether epoxy compound represented by I) or (II), in the following general formula (■) of A-1 to A-7 synthesized, R is ethylene? In the general formula (II), R is ethylene? H
3 groups, Y is -C-1n is 15, and X is ■ Hs? Ha-O-8t-.
Ｈ３ ・Ａ−３ニ一般式（…）において、ＲがエチレンＦＨ３ 基、Ｙが一〇−１ｎが２０、Ｘが ■ Ｈａ −ｏ−ｐ−。H3 ・In the A-3 general formula (...), R is ethylene FH3 group, Y is 10-1n is 20, X is ■ Ha -o-p-.
！
・Ａ−４ニ一般式（Ｉ）において、Ｒがプロビレ（ＦＨ
３
ン基／エチレン基、Ｙが一〇 −、ｎ
Ｈ３
が２００但し、プロピレン基／エチ
レン基： ３０／７０ （モル比）でランダム結合
。!・A-4D In general formula (I), R is probile (FH
3 N group/ethylene group, Y is 10 -, n H3 is 200 However, propylene group/ethylene group: 30/70 (mole ratio) random bond.
・Ａ−５ニ一般式（Ｉ）において、Ｒがプロビレン基／
エチレン基、Ｙが−８−、ｎ
が１５０但し、プロピレン基／エチ
レン基−３０／７０ （モル比）でランダム結合。・A-5D In general formula (I), R is a propylene group/
Ethylene group, Y is -8-, n is 150, however, random bonding with propylene group/ethylene group -30/70 (mole ratio).
・Ａ−６：一般式（Ｉ）において、Ｒがプロピレン基／
エチレン基、Ｙが一〇Ｈ２−１ｎが２０、Ｘが−０−Ｐ
。・A-6: In general formula (I), R is a propylene group/
Ethylene group, Y is 10H2-1n is 20, X is -0-P
.
曙 但し、プロピレン基／エチレン基＝ ７０／３０ （モル比）でランダム結合。dawn However, propylene group/ethylene group = Random combination at 70/30 (molar ratio).
・Ａ−７：Ａ−６と同じ。但し、プロピレン基／エチレ
ン基二 １０７９０ （モル比）でランダム結合０
Ａ−１〜Ａ−３につき、合成方法を以下に挙げる。Ａ−
４〜Ａ−７の合成はＡ−１〜Ａ−３の合成に準じて行な
った。・A-7: Same as A-6. However, propylene group/ethylene group 2 (molar ratio) 10790 (molar ratio) and random bond 0 The synthesis method for A-1 to A-3 is listed below. A-
The synthesis of 4 to A-7 was carried out according to the synthesis of A-1 to A-3.
・Ａ−１の合成方法：攪拌機、還流冷却器、滴下ロート
及び温度計を備える１１容の四つ目フラスコを使用した
。このフラスコに、ビスフェノールＡを出発物質として
エチレンオキサイドを付加重合した分子量１０００のポ
リアルキレンエーテル５００ｇ（０，５モル）とテトラ
エチルアンモニウムクロライド６．０ｇ（０，１重量係
）七を加え、更に６０〜８０℃でエピクロルヒドリン９
２．５ ｇ（Ｉ，０モル）を滴下した。滴下終了後、９
０〜１（Ｉ０℃で２時間攪拌し、８０〜１００℃で水酸
化カリウム５６．１９ （Ｉ，０モル）を加え、その温
度で３時間攪拌を続けた。- Synthesis method of A-1: An 11-volume, four-sided flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was used. To this flask were added 500 g (0.5 mol) of polyalkylene ether with a molecular weight of 1000, obtained by addition polymerization of ethylene oxide using bisphenol A as a starting material, and 6.0 g (0.1 mol) of tetraethylammonium chloride. Epichlorohydrin 9 at 80℃
2.5 g (I, 0 mol) was added dropwise. After finishing dropping, 9
The mixture was stirred at 0-1 (I) for 2 hours at 0°C, 56.19 (I, 0 mol) of potassium hydroxide was added at 80-100°C, and stirring was continued at that temperature for 3 hours.
そして、副生じた塩を除去し、生成物（Ａ−１）を得た
。Then, the by-produced salt was removed to obtain product (A-1).
・Ａ−２の合成方法：Ａ−１の場合と同様のフラスコに
、ジメチルジクロルシラン１２９ｇ（Ｉ、０モル）とピ
リジン７９．１ｆ（Ｉ，０モル）とを加え、更にビスフ
ェノールＡを出発物質としてエチレンオキサイドを付加
重合した分子量１０００のポリアルキレンエーテル５０
０ ｇ（０゜５モル）を４０℃以下で滴下し、滴下終了
後２時間攪拌した。次いで、ピリジン７９．１９ （Ｉ
゜０モル）とグリシドール７４ｇ（Ｉ，０モル）とを４
０℃以下で滴下し、滴下終了後室温で２時間攪拌した。・Synthesis method of A-2: Add 129 g (I, 0 mol) of dimethyldichlorosilane and 79.1f (I, 0 mol) of pyridine to the same flask as in the case of A-1, and then start with bisphenol A. Polyalkylene ether 50 with a molecular weight of 1000 obtained by addition polymerization of ethylene oxide as a substance
0 g (0.5 mol) was added dropwise at 40° C. or lower, and the mixture was stirred for 2 hours after the addition was completed. Then pyridine 79.19 (I
0 mol) and 74 g (I, 0 mol) of glycidol in 4
The mixture was added dropwise at 0° C. or below, and after the addition was completed, the mixture was stirred at room temperature for 2 hours.
そして、副生じた塩を除去し、生成物（Ａ−２）を得た
。Then, the by-produced salt was removed to obtain product (A-2).
・Ａ−３の合成方法：Ａ−１の場合と同様のフラスコに
、オキシ塩化リン１３３．３ ｇ（Ｉ，０％ル）とピリ
ジン７９．１ ｇ（Ｉ，０モル）とを加え、更にビスフ
ェノールＡを出発物質としてエチレンオキサイドを付加
重合した分子量１０００のポリアルキレンエーテル５０
０ｇ（０，５モル）を４０℃以下で滴下し、滴下終了後
２時間攪拌した。次いでピリジン１５８．２ｇ（２，０
モル）とグリシドール１４８ｇ（２，０モル）とを４０
℃以下で滴下し、以下Ａ−２の場合と同様にして生成物
（Ａ−３）を得た。・Synthesis method of A-3: Add 133.3 g (I, 0% mol) of phosphorus oxychloride and 79.1 g (I, 0 mol) of pyridine to the same flask as in the case of A-1, and then add Polyalkylene ether 50 with a molecular weight of 1000 obtained by addition polymerizing ethylene oxide using bisphenol A as a starting material.
0 g (0.5 mol) was added dropwise at 40° C. or lower, and the mixture was stirred for 2 hours after the dropwise addition was completed. Next, 158.2 g of pyridine (2,0
mol) and 148 g (2.0 mol) of glycidol in 40
The mixture was added dropwise at a temperature below .degree. C., and a product (A-3) was obtained in the same manner as in the case of A-2.
次に、かくして合成したＡ−１〜Ａ−７等を用い、第１
表記載のサイジング剤（実施例１〜７、比較例１〜３）
を調整した。Next, using A-1 to A-7 etc. synthesized in this way, the first
Sizing agent listed in the table (Examples 1 to 7, Comparative Examples 1 to 3)
adjusted.
そして、いずれも次のように、炭素繊維を処理し、コン
ポジットを成形して、試験乃至評価した。In each case, carbon fibers were treated and composites were molded and tested and evaluated as follows.
結果を第２表に示した。The results are shown in Table 2.
・炭素繊維のサイジング処理：市販のＰＡＮ系炭素繊維
（ｉμ／３０００フィラメント）を有機溶剤にて脱サイ
ズし、これに各サイジング剤を有効成分付着量が０．７
重量％となるようにディップ法で含浸させ、乾燥後、オ
ープン中で１５０℃×３０分間熱処理した。・Sizing treatment of carbon fiber: Commercially available PAN-based carbon fiber (iμ/3000 filament) was desized with an organic solvent, and each sizing agent was applied to it with an active ingredient adhesion amount of 0.7.
It was impregnated by a dipping method so as to have the same weight percent, and after drying, it was heat-treated at 150° C. for 30 minutes in an open environment.
・コンポジットの成形：前記のようにサイジング処理し
た炭素繊維に、エピコート８２８（シェル社製、ビスフ
ェノールＡジグリシジルエーテルモノマー）を１００ｇ
＋ボロントリフルオライドモノメチルアミンを５ｇ＋メ
チルエチルケトンを２５ｇからなる樹脂液を含浸させ、
１２０℃で半硬化させて一方向プリプレグを作成した。・Composite molding: Add 100 g of Epicoat 828 (manufactured by Shell, bisphenol A diglycidyl ether monomer) to the carbon fibers sized as described above.
+ impregnated with a resin liquid consisting of 5 g of boron trifluoride monomethylamine + 25 g of methyl ethyl ketone,
A unidirectional prepreg was produced by semi-curing at 120°C.
このプリプレグを金型中に積層して、１７０℃×１時間
加圧し、Ｖｆ（コンポジット中の炭素繊維の体積％）＝
６０％のコンポジットを成形した。This prepreg was laminated in a mold and pressurized at 170°C for 1 hour. Vf (volume % of carbon fiber in composite) =
A 60% composite was molded.
・毛羽、糸切れ試験：前記のようにサイジング処理した
炭素繊維について、ＴＭ式抱合カテスター（大栄化学精
機社製）を用い、荷重５０ｇ／３０００ フィラメン
ト、θ＝１５０度、擦過長３０朋、クロムメッキ金属櫛
を１５０回／分の速さで５００回往復運動させて、繊維
−金属間の擦過試験をした。また別に、ラビングテスタ
ー（東洋精機社製）を用い、内角３５度、１回撚り、擦
過長２０＋＋＋＋＋＋、１００回／分の速さで５００回
往復運動させて、繊維−繊維間の擦過試験をした。そし
て、ともに以下の５段階基準で評価した。・Fuzz and thread breakage test: Carbon fibers sized as described above were tested using a TM type conjugated catester (manufactured by Daiei Kagaku Seiki Co., Ltd.) at a load of 50 g/3000 filament, θ = 150 degrees, rubbing length of 30 mm, and chrome plating. A metal comb was reciprocated 500 times at a speed of 150 times/min to perform a fiber-to-metal abrasion test. Separately, using a rubbing tester (manufactured by Toyo Seiki Co., Ltd.), a fiber-to-fiber friction test was performed by reciprocating 500 times at a speed of 100 times/minute, twisting once at an internal angle of 35 degrees, and a friction length of 20++++++. . Both were evaluated using the following 5-level criteria.
Ａ＝毛羽が殆んど発生しない。A = Almost no fluff is generated.
Ｂ：＝：単数的な毛羽しか発生しない。B:=: Only singular fuzz is generated.
Ｃ＝毛羽が集団的に発生する。C=Fuzz occurs in clusters.
Ｄ−毛羽が多発し、一部が切断する。D-Fuzzing occurs frequently and some parts are cut off.
Ｅ＝３０００フィラメントが切断する。E=3000 filament breaks.
・層間剪断強度試験：前記のように成形したコンポジッ
トについて、ＡＳＴＭのＤ−２３４４に準じ測定した（
ＩＬＳＳ）。・Interlaminar shear strength test: The composite molded as described above was measured according to ASTM D-2344 (
ILSS).
・乳化安定性試験：各サイジング剤の有効成分１０重量
係エマルジョンを調整し、２０℃×７日間放置した。そ
して、以下の３段階基準で評価した。- Emulsion stability test: Emulsions based on 10 weight of the active ingredients of each sizing agent were prepared and left at 20°C for 7 days. Then, evaluation was made using the following three-level criteria.
〇−分離なし
△−クリーム状分離物が浮いた
×＝沈澱が生じた
第１表
注）表中数値は重量部。＊１はエピコート８２８（シェ
ル社製、ビスフェノールＡジグリシジルエーテルモノマ
ー）、＊２はエピコート１００１（シェル社製、ビスフ
ェノールＡジグリシジルエーテルオリゴマー）、以上は
従来のサイジング剤に使用のエポキシ化合物。〇 - No separation △ - Creamy separated product floated × = Precipitation occurred Table 1 Note) Values in the table are parts by weight. *1 is Epicote 828 (manufactured by Shell, bisphenol A diglycidyl ether monomer), *2 is Epicote 1001 (manufactured by Shell, bisphenol A diglycidyl ether oligomer), and the above are epoxy compounds used in conventional sizing agents.
＊３はポリオキシエチレン（Ｉ０モル）ラウリルエーテ
ル、＊４はポリオキシエチレン（Ｉ５モル）ノニルフェ
ニルクリシジルエーテル、＊５はポリオキシエチレン（
６モル）ノニルフェニルエーテル、＊６はポリオキシエ
チレン（２５モル）トリスチレン化フェニルエーテル、
＊７はポリオキシエチレン（３０モル）テトラヘンシル
化フェニルフェノールエーテル、以上は乳化剤。＊８は
水、＊９はメチルエチルケトン、以上は溶媒、この溶媒
を除いたものが各サイジング剤の有効成分。*3 is polyoxyethylene (I0 mol) lauryl ether, *4 is polyoxyethylene (I5 mol) nonylphenylcricidyl ether, *5 is polyoxyethylene (
6 mol) nonylphenyl ether, *6 is polyoxyethylene (25 mol) tristyrenated phenyl ether,
*7 is polyoxyethylene (30 mol) tetrahensylated phenylphenol ether, and the above is an emulsifier. *8 is water, *9 is methyl ethyl ketone, the above are solvents, and the active ingredient of each sizing agent is the solvent.
第２表 注）−印は水性エマルジョンとしなかったもの。Table 2 Note) - indicates that the water-based emulsion was not used.
第２表の結果からも、前述の如き本発明の効果が明白で
ある。From the results in Table 2, the effects of the present invention as described above are clear.
Claims (1)
ノール型ポリアルキレンエーテルエポキシ化合物を含有
することを特徴とする炭素繊維用サイジング剤。 一般式（ I ）： ▲数式、化学式、表等があります▼ 一般式（II）： ▲数式、化学式、表等があります▼ 〔但し、Ｒは炭素数２〜４のアルキレン基｛単独又は混
合のいずれでもよく、混合の場合にブロック結合又はラ
ンダム結合のいずれでもよい｝。Ｙは、▲数式、化学式
、表等があります▼、▲数式、化学式、表等があります
▼又は−ＣＨ＿２−。ｎは１〜３０の整数。Ｘは次のｉ
）又はｉｉ）より選ばれる残基｛これらの残基中、−Ｏ
−は一般式（II）の末端グリシジル基へ結合する）。 ｉ）▲数式、化学式、表等があります▼（Ｚ＿１、Ｚ＿
２はＣＨ＿３−又は▲数式、化学式、表等があります▼
）ｉｉ）▲数式、化学式、表等があります▼又は▲数式
、化学式、表等があります▼（Ｚ＿３はＲ′Ｏ−又は▲
数式、化学式、表等があります▼で、ここにＲ′は炭 素数１〜１８の、アルキル基、ア ルケニル基又は置換フェニル基） ２ 一般式（ I ）又は（II）において、ｎが５〜２０
の整数である特許請求の範囲第１項記載の炭素繊維用サ
イジング剤。 ３ 一般式（ I ）又は（II）において、Ｒがエチレン
基／プロピレン基＋ブチレン基≧８／２（モル比）であ
る特許請求の範囲第２項記載の炭素繊雑用サイジング剤
。[Scope of Claims] 1. A sizing agent for carbon fibers, characterized by containing a bisphenol type polyalkylene ether epoxy compound represented by the following general formula (I) or (II). General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, R is an alkylene group having 2 to 4 carbon atoms {single or mixed Either may be used, and in the case of mixing, either block combination or random combination may be used. Y is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or -CH_2-. n is an integer from 1 to 30. X is the next i
) or ii) {among these residues, -O
- is bonded to the terminal glycidyl group of general formula (II)). i) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(Z_1, Z_
2 is CH_3- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼
) ii) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Z_3 is R'O- or ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, where R' is an alkyl group, alkenyl group, or substituted phenyl group having 1 to 18 carbon atoms) 2 In general formula (I) or (II), n is 5 to 20
The sizing agent for carbon fibers according to claim 1, which is an integer of . 3. The sizing agent for carbon fibers according to claim 2, wherein in the general formula (I) or (II), R is ethylene group/propylene group+butylene group≧8/2 (molar ratio).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14517984A JPS6128074A (en) | 1984-07-12 | 1984-07-12 | Sizing agent for carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14517984A JPS6128074A (en) | 1984-07-12 | 1984-07-12 | Sizing agent for carbon fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6128074A true JPS6128074A (en) | 1986-02-07 |
| JPH048542B2 JPH048542B2 (en) | 1992-02-17 |
Family
ID=15379252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14517984A Granted JPS6128074A (en) | 1984-07-12 | 1984-07-12 | Sizing agent for carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6128074A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01272867A (en) * | 1988-04-22 | 1989-10-31 | Toray Ind Inc | Carbon fiber excellent in high-order processability |
| US4944932A (en) * | 1985-12-27 | 1990-07-31 | Toray Industries Inc. | Process for producing carbon fiber |
| US7094468B2 (en) | 2001-05-25 | 2006-08-22 | Mitsubishi Rayon Co., Ltd. | Sizing agent for carbon fiber, aqueous dispersion thereof, carbon fiber treated by sizing sheet-form object comprising the carbon fiber, and carbon fiber-reinforced coposite material |
| 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 |
| US7150913B2 (en) | 2001-07-24 | 2006-12-19 | Mitsubishi Rayon Co., Ltd. | Sizing agent for carbon fiber, aqueous dispersion of the same, carbon fiber treated by sizing, sheet comprising the carbon fiber, and carbon fiber-reinforced composite material |
| JP2009144303A (en) * | 2007-12-18 | 2009-07-02 | Mitsubishi Rayon Co Ltd | Sizing agent and sized carbon fiber bundle |
| WO2012002266A1 (en) | 2010-06-30 | 2012-01-05 | 東レ株式会社 | Method for producing sizing agent-coated carbon fibers, and sizing agent-coated carbon fibers |
| WO2013051404A1 (en) | 2011-10-04 | 2013-04-11 | 東レ株式会社 | Carbon fiber-reinforced thermoplastic resin composition, molding material, prepreg, and methods for producing same |
| WO2013084669A1 (en) | 2011-12-05 | 2013-06-13 | 東レ株式会社 | Carbon fiber molding material, molding material, and carbon fiber-strengthening composite material |
| WO2013099707A1 (en) | 2011-12-27 | 2013-07-04 | 東レ株式会社 | Carbon fiber coated with sizing agent, process for producing carbon fiber coated with sizing agent, prepreg, and carbon fiber reinforced composite material |
| WO2013172200A1 (en) | 2012-05-16 | 2013-11-21 | 株式会社ダイセル | Epoxy-amine adduct, resin composition, sizing agent, carbon fiber coated with sizing agent, and fiber-reinforced composite material |
| WO2014061336A1 (en) | 2012-10-18 | 2014-04-24 | 東レ株式会社 | Carbon fiber-reinforced resin composition, method for manufacturing carbon fiber-reinforced resin composition, molding material, method for manufacturing molding material, and carbon-fiber reinforced resin molded article |
| KR20200111411A (en) | 2019-03-19 | 2020-09-29 | 한국과학기술연구원 | Method and apparatus for surface-treating of carbon fiber coated with compound having benzene ring through rapid plasma treatment, and method for improving physical property of carbon fiber thereby and carbon fiber having improved physical property thereby |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50160380A (en) * | 1974-04-27 | 1975-12-25 | ||
| JPS5277289A (en) * | 1975-12-19 | 1977-06-29 | Asahi Chemical Ind | Carbon fibre use sizing agent |
-
1984
- 1984-07-12 JP JP14517984A patent/JPS6128074A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50160380A (en) * | 1974-04-27 | 1975-12-25 | ||
| JPS5277289A (en) * | 1975-12-19 | 1977-06-29 | Asahi Chemical Ind | Carbon fibre use sizing agent |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4944932A (en) * | 1985-12-27 | 1990-07-31 | Toray Industries Inc. | Process for producing carbon fiber |
| JPH01272867A (en) * | 1988-04-22 | 1989-10-31 | Toray Ind Inc | Carbon fiber excellent in high-order processability |
| US7094468B2 (en) | 2001-05-25 | 2006-08-22 | Mitsubishi Rayon Co., Ltd. | Sizing agent for carbon fiber, aqueous dispersion thereof, carbon fiber treated by sizing sheet-form object comprising the carbon fiber, and carbon fiber-reinforced coposite material |
| US7150913B2 (en) | 2001-07-24 | 2006-12-19 | Mitsubishi Rayon Co., Ltd. | Sizing agent for carbon fiber, aqueous dispersion of the same, carbon fiber treated by sizing, sheet comprising the carbon fiber, and carbon fiber-reinforced composite material |
| 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 |
| JP2009144303A (en) * | 2007-12-18 | 2009-07-02 | Mitsubishi Rayon Co Ltd | Sizing agent and sized carbon fiber bundle |
| WO2012002266A1 (en) | 2010-06-30 | 2012-01-05 | 東レ株式会社 | Method for producing sizing agent-coated carbon fibers, and sizing agent-coated carbon fibers |
| WO2013051404A1 (en) | 2011-10-04 | 2013-04-11 | 東レ株式会社 | Carbon fiber-reinforced thermoplastic resin composition, molding material, prepreg, and methods for producing same |
| KR20150055089A (en) | 2011-10-04 | 2015-05-20 | 도레이 카부시키가이샤 | Carbon fiber-reinforced thermoplastic resin composition, molding material, prepreg, and methods for producing same |
| WO2013084669A1 (en) | 2011-12-05 | 2013-06-13 | 東レ株式会社 | Carbon fiber molding material, molding material, and carbon fiber-strengthening composite material |
| US10184034B2 (en) | 2011-12-05 | 2019-01-22 | Toray Industries, Inc. | Carbon fiber forming raw material, formed material, and carbon fiber-reinforced composite material |
| WO2013099707A1 (en) | 2011-12-27 | 2013-07-04 | 東レ株式会社 | Carbon fiber coated with sizing agent, process for producing carbon fiber coated with sizing agent, prepreg, and carbon fiber reinforced composite material |
| US10138593B2 (en) | 2011-12-27 | 2018-11-27 | Toray Industries, Inc. | Sizing agent-coated carbon fibers, process for producing sizing agent-coated carbon fibers, prepreg, and carbon fiber reinforced composite material |
| WO2013172200A1 (en) | 2012-05-16 | 2013-11-21 | 株式会社ダイセル | Epoxy-amine adduct, resin composition, sizing agent, carbon fiber coated with sizing agent, and fiber-reinforced composite material |
| US9388294B2 (en) | 2012-05-16 | 2016-07-12 | Daicel Corporation | Epoxy-amine adduct, resin composition, sizing agent, carbon fiber coated with sizing agent, and fiber-reinforced composite material |
| US9777135B2 (en) | 2012-05-16 | 2017-10-03 | Daicel Corporation | Epoxy-amine adduct, resin composition, sizing agent, carbon fiber coated with sizing agent, and fiber-reinforced composite material |
| EP3287478A1 (en) | 2012-05-16 | 2018-02-28 | Daicel Corporation | Epoxy-amine adduct, resin composition, sizing agent, carbon fiber coated with sizing agent, and fiber-reinforced composite material |
| KR20150047638A (en) | 2012-10-18 | 2015-05-04 | 도레이 카부시키가이샤 | Carbon fiber-reinforced resin composition, method for manufacturing carbon fiber-reinforced resin composition, molding material, method for manufacturing molding material, and carbon-fiber reinforced resin molded article |
| WO2014061336A1 (en) | 2012-10-18 | 2014-04-24 | 東レ株式会社 | Carbon fiber-reinforced resin composition, method for manufacturing carbon fiber-reinforced resin composition, molding material, method for manufacturing molding material, and carbon-fiber reinforced resin molded article |
| US10501605B2 (en) | 2012-10-18 | 2019-12-10 | Toray Industries, Inc. | Carbon fiber-reinforced resin composition, method for manufacturing carbon fiber-reinforced resin composition, molding material, method for manufacturing molding material, and carbon fiber-reinforced resin molded article |
| KR20200111411A (en) | 2019-03-19 | 2020-09-29 | 한국과학기술연구원 | Method and apparatus for surface-treating of carbon fiber coated with compound having benzene ring through rapid plasma treatment, and method for improving physical property of carbon fiber thereby and carbon fiber having improved physical property thereby |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH048542B2 (en) | 1992-02-17 |
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